CN110660981B - Graphene-coated bimetallic selenide material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a graphene-coated bimetallic selenide material and a preparation method and application thereof. The preparation method comprises the following steps: (1) carrying out solvothermal reaction on cobalt salt, nickel salt, polyvinylpyrrolidone and trimesic acid in a solvent to obtain a reaction product NiCo-MOF; (2) selenizing and carbonizing NiCo-MOF to obtain NiCoSe product4(ii) a (3) Mixing NiCoSe4And carrying out solvothermal reaction on the graphene oxide GO to obtain the graphene-coated bimetallic selenide material. The graphene-coated bimetallic selenide material provided by the invention has mesoporous property and larger specific surface area, so that not only are the sodium ions and the surface effect increased and the conductivity enhanced, but also the problem of structural collapse caused by volume expansion in the charging and discharging processes of the bimetallic selenide is relieved, and the cycle performance of the battery is effectively improved.
Description
Technical Field
The invention belongs to the field of preparation methods and applications of sodium ion negative electrode materials, and mainly relates to a graphene-coated bimetallic selenide material and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) occupy the market leading position for a long time, have the advantages of large capacity, high voltage, long cycle life, no memory effect and the like, and are considered to be the first choice for the current energy storage application. However, the shortage of lithium limits further development due to the current expensive lithium resource. Compared with the lithium ion battery, the sodium ion battery has the advantages of low cost, abundant resources and similar physicochemical properties of lithium, is paid attention by a plurality of researchers, and is expected to replace the lithium ion battery in large-scale energy storage application.
Although the negative electrode material of the sodium ion battery has attracted much attention from researchers and has many advantages, the following serious problems still remain: due to Na+The ionic radius of the ions is larger, the diffusion kinetics is slower, and therefore the cycle and rate performance of the battery are poorer. Therefore, suitable host materials are sought for efficiently and reversibly containing Na+Ions are very necessary.
Currently, research into anode materials is relatively abundant, including promising high capacity metals (P, Sn, Ge, and Sb) and metal compounds (oxides, phosphides, sulfides, and selenides). The metal selenide has the advantages of abundant resources, low cost, strong theoretical sodium storage capacity and the like, so that the metal selenide has wide attention to various SIBs cathode materials. However, their low rate capability is due to their generally poor conductivity. In addition, they have large volume changes during continuous discharge/charge, resulting in poor cycle stability. Well-designed graphene hybridization is an effective way to solve the two problems. Therefore, the NiCo-MOF composite material synthesized based on NiCo-MOF as a precursor is hybridized with graphene to solve the problems of poor conductivity and volume expansion in the circulation process.
Disclosure of Invention
In order to improve the conductivity of the bimetallic selenide, the invention aims to provide a graphene-coated bimetallic selenide material and a preparation method and application thereof. Using NiCo-MOF as a precursor, then in a tube furnace 550oC one-step selenization and carbonization for 12h to synthesize NiCoSe4Finally 95oObtaining NiCoSe by C hydrothermal wrapping graphene4@rGO。
The object of the invention is achieved by at least one of the following solutions.
The invention aims to provide a preparation method of a graphene-coated bimetallic selenide material, which comprises the following steps:
(1) carrying out solvothermal reaction on cobalt salt, nickel salt, polyvinylpyrrolidone and trimesic acid in a solvent to obtain a reaction product NiCo-MOF;
(2) selenizing and carbonizing NiCo-MOF to obtain NiCoSe product4；
(3) Mixing NiCoSe4And carrying out solvothermal reaction on the graphene oxide GO to obtain the graphene-coated bimetallic selenide material.
Preferably, the cobalt salt in step (1) comprises more than one of cobalt nitrate hexahydrate, cobalt sulfide hexahydrate and cobalt sulfate; the nickel salt comprises more than one of nickel nitrate hexahydrate, nickel chloride hexahydrate and nickel sulfate hexahydrate.
Preferably, in the step (1), the mass ratio of the cobalt ions in the cobalt salt to the nickel ions in the nickel salt is (1-2): (2-1).
Preferably, the solvent in the step (1) is a mixed solvent of ethanol, N-dimethylformamide and water, and the volume ratio of ethanol, N-dimethylformamide and water in the mixed solvent is (1-1.5): (1-2): (1-3).
Preferably, the temperature of the solvothermal reaction in the step (1) is 120-180 DEGoAnd C, the reaction time is 3-12 h.
Preferably, the mass ratio of the cobalt ions in the cobalt salt to the trimesic acid in the step (1) is (1-1.2): 1;
the mass ratio of cobalt ions to polyvinylpyrrolidone in the cobalt salt is (432-864): 3000;
the volume ratio of the amount of the cobalt ion in the cobalt salt to the solvent is (1.49-2.98): 60 mol/L.
Preferably, in the step (2), NiCo-MOF is subjected to washing and centrifugal treatment by water and ethanol and then selenization and carbonization are carried out; in the selenizing and carbonizing treatment, the mass ratio of NiCo-MOF to selenium powder is 1 (2-4), and the heating rate is 1-5oC/min, and the temperature rise interval is 500-700oC, annealing for 3-12 hours in an inert atmosphere; the inert atmosphere is argon.
Preferably, the solvothermal reaction in the step (3) specifically comprises reacting NiCoSe4Dispersing in deionized water, adding graphene oxide GO, mixing uniformly, adding a reducing agent, reacting, washing, and freeze-drying, wherein the washing is deionized water washing for 3-5 times; the temperature of the solvothermal reaction is 90-120 DEG CoC; the reaction time is 1-4 h.
Preferably, NiCoSe in the step (3)4The mass ratio of the deionized water to the deionized water is (10-20): (2-8) g/L.
Preferably, the reducing agent in step (3) is ascorbic acid, NiCoSe4The mass ratio of GO to ascorbic acid is (3-10) to 1 (10-15)
The invention also provides the graphene-coated bimetallic selenide material prepared by the preparation method.
The invention also provides application of the graphene-coated bimetallic selenide material in preparation of a negative electrode of a sodium-ion battery.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) the graphene-coated bimetallic selenide material provided by the invention has mesoporous property and larger specific surface area, so that not only are the sodium ions and the surface effect increased and the conductivity enhanced, but also the problem of structural collapse caused by volume expansion in the charging and discharging processes of the bimetallic selenide is relieved, and the cycle performance of the battery is effectively improved;
(2) compared with the traditional preparation method of the bimetallic selenide, the preparation method of the bimetallic selenide material wrapped by the graphene is simpler, can be used for mass production, has uniform particle size, good carbon material wrapping and stable cycle performance, and is beneficial to providing the conductivity of the material;
(3) the bimetallic selenide material wrapped by the graphene is used as a negative electrode material of the sodium-ion battery to show good cycle performance and rate capability, which has positive significance for realizing industrialization of the sodium-ion battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments will be briefly described below.
FIG. 1 is SEM images of different magnifications of a porous metal organic framework NiCo-MOF-1 prepared in example 1;
FIG. 2 is a view of the bimetallic selenide NiCoSe prepared in example 14-SEM images at different magnifications of 1;
FIG. 3a is a NiCoSe microsphere structure prepared in example 14SEM picture of @ rGO-1; FIG. 3b is a NiCoSe prepared in example 14TEM image of @ rGO-1;
FIG. 4 is a NiCoSe prepared in example 14-1 and NiCoSe4XRD pattern of @ rGO-1;
FIG. 5 is a NiCoSe prepared in example 14-1 and NiCoSe4TG analysis profile of @ rGO-1;
FIG. 6 is a NiCoSe prepared in example 14@ rGO-1 and NiCoSe4-a nitrogen adsorption/desorption isotherm of 1;
FIG. 7 is a NiCoSe prepared in example 14@ rGO-1 and NiCoSe4-1 pore size distribution curve;
FIG. 8 is the microsphere structure of the double metal selenide NiCoSe in example 14The rate performance graph of the sodium ion battery with @ rGO-1 as a negative electrode material at different currents;
FIG. 9 is the microsphere structure of the double metal selenide NiCoSe in example 14And @ rGO-1 is taken as a negative electrode material, and the cycle performance of the sodium ion battery is shown when the current is 1A/g.
Detailed Description
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown.
Example 1
The embodiment provides a preparation method of a graphene-coated bimetallic selenide material, which comprises the following steps:
(1) 432 mg of nickel nitrate hexahydrate (Ni (NO)3)2•6H2O) with 432 mg of cobalt nitrate hexahydrate (Co (NO)3)2•6H2O), 300 mg of trimesic acid and 3 g of polyvinylpyrrolidone (PVP) were dissolved in 60 mL (1: 1:1:1 volume ratio of ethanol, water, N-dimethylformamide) of a mixed solvent and stirred for about 30 min to obtain a mixed solution, the mixed solution was transferred to a 100 mL autoclave, and the autoclave was placed in an oven and heated to 150%oC, preserving the temperature for 10 h, centrifuging the final product for 2 min at 10000 rpm, washing the product for 5 times by using water and ethanol, and finally drying the product in an oven at the temperature of 80 ℃ for 12h to obtain a reaction product NiCo-MOF-1;
(2) 200mg of NiCo-MOF-1 and 400 mg of selenium powder are mixed and ground uniformly and then are put into a quartz magnetic boat together for selenylation carbonization treatment. Provided that 2 isoHeating to 550 ℃ at the rate of C/minoC, preserving the heat for 12 hours in an argon atmosphere, and cooling to room temperature to obtain a product NiCoSe4-1；
(3) Mixing NiCoSe4Dispersing 1200 mg of the mixture in 50 mL of deionized water, adding 40 mg of GO, adding 400 mg of ascorbic acid serving as a reducing agent after ultrasonic dispersion, and adding 95 mg of ascorbic acid serving as a reducing agentoC, after hydrothermal reaction for 2 hours, washing the reaction product for 3 times by using deionized water, and freeze-drying the reaction product to obtain the graphene-coated bimetallic selenide material NiCoSe4@rGO-1。
FIG. 1 is an SEM image of NiCo-MOF-1 at different magnifications, and it can be seen that the obtained NiCo-MOF-1 is a microsphere composed of nano rods, and the diameter is about 10-12 μm.
FIG. 2 is a NiCoSe4SEM images of different magnifications of-1 show that the NiCo-MOF-1 precursor becomes reticular microspheres in an argon reduction atmosphere, although the size is reduced and is about 5-8 μm on average, the morphology is kept to be the original spherical shape.
FIG. 3 is a NiCoSe4SEM and TEM images of @ rGO-1, in FIG. 3a, NiCoSe prepared4-1 embedding microsphere materials into rGO nanoflakes to form three-dimensional graphic structures; FIG. 3b shows a lattice spacing of about 0.21 nm, which is comparable to NiCoSe in FIG. 44The (200) crystal face of the-1 XRD analysis pattern corresponds.
FIG. 4 is a NiCoSe4-1 and NiCoSe4XRD pattern of @ rGO-1 from diffraction peaks and NiSe in FIG. 42Two standard cards (JCPDS No. 65-5016) And CoSe2(JCPDS No. 65-3327); the peak position is in the middle of the two standard cards, indicating that selenium is completely converted to selenide with an equal molar ratio of nickel to cobalt.
FIG. 5 is a NiCoSe4-1 and NiCoSe4TG analytical profile of @ rGO-1, to study NiCose4rGO content in @ rGO-1 vs. NiCoSe4-1 and NiCoSe4@ rGO-1 was subjected to thermogravimetric analysis testing. For NiCoSe in oxygen4-1 and NiCoSe4@ rGO-1 was subjected to TGA analysis. As can be seen from FIG. 5, when the degradation temperature was further increased to 800 deg.CoC, due to oxidation of the carbon skeleton and NiSe2And CoSe2Decomposition to produce CoO, NiO and Se, oxidation of carbon skeleton to CO2And (5) volatilizing. According to the reaction that occurs on thermogravimetric scale: NiCose4（s）+ O2(g) = CoO (s)) + NiO (s)) +4Se (g), NiCoSe is obtained through calculation4NiCoSe in @ rGO-14And rGO content 83% and 17%, respectively. Description of NiCose4Active material NiCoSe in @ rGO-14The content of (A) is quite high, and the capacity is mainly derived from NiCoSe4。
As shown in fig. 6 and 7, are NiCoSe4@ rGO-1 and NiCoSe4-1 nitrogen adsorption/desorption isotherm and pore size distribution curve. The nitrogen adsorption/desorption isotherm is an IV-type isotherm, has a hysteresis loop under a higher relative pressure, and shows mesoporous characteristics. The pore diameter calculated by BJH method is 35 nm. NiCose from isotherms4@ rGO-1 and NiCoSe4Specific surface areas of-1 were 49 and 10.6 m, respectively2 g-1，NiCoSe4Specific surface area ratio NiCoSe of @ rGO-14-1 is larger. This may be due to the layer properties of graphene oxide.
NiCoSe prepared in example 14Grinding the @ rGO-1 into powder, adding acetylene black, CMC and SBR, grinding into slurry, coating the slurry on a copper foil, filling a battery in a glove box, and carrying out a sodium ion battery cycle performance test by utilizing a blue-electricity system.
As shown in FIG. 8, NiCoSe4@ rGO-1 and NiCoSe 41 cycling behavior at different current densities, from which it can be seen that NiCoSe is present at different current densities4Performance ratio NiCoSe of @ rGO-14Excellent-1, NiCoSe4The capacity of @ rGO-1 can still maintain 288.6 mAh/g under a large current of 10A/g, and excellent rate performance is shown.
As shown in FIG. 9, NiCoSe4@ rGO-1 and NiCoSe 41 cycle Performance at 1A/g Current, NiCoSe4-1 the initial discharge capacity of the electrode is 444.3 mA h/g, gradually reduced to 280 mA h/g after 220 cycles, and kept at 238.2 mA h/g after 1500 cycles; and NiCoSe4The discharge capacity of the @ rGO-1 electrode after 1500 cycles is 293 mA h/g, and the cycle is stable, so that the wrapping of the graphene is helpful for improving the conductivity of the material and relieving the problem of volume expansion in the cycle process.
Example 2
(1) 864 mg of nickel nitrate hexahydrate (Ni (NO)3)2•6H2O) with 432 mg of cobalt nitrate hexahydrate (Co (NO)3)2•6H2O), 285 mg of trimesic acid and 3 g of polyvinylpyrrolidone (PVP) were dissolved in 60 mL (1: 1:1:1 volume ratio of ethanol, water, N-dimethylformamide) of a mixed solvent and stirred for about 30 min to obtain a mixed solution, the mixed solution was transferred to a 100 mL autoclave, and the autoclave was placed in an oven and heated to 120%oC, preserving the heat for 12 hours, centrifuging the final product for 2 minutes at 10000 rpm, washing the product for 5 times by using water and ethanol, and finally drying the product in an oven at the temperature of 80 ℃ for 12 hours to obtain a reaction product NiCo-MOF-2;
(2) 200mg of NiCo-MOF-2 and 600 mg of selenium powder are mixed and ground uniformly and then are put into a quartz magnetic boat together for selenylation carbonization treatment. Provided that 2 isoHeating to 550 ℃ at the rate of C/minoC, preserving the heat for 12 hours in an argon atmosphere, and cooling to room temperature to obtain a product NiCoSe4-2；
(3) Mixing NiCoSe4-2120 mg of water was dispersed in 50 mL of deionized water, 40 mg of GO was added, and after ultrasonic dispersion 600 mg of ascorbic acid was added as a reducing agent, 95oC, after hydrothermal reaction for 2 hours, washing the reaction product for 3 times by using deionized water, and freeze-drying the reaction product to obtain the graphene-coated bimetallic selenide material NiCoSe4@rGO-2。
Prepared in this exampleNiCo-MOF-2、NiCoSe4-2 and NiCoSe4Properties of @ rGO-2 and NiCo-MOF-1, NiCoSe prepared in example 14-1 and NiCoSe4The relevant performance of @ rGO-1 is similar, as can be seen in particular in FIGS. 1-9.
Example 3
(1) 432 mg of nickel nitrate hexahydrate (Ni (NO)3)2•6H2O) and 864 mg of cobalt nitrate hexahydrate (Co (NO)3)2•6H2O), 522 mg of trimesic acid and 3 g of polyvinylpyrrolidone (PVP) were dissolved in 60 mL (1: 1:1:1 volume ratio of ethanol, water, N-dimethylformamide) of a mixed solvent and stirred for about 30 min to obtain a mixed solution, the mixed solution was transferred to a 100 mL autoclave, and the autoclave was placed in an oven and heated to 180 deg.CoC, preserving heat for 3 hours, centrifuging the final product for 2 minutes at 10000 rpm, washing the product for 5 times by using water and ethanol, and finally drying the product in an oven at the temperature of 80 ℃ for 12 hours to obtain a reaction product NiCo-MOF-3;
(2) 200mg of NiCo-MOF-3 and 800 mg of selenium powder are mixed and ground uniformly and then are put into a quartz magnetic boat together for selenylation carbonization treatment. Provided that 2 isoThe temperature rises to 550 ℃ at the rate of C/minoC, preserving the heat for 12 hours in an argon atmosphere, and cooling to room temperature to obtain a product NiCoSe4-3；
(3) Mixing NiCoSe4-3300 mg dispersed in 50 mL deionized water, 40 mg GO added and after ultrasonic dispersion ascorbic acid (400 mg) was added as a reducing agent, 95oC, after hydrothermal reaction for 2 hours, washing the reaction product for 3 times by using deionized water, and freeze-drying the reaction product to obtain the graphene-coated bimetallic selenide material NiCoSe4@rGO-3。
NiCo-MOF-3, NiCoSe prepared in this example4-3 and NiCoSe4Properties of @ rGO-3 and NiCo-MOF-1, NiCoSe prepared in example 14-1 and NiCoSe4The relevant performance of @ rGO-1 is similar, as can be seen in particular in FIGS. 1-9.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any equivalent alterations, modifications or improvements made by those skilled in the art to the above-described embodiments using the technical solutions of the present invention are still within the scope of the technical solutions of the present invention.
Claims (8)
1. A preparation method of a bimetallic selenide material wrapped by graphene is characterized by comprising the following steps:
(1) carrying out solvothermal reaction on cobalt salt, nickel salt, polyvinylpyrrolidone and trimesic acid in a solvent to obtain a reaction product NiCo-MOF;
(2) selenizing and carbonizing NiCo-MOF to obtain NiCoSe product4；
(3) Mixing NiCoSe4Carrying out hydrothermal reaction with graphene oxide GO to obtain a graphene-coated bimetallic selenide material;
in the step (1), the mass ratio of cobalt ions in the cobalt salt to nickel ions in the nickel salt is (1-2): (2-1); the mass ratio of cobalt ions to trimesic acid in the cobalt salt is (1-1.2): 1; the mass ratio of cobalt ions to polyvinylpyrrolidone in the cobalt salt is (432-864): 3000A; the volume ratio of the amount of the cobalt ion in the cobalt salt to the solvent is (1.49-2.98): 60 mol/L;
the hydrothermal reaction in the step (3) specifically comprises the step of reacting NiCoSe with NiCoSe4Dispersing in deionized water, adding graphene oxide GO, mixing uniformly, adding a reducing agent, reacting, washing, and freeze-drying, wherein the washing is deionized water washing for 3-5 times; the temperature of the hydrothermal reaction is 90-120 ℃; the reaction time is 1-4 h.
2. The method for preparing the graphene-coated bimetal selenide material according to claim 1, wherein the cobalt salt in the step (1) comprises one or more of cobalt nitrate hexahydrate, cobalt sulfide hexahydrate and cobalt sulfate; the nickel salt comprises more than one of nickel nitrate hexahydrate, nickel chloride hexahydrate and nickel sulfate hexahydrate.
3. The method for preparing the graphene-coated bimetallic selenide material according to claim 1, wherein the solvent in the step (1) is a mixed solvent of ethanol, N-dimethylformamide and water, and the volume ratio of ethanol, N-dimethylformamide and water in the mixed solvent is (1-1.5): (1-2): (1-3); the temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 3-12 h.
4. The method for preparing the graphene-coated bimetallic selenide material according to claim 1, wherein in the step (2), NiCo-MOF is subjected to washing and centrifugal treatment by water and ethanol, and then selenization and carbonization are performed; in the selenylation and carbonization treatment, the mass ratio of NiCo-MOF to selenium powder is 1 (2-4), the heating rate is 1-5 ℃/min, the heating interval is 500-700 ℃, and annealing is carried out for 3-12 h under inert atmosphere; the inert atmosphere is argon.
5. The method for preparing the graphene-coated bimetal selenide material of claim 1, wherein NiCoSe in the step (3)4The mass ratio of the deionized water to the deionized water is (10-20): (2-8) g/L.
6. The method for preparing the graphene-coated bimetal selenide material according to claim 1, wherein the reducing agent in the step (3) is ascorbic acid, NiCoSe4The mass ratio of GO to ascorbic acid is (3-10) to (1-10-15).
7. A graphene-coated bimetal selenide material prepared by the preparation method of any one of claims 1 to 6.
8. The use of the graphene-coated bimetallic selenide material of claim 7 in the preparation of a negative electrode for a sodium-ion battery.
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| Composition Engineering Boosts Voltage Windows for Advanced Sodium-Ion Batteries;Yunling Jiang等;《ACS Nano》;20190823;第10787-10797页 * |
| Multishelled NixCo3–xO4 Hollow Microspheres Derived from Bimetal–Organic Frameworks as Anode Materials for High-Performance Lithium-Ion Batteries;Lan-Lan Wu等;《Small》;20170503;第1604270（1-8）页 * |
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