CN112349889B - Preparation method of transition metal sulfide nano composite electrode material - Google Patents

Preparation method of transition metal sulfide nano composite electrode material Download PDF

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CN112349889B
CN112349889B CN201910728106.6A CN201910728106A CN112349889B CN 112349889 B CN112349889 B CN 112349889B CN 201910728106 A CN201910728106 A CN 201910728106A CN 112349889 B CN112349889 B CN 112349889B
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夏晖
孙铭卿
刘子恒
杨梅
徐萌
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Nanjing University of Science and Technology
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract

The invention discloses a preparation method of a transition metal sulfide nano composite electrode material. Dissolving metal salt in deionized water, stirring until the metal salt is completely dissolved, respectively putting PTA and metal salt solution into a microwave hydrothermal reaction kettle, dropwise adding hydrofluoric acid, and reacting at 210 ℃ for 1h to obtain the MOFs precursor. Then the metal organic framework precursor and sublimed sulfur are annealed for 1 to 8 hours at the temperature of 700 to 900 ℃ to obtain the composite material of metal sulfide and carbon. According to the invention, the MOFs precursor is synthesized, the MOFs precursor is taken as a hard template, the structural characteristics of the MOFs precursor are maintained while the metal sulfide is prepared through one-step carbonization and vulcanization, the MOFs precursor is suitable for various transition metal sulfides, the prepared material is small in size and uniform in carbon material distribution, the ion migration distance is shortened, the conductivity of the material is increased, the structure of the MOFs precursor before vulcanization is maintained after vulcanization, and the prepared material has higher reversible capacity, better rate performance and cycle stability in energy storage application.

Description

Preparation method of transition metal sulfide nano composite electrode material
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a preparation method of a transition metal sulfide nano composite electrode material.
Background
With the rapid development of mobile portable electronic devices and electric vehicles and power grids, the demand for energy storage is increasing and increasing. Moreover, the energy storage device greatly restricts the development of some electronic devices. Further development of energy storage devices is therefore highly desirable.
Lithium Ion Batteries (LIBs), one of the most reliable energy storage technologies, have been widely used in portable electronic products, electric vehicles, and even large-scale power grid energy storage. But the reserve of lithium resources is small due to the non-uniform distribution of lithium resources. The cost of lithium raw material is high. This is hardly reconciled with the rapidly growing demand for automotive applications LIBs in the near future. However, since the reserve of sodium resources on earth is far higher than that of lithium resources, sodium ions (Na) are used+) Replacing lithium ions (Li) in battery system of rocking chair+) And the shortage of lithium resources can be effectively relieved. Due to the involvement of solvated Na+Has a radius significantly larger than Li+And thus most electrode materials, especially anode materials commonly used in LIBs (e.g., graphite and silicon), cannot be directly used as sodium-based intercalation compounds because of their limited intercalation capabilities resulting in lower capacity and more significant volume changes leading to poor stability. While the demand for commercial Sodium Ion Batteries (SIB) is increasing, new cathode materials are needed to be found to achieve the mass specific capacity, power, cycle life and safety of LIB.
Transition metal sulfide has various reaction mechanisms in the reaction of the battery, has good reaction capability on the sodium ion battery, and is widely applied to the sodium ion battery, but the conductivity of the transition metal sulfide is poor, so that the transition metal sulfide needs to be compounded with a carbon material, the electronic conductivity of the material is increased, and the performance of the battery is improved. However, the transition metal sulfide prepared by the gel sol method, the coprecipitation method and the hydrothermal method has a low specific surface area, few reactive sites are used, the battery performance is not particularly ideal, and the preparation methods have more steps and are complicated to operate. Because different transition metal elements have different properties, the preparation methods are different, and thus a universal preparation method is required.
The metal organic framework compounds (MOFs) are prepared by the steps of forming a certain monomer by self-loading inorganic metal ions and organic ligands to coordinate, mutually bonding and linking, and then uniformly arranging to form a crystalline porous material with a periodic network structure. In addition, the MOFs have the advantages of large porosity, large specific surface area and the like, so that when the MOFs are used for preparing an electrode material, large active sites can be provided, and the performance of a battery is further improved. In addition, the method is simple and easy to operate, the product has uniform appearance and smaller particle size, and the factors are beneficial to improving the performance of the battery.
Disclosure of Invention
The invention aims to overcome the problems of complex preparation operation, long preparation time, uneven material appearance, large size and low specific capacity of the conventional transition metal sulfide, and provides a novel rapid preparation method of a metal sulfide nano composite electrode material, which is easy to operate, uniform in material appearance, small in product size and high in specific capacity, and the method is suitable for various transition metal sulfides.
In order to achieve the above object, the present invention adopts the following technical solutions.
A preparation method of a transition metal sulfide nano composite electrode material comprises the following steps:
step one, synthesizing MOFs precursors: the metal salt solution is mixed with PTA, and urea is added. Adjusting the pH value with a concentrated HF solution, putting the solution into a microwave reaction hydrothermal tank for microwave hydrothermal reaction, and after the reaction is finished, carrying out centrifugal washing by using deionized water.
Step two, activating the MOFs precursors: and (4) adding a certain amount of DMF solution into the MOFs precursor obtained in the step one, and putting the mixture into an oven for treatment.
Step three, one-step vulcanization and carbonization: and (4) mixing the MOFs precursor prepared in the third step with sulfur powder, putting the mixture into a porcelain boat, and sintering in a tubular furnace under the protection of argon.
Preferably, in the first step, the molar ratio of the metal salt to the urea and the PTA is 1:1: 1.5.
Preferably, in the first step, the pH is adjusted to 1 by using a concentrated HF solution, and the pressure of the hydrothermal tank is controlled to be 2 GPa-2.2 GPa.
Preferably, in the first step, the temperature of the microwave reaction is 190-210 ℃.
Preferably, in the second step, the temperature for activating the MOFs precursor is 80 ℃.
Preferably, in the third step, the mass ratio of the MOFs precursor to the sulfur powder is 1: 2-3.
Preferably, in the third step, the temperature rising rate of the MOFs precursor and the sulfur powder during sintering is
5～10℃/min。
Preferably, in the third step, the sintering temperature of the MOFs precursor and the sulfur powder is 700-900 ℃.
Preferably, in the third step, the sintering time of the MOFs precursors and the sulfur powder is 4 to 6 hours.
The urea is preferably added in the preparation process, so that the prepared product has the nitrogen doping effect, and the cycle performance of the material in the sodium-ion battery is improved.
Compared with the prior art, the invention has the following advantages:
1. the synthesis of the precursor material only needs 1h by using a microwave hydrothermal method, the preparation time is short, and the precursor material can be quickly prepared; 2. because MOFs are used as precursors, the specific surface area of the product is larger, and more reaction sites can be provided for the battery; 3. the urea is added during the preparation of the material, and the prepared material has the nitrogen doping effect, so that the cycle of the battery is promoted; 4. in addition, the MOFs precursor has a stable structure, and after further vulcanization and carbonization, the obtained material also maintains the structure of the MOFs precursor to a certain degree, so that the support is provided for stable circulation of the battery.
Drawings
FIG. 1 is an XRD pattern of MIL-101(Cr) which is a precursor of MOFs prepared in example 4.
FIG. 2 is a MOFs-derived carbon composite Cr prepared in example 42S3XRD pattern of the nano material.
FIG. 3 is an XRD pattern of MOFs-derived carbon composite NiS nanomaterials prepared by changing metal salts according to the method of example 4.
FIG. 4 is a MOFs-derived carbon composite Cr prepared in example 42S3SEM image of nanomaterial.
FIG. 5 is a MOFs-derived carbon composite Cr prepared in example 42S3BET spectra of the nanomaterials.
FIG. 6 shows MOFs-derived carbon composite Cr prepared in comparative example 12S3The capacity cycle curve diagram of the nano material under different raw material proportions.
FIG. 7 shows MOFs-derived carbon composite Cr prepared in comparative example 22S3Capacity cycling curves of nanomaterials at different annealing temperatures.
FIG. 8 is a MOFs-derived carbon composite Cr prepared in comparative example 32S3Capacity cycling plots of nanomaterials at different annealing times.
FIG. 9 is a MOFs-derived carbon composite Cr prepared in example 42S3The rate performance curve diagram of the nano material.
FIG. 10 shows the MOFs-derived carbon composite Cr prepared in example 42S3Linear cyclic voltammogram of nanomaterials.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the present invention and are not intended to limit the present invention.
Example 1
According to the metal salt Cr (NO)3)3·9H2The molar ratio of O to PTA is 1:1 and 0.1g of urea is weighed out as nitrogen source. Adding 3.2mmol of Cr (NO)3)3·9H2Dissolving O and urea in 20mL of deionized water, stirring to fully dissolve the O and the urea, adjusting the pH to 1 by using a concentrated HF solution, then putting 3.2mmol of PTA into a microwave hydrothermal reaction tank, reacting at 210 ℃ for 0.5h, and after the reaction is finished, washing the product by using deionized water for three times. The obtained MOFs precursor was mixed with 20mL of DMF solution and dried in an oven at 80 ℃ to obtain the dried MOFs precursor. Grinding and mixing MOFs precursor powder and sulfur powder according to the mass ratio of 1:3, putting a porcelain boat into a tube furnace, introducing argon gas, and sintering at the sintering temperature of 700 ℃ for 2 hours. The specific mass capacity of the prepared material is 450 mAh/g.
Example 2
According to the metal salt Cr (NO)3)3·9H2The molar ratio of O to PTA is 1:1.5 and 0.1g of urea is weighed out as nitrogen source. 4.5mmol of Cr (NO)3)3·9H2Dissolving O and urea in 20mL deionized water, stirring to fully dissolve the O and the urea, adjusting the pH to 1 by using a concentrated HF solution, then putting 3.2mmol of PTA into a microwave hydrothermal reaction tank,the reaction is carried out for 0.5h at 210 ℃, and after the reaction is finished, the product is washed three times by deionized water. The obtained MOFs precursor was mixed with 20mL of N, N-dimethylamide solution and dried in an oven at 80 ℃ to obtain the dried MOFs precursor. Grinding and mixing MOFs precursor powder and sulfur powder according to the mass ratio of 1:3, putting a porcelain boat into a tube furnace, introducing argon gas, and sintering at the sintering temperature of 800 ℃ for 2 hours. The specific mass capacity of the prepared material is 550 mAh/g.
Example 3
According to the metal salt Cr (NO)3)3·9H2The molar ratio of O to PTA is 1:1.5 and 0.1g of urea is weighed out as nitrogen source. 4.5mmol of Cr (NO)3)3·9H2Dissolving O and urea in 20mL of deionized water, stirring to fully dissolve the O and the urea, adjusting the pH to 1 by using a concentrated HF solution, then putting 3.2mmol of PTA into a microwave hydrothermal reaction tank, reacting for 1h at 210 ℃, and after the reaction is finished, washing the product for three times by using the deionized water. The obtained MOFs precursor was mixed with 20mL of DMF solution and dried in an oven at 80 ℃ to obtain the dried MOFs precursor. Grinding and mixing MOFs precursor powder and sulfur powder according to the mass ratio of 1:3, putting a porcelain boat into a tube furnace, introducing argon gas, and sintering at 900 ℃ for 2 hours. The specific mass capacity of the prepared material is 450 mAh/g.
Example 4
According to the metal salt Cr (NO)3)3·9H2The molar ratio of O to PTA is 1:1.5 and 0.1g of urea is weighed out as nitrogen source. 4.5mmol of Cr (NO)3)3·9H2Dissolving O and urea in 20mL of deionized water, stirring to fully dissolve the O and the urea, adjusting the pH to 1 by using a concentrated HF solution, then putting 3.2mmol of PTA into a microwave hydrothermal reaction tank, reacting for 1h at 210 ℃, and after the reaction is finished, washing the product for three times by using the deionized water. The obtained MOFs precursor was mixed with 20mL of DMF solution and dried in an oven at 80 ℃ to obtain the dried MOFs precursor. Grinding and mixing MOFs precursor powder and sulfur powder according to the mass ratio of 1:3, putting a porcelain boat into a tube furnace, introducing argon gas, and sintering at the sintering temperature of 800 ℃ for 6 hours. The specific mass capacity of the prepared material is 800mAh/g, and the cycle performance is shown to be stable when 100 circles are carried outCapacity.
As shown in figure 1, an XRD (X-ray diffraction) spectrum of MIL-101(Cr) with the morphology of the nanosheet array, prepared by the preparation method disclosed by the invention, is completely consistent with a standard card in a database, so that the crystalline phase composition of a product is MIL-101(Cr), and in addition, the peak type of a visible ray diffraction peak is sharp, the peak intensity is higher, and the crystal form development is good.
As shown in FIG. 2, the MOFs-derived carbon composite Cr with the nanosheet array morphology prepared by the preparation method provided by the invention2S3The XRD pattern of the nano material is completely consistent with that of the standard card No.11-0007 in the database, which shows that the crystal phase composition of the product is Cr2S3At this time, the peak type of the visible ray diffraction peak is sharp and the peak intensity is higher, which indicates that the crystal form is well developed.
As shown in FIG. 3, the XRD pattern of the MOFs-derived carbon composite NiS nano-material prepared by changing the metal salt according to the method of example 4 is completely consistent with that of the standard card No.02-1280 in the database, which indicates that the crystal phase composition of the product is NiS, and indicates that the method is also applicable to other sulfides.
As shown in FIG. 4, the particle material prepared by the preparation method of the invention has the size of about 100nm, the size is consistent, the distribution is uniform, and the structure of a nanocube is presented.
As shown in FIG. 5, the prepared product was tested by BET characterization and had a specific surface area of 186.4213m2In comparison with the sulfides produced by means of gel sol, coprecipitation or the like, the specific surface area of the products obtained here is approximately four times that of these. The larger specific surface area can provide more reactive active sites, thereby improving the mass specific capacity and the cycle performance of the battery.
As shown in FIG. 6, the figure shows that the electrochemical performance of the product prepared under different raw material ratios in the sodium ion battery is greatly different when Cr (NO) is added3)3·9H2The molar ratio of O to PTA is 1: at 1.5, the capacity is improved by about 100 mAh/g. The raw material proportion improves the reaction activity of the material to the maximum extent.
FIG. 7 shows different sinteringsThe application of the material prepared at the temperature in the sodium ion battery and the electrochemical performance of the material are that when the sintering temperature is 800 ℃ and 900 ℃, the mass specific capacity of the material is similar and higher than that of the material obtained at the sintering temperature of 700 ℃, but the cycle performance of the material obtained at the sintering temperature of 900 ℃ is poorer, the material begins to attenuate when the cycle is carried out for 40 circles, and the analysis of possible Cr is carried out2S3Structural failure of the material may occur, with a sintering temperature of 800 ℃ being most suitable.
Fig. 8 shows the electrochemical performance of the materials obtained by different sintering times in the sodium ion battery, and when the sintering time is shorter, the graphitization degree of carbon in the materials is not enough, the conductivity of the materials is poorer, and therefore the mass specific capacity of the battery is lower. And Cr when the sintering time is longer2S3The structure of (2) may be partially broken, and the specific mass capacity of the battery may be reduced. The optimal sintering time of the material is 6h, and the capacity does not obviously fade after the material is circulated for 100 weeks, and the mass specific capacity of the material is as high as 800 mAh/g.
Fig. 9 shows the rate performance of the material in the sodium ion battery, and it can be seen that when the battery is charged and discharged with a large current and then is charged and discharged with a small current, the specific mass capacity of the battery can be restored to the original level. The material has a more stable structure, is not damaged even after being impacted by large current, and has better rate performance.
Fig. 10 shows linear cyclic voltammetry curves of the material in a sodium ion battery, the material is scanned in a range from 0.01V to 3V, and the material has two pairs of reaction peaks at 1.79V, 1.59V, 1.23V and 0.38V, which indicates that the material has two potential platforms.

Claims (5)

1. A preparation method of a transition metal sulfide nano composite electrode material is characterized by comprising the following steps:
step one, synthesizing MOFs precursors of corresponding metals: weighing soluble metal salt, dissolving in deionized water, and adding urea; putting PTA into a microwave hydrothermal reaction tank, adding a metal salt solution, dropwise adding HF, and synthesizing MOFs precursor with metal ions as coordination centers through microwave hydrothermal reaction;
step two, activating MOFs precursors: washing and collecting the obtained MOFs precursor, adding corresponding N, N-dimethyl amide, and heating overnight; removing residual unreacted PTA in the MOFs precursor, and leaving the MOFs precursor containing channels;
step three, one-step vulcanization and carbonization: washing, centrifuging and collecting the activated MOFs, mixing with sublimed sulfur and sintering to obtain the composite material of MOFs derived carbon and transition metal sulfide;
the soluble metal salt is Cr (NO)3)3·9H2O；
In the first step, the molar ratio of the metal salt to the urea to the PTA is 1:1: 1-1.5;
in the first step, the microwave hydrothermal temperature is 180-220 ℃, the reaction time is 0.5-1 h, and the pressure of a hydrothermal reaction tank during the reaction is 2-2.2 GPa;
in the third step, the temperature rise rate of the one-step vulcanization carbonization is 5 ℃/min, the temperature is 800 ℃, and the heat preservation time is 6 h.
2. The method for preparing a transition metal sulfide nanocomposite electrode material as claimed in claim 1, wherein in the first step, the reaction solvent of microwave hydrothermal reaction is deionized water, and the pH of the reaction solution is adjusted to 1.
3. The method for preparing the transition metal sulfide nanocomposite electrode material as claimed in claim 1, wherein in the second step, the MOFs precursor obtained by the microwave hydrothermal reaction is activated in DMF solution, the temperature is controlled at 80 ℃, and the activation time is 12 h.
4. The method for preparing a transition metal sulfide nanocomposite electrode material as claimed in claim 1, wherein in step three, the mass ratio of the MOFs precursor to the sublimed sulfur is 1: 3.
5. A transition metal sulfide nanocomposite electrode material produced by the production method according to any one of claims 1 to 4.
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CN106531999A (en) * 2016-11-25 2017-03-22 武汉理工大学 Embedded cobalt sulfide and porous carbon nanorod composite electrode material and preparation method and application thereof
CN106571465A (en) * 2016-10-19 2017-04-19 北京化工大学 Hydrotalcite precursor technique nitrogen-sulfur co-doped carbon loaded transition metal sulfide solid solution, preparation method and application thereof

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CN106571465A (en) * 2016-10-19 2017-04-19 北京化工大学 Hydrotalcite precursor technique nitrogen-sulfur co-doped carbon loaded transition metal sulfide solid solution, preparation method and application thereof
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