CN113066953B - Preparation method of lithium-sulfur battery positive electrode heterojunction material - Google Patents
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Abstract
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method of a lithium-sulfur battery anode heterojunction material. The preparation method of the lithium-sulfur battery positive electrode heterojunction material comprises the following steps: (1) preparing a solution A; (2) preparing a solution B; (3) preparing a ferroferric oxide precursor; (4) preparing ferroferric oxide; (5) preparation of Fe3O4/Fe2An N heterojunction material. Prepared by the method is Fe3O4/Fe2The N heterojunction material has stable cycle life and rate capability, and improves the specific capacity of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method of a lithium-sulfur battery anode heterojunction material.
Background
Lithium-sulfur batteries have a high theoretical specific capacity (1675mAh/g) and a high energy density (2500Wh/kg), and generally utilize elemental sulfur (S)8) As a positive electrode material of the lithium-sulfur battery, lithium metal is a negative electrode material to form a full battery, and the full battery has a relatively stable average discharge voltage platform (2.15V). Meanwhile, the elemental sulfur has the advantages of rich source, environmental protection and the like, and is concerned by researchers. However, the important reason for hindering the commercial development of the lithium-sulfur battery at present is that the actual specific capacity and the energy density of the lithium-sulfur battery are difficult to reach theoretical values, the utilization rate of the sulfur cathode material is low due to poor cycling stability and low conductivity, and S is8With Li2S also expands in volume accompanying the charge and discharge processes, as well asTime S8Insoluble Li is continuously generated during discharge2S2、Li2S and other soluble lithium polysulfides (LiPS), just as this allows free migration near the separator, reducing the availability of active species. In view of these problems, researchers may try to utilize a transition metal compound with a framework structure as a sulfur carrier, and apply the transition metal compound to a lithium sulfur battery, so as to effectively improve the above-mentioned problems of low specific capacity, poor cycling stability and the like caused by an intermediate product generated during a discharge process, and generally include other compounds such as transition metal oxides, transition metal sulfides, transition metal nitrides and transition metal hydroxides.
The transition metal oxide generally has strong polarity, can form stronger chemical bond with other groups, or can enable transition metal ions to form more stable complex (MS) with sulfurx) Polysulfides can be effectively confined, e.g. TiO2、MnO、Co3O4、Fe3O4、V2O5In the application of the transition metal oxide serving as the positive electrode material of the lithium-sulfur battery, the transition metal oxide not only has better adsorption effect on LiPS, but also can help lithium polysulfide to transfer to a high-conductivity carbon matrix, so that electrochemical conversion is more complete, and insoluble Li can be used2S2、Li2Controllable growth of S on the surface of composite material to avoid Li2The aggregation of S loses the electric activity. Usually, transition metal nitrides easily form N-S bonds with LipS, so that the transition metal nitrides have strong chemical interaction, shuttle of the LipS is inhibited due to the strong chemical affinity, certain transition metal nitrides have better hardness and metal conductivity, and the firm structure of the transition metal nitrides can effectively bear the problem of volume expansion, such as TiN, VN, NbN and Co4N、Fe2N, and the like. Lone pair electrons in N atoms in the transition metal nitride are used as a conductive Lewis base catalyst matrix, so that the adsorption capacity of the LiPS to lithium atoms can be enhanced, and the redox process of the LiPS is promoted, so that the LiPS has good electro-catalysis performance and good electrochemical stability in the application of a lithium-sulfur battery.
In order to make the respective advantages of various materials mutually supplemented, a positive electrode material with high-efficiency electrocatalytic activity, high electrochemical performance and high lithium polysulfide adsorption capacity is developed, and the method is an effective method for inhibiting polysulfide shuttling and promoting polysulfide conversion. Two or more types of materials are synthesized into a composite material by a chemically controllable method, wherein the preparation method of the heterojunction structure material generally comprises electrochemical deposition, chemical vapor deposition, a chemical water bath method and the like, and homomorphic or heterotypic materials can be grown on the original solid nano material. However, the chemical water bath method is generally a method for growing a homogeneous or heterogeneous material on a base material, and a final material is obtained by immersing the base material in a specific solution to grow on the surface of the base material. The heterojunction material obtained by the method has the defects that the original appearance is slightly changed along with deposition, and the deposited material is uneven due to the change of the concentration of the soaking solution. In addition, the chemical water bath method is only suitable for low-temperature substance reaction (the boiling point of water is 100 ℃), and the chemical water bath method cannot be met for some materials which can be prepared by reaction and can be formed under the high-temperature condition. The electrochemical deposition is to form a coating by oxidation-reduction reaction on an electrode through the migration of positive and negative ions in an electrolyte solution under the action of an external electric field, is difficult to realize for powder materials, and has small yield through the mode of electrochemical deposition after electrode slice manufacturing.
《Fe3O4/Fe2The C nanoparticle inlaid Fe/N doped carbon nanofiber is used for high-efficiency electrocatalytic oxygen reduction reaction, and Fe is prepared in the form of MOF (metal organic framework)3O4/Fe2C @ Fe/N/C-800 material is obtained by one-step pyrolysis of Fe-conjugated microporous polymer, however, the product has the problem that the product has too many components, oxide and nitride of iron and doping of iron and nitrogen atoms are generated, and the components of the final material cannot be controlled.
《Fe3O4/Fe4N @ BiOCl and N-doped (001) -TiO2The photocatalytic performance research is based on an electrochemical oxidation preparation method, and has the defects of low yield and incapability of meeting the material consumption in application and battery materials.
The polyacrylonitrile precursor in-situ synthesized nano (iron nitride + ferroferric oxide)/carbon-based composite material and the electromagnetic performance research thereof are synthesized in situ (Fe/PAN composite film) on the basis of the alpha-Fe/PAN composite filmxNy+Fe3O4) A/carbon-based composite material, which is prepared by using a MOF (metal organic framework) form to prepare a composite material with iron oxide and nitride coexisting, is formed simultaneously during reaction, however, the insulation property of the MOF material is often limited to long-distance charge transmission.
In summary, Fe is currently essentially produced3O4/Fe3N and Fe3O4/Fe4N or doped with other components.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium-sulfur battery anode heterojunction material, aiming at solving the problem of poor comprehensive performance of the lithium-sulfur battery caused by volume expansion and polysulfide shuttling of the material in the charging and discharging processes, and Fe prepared by the method3O4/Fe2The N heterojunction material has stable cycle life and rate capability, and improves the specific capacity of the battery.
The technical scheme of the invention is as follows: a preparation method of a lithium-sulfur battery positive electrode heterojunction material comprises the following steps:
(1) preparing a solution A: mixing glycerol and isopropanol solution uniformly;
(2) preparing a solution B: mixing and dissolving ferric salt in the solution A, and performing ultrasonic treatment to obtain a solution B;
(3) preparing a ferroferric oxide precursor: firstly, adding deionized water into the solution B, magnetically stirring at room temperature to obtain a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 190 ℃, naturally cooling to room temperature after the reaction is finished, washing and drying the precipitate, and collecting the precipitate;
(4) preparing ferroferric oxide: placing the precipitate collected in the step (3) in a tube furnace under inert atmosphere, heating to 350 ℃ at a heating rate of 1 ℃/min, annealing for 3h, naturally cooling to room temperature, and collecting a product;
(5) preparation of Fe3O4/Fe2N heterojunction material: heating the ferroferric oxide obtained in the step (4) to 450-600 ℃ at a heating rate of 1-2 ℃/min in an ammonia atmosphere, carrying out heat treatment for 2-6 h, naturally cooling to room temperature, and collecting a product to obtain Fe3O4/Fe2An N heterojunction material.
The volume ratio of the glycerol to the isopropanol in the step (1) is 1: 7.
fe of the solution B in the step (2)3+The concentration is 0.005-0.01 mol/L.
Fe of the solution B in the step (2)3+The concentration was 0.008 mol/L.
And (3) carrying out ultrasonic treatment for 5min in the step (2).
In the step (2), the iron salt is Fe (NO)3)3·9H2O。
Adding 1mL of deionized water in the step (3); magnetically stirring for 10 min; centrifugally washing with ethanol for 3 times; air-blast drying at 70 deg.C for 12 h.
And (4) the inert gas in the step (4) is argon.
The heat treatment temperature in the step (5) is 500 ℃, and the treatment time is 3 h.
Fe obtained by the preparation method3O4/Fe2The N heterojunction material is of a hollow microsphere structure with the particle size of 1-1.5 mu m, and the hollow microsphere mainly comprises nanosheets. Compared with the amorphous particle aggregation solid particle material formed in the prior art, the hollow microsphere structure has obvious advantages in sulfur loading effect when applied to lithium-sulfur batteries.
The invention has the beneficial effects that: the preparation method comprises the steps of firstly synthesizing a ferroferric oxide precursor by a hot solvent method, then carrying out heat treatment and annealing in an inert atmosphere to obtain a ferroferric oxide material with a hollow nano microsphere structure, and finally synthesizing Fe by the ferroferric oxide through a heating nitridation method3O4/Fe2An N heterojunction material. The heterojunction material obtained by the method has regular morphology and structure, and the hardness of the hollow structure microsphere is enhanced after the ferroferric oxide surface is nitridedThe larger specific surface area can load more sulfur, thereby effectively improving the problem of volume expansion and improving the electrochemical performance of the lithium-sulfur battery.
The method is characterized in that a carbon-free coated ferroferric oxide base material with a hollow microsphere structure frame is used for conversion, a nitrogen source is doped on the surface of the base material by a high-temperature nitriding method to form nitride, the content of the heterojunction material component can be controlled by nitriding time, and Fe with a hollow microsphere structure is obtained3O4/Fe2An N heterojunction material.
1. Fe with hollow microsphere structure prepared by the method3O4/Fe2The N heterojunction material has particles with the particle size of about 1 mu m and uniform particle size distribution. The lithium-sulfur battery has a stable framework structure and a large specific surface area, can load more sulfur, can lock polysulfide inside, reduces the damage of the polysulfide, greatly improves the volume expansion and shuttle effect generated in the lithiation process of the lithium-sulfur battery, and improves the utilization rate of an active material, thereby further improving the specific capacity, cycle life and rate capability of the lithium-sulfur battery.
2. Synthesized Fe3O4/Fe2N heterojunction material applied to sulfur anode as host material of sulfur, Fe3O4Has good adsorption effect on lithium polysulfide, and can control Li2S2、Li2S grows on the surface of the material, so that the migration of polysulfide is inhibited, and the influence caused by sulfide shuttling is reduced. Further, Fe2N promotes the redox process of the LiPS, provides good electrocatalysis, and the LiPS and the N exert respective characteristics and act together, so that the lithium-sulfur battery has excellent electrochemical stability.
3. Compared with the composite material obtained by other methods, the invention adopts a simple temperature programming nitridation method, can accurately form iron nitride on the surface of ferroferric oxide, does not produce other products, and obtains the Fe with high purity3O4/Fe2An N heterojunction material. Decomposition of 2N by ammonia gas at high temperatureH3→3H2+2[N]So that the furnace has a large number of active nitrogen atoms, active nitrogen atoms [ N ]]Absorbed by the surface of the ferroferric oxide material and diffused inwards to ensure that O is generated2-Conversion to N3-Thereby forming a nitride layer (Fe)2N). The key point is to control the time and temperature of nitridation, and more active nitrogen atoms [ N ] are generated after the time is long]Excess active nitrogen entering the surface of the material will generate Fe3N or Fe4N affects the purity. For example, it is difficult to ensure high purity of the product by conventional methods such as high temperature melting, precipitation in aqueous solution, crystallization, etc.
4. The method of the invention can simply realize chemical control and can be used for Fe3O4Different amounts of Fe formed on the surface of the material2N, Fe with different contents can be obtained by adjusting the nitriding time2And N is added. And the method has high conversion efficiency and short synthesis time. The nitridation time is explored from 2h to 6h, and pure Fe can be obtained when the product obtained by XRD is 6h2N and 2h gave the material Fe3O4/Fe2N but Fe2The peak intensity of N is weak, and it can be known that Fe increases with time2The N content is increased. Compared with the existing electrochemical deposition, the method is different from the existing electrochemical deposition in that the reaction medium is different, the former is generated in a liquid state, and the latter is generated in a gaseous state, however, the active gaseous form particles are easier to invade into the small pore channels in the material to generate reaction compared with the liquid state, so the general conversion efficiency is higher. Compared with the existing chemical water bath deposition, the chemical water bath generally needs to be soaked for longer time such as 6h and 10h, the method relatively saves time and saves cost to a certain extent.
Drawings
FIG. 1 is a scanning electron microscope picture of ferroferric oxide.
FIG. 2 is Fe3O4/Fe2Scanning electron microscope pictures of N heterojunction materials.
FIG. 3 is Fe3O4/Fe2Transmission electron microscopy pictures of N heterojunction materials.
FIG. 4 is Fe3O4/Fe2N is heterogeneousThe XRD pattern of the junction material is compared with a PDF standard card.
FIG. 5 is Fe3O4/Fe2And a discharge cycle chart at a rate of 1C when the N heterojunction material is used as a positive electrode material in a lithium sulfur battery.
FIG. 6 is Fe3O4/Fe2And the charge-discharge rate performance graph of the N heterojunction material serving as the cathode material when the N heterojunction material is used for the lithium-sulfur battery.
Detailed Description
The present invention will be described in detail below with reference to examples.
Example 1
The preparation method of the lithium-sulfur battery positive electrode heterojunction material comprises the following steps:
(1) preparing a solution A: mixing 7.5mL of glycerin with 52.5mL of isopropanol solution uniformly;
(2) preparing a solution B: 0.194gFe (NO)3)3·9H2Mixing and dissolving O in the solution A, and performing ultrasonic treatment for 5min to obtain a solution B;
(3) preparing a ferroferric oxide precursor: firstly, adding 1mL of deionized water into the solution B, magnetically stirring for 10min at room temperature to obtain a mixed solution, transferring the mixed solution into a 100mL hydrothermal reaction kettle, carrying out hydrothermal reaction for 12h in a forced air oven at 190 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally washing the precipitate for 3 times by using ethanol, carrying out forced air drying at 70 ℃ for 12h, collecting and grinding the precipitate into powder;
(4) preparing ferroferric oxide: placing the powder collected in the step (3) in a tube furnace under argon atmosphere, heating to 350 ℃ at a heating rate of 1 ℃/min, annealing for 3 hours, naturally cooling to room temperature, and collecting a product to obtain ferroferric oxide;
(5) preparation of Fe3O4/Fe2N heterojunction material: placing the ferroferric oxide obtained in the step (4) in an ammonia atmosphere, heating to 500 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 3 hours, naturally cooling to room temperature, and collecting a product to obtain Fe3O4/Fe2An N heterojunction material.
From Fe3O4To obtain Fe3O4/Fe2The optimal reaction time of the N heterojunction material is 3h, the temperature is 500 ℃ and the temperature rise rate is 1 ℃/s). Obtaining pure Fe2The optimal reaction time of N is 6 h.
Example 2
The procedure of example 1 was repeated to obtain Fe (NO) in step (2)3)3·9H2The mass of O was adjusted to 0.121 g.
Example 3
The procedure of example 1 was repeated to obtain Fe (NO) in step (2)3)3·9H2The mass of O was adjusted to 0.242 g.
Example 4
The procedure of example 1 was repeated, and the temperature in step (5) was adjusted to 450 ℃.
Example 5
The procedure of example 1 was repeated, and the temperature in step (5) was adjusted to 550 ℃.
Example 6
The procedure of example 1 was repeated, and the heat-retaining time in step (5) was adjusted to 2 hours.
Example 7
The procedure of example 1 was repeated, and the holding time in step (5) was adjusted to 4 hours.
Example 8
The procedure of example 1 was repeated to adjust the temperature-keeping time in step (5) to 5 hours.
Example 9
The procedure of example 1 was repeated to adjust the temperature-keeping time in step (5) to 6 hours.
Example 10
The procedure of example 1 was repeated, and the temperature increase rate in step (5) was adjusted to 2 ℃/min.
Examples of the experiments
For Fe obtained in example 13O4/Fe2The N heterojunction material is used as a positive electrode material for performance test of the lithium-sulfur battery.
As can be seen from FIGS. 2 and 3, Fe3O4/Fe2The microscopic morphology of the N heterojunction material is in a regular microsphere structure. The surface of the microsphere is formed by randomly arranging nano sheets to form a sphere, and part of the sphere is thinnerThe nano sheets are agglomerated under high-temperature nitridation to form agglomerated particles, and the nano sheets and the particles jointly form a hollow microsphere structure.
Fe prepared by X-ray diffraction test3O4/Fe2The XRD pattern of the N heterojunction material is consistent with the peak of a PDF standard card as shown in figure 4, which proves that the synthesized material contains Fe3O4With Fe2N。
Mixing Fe3O4/Fe2The result of electrochemical cycling of the N heterojunction material as a lithium sulfur battery cathode material under the charge-discharge condition of a rate of 1C is shown in fig. 5, the first specific capacity reaches 817.4mAh/g, and 63.3% of the specific capacity is still maintained after 1000 cycles of charge-discharge.
The results of the rate performance test of the charge and discharge of the material are shown in fig. 6. As can be seen in FIGS. 5 and 6, the synthesized Fe3O4/Fe2The N heterojunction material shows higher and stable specific capacitance and better rate performance in the application of the lithium-sulfur battery.
The same tests were carried out on the materials of examples 2 to 10, and the results were similar to those of example 1.
Claims (10)
1. A preparation method of a lithium-sulfur battery positive electrode heterojunction material is characterized by comprising the following steps:
(1) preparing a solution A: mixing glycerol and isopropanol solution uniformly;
(2) preparing a solution B: mixing and dissolving ferric salt in the solution A, and performing ultrasonic treatment to obtain a solution B;
(3) preparing a ferroferric oxide precursor: firstly, adding deionized water into the solution B, magnetically stirring at room temperature to obtain a mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 190 ℃, naturally cooling to room temperature after the reaction is finished, washing and drying the precipitate, and collecting the precipitate;
(4) preparing ferroferric oxide: placing the precipitate collected in the step (3) in a tube furnace under inert atmosphere, heating to 350 ℃ at a heating rate of 1 ℃/min, annealing for 3h, naturally cooling to room temperature, and collecting a product;
(5) preparation of Fe3O4/Fe2N heterojunction material: heating the ferroferric oxide obtained in the step (4) to 450-600 ℃ at a heating rate of 1-2 ℃/min in an ammonia atmosphere, carrying out heat treatment for 2-6 h, naturally cooling to room temperature, and collecting a product to obtain Fe3O4/Fe2An N heterojunction material.
2. The method for preparing the heterojunction material of the positive electrode of the lithium-sulfur battery as claimed in claim 1, wherein the volume ratio of glycerol to isopropanol in the step (1) is 1: 7.
3. the method for preparing a lithium-sulfur battery cathode heterojunction material as claimed in claim 1, wherein the Fe of the solution B in the step (2)3+The concentration is 0.005-0.01 mol/L.
4. The method for preparing a lithium-sulfur battery cathode heterojunction material as claimed in claim 3, wherein the Fe of the solution B in the step (2)3+The concentration was 0.008 mol/L.
5. The method for preparing a lithium-sulfur battery cathode heterojunction material as claimed in claim 1, wherein the step (2) is ultrasonic-treated for 5 min.
6. The method for preparing the heterojunction material of the positive electrode of the lithium-sulfur battery as claimed in claim 1, wherein the iron salt in the step (2) is Fe (NO)3)3·9H2O。
7. The method for preparing the heterojunction material of the positive electrode of the lithium-sulfur battery as claimed in claim 1, wherein 1mL of deionized water is added in the step (3); magnetically stirring for 10 min; centrifugally washing with ethanol for 3 times; air-blast drying at 70 deg.C for 12 h.
8. The method for preparing a lithium-sulfur battery cathode heterojunction material as claimed in claim 1, wherein the inert gas in the step (4) is argon.
9. The method for preparing the positive electrode heterojunction material of the lithium-sulfur battery as claimed in claim 1, wherein the heat treatment temperature in the step (5) is 500 ℃ and the treatment time is 3 h.
10. The method for preparing a lithium-sulfur battery positive electrode heterojunction material according to claim 1, wherein the preparation method is used to obtain Fe3O4/Fe2The N heterojunction material is of a hollow microsphere structure with the particle size of 1-1.5 mu m, and the hollow microsphere mainly comprises nanosheets.
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