CN112086607B - Composite diaphragm material and preparation method and application thereof - Google Patents
Composite diaphragm material and preparation method and application thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention belongs to the field of battery materials, and particularly discloses a polymer @ two-dimensional material modified layered double-metal hydroxide composite diaphragm material which comprises a polymer film material and an active material compounded in the polymer film material; the active material is the two-dimensional material modified layered double hydroxide which comprises the layered double hydroxide and a two-dimensional material growing on the surface of the layered double hydroxide in situ; wherein, the two-dimensional material is at least one of molybdenum diselenide, tungsten diselenide, molybdenum disulfide and tungsten disulfide. The invention also provides the preparation of the diaphragm and the application of the diaphragm in a lithium-sulfur battery. The novel material can effectively solve the boundary effect of a two-dimensional material, can open more active sites, avoids agglomeration, and can unexpectedly improve the performance of the battery by adding the novel material into a battery diaphragm, such as improving the sulfur carrying amount and the catalytic degradation property of polysulfide, and improving the performance of the battery.
Description
Technical Field
The invention relates to the field of batteries, in particular to a polymer @ two-dimensional material modified layered double hydroxide composite diaphragm material for a lithium-sulfur battery.
Background
The development of a new generation of secondary battery system which is green and environmentally friendly and has high energy density and long cycle life is increasingly of great significance and value. In recent years, the lithium-sulfur battery is more and more emphasized as a novel lithium battery, the theoretical specific capacity of the lithium-sulfur battery is up to 1675mAH g-1, and the theoretical specific energy is up to 2500Wh Kg-1; in addition, the positive active material sulfur also has wide source and low price. However, the lithium sulfur battery at present has some problems, resulting in that it has not been widely introduced into people's daily lives. One of the more serious problems is the "shuttling effect" of lithium sulfur batteries. The lithium sulfur battery separator can function to prevent internal short circuits of the battery and to provide a lithium ion transfer path. However, while lithium ions freely pass through the separator, polysulfide ions dissolved in the electrolyte of the lithium-sulfur battery also diffuse through the separator to reach the lithium negative electrode, so that irreversible side reactions occur, and the stability and the capacity of the battery are seriously reduced. Therefore, the co-functional modification is carried out on the lithium-sulfur battery diaphragm, and the diffusion of excessive sulfide is avoided while the function of a lithium ion migration passage is realized, so that the key point for improving the performance of the lithium-sulfur battery is realized.
In the preparation of the lithium-sulfur battery, most of the used separators are polyolefin separators mainly based on commercial polypropylene (PP), and the suitable pore size structure of the separators is favorable for migration of lithium ions, however, the polyolefin separators cannot fundamentally and effectively solve the migration phenomenon of polysulfide. Song et al performed double-layer modification on a PP diaphragm, coated a graphene layer on the side facing a sulfur anode, and coated an alumina layer on the side of a lithium cathode, so as to improve the electrochemical performance of the battery. Li and the like treat a commercial PP diaphragm by using oxygen through a plasma technology, so that the diaphragm is provided with a certain amount of hydroxyl and carboxyl, and the electrochemical performance of the battery is improved to a certain extent.
Although the performance of the lithium-sulfur battery can be improved to a certain extent by the current researches such as membrane modification, the problems of accumulation and migration of polysulfide in the electrolyte cannot be fundamentally solved.
Disclosure of Invention
In view of the above-mentioned drawbacks and drawbacks of the background art, a first object of the present invention is to provide a composite separator material (also referred to as composite separator material, separator material or separator for short) of polymer @ two-dimensional material modified layered double hydroxide, which aims to improve the battery performance.
The second purpose of the invention is to provide a preparation method of the composite diaphragm material.
The third purpose of the invention is to provide the application of the composite separator material in the separator of the lithium-sulfur battery.
A fourth object of the present invention is to provide a lithium-sulfur battery equipped with the composite separator material.
Two-dimensional transition group sulfur (selenide) materials such as molybdenum diselenide and tungsten diselenide have obvious boundary effect, and the performance of the materials in the electrochemical aspect is seriously influenced. Solving the boundary effect is helpful to improve the performance, but there is no effective solution in the prior art. Based on long-term research practice in the industry, the invention develops a technical means which can effectively solve the boundary effect of the two-dimensional active material, avoid the agglomeration deterioration of particles and expose more active sites, and specifically comprises the following steps:
a composite diaphragm material of polymer @ two-dimensional material modified layered double hydroxide comprises a polymer film material and an active material compounded in the polymer film material; the active material is the two-dimensional material modified layered double hydroxide which comprises the layered double hydroxide and a two-dimensional material growing on the surface of the layered double hydroxide in situ;
wherein, the two-dimensional material is at least one of molybdenum diselenide, tungsten diselenide, molybdenum disulfide and tungsten disulfide.
According to the novel material, the two-dimensional material grows on the surface of the layered double hydroxide (hydrotalcite plate layer) and self-assembles with the layered double hydroxide in situ, so that the boundary effect of the two-dimensional material can be effectively solved, more active sites can be opened, agglomeration is avoided, and the performance of the material can be unexpectedly improved by adding the material into a battery diaphragm, such as the sulfur carrying amount and the catalytic degradation property of polysulfide can be improved, and the battery performance can be improved. For example, when the novel material is used as a separator of a lithium-sulfur battery, the shuttle effect of polysulfide of the lithium-sulfur battery can be fundamentally inhibited, and the capacity and the cycling stability of the lithium-ion battery can be effectively improved.
In the invention, the layered double hydroxide is in a single or thin-sheet layered hydrotalcite laminated structure. That is, the layered double hydroxide according to the present invention is a single or thin sheet material obtained by peeling hydrotalcite.
The layered double hydroxide is a layered hydroxide material assembled by divalent and trivalent metals, wherein divalent elements are at least one of Mg, Ni, Co, Zn and Cu; the trivalent element is at least one of Al, Cr, Fe and Sc.
Preferably, the active material is formed by MoO4 2-And/or WO4 2-The intercalated hydrotalcite and at least one selenium source and/or sulfur source are obtained by hydrothermal reduction at the temperature of 160-300 ℃. In the present invention, MoO4 2-And/or WO4 2-And a selenium source (and/or a sulfur source) react under the limitation of the hydrotalcite plate layer structure, so that the hydrotalcite grows in situ between the double-metal hydroxide plate layers, the multilayer structure of the hydrotalcite is promoted to be opened, and the hydrotalcite material with the in-situ grown single or thin-sheet layer of the diselenide is obtained by synchronous stripping. The method can effectively solve the diselenide boundary effect and can release more active sites.
Preferably, the polymer is at least one of polypropylene (PP), Polyethylene (PE), polyester film (PET), cellulose film, polyimide film (PI), polyamide film (PA), spandex, or aramid film; at least one of polyolefin porous films is preferable.
Preferably, in the composite diaphragm material, the loading amount of the active material is 0.002-0.050 mg/cm2。
The invention also provides a preparation method of the composite membrane material of the polymer @ two-dimensional material modified layered double hydroxide, which comprises the following steps:
step (1): at least one of a molybdic acid source and a tungstic acid source is used as an intercalation precursor source, and the intercalation precursor source is mixed with divalent metal ions M2+Source, trivalent metal ion M3+Stirring and reacting a source and alkali, then crystallizing, and performing post-treatment to obtain a hydrotalcite precursor polymer with molybdate and/or tungstate intercalation; wherein, the crystallization process and/or the post-treatment process are/is carried out with ultrasonic strengthening treatment;
step (2): adding at least one of a selenium source and a sulfur source (a selenium source and/or a sulfur source) and a reducing compound into the hydrotalcite precursor polymer obtained in the step (1), then carrying out hydrothermal reaction, and carrying out post-treatment after the hydrothermal reaction is finished to obtain the active material; wherein, the hydrothermal reaction and/or the post-treatment process is carried out with ultrasonic strengthening treatment;
and (3): and compounding the active material and the polymer membrane material to form a membrane, thus obtaining the composite membrane material.
Firstly, divalent metal ions M are put into the invention2+Source, trivalent metal ion M3+Stirring a source, soluble molybdate or tungstate (an intercalation precursor source) and alkali for reaction and crystallization to obtain a hydrotalcite precursor polymer with molybdate (and/or tungstate) intercalation, and then adding a selenium source (and/or a sulfur source) and a reducing agent into the hydrotalcite precursor polymer for hydrothermal reaction; in the hydrothermal reaction process, a selenium source (and/or a sulfur source) reacts with molybdate (and/or tungstate) in hydrotalcite intercalation to synthesize a two-dimensional material, the two-dimensional material grows in situ between hydrotalcite laminates, and agglomeration of the two-dimensional material is avoided due to the limitation of the hydrotalcite laminate structure, so that more active sites are exposed at the edge of the two-dimensional material laminate; meanwhile, the positive-charge hydrotalcite plate layer and the negative-charge two-dimensional material sheet layer are assembled into the active material with the double-sided brush structure through non-covalent interaction. The invention introduces ultrasonic field enhancement in the preparation process of the precursor and the active material of the hydrotalcite, can better realize the uniform dispersion and subsequent reduction stripping of molybdate (and/or tungstate) among the hydrotalcite plate layers, and obviously improves the activity of the material. The prepared active material is compounded into a polymer, which is beneficial to improving the performance of the prepared diaphragm material.
The MoO is obtained by constructing the in-situ anionic hydrotalcite construction method in the step (1)4 2-、WO4 2-Anion intercalation modified hydrotalcite. The chemical expression is as follows:
[M2+ 1-xM3+ x(OH)2]z+[An-]z/n·mH2O；
wherein M is2+Divalent metal ions, as known to those skilled in the art of hydrotalcite;
M3+trivalent metal ions known to those skilled in the art of hydrotalcite;
An-the anion for in situ intercalation is MoO4 2-And/or WO4 2-
x is not particularly required, and is in accordance with the conventional requirements of hydrotalcite, for example, 0.17 to 0.33.
Through the construction of the in-situ hydrotalcite anions and the subsequent in-situ reduction, MoO in the hydrotalcite can be reduced4 2-And/or WO4 2-And the two-dimensional material is formed by in-situ reduction and is stripped, so that the boundary effect of the two-dimensional material is solved, and more active sites are developed. Researches also find that compared with an ion exchange intercalation method, the method in the step (1) of the invention is matched with innovative ultrasonic strengthening treatment, so that in-situ high-efficiency intercalation of molybdate radicals and/or tungstate radicals can be unexpectedly realized, and the performance of the prepared active material can be improved.
Preferably, the divalent metal ion M2+The source being selected from Mg2+、Ni2+、Co2+、Zn2+、Cu2+At least one water-soluble salt of (a). For example, nitrate, chloride, sulfate, etc. of the metal ions may be mentioned.
Preferably, the trivalent metal ion M3+The source is selected from Al3+、Cr3+、Fe3+、Sc3+At least one water-soluble salt of (a); for example, nitrate, chloride, sulfate, etc. of the metal ions may be mentioned.
Preferably, the molybdic acid source is soluble molybdate, preferably at least one of sodium molybdate, ammonium molybdate, potassium molybdate and magnesium molybdate, and more preferably magnesium molybdate or sodium molybdate.
Preferably, the tungstic acid source is a soluble tungstate, more preferably at least one of sodium tungstate, calcium tungstate, zinc tungstate and cobalt tungstate, and more preferably sodium tungstate.
Preferably, the alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, the divalent metal ion M2+Source, trivalent metal ion M3+The molar ratio of source, intercalation precursor source, and base is 1: (0.3-0.5): (0.3-1): (1-3). Under the proportion, the hydrotalcite plate layer structure is favorably formed, and the intercalation of molybdenum diselenide (or tungsten diselenide and the like) between the hydrotalcite plate layers is favorably realized, so that the prepared composite material has better performance.
In a more preferred embodiment, in the step (1), the temperature of the stirring reaction is controlled to be 20 to 50 ℃, and more preferably 30 to 50 ℃. The stirring reaction time is controlled to be 1-4 h.
In a more preferable embodiment, in the step (1), the crystallization temperature is controlled to 70 to 95 ℃, and more preferably 80 to 90 ℃. The crystallization time is controlled to be 4 to 12 hours, and more preferably 6 to 8 hours.
In the step (1), ultrasonic strengthening treatment may be preferably performed in the crystallization process, or ultrasonic strengthening treatment may be performed in the post-treatment process after the crystallization process.
Preferably, the post-treatment of step (1) comprises centrifugal washing, ultrasonic enhancement and solid-liquid separation; wherein the ultrasonic strengthening time is 15-60 min; preferably 35-40 min.
In the invention, the method is innovatively utilized to obtain hydrotalcite precursor polymer with molybdate radical and/or tungstate radical intercalation; and (3) performing the hydrothermal reaction (also referred to as hydrothermal reduction reaction in the invention) in the step (2) to directly form the two-dimensional material in situ in the hydrotalcite slab structure.
Preferably, the selenium source is selected from selenium powder, trimethylphenylselenosilane, (phenylselenium) trimethylsilane, sodium selenocyanoacetate, and sodium selenite (at least one of selenium powder or trimethylphenylselenosilane is more preferable).
The sulfur source is at least one selected from thiourea, thioacetamide, sodium sulfide and potassium sulfide.
The adding amount of the selenium source or the sulfur source is 2-10 times of the mass of the molybdate intercalated hydrotalcite precursor polymer. For example, when only the selenium source is added, the adding amount of the selenium source is 2-10 times of the mass of the molybdate intercalated hydrotalcite precursor polymer; when only the sulfur source is added, the adding amount of the sulfur source is 2-10 times of the mass of the molybdate intercalated hydrotalcite precursor polymer; when the selenium source and the sulfur source are added, the total adding amount of the selenium source and the sulfur source is 2-10 times of the mass of the molybdate intercalated hydrotalcite precursor polymer.
In a preferred embodiment, the strongly reducing compound may be theoretically selected from at least one of hydrazine hydrate, sodium borohydride, hydroiodic acid, sulfite, and oxalate, and hydrazine hydrate is more preferable. The hydrazine hydrate compound added during the hydrothermal reaction has stronger reducing capability, and is used as a reducing medium to reduce selenium source (and/or sulfur source) and hydrotalcite pre-polymer interlayer anions (molybdate radical and/or tungstate radical) to realize the limited-area reduction growth of the two-dimensional material; meanwhile, a product of a reducing agent such as hydrazine hydrate after participating in the reduction reaction is easily dissolved in water and decomposed at low temperature, so that the generation of byproducts is reduced, and the stability of the composite material is improved.
In a preferable scheme, the using amount of the reducing compound is 0.3-5 times of the mass of the hydrotalcite precursor polymer.
In a preferred scheme, the temperature of the hydrothermal reaction is controlled to be 160-300 ℃, and further preferably 180-250 ℃; more preferably 200 to 230 ℃.
In a more preferable scheme, the time of the hydrothermal reaction of the molybdate radical (or tungstate radical) intercalation material is controlled to be 12-48 h, and further preferable to be 12-36 h.
Preferably, the present invention innovatively performs ultrasonic strengthening treatment during hydrothermal reaction and/or post-treatment, thus helping to obtain the active material.
Preferably, in the hydrothermal reduction preparation process, ultrasonic strengthening is performed for 1-2 times, and the ultrasonic strengthening time is 15-30 min each time.
Preferably, ultrasonic strengthening is further performed in a post-treatment process after the hydrothermal reaction.
The post-treatment of the step (2) comprises centrifugal washing, ultrasonic strengthening and solid-liquid separation; wherein the ultrasonic strengthening time is 15-30 min.
And (3) dispersing a polymer membrane material by using a solvent, and then adding the active material to form a membrane to obtain the composite diaphragm.
The film forming method may be any conventional method.
The invention also discloses a composite diaphragm material of the polymer @ two-dimensional material modified layered double hydroxide prepared by the preparation method.
The invention also provides application of the polymer @ two-dimensional material modified layered double hydroxide composite membrane material as a membrane of a lithium-sulfur battery.
The composite diaphragm material has good sulfur-carrying effect and good polysulfide catalytic degradation effect. The compound is used as a diaphragm of a lithium-sulfur battery, is beneficial to effectively solving the shuttle effect of polysulfide compounds, and is beneficial to improving the electrical performance of the lithium-sulfur battery.
The preparation method of the composite diaphragm prepared by the invention comprises the following steps: a. diluting the concentration of the sample by using deionized water, controlling the final solid content to be 0.3-1.5 mg/ml, and carrying out ultrasonic treatment for 30-60 min. b. Preparing a diaphragm of the PP @ molybdenum (or tungsten) diselenide/hydrotalcite composite material by adopting a vacuum filtration method, wherein the loading capacity is 0.002-0.050 mg/cm2。
The invention also provides a lithium-sulfur battery, and the diaphragm material is the composite diaphragm material of the polymer @ two-dimensional material modified layered double hydroxide.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a two-dimensional material modified layered double hydroxide active material with a brand new structure, limits the boundary effect of the two-dimensional material innovatively through the lamellar structure characteristics of hydrotalcite, and solves the technical problems of agglomeration, few active sites and the like of the two-dimensional material. Researches find that the hydrotalcite modified in situ on the surface of the two-dimensional material has good effects of carrying sulfur and catalyzing the degradation of polysulfide, and can effectively solve the shuttle effect of the polysulfide. The main reason is that the two-dimensional material modified layered double hydroxide material prepared by the invention is a self-assembly bonding material of a two-dimensional transition group compound with high catalytic activity and a single or thin layered hydrotalcite molecular layer, has high matching performance on the attraction and catalytic conversion of a polysulfide compound, and is particularly suitable for the performance improvement of a lithium-sulfur battery; this property cannot be achieved by other hydrothermal techniques or physical doping techniques.
(2) According to the preparation method, the molybdate radical (or tungstate radical) is firstly intercalated into a hydrotalcite plate layer structure, then in the process of reducing and preparing and generating molybdenum diselenide (or tungsten), the molybdenum diselenide (or tungsten) grows in situ between hydrotalcite plate layers, and due to the limitation of the hydrotalcite plate layer structure, the agglomeration of the molybdenum diselenide is avoided, so that more active sites are exposed at the edge of the molybdenum diselenide (or tungsten) plate layer; meanwhile, molybdenum diselenide (or tungsten) belongs to a two-dimensional lamellar structure, and in the preparation process, a hydrotalcite plate layer structure is gradually separated and opened along with the reaction, so that the exposure of hydrotalcite active sites is facilitated, and the sulfur-carrying and polysulfide degradation catalysis effects of the obtained composite material (active material) are improved.
(3) In the preparation process of the hydrotalcite precursor polymer and the composite material, the ultrasonic field is adopted for reinforcement, so that the intercalation distribution and occurrence state of molybdate radicals (or tungstate radicals) among hydrotalcite interlayer can be reinforced; on the other hand, the ultrasonic field has obvious functions of cavitation enhancement and the like, can promote the reduction degree of hydrothermal reaction in the hydrothermal reduction process of the composite material, enhances the stripping of the hydrotalcite plate layer, and obviously promotes the sulfur-carrying and polysulfide degradation of the composite material.
(4) Because the hydrotalcite plate layer is positively charged, and the molybdenum diselenide (or tungsten) sheet layer generated by reduction is a substance with negative charge, in the preparation process of the invention, the generated molybdenum diselenide (or tungsten) is assembled with the hydrotalcite sheet layer through the interaction of non-covalent bonds to form the composite active material with a two-sided brush structure, so that the specific surface area of the composite active material is larger, the active sites are more, and the degradation of sulfur and catalytic polysulfide of the composite diaphragm material is further improved.
(5) In the preparation process of the two-dimensional material modified layered double hydroxide, the adopted hydrazine hydrate and other compounds have various beneficial effects: on the one hand, the hydrazine hydrate compound has stronger reducing capability, and is used as a reducing medium to reduce the selenium source and molybdate (or tungstate) together to realize MoSe2Reducing and growing the two-dimensional material; on the other hand, the reduction product of the hydrazine hydrate compound is easily dissolved in water and easily decomposed at low temperature, and the yield is improvedPurity of the product and performance of the diaphragm are improved.
(6) The two-dimensional material modified layered double hydroxide is prepared by a hydrothermal method, has the advantages of mild reaction conditions, simple process, no waste discharge, safety, environmental protection and particular suitability for large-scale industrial production and application.
(7) The composite diaphragm provided by the invention can improve the energy storage and cycle performance of the lithium-sulfur battery. The composite material prepared by the invention has high activity, good stability and small dosage, and greatly reduces the use cost of the material.
In conclusion, the composite material has good performance and structural stability through the synergistic effect of each component in the composite material and each step in the preparation method; the preparation method has mild conditions, simple process, safety and environmental protection; the composite material has good industrial application prospect in the field of lithium sulfur.
Drawings
FIG. 1 is an SEM image of molybdate-intercalated MgAl hydrotalcite precursor material prepared after stirring in example 1 of the present invention under different magnification.
FIG. 2 is an EDS analysis chart of molybdate-intercalated MgAl hydrotalcite precursor material prepared after stirring in example 1 of the present invention.
Fig. 3 is an SEM image of the molybdenum diselenide/MgAl hydrotalcite composite material prepared by hydrothermal reduction in example 1 of the present invention under different times.
Fig. 4 is an EDS analysis chart of the molybdenum diselenide/MgAl hydrotalcite composite material prepared by hydrothermal reduction in example 1 of the present invention.
Fig. 5 shows the cell performance of the molybdenum diselenide/CoAl hydrotalcite composite material prepared in example 2 of the present invention as a Li-S cell separator at different hydrothermal times.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the preparation method of the molybdenum diselenide/MgAl hydrotalcite composite material comprises the following steps:
(1) adding 0.03mol of magnesium nitrate, 0.015mol of aluminum nitrate, 0.01mol of sodium molybdate and 0.1mol of sodium hydroxide into 100mL of water, and stirring for reaction at 45 ℃ for 1 h; then heating to 85 ℃ for crystallization for 6 h; after crystallization is finished, centrifugal washing is carried out, the mixture is filtered after an ultrasonic field acts for 30min, and filter cakes are dispersed in 50mL of water to prepare hydrotalcite prepolymer suspension;
(2) taking 0.632g of selenium powder and 10mL of hydrazine hydrate, stirring for 30min in a three-neck flask, adding 40mL of the hydrotalcite precursor polymer suspension, performing ultrasonic dispersion, placing in a high-pressure reaction kettle, heating to 200 ℃ at the heating rate of 5 ℃/min, performing heat preservation reaction for 720min (wherein, when the temperature is 360min, taking out the ultrasonic wave for 20min, and continuing to perform heat preservation after the ultrasonic wave is performed), cooling after the reaction is completed, washing for 7-10 times with a mixed solution of water and ethanol (the mass fraction is 50%), performing ultrasonic treatment for 20min, and performing freeze drying to obtain the molybdenum diselenide/MgAl hydrotalcite composite material A, wherein the percentage content of molybdenum diselenide is about 20%.
Fig. 1 is an SEM image of the molybdate-intercalated MgAl hydrotalcite precursor material prepared after the stirring reaction, and table 1 is the EDS analysis result of the molybdate-intercalated MgAl hydrotalcite material. As can be seen from fig. 1 and table 1, the MgAl hydrotalcite material is mainly in a massive plate layer structure, the plate layers are closely connected, and the main elements are Mg, Al, Mo, O, and the like. Fig. 2 is an SEM image of the molybdenum diselenide/MgAl hydrotalcite composite light material a prepared after the hydrothermal reaction, and it can be seen from fig. 2 that the bulk slab layer structure of the MgAl hydrotalcite material has been opened after the hydrothermal reaction, and is in a lamellar structure. In addition, fig. 2 and table 2 are EDS analysis results of the molybdenum diselenide/MgAl hydrotalcite composite material a. As can be seen from fig. 2 and table 2, the main elements of the material at this time are Mg, Al, Mo, Se, O, etc., and the molar contents of the two elements of Mo and Se are close to 1:2, which indicates that molybdenum diselenide is successfully prepared and the lamellar structure of hydrotalcite is successfully opened during the preparation process.
TABLE 1 EDS analysis results of molybdate intercalated MgAl hydrotalcite materials
| Element(s) | By weight% | |
| O | ||
| 60 | 71.79 | |
| Mg | 26.07 | 20.43 |
| Al | 9.87 | 6.97 |
| Mo | 4.06 | 0.81 |
TABLE 2 EDS analysis results of molybdenum diselenide/MgAl hydrotalcite composite material A
| Element(s) | By weight% | Atom% |
| O | 45.53 | 67.80 |
| Mg | 16.54 | 16.20 |
| Al | 8.66 | 7.65 |
| Se | 20.20 | 6.10 |
| Mo | 9.06 | 2.25 |
(3) Preparing a Li-S battery diaphragm: firstly, carrying out ultrasonic treatment on the composite material A for 30min, and then measuring the solid content of the composite material A. ② the concentration of the sample is diluted by deionized water, the final solid content is controlled to be 0.5mg/ml, and the ultrasonic treatment is carried out for 30 min. Thirdly, in the preparation of the PP @ two-dimensional material modified layered double-metal hydroxide composite diaphragm (PP @ composite material A diaphragm) by adopting a vacuum filtration method, the loading capacity of the composite material A is 0.005mg/cm2. Preparing a positive pole piece: a. weighing sulfur powder: 2.1 g; carbon nanotube: 0.9g (S: CNT 7: 3); ground well in an agate mortar. Putting into a ceramic square boat, and wrapping the square boat with tinfoil paperThe boat was calcined at 155 ℃ for 12h under an argon atmosphere. b. Taking calcined S/CNT powder: 360mg was put into a volumetric flask, and 800mg of 5% PVDF (S/CNT: PVDF 9:1) was added thereto at 450r/min and stirred for 24 hours. c. Adjusting the thickness of the scraper: 20 μm, and the prepared slurry was coated on a carbon-coated aluminum foil. Drying in a 60 deg.C oven; and (6) slicing. Obtaining the anode piece with the sulfur content of 63 percent.
The button cell equipped with the PP @ composite material A diaphragm is subjected to constant-current charge-discharge and cycle performance tests, and the result shows that the initial discharge capacity at 0.1 ℃ is 1360mAh g-11030mAh g compared to PP separator alone-1Increase 330mAh g-1(ii) a After 50 times of circulation, the PP @ composite A diaphragm battery still has 680mAh g-1Is much higher than 470mAh g of PP separator cell-1. Therefore, the molybdenum diselenide/MgAl hydrotalcite composite material prepared by the invention is introduced into the lithium-sulfur battery, so that the battery capacity and the cycle performance of the lithium-sulfur battery are obviously improved.
Example 2:
the invention discloses a preparation method of a Li-S battery diaphragm by using a molybdenum diselenide/CoAl hydrotalcite composite material, which comprises the following specific steps:
(1) adding 0.03mol of cobalt nitrate, 0.015mol of aluminum nitrate, 0.01mol of sodium molybdate and 0.1mol of sodium hydroxide into 100mL of water, stirring for 1h at 45 ℃, then heating to 85 ℃, crystallizing for 6h, after crystallization is finished, centrifugally washing, performing ultrasonic treatment for 30min, and dispersing a filter cake into 50mL of water to prepare a hydrotalcite prepolymer suspension;
(2) stirring 0.632g of selenium powder and 10mL of hydrazine hydrate in a three-neck flask for 30min, adding 40mL of the hydrotalcite precursor polymer suspension, performing ultrasonic dispersion, heating to 200 ℃ at the heating rate of 5 ℃/min, keeping the temperature for different times (when the temperature is kept for half, taking out the hydrotalcite precursor polymer suspension for ultrasonic treatment for 20min, and keeping the temperature after the ultrasonic treatment is finished), cooling after the reaction is finished, centrifugally washing for 7-10 times by using a mixed solution of water and ethanol (the mass fraction is 50%), performing ultrasonic treatment for 20min, and performing freeze drying to obtain the molybdenum diselenide in-situ modified CoAl hydrotalcite composite material. Wherein, the molybdenum diselenide in-situ modified CoAl hydrotalcite composite materials prepared in different hydrothermal times (6h, 18h, 24h and 60h) are respectively marked as No. 1, No. 2, No. 3 and No. 4.
(3) Preparing a Li-S battery diaphragm: ultrasonic treatment is carried out on No. 1, No. 2, No. 3 and No. 4 samples for 30min, and then solid content is respectively measured. ② the concentration of the sample is diluted by deionized water, the final solid content is controlled to be 0.5mg/ml, and the ultrasonic treatment is carried out for 30 min. Thirdly, preparing the PP @1,2,3 and 4 diaphragm by adopting a vacuum filtration method, wherein the loading capacity is 0.005mg/cm2。
Preparing a positive pole piece: a. weighing sulfur powder: 2.1 g; carbon nanotube: 0.9g (S: CNT 7: 3); ground well in an agate mortar. Putting into a ceramic square boat, wrapping the square boat with tin foil paper, and calcining at 155 ℃ for 12h in an argon atmosphere. b. Taking calcined S/CNT powder: 360mg was put into a volumetric flask, and 800mg of 5% PVDF (S/CNT: PVDF 9:1) was added thereto at 450r/min and stirred for 24 hours. c. Adjusting the thickness of the scraper: 20 μm, and the prepared slurry was coated on a carbon-coated aluminum foil. Drying in a 60 deg.C oven; and (6) slicing. Obtaining the anode piece with the sulfur content of 63 percent.
Fig. 5 is a battery performance evaluation of PP and PP mixed with molybdenum diselenide/CoAl hydrotalcite composite material prepared by different hydrothermal times, and the result shows that the introduction of the molybdenum diselenide/CoAl hydrotalcite composite material also significantly improves the battery capacity and cycle performance of a lithium sulfur battery, which is mainly due to the fact that the composite material prepared by the method has good sulfur adsorption capacity and catalytic conversion activity. The results showed that the initial discharge capacities of samples No. 1,2,3 and 4 were 1106mAh g at 0.1C, respectively-1、1230mAh g-1、1208mAh g-1、1104mAh g-1(ii) a After 50 cycles, the reversible capacity of the diaphragm batteries prepared from samples No. 1,2,3 and 4 is 598mAh g-1、625mAh g-1、550mAh g-1、530mAh g-1。
In example 2, the hydrothermal reduction time for preparing the molybdenum diselenide/hydrotalcite composite material also directly affects the membrane activity and the performance of the lithium-sulfur battery product, and both a shorter hydrothermal time and a longer hydrothermal time are not beneficial to the improvement of the membrane performance.
Comparative example 1:
a preparation method of a CoAl hydrotalcite material comprises the following steps:
adding 0.03mol of cobalt nitrate, 0.015mol of aluminum nitrate and 0.01mol of sodium molybdate into 100mL of water, stirring and reacting for 1h at 45 ℃, then heating to 85 ℃ for crystallization for 6h, and after crystallization, carrying out centrifugal washing, ultrasonic treatment and freeze drying to obtain the MgAl hydrotalcite material B.
The obtained MgAl hydrotalcite material B was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The electrical properties were tested as in example 1:
the initial discharge capacity at 0.1C was 1091mAh g-11030mAh g compared to PP separator alone-1Increase 61mAh g-1(ii) a After 50 cycles, the PP @ composite B separator cell had a capacity of 476mAh g-1Reversible capacity of (2), substantially equivalent to 470mAh g of PP separator cell-1And (4) the equivalent. Therefore, the hydrotalcite material prepared by the invention is introduced into the lithium-sulfur battery, although the initial battery capacity of the lithium-sulfur battery can be improved to a certain extent, the cycle performance is not obviously improved. The main reason is that the sulfur carrying amount of the diaphragm can be increased by the hydrotalcite, but the dissolution and accumulation of polysulfide in electrolyte cannot be improved because of no existence of catalytic active materials such as molybdenum diselenide, and the battery capacity is obviously reduced after multiple cycles.
Comparative example 2:
the preparation method of the molybdenum diselenide nano material comprises the following steps:
stirring and dispersing 0.01mol of sodium molybdate, 0.02mol of selenium powder and 10mL of hydrazine hydrate into 50mL of water, placing the solution into a high-pressure reaction kettle, heating to 200 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation reaction for 720min, cooling after the reaction is finished, centrifugally washing for 7-10 times by using a mixed solution of water and ethanol (the mass fraction is 50%), and carrying out ultrasonic treatment and freeze drying to obtain the molybdenum diselenide material C.
The obtained bulk molybdenum diselenide material C was subjected to cell preparation and electrochemical performance tests under the same test conditions as in example 2.
The electrical properties were tested as in example 1:
initial discharge capacity at 0.1C of 1038mAh g-11030mAh g compared to PP separator alone-1Increase 8mAh g-1(ii) a After 50 times of circulation, the PP @ molybdenum diselenide diaphragm cell has 496mAh g-1Compared with 470mAh g of a PP diaphragm battery-1The effect is not obvious but is improved to some extent. Therefore, the introduction of the molybdenum diselenide nano material prepared by the invention into the lithium-sulfur battery can improve the cycle performance of the lithium-sulfur battery to a certain extent, but the improvement is not obvious.
Comparative example 3:
and (3) physically mixing the CoAl hydrotalcite material prepared in the comparative example 1 and the molybdenum diselenide nano material prepared in the comparative example 2 (in-situ surface in-situ modification is not carried out, and the content of molybdenum diselenide is 20 percent) to obtain a composite material D.
The obtained material D was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1087mAh g-11030mAh g compared to PP separator alone-1Increase 57mAh g-1(ii) a After 50 times of circulation, the PP @ composite material D diaphragm battery has 401mAh g-1Compared with 470mAh g of a PP diaphragm battery-1And is reduced. Therefore, the hydrotalcite and the molybdenum diselenide are physically mixed and then introduced into the lithium-sulfur battery diaphragm, so that the initial capacity and the cycle performance of the battery can be improved to a certain degree, but the performance of the battery is obviously poorer than that of the battery with the PP @ composite diaphragm prepared in the embodiment 2 of the invention. The main reason is that the high activity of substances such as molybdenum diselenide and the like is kept in the preparation process, and meanwhile, the in-situ self-assembly mode of molybdenum diselenide and hydrotalcite is more favorable for the adsorption and catalytic conversion of polysulfide, which is also a unique advantage formed by introducing the composite material prepared by the invention into a diaphragm material.
Comparative example 4:
the preparation of the molybdenum diselenide/CoAl hydrotalcite composite material E is carried out in the same way as the example 2 except that the ultrasonic strengthening is cancelled in the whole process.
The obtained material was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1044mAh g-11030mAh g compared to PP separator alone-1Increase 14mAh g-1(ii) a After 50 times of circulation, the PP @ composite E diaphragm battery has 427mAh g-1Compared with 470mAh g of a PP diaphragm battery-1And is reduced. Therefore, ultrasonic field enhancement is required in the process of preparing the molybdenum disulfide in-situ modified hydrotalcite composite material, otherwise, the capacitance and the cycle performance of the lithium-sulfur battery are obviously influenced.
Comparative example 5:
the preparation method is similar to that of example 2, except that the hydrothermal reduction temperature of the CoAl hydrotalcite composite material is reduced from 200 ℃ to 150 ℃; and preparing the molybdenum diselenide/CoAl hydrotalcite composite material F.
The obtained material F was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 968mAh g-11030mAh g compared to PP separator alone-1Decrease 62mAh g-1(ii) a After circulating for 50 times, the PP @ composite material F diaphragm battery keeps 440mAh g-1Compared with 470mAh g of a PP diaphragm battery-1Is also reduced.
Example 2:
the preparation method is similar to that of example 2, except that the hydrothermal reduction temperature of the CoAl hydrotalcite composite material is increased from 200 ℃ to 230 ℃; and preparing the molybdenum diselenide/CoAl hydrotalcite composite material G.
The electrochemical performance of the obtained material G was tested under the same conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1342mAh g-11030mAh g compared to PP separator alone-1And improve 312mAh g-1(ii) a After circulating for 50 times, the PP @ composite material diaphragm battery keeps 767mAh g-1Compared with 470mAh g of a PP diaphragm battery-1Is remarkably increased.
Example 3:
the preparation method is similar to that of example 2, except that the hydrothermal reduction temperature of the CoAl hydrotalcite composite material is increased from 200 ℃ to 250 ℃; and preparing the molybdenum diselenide/CoAl hydrotalcite composite material H.
The obtained material H was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1237mAh g-11030mAh g compared to PP separator alone-1And increase 207mAh g-1(ii) a After circulating for 50 times, the PP @ composite material H diaphragm battery keeps 567mAh g-1Compared with 470mAh g of a PP diaphragm battery-1And increased.
As can be seen from comparative example 5, example 2 and example 3, the hydrothermal reduction temperature of the composite material has a significant effect on the activity of the separator and the performance of the lithium sulfur battery, and both the reduced temperature and the higher temperature may reduce the performance of the battery.
Example 4
The invention relates to a preparation method of a molybdenum disulfide modified CoAl hydrotalcite composite material I, which specifically comprises the following steps:
(1) adding 0.05mol of cobalt chloride, 0.02mol of aluminum nitrate, 0.04mol of sodium molybdate and 0.06mol of sodium hydroxide into 100mL of water, and stirring for reaction at 35 ℃ for 1 h; then heating to 85 ℃ for crystallization for 6 h; after crystallization is finished, performing suction filtration and washing, and dispersing a filter cake into 50mL of water to prepare a hydrotalcite precursor polymer suspension;
(2) and adding 2.5g of thiourea into 50mL of the hydrotalcite precursor suspension, performing ultrasonic dispersion, placing the mixture in a high-pressure reaction kettle, heating to 200 ℃ at the heating rate of 3 ℃/min, performing heat preservation reaction for 900min, cooling after the reaction is finished, washing for 3-5 times by using a mixed solution of water and ethanol (the mass fraction is 50%), and performing freeze drying to obtain the molybdenum disulfide modified CoAl hydrotalcite composite material I.
The obtained composite material I was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1298mAh g-11030mAh g compared to PP separator alone-1Increase 268mAh g-1(ii) a After 50 times of circulation, the PP @ composite I diaphragm battery has 740mAh g-1Compared with 470mAh g of a PP diaphragm battery-1And (4) the improvement is remarkable. Therefore, the molybdenum disulfide modified hydrotalcite composite material prepared by the invention can also be used as a diaphragm active component, and the capacitance and the cycle performance of the lithium-sulfur battery are obviously improved.
Example 5:
the invention relates to a preparation method of a tungsten disulfide modified MgAl hydrotalcite composite material, which specifically comprises the following steps:
(1) adding 0.05mol of magnesium chloride, 0.02mol of aluminum nitrate, 0.06mol of sodium tungstate and 0.06mol of sodium hydroxide into 100mL of water, and stirring and reacting for 1h at 35 ℃; then heating to 85 ℃ for crystallization for 6 h; after crystallization is finished, performing suction filtration and washing, and dispersing a filter cake into 50mL of water to prepare a hydrotalcite precursor polymer suspension;
(2) and adding 2.5g of thiourea into 50mL of the hydrotalcite precursor suspension, performing ultrasonic dispersion, placing the mixture in a high-pressure reaction kettle, heating to 200 ℃ at the heating rate of 3 ℃/min, performing heat preservation reaction for 900min, cooling after the reaction is finished, washing for 3-5 times by using a mixed solution of water and ethanol (the mass fraction is 50%), and performing freeze drying to obtain the tungsten disulfide modified MgAl hydrotalcite composite material J.
The obtained composite material J was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1309mAh g-11030mAh g compared to PP separator alone-1Increase 279mAh g-1(ii) a After 50 times of circulation, the PP @ composite J diaphragm battery has 627mAh g-1Compared with 470mAh g of a PP diaphragm battery-1And (4) the improvement is remarkable. Therefore, the tungsten disulfide modified hydrotalcite composite material prepared by the invention can be used as a diaphragm active component, and the capacitance and the cycle performance of the lithium-sulfur battery are obviously improved.
Example 6:
the preparation method of the tungsten diselenide/CoAl hydrotalcite composite material comprises the following steps:
(1) adding 0.03mol of cobalt nitrate, 0.015mol of aluminum nitrate, 0.01mol of sodium tungstate and 0.1mol of sodium hydroxide into 100mL of water, and stirring and reacting for 1h at the temperature of 45 ℃; then heating to 85 ℃ for crystallization for 6 h; after crystallization is finished, centrifugal washing is carried out, the mixture is filtered after an ultrasonic field acts for 30min, and filter cakes are dispersed in 50mL of water to prepare hydrotalcite prepolymer suspension;
(2) and (2) stirring 0.632g of selenium powder and 10mL of hydrazine hydrate in a three-neck flask for 30min, adding 40mL of the hydrotalcite precursor polymer suspension, performing ultrasonic dispersion, placing the mixture in a high-pressure reaction kettle, heating to 200 ℃ at the heating rate of 5 ℃/min, performing heat preservation reaction for 720min (wherein, when the temperature is 360min, taking out the mixture for ultrasonic treatment for 20min, and continuing to perform heat preservation after the ultrasonic treatment), cooling after the reaction is finished, washing the mixture for 7-10 times by using a mixed solution of water and ethanol (the mass fraction is 50%), performing ultrasonic treatment for 20min, and performing freeze drying to obtain the tungsten diselenide/MgAl hydrotalcite composite material K.
The obtained composite material K was subjected to battery preparation and electrochemical performance test under the same test conditions as in example 2.
The test results showed that the initial discharge capacity at 0.1C was 1346mAh g-11030mAh g compared to PP separator alone-1Increase 316mAh g-1(ii) a After 50 times of circulation, the PP @ composite material K diaphragm battery has 728mAh g-1Compared with 470mAh g of a PP diaphragm battery-1And (4) the improvement is remarkable. Therefore, the tungsten diselenide modified hydrotalcite composite material prepared by the invention can be used as a diaphragm active component, and the electric capacity and the cycle performance of the lithium-sulfur battery are obviously improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A preparation method of a composite membrane material of polymer @ two-dimensional material modified layered double hydroxide is characterized by comprising the following steps:
step (1): at least one of a molybdic acid source and a tungstic acid source is used as an intercalation precursor source, and the intercalation precursor source is mixed with divalent metal ions M2+Source, trivalent metal ion M3+Stirring and reacting a source and alkali, then crystallizing, and performing post-treatment to obtain a hydrotalcite precursor polymer with molybdate and/or tungstate intercalation; wherein, the crystallization process and/or the post-treatment process are/is carried out with ultrasonic strengthening treatment;
step (2): adding at least one of a selenium source and a sulfur source and a reducing compound into the hydrotalcite precursor polymer obtained in the step (1), then carrying out hydrothermal reaction, and carrying out post-treatment after hydrothermal reaction to obtain an active material; wherein, the hydrothermal reaction and/or the post-treatment process is carried out with ultrasonic strengthening treatment; the temperature of the hydrothermal reaction is 160-300 ℃;
and (3): and compounding the active material and the polymer membrane material to form a membrane, thus obtaining the composite membrane material.
2. The production method according to claim 1, wherein in the step (1),
divalent metal ion M2+The source being selected from Mg2+、Ni2+、Co2+、Zn2+、Cu2+At least one water-soluble salt of (a);
trivalent metal ion M3+The source is selected from Al3+、Cr3+、Fe3+、Sc3+At least one water-soluble salt of (a);
the molybdic acid source is selected from at least one of sodium molybdate, ammonium molybdate, potassium molybdate and magnesium molybdate;
the tungstic acid source is at least one selected from sodium tungstate, calcium tungstate, zinc tungstate and cobalt tungstate;
the alkali is at least one of sodium hydroxide, potassium hydroxide and ammonia water.
3. The method according to claim 2, wherein the divalent metal ion M is2+Source, trivalent metal ion M3+Moles of source, intercalated precursor source and baseThe ratio is 1: (0.3-0.5): (0.3-1): (1-3).
4. The preparation method according to claim 1, wherein in the step (1), the stirring reaction temperature is 20 ℃ to 50 ℃, and the stirring reaction time is 1h to 4 h;
the crystallization temperature is 70-95 ℃, and the crystallization time is 4-12 h;
the post-treatment of the step (1) comprises centrifugal washing, ultrasonic strengthening and solid-liquid separation; wherein the ultrasonic strengthening time is 15-60 min.
5. The method according to claim 1, wherein in the step (2), the selenium source is at least one selected from selenium powder, trimethylphenylselenosilane, (phenylselenium) trimethylsilane, sodium selenocyanate, sodium selenite;
the sulfur source is at least one of thiourea, thioacetamide, sodium sulfide and potassium sulfide;
the reducing compound is at least one of hydrazine hydrate, sodium borohydride, hydroiodic acid, sulfite and oxalate;
the adding amount of the selenium source or the sulfur source is 2-10 times of the mass of the hydrotalcite precursor polymer;
the addition amount of the reducing compound is 0.3-5 times of the mass of the hydrotalcite prepolymer.
6. The preparation method according to claim 5, wherein in the hydrothermal reduction preparation process, ultrasonic strengthening is performed for 1-2 times, and the ultrasonic strengthening time is 15-30 min each time.
7. The preparation method according to claim 5, wherein the hydrothermal reaction time is 12 to 48 hours.
8. The production method according to claim 5, wherein the post-treatment of step (2) includes centrifugal washing, ultrasonic strengthening and solid-liquid separation; wherein the ultrasonic strengthening time is 15-30 min.
9. The production method according to claim 5, wherein in the step (3), the composite separator is obtained by dispersing a polymer film material with a solvent and then adding the active material to form a film.
10. The composite diaphragm material of the polymer @ two-dimensional material modified layered double hydroxide is characterized by being prepared by the preparation method of any one of claims 1 to 9, and comprising a polymer film material and an active material compounded in the polymer film material; the active material is the two-dimensional material modified layered double hydroxide which comprises the layered double hydroxide and a two-dimensional material growing on the surface of the layered double hydroxide in situ;
wherein, the two-dimensional material is at least one of molybdenum diselenide, tungsten diselenide, molybdenum disulfide and tungsten disulfide.
11. The polymer @ two-dimensional material modified layered double hydroxide composite membrane material according to claim 10, wherein the layered double hydroxide is a single or flake layered hydrotalcite sheet layer structure.
12. The polymer @ two-dimensional material modified layered double hydroxide composite membrane material of claim 10, wherein the polymer is at least one of polypropylene, polyethylene, a polyester film, a cellulose film, a polyimide film, a polyamide film, spandex, or an aramid film.
13. The polymer @ two-dimensional material modified layered double hydroxide composite membrane material as claimed in claim 10, wherein the loading amount of the active material in the composite membrane material is 0.002-0.050 mg/cm2。
14. The application of the polymer @ two-dimensional material modified layered double hydroxide composite membrane material prepared by the preparation method of any one of claims 1 to 9 is characterized in that the polymer @ two-dimensional material modified layered double hydroxide composite membrane material is used as a membrane of a lithium-sulfur battery.
15. The lithium-sulfur battery is characterized in that the diaphragm material is a polymer @ two-dimensional material modified layered double hydroxide composite diaphragm material prepared by the preparation method of any one of claims 1 to 9.
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