CN110571392B - Functional interlayer material of lithium-sulfur battery and preparation method thereof - Google Patents

Functional interlayer material of lithium-sulfur battery and preparation method thereof Download PDF

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CN110571392B
CN110571392B CN201810700303.2A CN201810700303A CN110571392B CN 110571392 B CN110571392 B CN 110571392B CN 201810700303 A CN201810700303 A CN 201810700303A CN 110571392 B CN110571392 B CN 110571392B
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mesoporous silica
lithium
graphite oxide
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解孝林
向晓
叶昀昇
周兴平
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Huazhong 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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Abstract

The invention belongs to the technical field of lithium-sulfur batteries, and particularly discloses a functional interlayer material of a lithium-sulfur battery and a preparation method thereof, wherein the functional interlayer material mainly comprises amino mesoporous silica nanosheets and a binder, the amino mesoporous silica nanosheets and the binder are mixed with each other, the amino mesoporous silica nanosheets are amino-modified silica nanosheets with mesoporous structures, the specific surface area of the amino mesoporous silica nanosheets is 750-1200 cm2And/g, the mass ratio of the amino mesoporous silica nanosheet to the binder is 5/1-1/2. By improving the components of the functional interlayer material and the corresponding preparation method, compared with the prior art, the invention can simultaneously and effectively solve the problem of the shuttle effect of polysulfide in the lithium-sulfur battery and the problems of excessive functional interlayer components, complex preparation method and incapability of realizing industrialization in batch production of the lithium-sulfur battery.

Description

Functional interlayer material of lithium-sulfur battery and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a functional interlayer material of a lithium-sulfur battery and a preparation method thereof.
Background
Lithium-sulfur battery with higher theoretical specific capacity (1675 mA. hg)-1) And energy density (2600 Wh. Kg)-1) Is widely concerned by researchers at home and abroad, and simultaneously, the elemental sulfur has the advantages of low price, environmental protection, no toxicity, wide source and the like. Therefore, lithium-sulfur batteries are expected to be the next generation of energy storage systems with great development prospects. The greatest problem in lithium sulfur batteries is the "shuttle effect" of polysulfides, i.e. the reduction of elemental sulfur to polysulfides during discharge, where it may beThe soluble polysulfide dissolves in the electrolyte through the separator to the negative electrode and undergoes a series of side reactions with the negative electrode lithium to cause a loss of the active material of the battery, resulting in a decrease in various performances of the battery.
The functional interlayer material is added between the positive electrode and the diaphragm of the battery, so that the dissolution and diffusion of polysulfide can be inhibited, the shuttle effect is prevented, the loss of active substances is reduced, the capacity and the cycle performance of the lithium-sulfur battery are improved, and the functional interlayer material is one of effective ways for inhibiting the shuttle effect of the polysulfide. The method for preparing the interlayer by scientific researchers generally comprises suction filtration, spin coating, blade coating and the like, for example, one of porous carbon, carbon nano tube or acetylene black and graphite oxide are used for suction filtration to form a film, and the suction filtration method is long in time consumption and small in film forming area, so that industrialization can not be realized in batch production; for example, polyvinylidene fluoride powder is used as a binder to prepare slurry of boron nitride and graphite for blade coating, the blade coating mode is simple, convenient and fast, and can realize batch production, but the interlayer component also comprises a conductive agent graphite besides the necessary binder and a functional component of boron nitride, and the increase of the interlayer component increases the weight and the volume of the interlayer and reduces the energy density of the battery; for example, polystyrene sodium sulfonate and poly 3, 4-ethylenedioxythiophene are used for spin coating to form a film, a solvent used for spin coating is required to have a low boiling point, so that the range of the usable solvent is reduced, and the spin coating area is small, so that the production efficiency is low.
Therefore, the suction filtration and spin coating processes are complex, time-consuming, high in equipment requirement and high in cost, and therefore mass production is not facilitated; the knife coating method has simple process, high production efficiency and easy industrial production, but the coating is often added with a conductive agent besides necessary functional materials and adhesives, the volume and the thickness of an interlayer are increased due to the increase of the components of the interlayer, and the volume and the weight of a battery are increased, so that the energy density of the battery is reduced. Therefore, a functional interlayer material having a small amount of components and a simple and efficient preparation method has yet to be developed for a lithium sulfur battery.
Disclosure of Invention
In view of the above-mentioned drawbacks and needs of the prior art, it is an object of the present invention to provide a functional interlayer material for a lithium sulfur battery and a method for preparing the same, wherein the components of the functional interlayer material and the corresponding preparation method are improved, compared with the prior art, the method can simultaneously and effectively solve the problems of shuttle effect of polysulfide in the lithium-sulfur battery and the problems of excessive functional interlayer components, complex preparation method and incapability of realizing industrialization of batch production of the lithium-sulfur battery, adopts the amino mesoporous silica nanosheets, and has electrostatic attraction between amino functional groups modified on silica and polysulfide, the migration of polysulfide can be blocked, and the captured polysulfide can be released in the next charge-discharge cycle to carry out electrochemical reaction, so that the problem of shuttle effect of polysulfide in the lithium-sulfur battery is solved; the sandwich material can only consist of amino mesoporous silica nanosheets and a binder, and slurry prepared from the amino mesoporous silica nanosheets and the binder can be directly blade-coated on a lithium-sulfur battery positive plate or a commercial diaphragm during preparation, so that the functional sandwich material is a functional sandwich material which is few in components and can be prepared in a blade coating mode, and a new way is provided for preparation and application of the functional sandwich material in the aspect of lithium-sulfur batteries.
In order to achieve the above object, according to one aspect of the present invention, there is provided a functional interlayer material for a lithium-sulfur battery, the functional interlayer material mainly comprises amino mesoporous silica nanosheets and a binder, the amino mesoporous silica nanosheets and the binder being intermixed, wherein the amino mesoporous silica nanosheets are amino-modified silica nanosheets having a mesoporous structure, and have a specific surface area of 750-1200 cm2And/g, the mass ratio of the amino mesoporous silica nanosheet to the binder is 5/1-1/2.
In a further preferred embodiment of the present invention, the binder is one of Nafion, polyvinylidene fluoride powder, and carboxymethyl cellulose powder, and Nafion is
Figure BDA0001714155970000031
Effective components in the D-521 dispersion liquid.
In a further preferred embodiment of the present invention, the mesoporous structure in the amino mesoporous silica nanosheet has a pore diameter of 3 to 9 nm.
In a further preferred embodiment of the present invention, the thickness of the functional interlayer material for a lithium-sulfur battery is 1 to 30 μm.
According to another aspect of the present invention, there is provided a method for preparing a functional interlayer material for a lithium-sulfur battery, comprising the steps of:
(1) preparing amino mesoporous silica nanosheets: dispersing mesoporous silica nanosheets with mesoporous structures and an aminosilane coupling agent in a solvent according to a mass ratio of 5: 1-1: 5, refluxing and stirring at 80-100 ℃ for 12-24 hours, and then performing suction filtration, washing and drying to obtain amino mesoporous silica nanosheets;
the specific surface area of the mesoporous silica nanosheet is 750-1200 cm2/g；
(2) Preparing the amino mesoporous silica nanosheets obtained in the step (1) and an adhesive into slurry by using water or an organic solvent, and uniformly mixing to obtain uniformly dispersed slurry; and then, the slurry is coated on a load material in a blade mode, and the functional interlayer material can be obtained after the slurry is fully dried.
In a further preferred aspect of the present invention, in the step (1), the mesoporous silica nanosheet having a mesoporous structure is synthesized by:
adding a cationic surfactant and a pH regulator into a graphite oxide aqueous solution with the concentration of graphite oxide of 0.1-5.0 g/L, uniformly dispersing, and continuously stirring at 30-80 ℃ to obtain a uniformly dispersed graphite oxide dispersion liquid, wherein the pH value of the graphite oxide dispersion liquid is 10-13, and the mass ratio of the cationic surfactant to the graphite oxide in the graphite oxide aqueous solution is 20: 1-10: 1; measuring a liquid silicon source and a liquid alcohol compound, mixing to obtain a silicon/alcohol mixed solution, slowly dropwise adding the silicon/alcohol mixed solution into the graphite oxide dispersion solution to form a reaction solution A, continuously stirring and reacting the reaction solution A at 30-80 ℃ for 8-24 hours to obtain a product B, wherein the volume ratio of the silicon source to the alcohol compound is 1: 3-1: 8, and the mass ratio of the graphite oxide to the silicon source in the graphite oxide aqueous solution is 20: 1-60: 1; then, centrifugally separating the product B to obtain precipitate, washing and fully drying at 50-70 ℃ to obtain solid powder C; then, carrying out reflux reaction on the solid powder C for 6-10 h at 85-95 ℃ by using an ammonium nitrate/ethanol solution with the ammonium nitrate concentration of 1.0-10.0 g/L, then carrying out suction filtration, fully drying at 50-70 ℃, and calcining for 4-8 h at 500-700 ℃ in the air to obtain the mesoporous silica nanosheet.
As a further preferred aspect of the present invention, the cationic surfactant is a quaternary ammonium salt, and is one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride;
the pH regulator is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate and disodium hydrogen phosphate;
the dispersion is preferably ultrasonic dispersion;
the silicon source is one of tetraethyl orthosilicate, hexamethyldisiloxane and silica sol.
In a further preferred aspect of the present invention, in the step (1), the aminosilane coupling agent is one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and polyaminoalkyltrialkoxysilane; the solvent is one of water, acetone, ethanol, methanol, isopropanol, benzene and toluene; the drying is carried out for 4-8 h under the temperature of 50-80 ℃ in vacuum.
As a further preferred aspect of the present invention, in the step (2), the binder is one of Nafion, polyvinylidene fluoride powder, and carboxymethyl cellulose powder; when the binder is Nafion, it is specifically adopted
Figure BDA0001714155970000041
D-521 dispersion as Nafion solution, the
Figure BDA0001714155970000042
The D-521 dispersion liquid is preferably a water/1-propanol solution with 5% of active ingredient mass percentage concentration, the step (2) of preparing the slurry by using water or an organic solvent to prepare the amino mesoporous silica nanosheet and the binder is to directly and uniformly mix the Nafion solution and the amino mesoporous silica nanosheet to obtain the slurry, or the step (2) of preparing the slurry by using a water or alcohol reagent to prepare the amino mesoporous silica nanosheet and the Nafion solution;
in addition, in the step (2), the mass ratio of the amino mesoporous silica nanosheets to the binder is 5/1-1/2; the mixing mode is one of ultrasonic dispersion and magnetic stirring; the load material is one of a lithium-sulfur battery positive plate and a diaphragm for a lithium-sulfur battery; the thickness of the interlayer material is 1-30 mu m; the full drying is vacuum drying for 4-8 h at 50-80 ℃.
According to still another aspect of the present invention, the present invention provides the use of the above-described functional interlayer material for a lithium sulfur battery as a functional interlayer material disposed between a positive electrode and a separator of the lithium sulfur battery in the lithium sulfur battery.
Compared with the prior art, the technical scheme of the invention has the following technical effects:
1. the silicon dioxide adopted by the functional interlayer material of the lithium-sulfur battery is flaky and has a rich mesoporous structure, and can provide a lithium ion migration channel and increase the ionic conductivity, so that a conductive agent is not required to be added, and the volume and the weight of an interlayer are reduced.
2. The rich mesoporous structure and the larger specific surface area of the silicon dioxide enable the silicon dioxide to have large liquid absorption capacity and absorb more electrolyte.
3. Silica is an inorganic rigid material that can inhibit the growth of lithium dendrites.
4. The modified amino functional group on the silicon dioxide has electrostatic attraction with polysulfide, so that the migration of the polysulfide can be blocked, and the captured polysulfide can be released in the next charge-discharge cycle to carry out electrochemical reaction.
5. The interlayer preparation method can be knife coating, the operation is simple, the equipment cost is low, the implementation condition is easy to realize, the batch production can be carried out, and the industrial prospect is realized.
6. The interlayer material can be coated on the positive plate and the commercial diaphragm, and has multiple functions.
7. The thickness of the interlayer material can be regulated and controlled according to different requirements, and controllability is achieved.
8. The preparation process of the sandwich material has various types of optional reagents and solvents, so that the reagents and solvents which are non-toxic, harmless, environment-friendly and low in price can be selected.
The mesoporous silica nanosheets are used as key components of the functional interlayer material of the lithium-sulfur battery, can conduct ions, can adsorb electrolyte due to the large specific surface area, and have the advantages of being modifiable and certain in mechanical strength, and being capable of being continuously charged and discharged by the battery.
The invention also preferably improves the whole process of the preparation method, and controls the parameter conditions such as the specific types and the proportions of the raw materials adopted in each step of the preparation method, so that on one hand, the functional interlayer material with the mass ratio of the amino mesoporous silica nanosheet to the binder of 5/1-1/2 can be obtained, and on the other hand, the mesoporous structure and the distribution of amino functional groups in the functional interlayer material can be effectively controlled, and the shuttle effect of polysulfide in the lithium-sulfur battery can be effectively prevented.
In a word, the functional interlayer material prepared by directly blade-coating the amino mesoporous silica nanosheet and the adhesive on the lithium-sulfur battery positive plate or the commercial diaphragm can utilize the electrostatic attraction effect to block the shuttle effect of polysulfide, the preparation method is simple, convenient and quick, and the process is energy-saving and environment-friendly.
Drawings
In fig. 1, (a) is a Scanning Electron Microscope (SEM) of the mesoporous silica nanosheets described in example 1, and (b) is a projection electron microscope (TEM) of the mesoporous silica nanosheets described in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the surface of the functional interlayer formed by coating the amino mesoporous silica nanosheets and the adhesive on the surface of the pole piece in example 2.
Fig. 3 is a constant rate charge and discharge test at 0.5C for the assembled lithium sulfur battery of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In summary, the functional interlayer material of the lithium-sulfur battery comprises the aminated mesoporous silica nanosheet and the binder, and can be prepared by preparing a solution of the synthesized aminated mesoporous silica nanosheet and the binder, uniformly mixing the solution to form slurry, then blade-coating the slurry on a lithium-sulfur battery positive plate or a commercial diaphragm, and then carrying out vacuum drying. Wherein the amino silicon dioxide is flaky and has a mesoporous structure, and the specific surface area can be 750-1200 cm2The pore diameter can be 3-9 nm; the binder may be Nafion (e.g., corresponding to
Figure BDA0001714155970000071
D-521 dispersion liquid; the
Figure BDA0001714155970000072
D-521 dispersion, namely water and 1-propanol solution with the mass percentage concentration of the effective component of 5%, wherein the water and the 1-propanol are used as solvents, polyvinylidene fluoride (PVDF) powder and carboxymethyl cellulose (CMC) powder; the thickness of the prepared functional interlayer material can be 1-30 mu m.
The following are specific examples:
example 1:
a functional interlayer material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and a binder Nafion, wherein the amino mesoporous silica nanosheets have mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 750cm2(ii)/g, pore diameter of 9nm, mass ratio of silica to binder of 5:1, and thickness of interlayer of 1 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 2.0g of hexadecyl trimethyl ammonium bromide, adjusting the pH value of the solution to 10 by using sodium hydroxide, uniformly dispersing, and continuously stirring at 30 ℃ to obtain a graphite oxide dispersion liquid. Measuring 5.0mL of tetraethyl orthosilicate, adding the tetraethyl orthosilicate into 15.0mL of ethanol, slowly and dropwise adding the tetraethyl orthosilicate into the graphite oxide dispersion liquid to form a reaction liquid A, and continuously stirring and reacting at 30 ℃ for 8 hours to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 50 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using 1.0g/L ammonium nitrate/ethanol solution at 85 ℃ for 6h, carrying out suction filtration, fully drying at 50 ℃, and calcining in air at 500 ℃ for 8h to obtain the mesoporous silica nanosheet. The synthesized mesoporous silica nanosheet is observed by a Scanning Electron Microscope (SEM) and a projection electron microscope (TEM), and the silica is flaky and has a rich mesoporous structure as can be seen from the SEM and the TEM (figure 1).
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 1.0g of gamma-aminopropyltriethoxysilane into 50mL of water, ultrasonically dispersing 5.0g of mesoporous silica nanosheets into 50mL of water, dropwise adding a gamma-aminopropyltriethoxysilane aqueous solution into the aqueous dispersion of the mesoporous silica nanosheets while stirring, raising the temperature to 100 ℃, reacting for 12 hours, carrying out suction filtration, washing, and carrying out vacuum drying for 4 hours at 50 ℃.
(2) Preparing the functional interlayer material and assembling a battery:
(2-1) preparing the functional interlayer material: 0.05g of aminated mesoporous silica nanosheet was weighed out with 0.2g of Nafion solution (i.e., D-521 dispersed)Liquid, 5% w/w water/1-propanol solution) was dispersed by sonication (since Nafion solution was used)
Figure BDA0001714155970000081
D-521 dispersion liquid, namely water/1-propanol solution with the mass percentage concentration of the effective component of 5%, wherein the water and the 1-propanol are used as solvents, so when Nafion is used as an adhesive, the Nafion solution and the amino mesoporous silica nanosheet can be directly and uniformly mixed to prepare slurry without additionally using other solvents, and certainly, water or alcohol reagents can be additionally used for adjusting the consistency of the slurry), the uniformly dispersed slurry is blade-coated on a lithium-sulfur battery positive plate, the thickness of the sandwich material obtained by blade-coating is 1 mu m, and the functional sandwich material is prepared by vacuum drying for 4 hours at 50 ℃.
(2-2) assembling a battery: assembling the lithium-sulfur battery positive plate coated with the functional interlayer material into a battery, and testing the electrochemical performance of the battery at the multiplying power of 0.5C, wherein the result is as follows: the initial discharge specific capacity is 1210mAh g-1And the specific discharge capacity after 200 cycles is 70 percent. As shown in table 1.
Example 2:
a functional interlayer material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and polyvinylidene fluoride powder serving as a binder, wherein the amino mesoporous silica nanosheets have mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 1200cm2(g), the pore diameter is 3nm, and the mass ratio of the silicon dioxide to the adhesive is 1: 2, the thickness of the interlayer is 30 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 1.0g of dodecyl trimethyl ammonium bromide, adjusting the pH value of the solution to 13 by using potassium hydroxide, uniformly dispersing, and continuously stirring at 80 ℃ to obtain a graphite oxide dispersion liquid. 3.0mL of hexamethyldisiloxane is weighed and added into 24.0mL of ethanol, and slowly and dropwise added into the graphite oxide dispersion liquid to form a reaction liquid A, and the reaction is continued for 24 hours under stirring at 80 ℃ to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 70 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using a 10.0g/L ammonium nitrate/ethanol solution at 95 ℃ for 10h, carrying out suction filtration, fully drying at 70 ℃, and calcining in air at 700 ℃ for 4h to obtain the mesoporous silica nanosheet.
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 5.0g of gamma-aminopropyltrimethoxysilane into 50mL of acetone, ultrasonically dispersing 1.0g of mesoporous silica nanosheets into 50mL of acetone, dropwise adding a gamma-aminopropyltrimethoxysilane acetone solution into an acetone dispersion liquid of the mesoporous silica nanosheets while stirring, raising the temperature to 80 ℃, reacting for 24 hours, carrying out suction filtration and washing, and carrying out vacuum drying for 8 hours at 80 ℃.
(2) Preparing the functional interlayer material and assembling a battery:
(2-1) preparing the functional interlayer material: weighing 0.05g of aminated mesoporous silica nanosheet and 0.1g of polyvinylidene fluoride powder, dissolving the aminated mesoporous silica nanosheet and the polyvinylidene fluoride powder in 1-methyl pyrrolidone by magnetic stirring to form uniform slurry, blade-coating the slurry on a commercial diaphragm to obtain a sandwich material with the thickness of 30 microns, and carrying out vacuum drying at 80 ℃ for 8 hours to obtain the functional sandwich material.
(2-2) assembling a battery: assembling the lithium-sulfur battery positive plate coated with the functional interlayer material into a battery, and testing the electrochemical performance of the battery at the multiplying power of 0.5C, wherein the result is as follows: the initial discharge specific capacity is 1218mAh g-1And the specific discharge capacity after 200 cycles is 76%. As shown in table 1.
Example 3:
a functional interlayer material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and binder carboxymethyl cellulose powder, wherein the amino mesoporous silica nanosheets have mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 900cm2G, pore diameter of 4nm, mass ratio of silica to binder of 3:1, and thickness of interlayer of 10 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 1.5g of hexadecyl trimethyl ammonium chloride, adjusting the pH value of the solution to 11 by using lithium hydroxide, uniformly dispersing, and continuously stirring at 40 ℃ to obtain a graphite oxide dispersion liquid. Measuring 4.0mL of silica sol, adding the silica sol into 10.0mL of ethanol, slowly and dropwise adding the silica sol into the graphite oxide dispersion liquid to form a reaction liquid A, and continuously stirring and reacting at 40 ℃ for 4 hours to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 60 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using a 5.0g/L ammonium nitrate/ethanol solution at 90 ℃ for 8 hours, carrying out suction filtration, fully drying at 60 ℃, and calcining at 600 ℃ in the air for 5 hours to obtain the mesoporous silica nanosheet.
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 1.0g N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane into 50mL of ethanol, ultrasonically dispersing 3.0g of mesoporous silica nanosheets into 50mL of ethanol, dropwise adding an N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane ethanol solution into the ethanol dispersion liquid of the mesoporous silica nanosheets while stirring, raising the temperature to 90 ℃, reacting for 24 hours, carrying out suction filtration, washing, and carrying out vacuum drying for 4 hours at 60 ℃.
(2) Preparing the functional interlayer material and assembling a battery:
(2-1) preparing the functional interlayer material: weighing 0.03g of aminated mesoporous silica nanosheet and 0.1g of carboxymethyl cellulose powder, stirring in water by magnetic force to prepare slurry, blade-coating the slurry on a lithium-sulfur battery positive plate to obtain a sandwich material with the thickness of 20 microns, and vacuum-drying at 60 ℃ for 4 hours to obtain the functional sandwich material.
(2-2) assembling a battery: assembling the lithium-sulfur battery positive plate coated with the functional interlayer material into a battery, and testing the electrochemical performance of the battery at the multiplying power of 0.5C, wherein the result is as follows: initial specific discharge capacity of 1230mAh g-1And the specific discharge capacity after 200 cycles is 80 percent. As shown in table 1.
Example 4:
a functional sandwich material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and adhesiveThe amino silicon dioxide nanosheet has a mesoporous structure and a specific surface area of 800cm2G, pore diameter of 4nm, mass ratio of silica to binder of 5:1, and thickness of interlayer of 1 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 2.0g of dodecyl trimethyl ammonium bromide, adjusting the pH value of the solution to 12 by using sodium bicarbonate, uniformly dispersing, and continuously stirring at 30 ℃ to obtain a graphite oxide dispersion liquid. Measuring 5.0mL of tetraethyl orthosilicate, adding the tetraethyl orthosilicate into 15.0mL of ethanol, slowly and dropwise adding the tetraethyl orthosilicate into the graphite oxide dispersion liquid to form a reaction liquid A, and continuously stirring and reacting at 30 ℃ for 8 hours to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 50 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using 1.0g/L ammonium nitrate/ethanol solution at 85 ℃ for 6h, carrying out suction filtration, fully drying at 50 ℃, and calcining in air at 500 ℃ for 8h to obtain the mesoporous silica nanosheet.
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 1.0g N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane into 50mL of methanol, ultrasonically dispersing 5.0g of mesoporous silica nanosheets into 50mL of methanol, dropwise adding a gamma-aminopropyltriethoxysilane methanol solution into the methanol dispersion liquid of the mesoporous silica nanosheets while stirring, raising the temperature to 100 ℃, reacting for 12 hours, carrying out suction filtration, washing, and vacuum drying at 50 ℃ for 4 hours.
(2) Preparing the functional interlayer material and assembling a battery:
(2-1) preparing the functional interlayer material: 0.05g of aminated mesoporous silica nanosheet and 0.2g of Nafion solution (namely D-521 dispersion liquid, 5% w/w of water/1-propanol solution) are weighed and ultrasonically dispersed uniformly, the uniformly dispersed slurry is blade-coated on a lithium-sulfur battery positive plate, the thickness of a sandwich material obtained by blade-coating is 1 mu m, and the functional sandwich material is prepared by vacuum drying for 4 hours at 50 ℃.
Group (2-2)Battery installation: assembling the lithium-sulfur battery positive plate coated with the functional interlayer material into a battery, and testing the electrochemical performance of the battery at the multiplying power of 0.5C, wherein the result is as follows: initial discharge specific capacity of 1225mAh g-1And the specific discharge capacity after 200 cycles is 75 percent. As shown in table 1.
The initial specific discharge capacity and the percentage of the specific discharge capacity remaining after 200 cycles of the battery assembled in examples 1-4 at a rate of 0.5C are shown in table 1.
TABLE 1
Figure BDA0001714155970000121
Example 5:
a functional interlayer material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and a binder Nafion, wherein the amino mesoporous silica nanosheets have mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 750cm2(ii)/g, pore diameter of 5nm, mass ratio of silica to binder of 5:1, and thickness of interlayer of 1 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 2.0g of hexadecyl trimethyl ammonium bromide, adjusting the pH value of the solution to 13 by using disodium hydrogen phosphate, uniformly dispersing, and continuously stirring at 30 ℃ to obtain a graphite oxide dispersion liquid. Measuring 5.0mL of tetraethyl orthosilicate, adding the tetraethyl orthosilicate into 15.0mL of ethanol, slowly and dropwise adding the tetraethyl orthosilicate into the graphite oxide dispersion liquid to form a reaction liquid A, and continuously stirring and reacting at 30 ℃ for 8 hours to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 50 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using 1.0g/L ammonium nitrate/ethanol solution at 85 ℃ for 6h, carrying out suction filtration, fully drying at 50 ℃, and calcining in air at 500 ℃ for 8h to obtain the mesoporous silica nanosheet.
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 1.0g of phenylaminomethyl triethoxysilane into 50mL of isopropanol, ultrasonically dispersing 5.0g of mesoporous silica nanosheets into 50mL of isopropanol, dropwise adding phenylaminomethyl triethoxysilane isopropanol solution into isopropanol dispersion liquid of the mesoporous silica nanosheets while stirring, raising the temperature to 100 ℃, reacting for 12 hours, performing suction filtration, washing, and performing vacuum drying at 50 ℃ for 4 hours.
(2) Preparing the functional interlayer material:
0.05g of aminated mesoporous silica nanosheet and 0.2g of Nafion solution (namely D-521 dispersion liquid, 5% w/w of water/1-propanol solution) are weighed and ultrasonically dispersed uniformly, the uniformly dispersed slurry is blade-coated on a lithium-sulfur battery positive plate, the thickness of a sandwich material obtained by blade-coating is 1 mu m, and the functional sandwich material is prepared by vacuum drying for 4 hours at 50 ℃.
Example 6:
a functional interlayer material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and binder carboxymethyl cellulose powder, wherein the amino mesoporous silica nanosheets have mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 900cm2G, pore diameter of 4nm, mass ratio of silica to binder of 3:1, and thickness of interlayer of 10 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 1.5g of hexadecyl trimethyl ammonium chloride, adjusting the pH value of the solution to 13 by using lithium hydroxide, uniformly dispersing, and continuously stirring at 40 ℃ to obtain a graphite oxide dispersion liquid. Measuring 4.0mL of silica sol, adding the silica sol into 10.0mL of ethanol, slowly and dropwise adding the silica sol into the graphite oxide dispersion liquid to form a reaction liquid A, and continuously stirring and reacting at 40 ℃ for 4 hours to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 60 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using a 5.0g/L ammonium nitrate/ethanol solution at 90 ℃ for 8 hours, carrying out suction filtration, fully drying at 60 ℃, and calcining at 600 ℃ in the air for 5 hours to obtain the mesoporous silica nanosheet.
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 1.0g of phenylaminomethyltrimethoxysilane into 50mL of benzene, ultrasonically dispersing 3.0g of mesoporous silica nanosheets into 50mL of benzene, dropwise adding phenylaminomethyltrimethoxysilane benzene solution into benzene dispersion liquid of the mesoporous silica nanosheets while stirring, raising the temperature to 90 ℃, reacting for 24 hours, carrying out suction filtration and washing, and carrying out vacuum drying for 4 hours at 60 ℃.
(2) Preparing the functional interlayer material: weighing 0.03g of aminated mesoporous silica nanosheet and 0.1g of carboxymethyl cellulose powder, stirring in water by magnetic force to prepare slurry, blade-coating the slurry on a lithium-sulfur battery positive plate to obtain a sandwich material with the thickness of 20 microns, and vacuum-drying at 60 ℃ for 4 hours to obtain the functional sandwich material.
Example 7:
a functional interlayer material of a lithium-sulfur battery comprises amino mesoporous silica nanosheets and binder carboxymethyl cellulose powder, wherein the amino mesoporous silica nanosheets have mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 900cm2G, pore diameter of 4nm, mass ratio of silica to binder of 3:1, and thickness of interlayer of 10 μm.
The preparation method of the functional interlayer of the lithium-sulfur battery comprises the following steps:
(1) preparing mesoporous silica nanosheets and modifying:
(1-1) preparing a mesoporous silica nanosheet: weighing 1L of 0.1g/L graphite oxide, adding 1.5g of dodecyl trimethyl ammonium chloride, adjusting the pH value of the solution to 10 by using lithium hydroxide, uniformly dispersing, and continuously stirring at 40 ℃ to obtain a graphite oxide dispersion liquid. Measuring 4.0mL of silica sol, adding the silica sol into 10.0mL of ethanol, slowly and dropwise adding the silica sol into the graphite oxide dispersion liquid to form a reaction liquid A, and continuously stirring and reacting at 40 ℃ for 4 hours to obtain a product B. And (4) centrifuging the product B to obtain a precipitate, washing, and fully drying at 60 ℃ to obtain solid powder C. And (3) carrying out reflux reaction on the solid powder C by using a 5.0g/L ammonium nitrate/ethanol solution at 90 ℃ for 8 hours, carrying out suction filtration, fully drying at 60 ℃, and calcining at 600 ℃ in the air for 5 hours to obtain the mesoporous silica nanosheet.
(1-2) modifying mesoporous silica nanosheets with a silane coupling agent: adding 1.0g of polyamino alkyl trialkoxysilane into 50mL of toluene, ultrasonically dispersing 3.0g of mesoporous silica nanosheets into 50mL of toluene, dropwise adding a polyamino alkyl trialkoxysilane toluene solution into a toluene dispersion liquid of the mesoporous silica nanosheets while stirring, raising the temperature to 90 ℃, reacting for 24 hours, then carrying out suction filtration and washing, and carrying out vacuum drying for 4 hours at 60 ℃.
(2) Preparing a functional interlayer material: weighing 0.03g of aminated mesoporous silica nanosheet and 0.1g of carboxymethyl cellulose powder, stirring in water by magnetic force to prepare slurry, blade-coating the slurry on a lithium-sulfur battery positive plate to obtain a sandwich material with the thickness of 20 microns, and vacuum-drying at 60 ℃ for 4 hours to obtain the functional sandwich material.
Besides the mesoporous silica nanosheet with the mesoporous aperture of 3-9 nm, the mesoporous aperture of the mesoporous silica nanosheet can be other values in the conventional size of the mesoporous of 2-50 nm. The various starting materials and reagents used in the above examples are commercially available. The liquid silicon source and the liquid alcohol compound are both liquid at room temperature.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. The functional interlayer material of the lithium-sulfur battery is characterized by mainly comprising amino mesoporous silica nanosheets and a binder, wherein the amino mesoporous silica nanosheets and the binder are mixed with each other, the amino mesoporous silica nanosheets are amino-modified silica nanosheets with mesoporous structures, and the specific surface area of the amino mesoporous silica nanosheets is 750-1200 cm2The mass ratio of the amino mesoporous silica nanosheet to the binder is 5/1-1/2;
the adhesive is Nafion and polyvinylidene fluoride powderAnd carboxymethyl cellulose powder, wherein the Nafion is
Figure FDA0002694891700000011
The effective component in the D-521 dispersion liquid;
and the functional interlayer material of the lithium-sulfur battery is prepared by a preparation method comprising the following steps of:
(1) preparing amino mesoporous silica nanosheets: dispersing mesoporous silica nanosheets with mesoporous structures and an aminosilane coupling agent in a solvent according to a mass ratio of 5: 1-1: 5, refluxing and stirring at 80-100 ℃ for 12-24 hours, and then performing suction filtration, washing and drying to obtain amino mesoporous silica nanosheets;
the specific surface area of the mesoporous silica nanosheet is 750-1200 cm2/g；
(2) Preparing the amino mesoporous silica nanosheets obtained in the step (1) and an adhesive into slurry by using water or an organic solvent, and uniformly mixing to obtain uniformly dispersed slurry; then, the slurry is coated on a load material in a blade mode, and the functional interlayer material can be obtained after the slurry is fully dried;
in addition, in the step (1), the mesoporous silica nanosheet having a mesoporous structure is synthesized by the following method:
adding a cationic surfactant and a pH regulator into a graphite oxide aqueous solution with the concentration of graphite oxide of 0.1-5.0 g/L, uniformly dispersing, and continuously stirring at 30-80 ℃ to obtain a uniformly dispersed graphite oxide dispersion liquid, wherein the pH value of the graphite oxide dispersion liquid is 10-13, and the mass ratio of the cationic surfactant to the graphite oxide in the graphite oxide aqueous solution is 20: 1-10: 1; measuring a liquid silicon source and a liquid alcohol compound, mixing to obtain a silicon/alcohol mixed solution, slowly dropwise adding the silicon/alcohol mixed solution into the graphite oxide dispersion solution to form a reaction solution A, continuously stirring and reacting the reaction solution A at 30-80 ℃ for 8-24 hours to obtain a product B, wherein the volume ratio of the silicon source to the alcohol compound is 1: 3-1: 8, and the mass ratio of the graphite oxide to the silicon source in the graphite oxide aqueous solution is 20: 1-60: 1; then, centrifugally separating the product B to obtain precipitate, washing and fully drying at 50-70 ℃ to obtain solid powder C; then, carrying out reflux reaction on the solid powder C for 6-10 h at 85-95 ℃ by using an ammonium nitrate/ethanol solution with the ammonium nitrate concentration of 1.0-10.0 g/L, then carrying out suction filtration, fully drying at 50-70 ℃, and calcining for 4-8 h at 500-700 ℃ in the air to obtain the mesoporous silica nanosheet.
2. The functional interlayer material for lithium-sulfur batteries according to claim 1, wherein the mesoporous structure in the amino mesoporous silica nanosheets has a pore size of 3-9 nm.
3. The functional interlayer material for a lithium-sulfur battery according to claim 1, wherein the thickness of the functional interlayer material for a lithium-sulfur battery is 1 to 30 μm.
4. A preparation method of a functional interlayer material of a lithium-sulfur battery is characterized by comprising the following steps:
(1) preparing amino mesoporous silica nanosheets: dispersing mesoporous silica nanosheets with mesoporous structures and an aminosilane coupling agent in a solvent according to a mass ratio of 5: 1-1: 5, refluxing and stirring at 80-100 ℃ for 12-24 hours, and then performing suction filtration, washing and drying to obtain amino mesoporous silica nanosheets;
the specific surface area of the mesoporous silica nanosheet is 750-1200 cm2/g；
(2) Preparing the amino mesoporous silica nanosheets obtained in the step (1) and an adhesive into slurry by using water or an organic solvent, and uniformly mixing to obtain uniformly dispersed slurry; then, the slurry is coated on a load material in a blade mode, and the functional interlayer material can be obtained after the slurry is fully dried;
in the step (1), the mesoporous silica nanosheet having a mesoporous structure is synthesized by the following method:
adding a cationic surfactant and a pH regulator into a graphite oxide aqueous solution with the concentration of graphite oxide of 0.1-5.0 g/L, uniformly dispersing, and continuously stirring at 30-80 ℃ to obtain a uniformly dispersed graphite oxide dispersion liquid, wherein the pH value of the graphite oxide dispersion liquid is 10-13, and the mass ratio of the cationic surfactant to the graphite oxide in the graphite oxide aqueous solution is 20: 1-10: 1; measuring a liquid silicon source and a liquid alcohol compound, mixing to obtain a silicon/alcohol mixed solution, slowly dropwise adding the silicon/alcohol mixed solution into the graphite oxide dispersion solution to form a reaction solution A, continuously stirring and reacting the reaction solution A at 30-80 ℃ for 8-24 hours to obtain a product B, wherein the volume ratio of the silicon source to the alcohol compound is 1: 3-1: 8, and the mass ratio of the graphite oxide to the silicon source in the graphite oxide aqueous solution is 20: 1-60: 1; then, centrifugally separating the product B to obtain precipitate, washing and fully drying at 50-70 ℃ to obtain solid powder C; then, carrying out reflux reaction on the solid powder C for 6-10 h at 85-95 ℃ by using an ammonium nitrate/ethanol solution with the ammonium nitrate concentration of 1.0-10.0 g/L, then carrying out suction filtration, fully drying at 50-70 ℃, and calcining for 4-8 h at 500-700 ℃ in the air to obtain the mesoporous silica nanosheet.
5. The method of claim 4, wherein the cationic surfactant is quaternary ammonium salt, and is one or more of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride;
the pH regulator is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate and disodium hydrogen phosphate;
the dispersion is ultrasonic dispersion;
the silicon source is one of tetraethyl orthosilicate, hexamethyldisiloxane and silica sol.
6. The method according to claim 4, wherein in the step (1), the aminosilane coupling agent is one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldiethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and polyaminoalkyltrialkoxysilane; the solvent is one of water, acetone, ethanol, methanol, isopropanol, benzene and toluene; the drying is carried out for 4-8 h under the temperature of 50-80 ℃ in vacuum.
7. The method according to claim 4, wherein in the step (2), the binder is one of Nafion, polyvinylidene fluoride powder, and carboxymethylcellulose powder; when the binder is Nafion, it is specifically adopted
Figure FDA0002694891700000041
The D-521 dispersion liquid is used as a Nafion solution, and the step (2) of preparing the slurry by using water or an organic solvent and the amino mesoporous silica nanosheet and the binder is to directly and uniformly mix the Nafion solution and the amino mesoporous silica nanosheet to obtain the slurry, or to prepare the slurry by using a water or alcohol reagent and the amino mesoporous silica nanosheet and the Nafion solution;
in addition, in the step (2), the mass ratio of the amino mesoporous silica nanosheets to the binder is 5/1-1/2; the mixing mode is one of ultrasonic dispersion and magnetic stirring; the load material is one of a lithium-sulfur battery positive plate and a diaphragm for a lithium-sulfur battery; the thickness of the interlayer material is 1-30 mu m; the full drying is vacuum drying for 4-8 h at 50-80 ℃.
8. The method according to claim 7, wherein in the step (2), the step (2) is carried out
Figure FDA0002694891700000042
The D-521 dispersion liquid is a water/1-propanol solution with the mass percentage concentration of the active ingredient of 5%.
9. Use of a functional interlayer material of a lithium sulfur battery according to any one of claims 1 to 3 as a functional interlayer material disposed between a positive electrode and a separator of a lithium sulfur battery in a lithium sulfur battery.
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