CN109888183B - Preparation method and application of organic-inorganic hybrid film - Google Patents
Preparation method and application of organic-inorganic hybrid film Download PDFInfo
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- CN109888183B CN109888183B CN201910261006.7A CN201910261006A CN109888183B CN 109888183 B CN109888183 B CN 109888183B CN 201910261006 A CN201910261006 A CN 201910261006A CN 109888183 B CN109888183 B CN 109888183B
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Abstract
The invention discloses a preparation method and application of an organic-inorganic hybrid film. The preparation method comprises the following steps: step 1: uniformly mixing a graphene oxide solution and an oxidant solution in a solvent to obtain a mixed solution; step 2: filtering the mixed solution obtained in the step 1 to form a film or drying the mixed solution in a polytetrafluoroethylene bottle to form a film; and step 3: and (3) placing the membrane obtained in the step (2) in pyrrole steam to polymerize pyrrole monomers, and cleaning to obtain an inorganic graphene oxide membrane which is an organic-inorganic hybrid membrane and is covalently modified by organic sulfonated polypyrrole. The method has simple process, low cost and environmental protection, and can be used for large-scale production. The obtained sulfonated polypyrrole and graphene oxide hybrid film has excellent lithium ion conductivity, can be used as an artificial SEI film, a diaphragm modification layer and the like, can remarkably inhibit the growth of lithium metal dendrites and lithium polysulfide shuttling, and improves the operation stability and safety of a lithium metal battery.
Description
Technical Field
The invention relates to a preparation method and application of an organic-inorganic hybrid film for inhibiting growth of lithium dendrite and polysulfide shuttling effect in a lithium-sulfur battery.
Background
With the increasing demand of people for high-capacity energy storage batteries, the high-specific energy lithium metal battery becomes one of the leading research hotspots in the current energy storage field. The specific capacity of lithium metal is about 3860mAh/g, which is more than 10 times of that of a graphite cathode, and the cathode of the battery can be made of lithium-free materials due to the fact that lithium is contained, and for example, a sulfur/carbon composite material and the like can be used as the cathode, so that the selection range of the battery materials is widened. However, when metallic lithium is used as a negative electrode, lithiumIons are unevenly deposited on the surface of the negative electrode, lithium in a dendritic crystal form is induced to grow on the surface of the negative electrode, and the safety of the battery is greatly influenced; on the other hand, in a lithium-sulfur battery using a sulfur/carbon composite material as a positive electrode, lithium polysulfide, an intermediate product of the reaction, is dissolved in an electrolyte, resulting in loss of active material during transfer, and finally, in degradation of cycle performance. To solve these problems, many international famous experimental teams have conducted related research works. Protection for metallic lithium negative electrode: covering a layer of Al on the surface of a lithium metal cathode by utilizing an atomic layer deposition technology 2 O 3 Layer as an artificial SEI film (ACS Nano,2015,9, 5884); a film forming additive is added into the electrolyte, so that a protective SEI film is formed on the surface of a lithium cathode in the first charging process of the metal lithium battery (nat. Energy,2017,2, 17012); researchers have constructed a three-dimensional network structure on the surface of a lithium metal cathode to adjust the concentration distribution of lithium ions on the surface of the lithium metal cathode, so as to realize uniform deposition of lithium ions (adv. Mater.,2016,28, 2888). These operations can suppress the growth of metallic lithium dendrites to some extent, but use relatively expensive equipment and consume the electrolyte to some extent. For inhibiting the dissolution of lithium polysulphides: researchers started with the compounding of sulfur and other substances, inhibiting the occurrence of lithium polysulfide dissolution (nat. Commun.,2013,5, 5002), and continuously optimized and improved the components of the electrolyte, and designed a novel electrolyte system to improve the electrochemical cycle performance of the sulfur positive electrode (electrochim. Acta,2012,70, 344). The invention synthesizes an organic-inorganic hybrid film by a chemical method, and shows good effect on the aspect of inhibiting the shuttle effect of lithium dendrite and lithium polysulfide. The method for preparing the organic-inorganic hybrid thin film and applying the organic-inorganic hybrid thin film to the metal lithium battery is not reported at present.
Disclosure of Invention
The invention aims to solve the technical problem of developing a film capable of improving the safety and the cycle life of a metal lithium battery.
In order to solve the technical problems, the invention provides a preparation method of an organic-inorganic hybrid film, which is characterized in that graphene oxide is used as a raw material, and an organic sulfonated polypyrrole covalent modified inorganic graphene oxide film, namely the organic-inorganic hybrid film, is prepared by coprecipitation and gas-phase polymerization.
Preferably, the preparation method of the organic-inorganic hybrid thin film comprises the following steps:
step 1: uniformly mixing a graphene oxide solution and an oxidant solution in a solvent to obtain a mixed solution;
and 2, step: filtering the mixed solution obtained in the step 1 to form a film or drying the mixed solution in a polytetrafluoroethylene bottle to form a film;
and step 3: and (3) placing the membrane obtained in the step (2) in pyrrole steam to polymerize pyrrole monomers, and cleaning to obtain an inorganic graphene oxide membrane which is an organic-inorganic hybrid membrane and is covalently modified by organic sulfonated polypyrrole.
Preferably, the weight ratio of the graphene oxide solution to the oxidant solution in step 1 is 1.
More preferably, the weight ratio of the graphene oxide solution to the oxidant solution in step 1 is 1.
Preferably, the oxidizing agent in the step 1 is any one of P-toluene sulfonate, benzene sulfonate, 4-ethyl benzene sulfonate, 4-N-octyl benzene sulfonate, dodecyl benzene sulfonate, 1, 3-trimethyl benzene sulfonate, m-xylene-4-sulfonate and tetraethylammonium-P-methyl benzene sulfonate.
Preferably, the solvent in step 1 is any one of water, methanol, ethanol, ethylene glycol, acetonitrile, diethyl ether, n-butanol and dimethyl carbonate.
Preferably, in the step 1, the concentration of the graphene oxide solution is 0.1-10 mg/mL, and the mass fraction of the oxide in the solution is 10-60 wt.%.
Preferably, the mixing in the step 1 is ultrasonic dispersion mixing, the dispersion power is 50-1000W, and the dispersion time is 0.5-2 h.
Preferably, the graphene oxide in the step 1 is prepared by the following preparation method: adding 1 part by weight of crystalline flake graphite, 0.8-1 part by weight of sodium nitrate and 4-6 parts by weight of potassium permanganate into 100-150 parts by weight of concentrated sulfuric acid, wherein the concentration of sulfuric acid in the concentrated sulfuric acid is more than 70wt%, stirring for 75-150 h, adding 300-600 parts by weight of deionized water in the stirring process, simultaneously adding 30-80 parts by weight of 30wt% hydrogen peroxide, filtering and washing to obtain the catalyst.
Preferably, the thickness of the film in the step 2 is 0.1 to 100 μm.
Preferably, the polymerization time of the pyrrole in the step 3 is 10 min-24 h.
Preferably, the solvent used for washing in step 3 is any one of methanol, ethanol, ethylene glycol, acetonitrile, diethyl ether, n-butanol and dimethyl carbonate.
The invention also provides application of the organic-inorganic hybrid film prepared by the method in preparation of a lithium battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the organic polymer is doped in the middle of the graphene oxide layer, and the re-stacking caused by mutual attraction of graphene oxide under the action of pi bonds is firstly inhibited, so that the capability of the graphene oxide for longitudinally conducting lithium ions is improved, and the high-rate charge and discharge of the lithium metal battery can be realized.
(2) According to the organic-inorganic hybrid film, a large number of sulfonate groups with negative charges are doped in polypyrrole, so that polysulfide can be prevented from shuttling to the surface of a lithium cathode under the action of electrostatic repulsion, and the stability of the lithium-sulfur battery is improved.
(3) According to the invention, the ratio of organic and inorganic components can be adjusted by adjusting the ratio of graphene oxide and polypyrrole, so that the functionality of the graphene oxide can be adjusted. The organic-inorganic hybrid film with any shape and area can be obtained by adjusting the shape and the size of the substrate. The obtained organic-inorganic hybrid film has good chemical stability and does not react with negative metal lithium; the material has good toughness and high plasticity, and can be used for electrodes in various shapes, even flexible lithium metal batteries; low cost, no need of large-scale equipment, simple preparation process and easy large-scale production.
Drawings
FIG. 1 is a digital photograph of the organic-inorganic hybrid thin film synthesized in example 1;
FIG. 2 is a SEM sectional view of the organic-inorganic hybrid thin film synthesized in example 1;
FIG. 3 is a graph comparing the cycle performance of the organic-inorganic hybrid thin film synthesized in example 1 for a Li-Li symmetric battery;
FIG. 4 is a photograph of the organic-inorganic hybrid thin film synthesized in example 2, which prevents lithium polysulfide from diffusing over time;
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The preparation method of the graphene oxide in each embodiment of the invention comprises the following steps: adding 1 part by weight of crystalline flake graphite, 0.5 part by weight of sodium nitrate and 3 parts by weight of potassium permanganate into 30 parts by weight of concentrated sulfuric acid, wherein the concentration of sulfuric acid in the concentrated sulfuric acid is more than 70wt%, stirring for 4 hours, adding 80 parts by weight of deionized water during stirring, simultaneously adding 4 parts by weight of 30wt% hydrogen peroxide, and centrifugally cleaning for 5-6 times until the pH value is 7.
Example 1
A preparation method of an organic-inorganic hybrid film comprises the following specific preparation steps:
step 1: carrying out ultrasonic mixing on 10mL of ethanol solution of graphene oxide of 2mg/mL and 5mL of ethanol solution of 4-ferric ethyl benzene sulfonate with the mass fraction of 30wt.% for 1h to obtain a mixed solution, wherein the dispersion power is 600 w;
and 2, step: heating the mixed solution obtained in the step (1) in a polytetrafluoroethylene bottle to 80 ℃, drying for 1h and forming a film;
and 3, step 3: and (3) placing the membrane obtained in the step (2) in pyrrole steam for 30min to polymerize pyrrole monomers, then placing the membrane in an ethanol solution for washing for 2 times, and washing in a dimethyl carbonate solution for 1 time to obtain an organic sulfonated polypyrrole covalently modified inorganic graphene oxide membrane with the thickness of about 10 mu m, namely an organic-inorganic hybrid membrane.
From fig. 1, it can be seen that the synthesized organic-inorganic hybrid film presents a transparent brown-yellow color, i.e. the colors of graphene oxide and polypyrrole.
From the SEM image of fig. 2, it is apparent that the prepared film is multilayered, and polypyrrole is intercalated between graphene oxide layers, which is advantageous for lithium ion conduction.
The prepared organic-inorganic hybrid film is soaked in electrolyte (1 mol. L) -1 Lithium hexafluorophosphate, ethylene carbonate and dimethyl carbonate (volume ratio 1. The lithium metal sheet attached to the organic-inorganic hybrid film is used as a negative electrode, the other lithium metal sheet is used as a positive electrode, an ENTEK PE porous membrane is used as a diaphragm, and 1 mol.L -1 A mixed solution of ethylene carbonate and dimethyl carbonate (volume ratio is 1. As shown in fig. 3, no short circuit occurred during the cycle exceeding 400 h.
Example 2
A preparation method of an organic-inorganic hybrid film comprises the following specific preparation steps:
step 1: uniformly mixing 5mL of 5mg/mL of graphene oxide ethanol solution and 5mL of 50% ethanol solution of 4-ferric ethyl benzene sulfonate by mass fraction for 1 hour in an ultrasonic mode, wherein the dispersion power is 600w, and thus obtaining a mixed solution;
step 2: taking a glass fiber diaphragm as a filter membrane, and carrying out vacuum filtration on the mixed solution in the step 1 for 10 hours by using a water pump to form a film;
and 3, step 3: and (3) placing the membrane obtained in the step (2) in pyrrole steam for 1.5h to polymerize pyrrole monomers, and then placing the membrane in an acetonitrile solution to wash for 3 times to obtain an organic sulfonated polypyrrole covalently modified inorganic graphene oxide membrane with the thickness of about 20 mu m, namely an organic-inorganic hybrid membrane.
As shown in FIG. 4, the organic-inorganic hybrid film is placed in the middle of a communicated home-made vial, and the solution is 1M LiTFSI + DOL&DME (1 2 S 6 ) It is brown. As can be seen from FIG. 4, after 14h, the brown solution did not diffuse to the other side, demonstrating that the film has a good effect of inhibiting the diffusion of lithium polysulfide.
According to the above experimental parameters, the method of example 1 or example 2 is referenced to obtain the corresponding organic-inorganic hybrid thin film for suppressing lithium dendrite and preventing polysulfide diffusion.
Claims (5)
1. A preparation method of an organic-inorganic hybrid film is characterized by comprising the following steps:
step 1: uniformly mixing a graphene oxide solution and an oxidant solution in a solvent to obtain a mixed solution;
the weight ratio of the solute of the graphene oxide solution to the oxidant solution is 1; the oxidant is any one of P-toluene sulfonate, benzene sulfonate, 4-ethyl benzene sulfonate, 4-N-octyl benzene sulfonate, dodecyl benzene sulfonate, 1, 3-trimethyl benzene sulfonate, m-xylene-4-sulfonate and tetraethylammonium-P-methyl benzene sulfonate;
the solvent is any one of water, methanol, ethanol, glycol, acetonitrile, diethyl ether, n-butanol and dimethyl carbonate;
the concentration of the graphene oxide solution is 0.1-10 mg/mL, and the mass fraction of the oxidant in the oxidant solution is 10-60 wt.%;
the mixing is ultrasonic dispersion mixing, the dispersion power is 50-1000W, and the dispersion time is 0.5-2 h;
step 2: filtering the mixed solution obtained in the step 1 to form a film or drying the mixed solution in a polytetrafluoroethylene bottle to form a film;
and step 3: placing the membrane obtained in the step 2 in pyrrole steam to polymerize pyrrole monomers, and cleaning to obtain an inorganic graphene oxide membrane covalently modified by organic sulfonated polypyrrole, namely an organic-inorganic hybrid membrane for inhibiting lithium dendrites or preventing diffusion of polysulfide; the organic-inorganic hybrid film is in a multilayer shape, and polypyrrole is embedded between graphene oxide layers;
the graphene oxide in the step 1 is prepared by the following preparation method: adding 1 part by weight of crystalline flake graphite, 0.8-1 part by weight of sodium nitrate and 4-6 parts by weight of potassium permanganate into 100-150 parts by weight of concentrated sulfuric acid, wherein the concentration of sulfuric acid in the concentrated sulfuric acid is more than 70wt%, stirring for 75-150 h, adding 300-600 parts by weight of deionized water in the stirring process, simultaneously adding 30-80 parts by weight of 30wt% hydrogen peroxide, filtering and washing to obtain the catalyst.
2. The method for preparing an organic-inorganic hybrid film according to claim 1, wherein the film thickness in step 2 is 0.1 to 100 μm.
3. The method for preparing an organic-inorganic hybrid film according to claim 1, wherein the polymerization time of pyrrole in step 3 is 10min to 24h.
4. The method for preparing an organic-inorganic hybrid film according to claim 1, wherein the solvent used for washing in step 3 is any one of methanol, ethanol, ethylene glycol, acetonitrile, diethyl ether, n-butanol and dimethyl carbonate.
5. The use of the organic-inorganic hybrid film prepared by the method of claim 1 for preparing a negative electrode material for a lithium battery.
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| CN102765714A (en) * | 2012-06-18 | 2012-11-07 | 河北工业大学 | Preparation method of graphite oxide with high degree of oxidation and high dispersibility |
| CN102800432A (en) * | 2012-08-23 | 2012-11-28 | 上海第二工业大学 | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material |
| CN106025183A (en) * | 2016-05-19 | 2016-10-12 | 上海理工大学 | Preparation method of carbon-based flexible film electrode for lithium ion batteries |
| CN106450245A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Flexible cathode material of chargeable/dischargeable lithium-sulfur battery and preparation method thereof |
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| CN103390511A (en) * | 2013-07-30 | 2013-11-13 | 河海大学 | Preparation method for graphene oxide/polypyrrole composite material of lamellar microstructure |
| CN108539143A (en) * | 2018-03-08 | 2018-09-14 | 上海理工大学 | A method of quickly preparing high-capacity lithium ion cell silicon based anode material |
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| CN102765714A (en) * | 2012-06-18 | 2012-11-07 | 河北工业大学 | Preparation method of graphite oxide with high degree of oxidation and high dispersibility |
| CN102800432A (en) * | 2012-08-23 | 2012-11-28 | 上海第二工业大学 | Method for preparing oxidized graphene/conductive polypyrrole nano wire composite material |
| CN106025183A (en) * | 2016-05-19 | 2016-10-12 | 上海理工大学 | Preparation method of carbon-based flexible film electrode for lithium ion batteries |
| CN106450245A (en) * | 2016-12-23 | 2017-02-22 | 合肥工业大学 | Flexible cathode material of chargeable/dischargeable lithium-sulfur battery and preparation method thereof |
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