CN111599970B - Magnesium oxide/iron composite material modified diaphragm and preparation method thereof - Google Patents
Magnesium oxide/iron composite material modified diaphragm and preparation method thereof Download PDFInfo
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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
- 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
- H01M50/431—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- 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
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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
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a magnesium oxide/iron composite material modified diaphragm and a preparation method thereof. The magnesium oxide particles are prepared by a solvothermal synthesis method, and then iron particles are loaded on the surfaces of the particles by a hydrogen thermal reduction method. And finally, loading the membrane on the surface of the membrane by using an ethanol dispersion, blending and filtration method to obtain the modified membrane. The magnesium oxide/iron composite material modified diaphragm integrates the physical barrier effect of the carbon nano tube, the adsorption effect of magnesium oxide and the catalytic effect of iron particles, and synergistically improves the performance of the lithium-sulfur battery.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry, more particularly relates to the field of electrochemistry, and particularly relates to a modified diaphragm of a magnesium oxide/iron composite material and a preparation method thereof.
Background
The lithium-sulfur battery is an energy storage system with higher energy density and has very high development prospect. The shuttling effect of polysulfides generated during charge and discharge results in a significant reduction in the cycle performance of the battery. The prior art is therefore mostly concerned with how to suppress the shuttle effect deployment.
Currently, the main solutions are physical adsorption, chemical adsorption, and electrochemical catalysis. The physical adsorption mostly adopts carbon materials as a matrix for blocking the shuttle of polysulfide. Chemisorption often uses electrostatic interactions between the adsorption matrix and polysulfides to suppress the shuttling effect. Whereas the effect of electrochemical catalysis is generally based on increasing the rate of conversion of the intermediate products reducing the time of presence of polysulphides achieving suppression of the shuttle effect.
The invention CN201710042856.9 discloses a preparation method of a heat-resistant lithium battery diaphragm, which comprises the following steps: 1) preparing magnesium hydroxide ceramic slurry: mixing 30-85% of deionized water and 1-10% of binder by mass ratio, stirring in a stirrer to prepare a uniform solution, adding 10-60% of magnesium hydroxide particles by mass ratio, mixing and stirring for 10-40min, and grinding for 1-3h to obtain magnesium hydroxide ceramic slurry; 2) coating: coating the magnesium hydroxide ceramic slurry prepared in the step 1) on one side or two sides of a base film in a certain coating mode to obtain a magnesium hydroxide ceramic coating, and then baking for 2-4min at the temperature of 40-80 ℃ to obtain the heat-resistant ceramic diaphragm. The lithium battery can effectively inhibit the temperature of the lithium battery from rapidly rising when the lithium battery is in short circuit, and improves the thermal stability, rate discharge and cycle performance of the lithium battery.
The invention of China CN201710307027.9 discloses a composite diaphragm for a lithium ion battery, which comprises a microporous base film and a ceramic layer coated on one surface or two surfaces of the microporous base film, wherein the main component of ceramic powder in the ceramic layer is lithium iron phosphate. The composite diaphragm can effectively improve the electrolyte wettability, the ionic conductivity, the thermal stability and the processability of the diaphragm.
The magnesium oxide is used as an adsorption matrix and is widely applied and explored in the field of sewage treatment. In the prior art, a multilevel structure of mesoporous silica shell coated nano magnesium oxide particles is prepared, wherein magnesium oxide shows a good water treatment effect as an adsorption matrix. In the present invention, the shuttle effect is suppressed in the lithium-sulfur battery by using the adsorption of magnesium oxide.
The nano-scale iron particles have better electrocatalytic effect and are used as an electrocatalytic matrix for accelerating the polysulfide conversion rate in the invention.
At present, the adsorption or catalysis effect shown by a single matrix is mostly used for modifying the lithium-sulfur battery, but a method for combining the matrixes respectively having two functions into a composite material is not reported.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a magnesium oxide/iron composite material modified diaphragm which is simple and low in cost and has both an adsorption effect and an electrocatalysis effect, and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme: a magnesium oxide/iron composite material modified diaphragm is characterized in that a magnesium oxide/iron composite material and a carbon nano tube are loaded on the surface of the diaphragm, and the magnesium oxide/iron composite material is formed by loading iron particles on the surface of magnesium oxide particles. In the invention, magnesium oxide is used as an adsorption matrix, iron particles loaded on the surfaces of the magnesium oxide particles are used as a catalytic matrix, and the blended carbon nano tube is used as a conductive matrix to synergistically modify the lithium-sulfur battery diaphragm.
In a preferred embodiment of the invention, the magnesium oxide and iron are used in a ratio of 10:1, and the mass ratio of the carbon nano tube to the magnesium oxide/iron composite material is 7: 3.
The invention also provides a preparation method of the magnesium oxide/iron composite material modified diaphragm, which comprises the following steps:
(1) preparing magnesium oxide particles by a solvothermal method;
(2) loading iron particles on the surfaces of the magnesium oxide particles by a hydrogen thermal reduction method;
(3) the carbon nano tube is loaded on the surface of the membrane by an ethanol dispersion, blending and filtration method.
In a preferred embodiment of the present invention, in step (1), magnesium acetate tetrahydrate (Mg (COOCH)3)2·4H2O) is dissolved in a solvent, a surfactant is added, white powder, namely a precursor of the magnesium oxide particles, is obtained after reaction, and the magnesium oxide particles are obtained after the magnesium oxide precursor is calcined.
More preferably, in the step (1), the solvent is ethylene glycol; the surfactant is polyvinylpyrrolidone PVP; the mass ratio of the magnesium acetate tetrahydrate to the surfactant is 4: 10; the reaction is carried out for 2 to 3 hours at the temperature of between 170 and 200 ℃; the calcination is carried out for 3 to 5 hours at the temperature of 450 to 550 ℃.
In a preferred embodiment of the invention, in the step (2), the magnesium oxide particles are dispersed in an ethanol solution by an ultrasonic method, and the ethanol solution of ferric trichloride is added, the mixture is uniformly mixed and dried, after the ethanol is completely evaporated to dryness, the magnesium oxide particles adsorbing ferric salt are obtained, and the treated magnesium oxide particles are placed in a hydrogen argon mixed atmosphere (the mass fraction of hydrogen is 10 wt%), and heated for 1-2 h at 800-1000 ℃ to reduce the iron particles, so as to obtain the magnesium oxide/iron composite material.
More preferably, in the step (2), the magnesium oxide and ferric trichloride are mixed by the following ratio of 10:1 in a molar ratio; the ferric trichloride is ferric trichloride hexahydrate (FeCl)3·6H2O）。
In a preferred embodiment of the invention, in the step (3), the composite material and the carbon nanotubes are jointly dispersed in ethanol, and loaded on the surface of the separator by a vacuum filtration method, so as to obtain the modified lithium-sulfur battery separator.
More preferably, in the step (3), the mass ratio of the carbon nanotubes to the magnesium oxide/iron composite material is 7: 3.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the invention, the magnesium oxide has an adsorption effect on a polysulfide intermediate product of charge and discharge of the lithium-sulfur battery, so that the shuttle effect of the lithium-sulfur battery is inhibited; the iron particles have electrocatalysis to accelerate the conversion of polysulfide to short-chain compounds, and the existence time of polysulfide is shortened so as to inhibit shuttle effect; due to the low conductivity of magnesium oxide, sulfur and lithium sulfide, the composite carbon nanotube can improve the overall conductivity and inhibit the shuttle effect from the perspective of physical barrier; the ternary composite system integrates the physical barrier effect of the carbon nano tube, the adsorption effect of magnesium oxide and the catalytic effect of iron particles, and synergistically improves the performance of the lithium-sulfur battery.
(2) The magnesium oxide adopted by the invention has lighter weight, reduces the influence on energy density, and the obtained magnesium oxide/iron composite material has the functions of adsorption and catalysis, is simple to prepare, and is suitable for being used as a diaphragm modification method of a lithium-sulfur battery.
(3) The process flow of the invention has simple operation steps, green and environment-friendly reaction system and low cost.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is the preparation process of the composite nanosphere and the preparation process of the modified membrane of the present invention;
FIG. 2 is a graph of the morphology of the magnesium oxide and magnesium oxide/iron composite prepared in example 1;
wherein, a) a magnesium oxide precursor b) magnesium oxide particles c) a magnesium oxide/iron composite;
figure 3 is a cycle performance characterization of four different battery separators.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
0.3-0.6g of magnesium acetate tetrahydrate (Mg (CH)3COO)2·4H2O) and 1-2g of polyvinylpyrrolidone (PVP, K30), 40 mL of ethylene glycol ((CH)2OH)2) And then poured into a single-neck flask. And heating the mixed solution for 2 hours at 180 ℃ in an oil bath stirring manner, cooling to room temperature, then centrifugally cleaning the product for three times by using ethanol, and drying in an oven at 60 ℃ overnight to obtain the magnesium oxide precursor. And putting the obtained magnesium oxide precursor into a muffle furnace to calcine for 5 hours at 500 ℃ to obtain white magnesium oxide powder.
Weighing a certain amount of 0.3-0.5g magnesium oxide and 0.1-0.2g ferric chloride hexahydrate (FeCl)3·6H2O) is dissolved and dispersed in 40 mL of ethanol, and the mixture is ultrasonically treated for 15 min to be uniformly dispersed. The mixed solution is dried in a 60 ℃ oven to obtain magnesium oxide light yellow powder absorbing ferric trichloride. Mixing the above powders with water2Calcining for 1 h at 800 ℃ under the Ar atmosphere to obtain the magnesium oxide loaded with the iron particles.
0.2-0.4g of MgO @ Fe powder and 0.6-0.7g of CNTs are mixed in 40 mL of ethanol, the mixture is subjected to ultrasonic treatment for 30 min to be uniformly dispersed, and the MgO @ Fe and the CNTs are subjected to suction filtration on a PP diaphragm (Celgard 2400) by a vacuum filtration method. After vacuum drying at 60 ℃ for 12 h, the diaphragm was cut into disks with a diameter of 16 mm for use.
As shown in fig. 1, the preparation process adopts a hydrothermal-calcination two-step method to prepare magnesium oxide nanoparticles, and then adopts an adsorption-thermal reduction two-step method to prepare magnesium oxide/iron composite nanospheres capable of reducing iron particles on the surface. And finally, modifying the traditional PP diaphragm by an ultrasonic dispersion-vacuum filtration method.
Example 2:
weighing 5-6g magnesium acetate tetrahydrate (Mg (CH)3COO)2·4H2O) and 15-20g of polyvinylpyrrolidone (PVP, K30), 0.5L of ethylene glycol ((CH) was measured2OH)2) And then poured into a single-neck flask. And heating the mixed solution for 2 hours at 180 ℃ in an oil bath stirring manner, cooling to room temperature, then centrifugally cleaning the product for three times by using ethanol, and drying in an oven at 60 ℃ overnight to obtain the magnesium oxide precursor. And putting the obtained magnesium oxide precursor into a muffle furnace to calcine for 5 hours at 500 ℃ to obtain white magnesium oxide powder.
Weighing a certain amount of 4-5g of magnesium oxide and 1-2g of ferric chloride hexahydrate (FeCl)3·6H2O) is dissolved and dispersed in 300mL of ethanol for 15 min by ultrasonic treatment to ensure that the mixture is uniformly dispersed. The mixed solution is dried in a 60 ℃ oven to obtain magnesium oxide light yellow powder absorbing ferric trichloride. Mixing the above powders with water2Calcining for 1 h at 800 ℃ under the Ar atmosphere to obtain the magnesium oxide loaded with the iron particles.
Mixing 2-4g of MgO @ Fe powder and 6-7g of CNTs in 200 mL of ethanol, performing ultrasonic treatment for 30 min to uniformly disperse the mixture, and performing suction filtration on the MgO @ Fe and the CNTs on a PP diaphragm (Celgard 2400) by using a vacuum filtration method. After vacuum drying at 60 ℃ for 12 h, the diaphragm was cut into disks with a diameter of 16 mm for use.
As shown in figure 3, the CR2025 button cell is assembled by respectively adopting a PP diaphragm, a carbon nanotube diaphragm, a magnesium oxide/carbon nanotube diaphragm and a magnesium oxide/iron composite nanosphere/carbon nanotube modified diaphragm and tested for cycle performance, and the cycle performance of the cell is obtained after the carbon nanotubes are compoundedThe most significant improvement. With the addition of the magnesium oxide particles, the introduction of adsorption improves the cycle performance of the battery. After the iron particles are continuously compounded, the addition of the electrocatalysis action continuously improves the cycle performance, and the capacity of the first circle reaches 1292 mAh.g under the current density of 0.2C-1810.3 mAh g higher than that of the traditional PP diaphragm-1After 100 circles, the modified diaphragm still has 910.5 mAh g-1The specific capacity of the battery is reduced to 427.3 mAh g-1The battery achieves the best cycle performance after the magnesium oxide/iron nano particles are compounded.
Although the specific embodiments of the present invention have been described with reference to the examples, the scope of the present invention is not limited thereto, and those skilled in the art will appreciate that various modifications and variations can be made without inventive effort by those skilled in the art based on the technical solution of the present invention.
Claims (8)
1. The magnesium oxide/iron composite material modified diaphragm is characterized in that a magnesium oxide/iron composite material and a carbon nano tube are loaded on the surface of the diaphragm, the magnesium oxide/iron composite material is iron particles loaded on the surface of magnesium oxide particles, and the magnesium oxide and the iron adopt a formula of 10:1, and the mass ratio of the carbon nano tube to the magnesium oxide/iron composite material is 7: 3.
2. The method for producing a modified separator according to claim 1, comprising the steps of:
(1) preparing magnesium oxide particles by a solvothermal method;
(2) loading iron particles on the surfaces of the magnesium oxide particles by a hydrogen thermal reduction method;
(3) the carbon nano tube is loaded on the surface of the membrane by an ethanol dispersion, blending and filtration method.
3. The method according to claim 2, wherein in the step (1), magnesium acetate tetrahydrate (Mg (COOCH)3)2·4H2O) is dissolved in a solvent, a surfactant is added, white powder, namely a precursor of the magnesium oxide particles, is obtained after reaction, and the magnesium oxide particles are obtained after the magnesium oxide precursor is calcined.
4. The process according to claim 3, wherein in the step (1), the solvent is ethylene glycol; the surfactant is polyvinylpyrrolidone PVP; the mass ratio of the magnesium acetate tetrahydrate to the surfactant is 4: 10; the reaction is carried out for 2 to 3 hours at the temperature of between 170 and 200 ℃; the calcination is carried out for 3 to 5 hours at the temperature of 450 to 550 ℃.
5. The preparation method according to claim 2, wherein in the step (2), the magnesium oxide particles are dispersed in the ethanol solution by an ultrasonic method, the ethanol solution of ferric trichloride is added, the mixture is uniformly mixed and dried, the magnesium oxide particles adsorbing ferric salt are obtained after ethanol is completely evaporated to dryness, and the treated magnesium oxide particles are put in a hydrogen-argon mixed atmosphere and heated at 800-1000 ℃ for 1-2 h for reduction to obtain the magnesium oxide/iron composite material.
6. The method according to claim 5, wherein in the step (2), the molar ratio of magnesium oxide to ferric trichloride is 10: 1; the ferric trichloride is ferric trichloride hexahydrate (FeCl)3·6H2O）。
7. The preparation method according to claim 2, wherein in the step (3), the composite material and the carbon nanotubes are dispersed in ethanol together, and loaded on the surface of the separator by a vacuum filtration method to obtain the modified lithium-sulfur battery separator.
8. The method according to claim 7, wherein in the step (3), the mass ratio of the carbon nanotubes to the magnesium oxide/iron composite material is 7: 3.
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