CN111192997A - Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof - Google Patents
Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof Download PDFInfo
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- 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
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- 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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- 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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Abstract
The invention discloses a diaphragm for an active carbon loaded tin oxide lithium sulfur battery and a preparation method thereof. The method uses waste acorn shells as raw materials, and prepares the modified diaphragm material through the processes of high-temperature carbonization, etching by an etchant and in-situ growth of tin oxide nano particles. The acorn shell derived activated carbon has a hierarchical porous structure, can physically adsorb polysulfide, and has strong chemical action between polar tin oxide nanoparticles and polar polysulfide, thereby decomposingThe problem of serious shuttle effect of the lithium-sulfur battery is solved, and the coulomb efficiency and the cycling stability of the lithium-sulfur battery are further improved. The initial capacity of the lithium-sulfur battery assembled by the activated carbon-supported tin oxide diaphragm is 1019.2mAh g at the current density of 0.2C‑1After 270 cycles, the loss per cycle was 0.16% and the coulombic efficiency was still 100%. After 440 cycles at 1C current density, the capacity loss per cycle was 0.1%.
Description
Technical Field
The invention relates to a diaphragm for an active carbon loaded tin oxide lithium sulfur battery, and a preparation method and application thereof, and belongs to the technical field of composite materials and electrochemical batteries.
Background
With the rapid development of the fields of electric automobiles, mobile terminals, unmanned aerial vehicles and the like, the energy density of the commercialized lithium ion battery is difficult to meet various application requirements at the present stage. The sulfur anode material of the lithium-sulfur battery has the advantages of environmental friendliness and low cost, the theoretical energy density of the sulfur anode material is about 3-5 times that of the lithium-ion battery, and the sulfur anode material is a powerful competitor of the next generation of high-energy-density secondary battery. However, during the charging and discharging process of the lithium-sulfur battery, the intermediate polysulfide easily shuttles from the sulfur positive electrode to the negative electrode through the separator (shuttle effect), resulting in a large capacity loss and a low coulombic efficiency of the lithium-sulfur battery, which severely limits the practical application of the lithium-sulfur battery.
To overcome the above challenges, coating one side of the separator with a functional material is a simple, effective strategy. The activated carbon material having a large specific surface area can block shuttling of polysulfides by virtue of physical adsorption, but the shuttling effect in a lithium-sulfur battery can still occur due to the weak interaction of the nonpolar carbon material and the polar polysulfides. Polar metal oxides limit the shuttling behavior of polysulfides by strong chemisorption, but the particles themselves are extremely prone to agglomeration, making their active surfaces unable to maximize chemisorption. Meanwhile, the direct exposure of the metal oxide to the electrolyte may also cause some side reactions to occur. In addition, metal oxides with low conductivity can limit the conversion and reuse of polysulfides.
Disclosure of Invention
In order to solve the problems, the invention provides a diaphragm for an active carbon-loaded tin oxide lithium sulfur battery, and a preparation method and application thereof. The invention selects a novel biomass acorn shell as a precursor, and prepares the hierarchical porous activated carbon with high specific surface area through carbonization and etching processes. Tin oxide particles are loaded on the surface of the activated carbon through an in-situ low-temperature oxidation process, and the finally obtained activated carbon/tin oxide composite material further modifies the diaphragm and is further matched with a carbon nano tube/sulfur anode material. Finally, lithium sulfur batteries achieve good cycling stability at different current densities.
The invention claims an active carbon-loaded tin oxide nanoparticle material, which is prepared by loading tin oxide nanoparticles on active carbon serving as a carrier.
In the activated carbon-loaded tin oxide nanoparticle material, the particle size of the tin oxide nanoparticles is 3-200 nm;
the mass ratio of the activated carbon to the tin oxide nanoparticles is 1: 2-3;
the active carbon is prepared from acorn shell.
The invention provides a method for preparing an activated carbon-supported tin oxide nanoparticle material, which comprises the following steps:
1) carbonizing the acorn shell to obtain acorn shell derived carbon;
2) mixing the acorn shell derived carbon obtained in the step 1) with an activator solution for etching and drying to obtain activated carbon;
3) dispersing the activated carbon obtained in the step 2) in a solvent, adding tin salt by ultrasonic, sealing for reaction, drying after the reaction is finished, and calcining to obtain the activated carbon.
In the step 1) of the method, the temperature is 800-; specifically 900 ℃; the time is 1-5 h; in particular 2-3 h; the temperature rising rate from room temperature to carbonization temperature is 1-10 ℃ for min-1(ii) a Specifically 2-5 deg.C for min-1Or 4 ℃ min-1(ii) a The atmosphere used is inert atmosphere; specifically argon atmosphere;
in the step 2), in the etchant solution, the etchant is at least one selected from sodium hydroxide, potassium hydroxide, calcium chloride, zinc chloride, potassium carbonate and HCl; the solvent is at least one selected from water, ethanol and methanol; the mass percentage concentration is 20-40%; specifically, the sodium hydroxide solution with the mass percentage concentration of 32 percent or the hydrochloric acid with the mass percentage concentration of 30 percent;
the mass ratio of the acorn shell derived carbon to the etchant solution is 1: 1-10; specifically 1:3-8 or 1:4 or 1: 5;
in the step 2), the temperature in the etching step is 700-900 ℃; in particular 800 ℃; the time is 0.5 to 4 hours; in particular 2-3 h; the atmosphere used is inert atmosphere; specifically argon atmosphere; the temperature rising rate from room temperature to etching temperature is 2-8 deg.C for min-1(ii) a In particular 4 ℃ min-1；
In the drying step in the step 2), the temperature is 60-150 ℃; in particular to 90 ℃; the time is 12-24 h;
the method further comprises the following steps: after the etching step in the step 2) and before the drying step, washing an obtained etching product; the used detergent is hydrochloric acid or water; the concentration of the hydrochloric acid is specifically 0.8M;
in the step 3), the solvent is at least one selected from ethanol, water and isopropanol; in particular to a mixed solution consisting of ethanol and water; in the mixed liquid composed of the ethanol and the water, the volume ratio of the ethanol to the water is 1: 1-3;
the tin salt is selected from at least one of stannic chloride, stannous sulfate and stannic nitrate;
the mass ratio of the activated carbon to the tin salt is 1: 1-3; specifically 1: 1-1.5;
in the reaction step, the temperature is 60-100 ℃; in particular 80-90 ℃; the time is 6-24 h; in particular 12 h;
in the calcining step, the temperature is 200-700 ℃; in particular to 400 ℃; the time is 0.5 to 4 hours; in particular for 2 h.
In addition, the application of the activated carbon loaded tin oxide nanoparticle material provided by the invention in preparing a diaphragm or a battery also belongs to the protection scope of the invention.
The invention also claims a modified diaphragm material, and the modified diaphragm material is the activated carbon loaded tin oxide nanoparticle material provided by the invention.
In the modified membrane material, the modified material further comprises at least one of a conductive agent, a binder and a solvent;
specifically, the conductive agent is selected from at least one of acetylene black, carbon nanotubes and Ketjen black;
the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene and acrylonitrile multipolymer; the number average molecular weight of the binder is 7000-50000; specifically 15000-30000;
the solvent is at least one selected from N-methyl pyrrolidone, N dimethylformamide and acetonitrile;
the mass ratio of the activated carbon loaded tin oxide nanoparticles to the adhesive to the conductive agent is 1: 0.1-0.5: 0.1-0.25; specifically 7:2: 1.
The invention provides a method for preparing the modified diaphragm material, which comprises the following steps:
uniformly mixing the activated carbon-loaded tin oxide nanoparticles, the conductive agent and the adhesive in the solvent, preparing a modified diaphragm layer on one side of a diaphragm by taking the mixture as a raw material, and drying to obtain the modified diaphragm material;
or, uniformly mixing the activated carbon-loaded tin oxide nanoparticles and the adhesive in the solvent, preparing a modified diaphragm layer on one side of the diaphragm by taking the mixture as a raw material, and drying to obtain the modified diaphragm material.
The method for preparing the modified diaphragm layer is coating or suction filtration;
the thickness of the modified membrane layer is 30-100 μm; specifically 50 μm;
in the drying step, the temperature is 40-80 ℃; the time is 6-24 h.
In addition, the application of the modified diaphragm material provided by the invention in preparing batteries or sulfur batteries and the batteries or sulfur batteries containing the modified diaphragm material also belong to the protection scope of the invention.
The beneficial effects of the invention include:
the invention designs a diaphragm material for an active carbon loaded tin oxide lithium sulfur battery. Selecting waste acorn shells as an active carbon precursor, preparing novel active carbon through simple carbonization and activation, and further growing tin oxide on the active carbon in situ to obtain the active carbon-loaded tin oxide material. Renewable waste is used as a raw material in the experiment, the cost is low, and the preparation process is simple.
The active carbon-loaded tin oxide material prepared by the invention is applied to a lithium-sulfur battery modified diaphragm, and the active carbon and the tin oxide respectively play roles of physical adsorption and chemical adsorption, so that the shuttle of polysulfide is limited through double functions. Finally, lithium sulfur batteries exhibit good cycling performance at different current densities. The method uses waste acorn shells as raw materials, and prepares the modified diaphragm material through the processes of high-temperature carbonization, etching by an etchant and in-situ growth of tin oxide nano particles. The acorn shell derived activated carbon has a hierarchical porous structure, and can physically adsorb polysulfide, and the polar tin oxide nanoparticles and the polar polysulfide have strong chemical action, so that the problem of serious shuttle effect of the lithium-sulfur battery is solved, and the coulombic efficiency and the cycle stability of the lithium-sulfur battery are further improved. The initial capacity of the lithium-sulfur battery assembled by the activated carbon-supported tin oxide diaphragm is 1019.2mAh g at the current density of 0.2C-1After 270 cycles, the loss per cycle was 0.16% and the coulombic efficiency was still 100%. After 440 cycles at 1C current density, the capacity loss per cycle was 0.1%.
Drawings
FIG. 1 is an X-ray diffraction pattern of the activated carbon-supported tin oxide material prepared in example 1.
FIG. 2 is a scanning electron micrograph of the acorn shell activated carbon prepared in example 1.
FIG. 3 is a scanning electron micrograph of the activated carbon-supported tin oxide material prepared in example 1.
Fig. 4 is a scanning electron microscope image of the separator for the activated carbon-supported tin oxide lithium sulfur battery prepared in example 1.
Fig. 5 is a cycle performance curve at 0.2C for the assembled lithium sulfur battery of example 1.
Fig. 6 is a cycle performance curve at 1C for the assembled lithium sulfur battery of example 2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
1) Drying the cleaned acorn shells in an oven at 80 ℃ for 24 h. Then putting the mixture into an alumina porcelain boat, carbonizing the mixture for 3 hours at 1200 ℃ under the protection of argon atmosphere, and raising the temperature for 2 min-1Obtaining acorn shell derived carbon;
2) uniformly stirring the acorn shell derived carbon obtained in the step 1) and a sodium hydroxide aqueous solution with the concentration of 32 wt% of the etchant solution according to the mass ratio of 1:3, drying at 110 ℃ for 12h, etching at 900 ℃ for 2h in a tubular furnace, and raising the temperature rate for 4 ℃ for min-1The atmosphere is argon atmosphere; then washing the obtained sample with 0.8M hydrochloric acid, and drying at 60 ℃ for 12 hours to obtain activated carbon;
3) dispersing 0.2g of the activated carbon obtained in the step 2) in 10ml of ethanol and water (volume ratio is 1:1), and carrying out ultrasonic treatment for 20 min. Then 0.2g of tin chloride is added into the solution and stirred for 30min, and then the solution is sealed in an oven at 90 ℃ for reaction for 6h, and then the solution is calcined for 4h at 200 ℃ in a tube furnace argon atmosphere to obtain the activated carbon supported tin oxide nanoparticle material.
Mixing the activated carbon-supported tin oxide nanoparticle material with polyvinylidene fluoride (with the number average molecular weight of 15000) and acetylene black according to the weight ratio of 7:2:1, evenly mixing the components in N-methyl pyrrolidone, coating the mixture on a diaphragm by a 50 mu m scraper, drying the diaphragm, and cutting the diaphragm into a diaphragm (the mass is 0.1mg cm)-2) The lithium sheet is used as a negative electrode, the carbon nano tube/sulfur composite material is used as a positive electrode, 1mol/L lithium bis (trifluoromethylsulfonyl) imide solution is used as an electrolyte solution, a solvent is a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether (the volume ratio V/V is 1:1), 0.2M lithium nitrate is used as an electrolyte, and after standing for 24 hours, the cycle performance of the lithium-sulfur battery is tested under the voltage of 1.8-2.8V and the current density of 0.2C.
Fig. 1 is an X-ray diffraction pattern of the activated carbon-supported tin oxide material prepared in this example, which proves that the composite material was successfully prepared.
Fig. 2 is a scanning electron microscope image of the acorn shell activated carbon material prepared in the embodiment, and the scanning electron microscope image clearly shows that the activated carbon is in an amorphous block and porous structure.
Fig. 3 is a scanning electron microscope image of the activated carbon-supported tin oxide material prepared in this example, which shows that the acorn shell porous carbon block is uniformly supported with tin oxide nanoparticles.
Fig. 4 is a scanning electron microscope image of the surface of the diaphragm for the activated carbon-supported tin oxide lithium sulfur battery prepared in this embodiment, and it can be seen that a layer of micro-nano structured activated carbon/tin oxide composite material is coated on the surface of the diaphragm.
FIG. 5 shows the cycle performance at 0.2C of the separator for lithium-sulfur battery with carbon-supported tin oxide prepared in this example, and the initial capacity is 1019.2mAh g at 0.2C current density-1After 270 cycles, the loss per cycle was 0.16% and the coulombic efficiency was still 100%.
Example 2:
1) drying the cleaned acorn shells in an oven at 80 ℃ for 24 h. Then putting the mixture into an alumina porcelain boat, carbonizing the mixture for 2 hours at 900 ℃ under the protection of argon atmosphere, and raising the temperature for 5 ℃ for min-1Obtaining acorn shell derived carbon;
2) mixing the acorn shell derived carbon obtained in the step 1) with 30 wt% hydrochloric acid of an etchant solution according to the weight ratio of 1: 8, drying at 100 ℃ for 6h, etching at 800 ℃ for 3h in a tube furnace at the temperature rise rate of 2 ℃ for min-1The atmosphere is argon atmosphere; then washing the obtained sample with water, and drying for 24 hours at 90 ℃ to obtain activated carbon;
3) dispersing 0.1g of the activated carbon obtained in the step 2) in 10ml of ethanol and water (volume ratio is 1:1), performing ultrasonic treatment for 20min, adding 0.15g of stannic chloride into the solution, stirring for 30min, sealing the solution in an oven at 80 ℃, reacting for 12h, and calcining for 2h at 400 ℃ in an argon atmosphere of a tube furnace to obtain the activated carbon-supported stannic oxide nanoparticle material.
The X-ray diffraction spectrum of the activated carbon-loaded tin oxide material, the scanning electron microscope image of the acorn shell activated carbon material, the scanning electron microscope image of the activated carbon-loaded tin oxide material and the scanning electron microscope image of the surface of the diaphragm for the activated carbon-loaded tin oxide lithium sulfur battery obtained in the embodiment are not substantially different from those of the embodiment 1.
Mixing the above active carbon loaded tin oxide nanoparticle material with polyvinylidene fluoride (number average)Molecular weight 30000) and carbon nanotubes according to 7:2:1 proportion is evenly mixed in N-methyl pyrrolidone, a 50um scraper is coated on a diaphragm, and the diaphragm is cut into a diaphragm (the mass is 0.1mg cm) with the diameter of 19mm after being dried-2) The lithium sheet is used as a negative electrode, the carbon nano tube/sulfur composite material is used as a positive electrode, 1mol/L lithium bis (trifluoromethylsulfonyl) imide solution is used as an electrolyte solution, a solvent is a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether (the volume ratio V/V is 1:1), 0.2M lithium nitrate is used as an electrolyte, and after standing for 24 hours, the cycle performance of the lithium-sulfur battery is tested under the voltage of 1.8-2.8V and the current density of 1C.
FIG. 6 shows the cycle performance of lithium-sulfur battery assembled by the activated carbon-supported tin oxide membrane prepared in this example, with initial capacity of 1018.1mAh g-1After the circulation for 440 circles under the current density of 1C, the capacity loss rate of each circle is 0.1 percent.
Claims (10)
1. An active carbon loaded tin oxide nanoparticle material is prepared by loading tin oxide nanoparticles on active carbon as a carrier.
2. The activated carbon-supported tin oxide nanoparticle material of claim 1, wherein: the grain diameter of the tin oxide nano-particles is 3-200 nm;
the mass ratio of the activated carbon to the tin oxide nanoparticles is 1: 2-3;
the active carbon is prepared from acorn shell.
3. A method of preparing the activated carbon-supported tin oxide nanoparticle material of claim 1 or 2, comprising:
1) carbonizing the acorn shell to obtain acorn shell derived carbon;
2) mixing the acorn shell derived carbon obtained in the step 1) with an etchant solution for etching, and drying to obtain activated carbon;
3) dispersing the activated carbon obtained in the step 2) in a solvent, adding tin salt by ultrasonic, sealing for reaction, drying after the reaction is finished, and calcining to obtain the activated carbon.
4. According to claimThe method of claim 3, wherein: in the step 1) of carbonization, the temperature is 800-1200 ℃; the time is 1-5 h; the temperature rising rate from room temperature to carbonization temperature is 1-10 ℃ for min-1(ii) a The atmosphere used is inert atmosphere; specifically argon atmosphere;
in the step 2), in the etchant solution, the etchant is at least one selected from sodium hydroxide, potassium hydroxide, calcium chloride, zinc chloride, potassium carbonate and HCl; the solvent is at least one selected from water, ethanol and methanol; the mass percentage concentration is 20-40%;
the mass ratio of the acorn shell derived carbon to the etchant solution is 1: 1-10;
in the step 2), the temperature in the etching step is 700-900 ℃; the time is 0.5 to 4 hours; the atmosphere used is inert atmosphere; the temperature rising rate from room temperature to etching temperature is 2-8 deg.C for min-1；
In the drying step in the step 2), the temperature is 60-150 ℃; the time is 12-24 h;
in the step 3), the solvent is at least one selected from ethanol, water and isopropanol;
the tin salt is selected from at least one of stannic chloride, stannous sulfate and stannic nitrate;
the mass ratio of the activated carbon to the tin salt is 1: 1-3;
in the step of hydrolysis reaction, the temperature is 60-100 ℃; the time is 6-24 h;
in the calcining step, the temperature is 200-700 ℃; the time is 0.5-4 h.
5. Use of the activated carbon-supported tin oxide nanoparticle material of claim 1 or 2 in the preparation of a separator or a battery.
6. A modified membrane material, wherein the modified material is the activated carbon-supported tin oxide nanoparticle material as defined in claim 1 or 2.
7. The modified membrane material of claim 6, wherein: the modified material also comprises at least one of a conductive agent, a binder and a solvent;
specifically, the conductive agent is selected from at least one of acetylene black, carbon nanotubes and Ketjen black;
the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene and acrylonitrile multipolymer; the number average molecular weight of the binder is 7000-50000;
the solvent is at least one selected from N-methyl pyrrolidone, N dimethylformamide and acetonitrile;
the mass ratio of the activated carbon loaded tin oxide nanoparticles to the adhesive to the conductive agent is 1: 0.1-0.5: 0.1-0.25.
8. A method of making the modified separator material of claim 6 or 7, comprising:
uniformly mixing the activated carbon-loaded tin oxide nanoparticles, the conductive agent and the adhesive in the solvent, preparing a modified diaphragm layer on one side of a diaphragm by taking the mixture as a raw material, and drying to obtain the modified diaphragm material;
or, uniformly mixing the activated carbon-loaded tin oxide nanoparticles and the adhesive in the solvent, preparing a modified diaphragm layer on one side of the diaphragm by taking the mixture as a raw material, and drying to obtain the modified diaphragm material.
9. The method of claim 8, wherein: the method for preparing the modified diaphragm layer is coating or suction filtration;
the thickness of the modified membrane layer is 30-100 μm;
in the drying step, the temperature is 40-80 ℃; the time is 6-24 h.
10. Use of the modified separator material of claim 6 or 7 in the manufacture of a battery or sulphur battery;
a battery or sulfur battery comprising the modified separator material of claim 6 or 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112688024A (en) * | 2020-12-31 | 2021-04-20 | 界首市天鸿新材料股份有限公司 | Diaphragm material of power lithium battery |
| CN114665074A (en) * | 2022-03-21 | 2022-06-24 | 西安航空学院 | Sn simple substance modified biological carbon/sulfur composite material and preparation method and application thereof |
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Application publication date: 20200522 |