CN112786829A - Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents
Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Co-HCS/CNT/S composite lithium-sulfur battery anode material and a preparation method thereof. The preparation method comprises (1) preparing a precursor; (2) obtaining an intermediate of SiO2@ Co-HCS/CNT; (3) processing to obtain Co-HCS/CNT; (4) obtaining the Co-HCS/CNT/S composite lithium-sulfur battery cathode material. Co is used as a catalyst, not only can the oxidation-reduction reaction of the polysulfide be promoted, but also the high-efficiency chemical adsorption of the polysulfide can be provided, the special structure of the HCS/CNT can improve the loading capacity of sulfur, and meanwhile, the special hollow structure can also provide high-efficiency transmission of lithium ions and electrons, so that the utilization rate of sulfur is improved, and the oxidation-reduction reaction is further accelerated.
Description
Technical Field
The invention relates to a Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material and a preparation method thereof, belonging to the field of preparation of lithium-sulfur battery electrode materials.
Background
The traditional lithium ion battery faces the situation that the energy density of the traditional lithium ion battery cannot completely meet the increasing demand of large energy storage equipment on a novel energy storage system with high energy density, so that the optimization of the lithium ion battery and the development of novel batteries are urgent. Lithium-sulfur batteries are used for their high theoretical specific energy (2600 Wh kg) -1) And the advantages of low cost, wide source, no toxicity and the like, and is regarded as a novel battery which has the most potential to replace a lithium ion battery. However, problems such as sulfur conductivity and shuttle effect of soluble lithium polysulfides, which result in poor rate performance and rapid capacity fade, lead to low sulfur utilization and poor cycle life of the battery, thus greatly limiting the practical application of lithium sulfur batteries.
In order to overcome the above problems, researchers have been devoted to solving and improving these problems by improving the design of the battery structure, introducing a carrier material, and developing a solid electrolyte. The invention prepares the composite material with the special structure of the hollow carbon nano tube composite hollow carbon nano sphere and doped with cobalt as a sulfur carrier based on further research, development and innovation of the carrier material, effectively enhances the conductivity of the sulfur/carbon composite anode material, shortens the ion transmission path of the sulfur/carbon composite anode material, accelerates the electron transmission and ensures that the sulfur/carbon composite anode material has excellent cycle stability.
Disclosure of Invention
Aiming at the problems, the invention researches and innovates a carrier material, and prepares a material with a special structure of doping cobalt into the hollow carbon nano tube composite hollow carbon nano sphere by adopting a template method as a sulfur carrier, thereby effectively enhancing the conductivity of the composite anode material of the lithium-sulfur battery, accelerating the electron transmission speed, accelerating the oxidation-reduction reaction and ensuring that the material has excellent cycle stability.
The technical scheme of the invention is as follows:
a Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material is characterized in that hollow carbon nano-tubes (CNTs) are attached with hollow carbon nano-spheres (HCS) and are doped with Co, and S is loaded on the composite material. Co is used as a catalyst, not only can the oxidation-reduction reaction of polysulfide be promoted, but also high-efficiency chemical adsorption of polysulfide can be provided, the special structure of the HCS/CNT can improve the loading capacity of sulfur, and meanwhile, the special hollow structure can also provide high-efficiency transmission of lithium ions and electrons, so that the utilization rate of sulfur is improved, and the oxidation-reduction reaction is further accelerated.
The preparation method of the Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) firstly, tetrapropyl orthosilicate, ethanol and H2O and NH3·H2Mixing and stirring O, adding resorcinol, formaldehyde, polypyrrole (PPy) and cobalt salt, stirring, centrifuging and drying to obtain a precursor;
(2) putting the precursor obtained in the step (1) into a tube furnace, and calcining under inert gas to obtain SiO2@Co-HCS/CNT；
(3) SiO obtained in the step (2)2@ Co-HCS/CNT is put into sodium hydroxide solution to be mixed and stood for treatment, and then the mixture is centrifuged, washed and dried to obtain Co-HCS/CNT;
(4) and (4) mixing the Co-HCS/CNT obtained in the step (3) with sulfur, grinding uniformly, and annealing in an inert atmosphere to obtain the Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material, wherein the sulfur is uniformly loaded on the Co-HCS/CNT.
The anode material prepared by the invention has the advantages of adsorption, catalysis and high conductivity, and Co can be chemically adsorbed and used as a catalyst. The carbon material HCS/CNT can be physically adsorbed and can also improve the conductivity.
According to the present invention, in the step (1), the synthesis method of PPy is as follows:
methyl orange and FeCl3And magnetically stirring deionized water and pyrrole monomer at room temperature for 24 hours, centrifuging, washing and drying to obtain the compound.
In the step (1), 5wt% of ammonia water, 37wt% of formaldehyde, cobalt salt, cobalt nitrate hexahydrate and tetrapropyl orthosilicate and ethanol are mixed according to a volume ratio of (2-4): (46.6-93.3), the volume ratio of tetrapropyl orthosilicate to deionized water is (2-4): (6.66-13.33), and the volume ratio of tetrapropyl orthosilicate to ammonia water is (2-4): (2-4), the volume ratio of tetrapropyl orthosilicate to formaldehyde is (2-4): (0.37-0.74); the mass-volume ratio of the resorcinol to the tetrapropyl orthosilicate is (0.13-0.52): (2-4), the mass-to-volume ratio of PPy to tetrapropyl orthosilicate is 0.1: 3/0.2: 3, unit: g/mL; the molar volume ratio of cobalt nitrate hexahydrate to tetrapropyl orthosilicate is (0.45-0.9): (2-4), unit: mmoL/mL.
Further preferably, the volume ratio of tetrapropyl orthosilicate to ethanol is 3: 70, the volume ratio of tetrapropyl orthosilicate to deionized water is 3: 10, the volume ratio of tetrapropyl orthosilicate to ammonia water is 1: 1, the volume ratio of tetrapropyl orthosilicate to formaldehyde is 3: 0.56; the mass volume ratio of the resorcinol to the tetrapropyl orthosilicate is 0.2: 3, the mass-volume ratio of PPy to tetrapropyl orthosilicate is 0.15: 3, unit, g/mL; the molar volume ratio of the cobalt nitrate hexahydrate to the tetrapropyl orthosilicate is 0.68: 3, unit: mmoL/mL.
Preferably, according to the invention, in step (1), tetrapropyl orthosilicate, ethanol, H2O and NH3·H2O, stirring for 15 minutes; adding resorcinol, formaldehyde, PPy, and Co (NO)3)2·6H2And O, stirring for 24 hours.
According to the invention, in the step (2), the calcination temperature is 650-750 ℃, and the calcination time is 3-5 h; more preferably, the calcining temperature is 700 ℃ and the calcining time is 5 h.
Preferably, in the step (3), the concentration of the sodium hydroxide is 2moL/mL, and the soaking time is 24-48 h; more preferably, the soaking time is 36 h.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a Co-HCS/CNT/S composite material, a unique cavity structure not only provides physical adsorption for polysulfide, but also provides stronger chemisorption and activation sites for Co for chemisorption and catalytic conversion. The polar action of Co can inhibit the dissolution of polysulfide in organic electrolyte, so as to reduce shuttle effect, accelerate oxidation-reduction reaction power of polysulfide and greatly raise capacity and cycle performance of battery. In addition, HCS/CNT provides a highly conductive structure and also provides physical adsorption to polysulfides.
2. The three-dimensional structure prepared by the invention not only keeps the initial appearances of the carbon tube and the carbon sphere, but also is doped with Co on the basis, and the cavity of the carbon material can have a certain slow release effect on the volume change in the charging and discharging processes.
3. The lithium-sulfur battery cathode material prepared by the invention has higher electron and ion transmission performance and good electrochemical performance.
4. The preparation method provided by the invention is simple and easy to obtain; compared with other metal compound raw materials, the raw materials are low in price and wide in source; waste liquid and waste materials which cannot be treated are not generated in the preparation process, the energy consumption is low, the environment is friendly, the operability is strong, and a new direction is provided for preparing the lithium-sulfur battery cathode material.
Drawings
FIG. 1 is an SEM image of Co-HCS/CNT prepared in example 1
FIG. 2 is a graph showing long cycle performance curves of the Co-HCS/CNT/S composite positive electrode material prepared in example 1 compared with the HCS/S lithium sulfur battery composite positive electrode material prepared in the comparative example.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. The examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Example 1: Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material and preparation method thereof
The method specifically comprises the following steps:
(1) 3 mL of tetrapropyl orthosilicate, 70 mL of ethanol and 10 mL of H2O and 3 mL, 5% (wt%) NH3·H2O, stirring for 15 minutes; 0.4 g resorcinol, 0.56 ml,37% wt formaldehyde, 0.1g PPy, 0.2 g Co (NO) was added3)2·6H2O, stirring for 24 hours; centrifuging, washing and drying.
The synthesis method of PPy comprises the following steps:
0.1g methyl orange, 1.96 g FeCl 3150 mL of deionized water, 500. mu.L of pyrrole monomer, and stirring magnetically at room temperature for 24 hours. Centrifuging, washing and drying.
(2) Annealing at 700 ℃ for 5 hours in argon atmosphere to obtain SiO2@Co-HCS/CNT。
（3）SiO2@ Co-HCS/CNT and 2 mol/L sodium hydroxide solution were mixed and left to stand for 36 hours, centrifuged, and dried. Co-HCS/CNT was obtained.
(4) And (2) mixing sulfur powder and Co-HCS/CNT according to the mass ratio of 7:3, mixing, keeping the temperature at 155 ℃ for 12 hours under the argon atmosphere, and keeping the temperature of the sample at 200 ℃ for 30 min.
The prepared Co-HCS/CNT/S composite material is used as a positive electrode material of a lithium-sulfur battery, and the positive electrode material, acetylene black and PVDF are mixed according to the weight ratio of 7: 2: 1, dropwise adding a certain amount of solvent (azomethylpyrrolidone), uniformly mixing, ball-milling, drying, slicing, weighing, and assembling the battery by using the prepared electrode plate to obtain the battery for testing.
Scanning electron microscopy characterization
And (4) performing scanning electron microscope characterization on the Co-HCS/CNT crystalline phase obtained in the step (3), wherein a strip-shaped hollow Carbon Nanotube (CNT) is attached with a hollow carbon nanosphere (HCS), and Co is doped on the composite material in the figure 1.
Comparative example
A preparation method of a positive electrode material of an HCS/CNT/S composite lithium-sulfur battery comprises the following steps:
(1) 3 mL of tetrapropyl orthosilicate, 70 mL of ethanol and 10 mL of H2O and 3 mL, 5% wt. NH3·H2O stirred for 15 minutes. Adding 0.4 g of resorcinol, 0.56 ml of 37wt% formaldehyde and 0.2 g of PPy, and stirring for 24 hours; centrifuging, washing and drying.
The synthesis method of PPy comprises the following steps: 0.1g methyl orange, 1.96 g FeCl 3150 mL of deionized water, 500. mu.L of pyrrole monomer, and stirring magnetically at room temperature for 24 hours. Centrifuging, washing and drying.
(2) Annealing: SiO is obtained after 5 hours at 700 ℃ under the atmosphere of argon2@HCS/CNT。
（3）SiO2Mixing and standing @ HCS/CNT and 2 moL/L sodium hydroxide solution for 36 hours; centrifuging, washing and drying.
(4) Mixing sulfur powder and HCS/CNT according to the mass ratio of 7: 3; keeping the temperature at 155 ℃ for 12 hours under the argon atmosphere; the sample was then incubated at 200 ℃ for 30 min.
(5) The prepared HCS/CNT/S composite material is used as a positive electrode material of a lithium-sulfur battery, and the positive electrode material, acetylene black and PVDF are mixed according to the weight ratio of 7: 2: 1, dropwise adding a certain amount of solvent (azomethylpyrrolidone), uniformly mixing, ball-milling, drying, slicing, weighing, and assembling the battery by using the prepared electrode plate to obtain the battery for testing.
Electrical Performance testing
And (2) testing the electrical property of the prepared Co-HCS/CNT/S composite lithium-sulfur battery positive electrode, mixing the prepared Co-HCS/CNT/S composite material with acetylene black and PVDF according to a certain proportion, dropwise adding a certain amount of solvent (nitrogen methyl pyrrolidone) to the mixture, uniformly mixing, carrying out ball milling, drying, slicing and weighing, and finally carrying out battery assembly by using the prepared electrode slice to obtain the battery for testing. Then testing the cycle stability performance of the test system on a Xinwei test system, wherein the charge-discharge voltage range is 1.7-2.8V.
As shown in FIG. 2, the Co-HCS/CNT/S composite positive electrode material of the lithium-sulfur battery has higher specific discharge capacity than the HCS/S composite positive electrode material at 0.5C.
Example 2: Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material and preparation method thereof
The method specifically comprises the following steps:
(1) 2 mL of tetrapropyl orthosilicate, 46.6 mL of ethanol, 6.66 mL of H2O and 2 mL, 5% wt. NH3·H2O, stirring for 15 minutes; add 0.13 g resorcinol, 0.37 mL,37% wt formaldehyde, 0.2 g PPy, 0.13 g Co (NO)3)2·6H2O, stirring for 24 hours; centrifuging, washing and drying.
The synthesis method of PPy comprises the following steps:
0.1g methyl orange, 1.96 g FeCl 3150 mL of deionized water, 500 mu L of pyrrole monomer, and stirring for 24 hours at room temperature by magnetic force; centrifuging, washing and drying.
(2) Annealing at 700 ℃ for 5 hours in argon atmosphere to obtain SiO2@Co-HCS/CNT。
(3) SiO2@ Co-HCS/CNT and 2 moL/L sodium hydroxide solution are mixed, stood for treatment for 36 hours, centrifuged and dried.
(4) And (2) mixing sulfur powder and Co-HCS/CNT according to the mass ratio of 7:3, mixing. Keeping the temperature at 155 ℃ for 12 hours under the argon atmosphere; the sample was then incubated at 200 ℃ for 30 min.
The prepared Co-HCS/CNT/S composite material is used as a positive electrode material of a lithium-sulfur battery, and the positive electrode material, acetylene black and PVDF are mixed according to the weight ratio of 7: 2: 1, dropwise adding a certain amount of solvent (azomethylpyrrolidone), uniformly mixing, ball-milling, drying, slicing, weighing, and assembling the battery by using the prepared electrode plate to obtain the battery for testing.
The lithium-sulfur battery obtained by the invention and the lithium-sulfur battery prepared from the cathode material of the comparative example 1 were tested for cycling stability performance on a Xinwei test system. Through comparison of the electrical properties of the invention in the comparative example 1, it can be seen that the cycle performance of the lithium-sulfur battery prepared from the anode material in the comparative example 1 is far smaller than that of the lithium-sulfur battery prepared from the anode material in the invention, the excellent coating of the hollow tube and hollow sphere structures on sulfur is reserved in the invention, and Co is doped, so that the doped Co plays a catalytic role, the redox reaction is promoted, and the capacity and the cycle performance of the battery are greatly improved.
Claims (10)
1. The Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material is characterized in that hollow carbon nano-tubes (CNTs) in the positive electrode material are attached with hollow carbon nano-spheres (HCS) and are doped with Co, and S is loaded on the composite material.
2. The method for preparing the Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material as claimed in claim 1, comprising the following steps:
(1) firstly, tetrapropyl orthosilicate, ethanol and H2O and NH3·H2Mixing and stirring O, adding resorcinol, formaldehyde, polypyrrole (PPy) and cobalt salt, stirring, centrifuging and drying to obtain a precursor;
(2) putting the precursor obtained in the step (1) into a tube furnace, and calcining under inert gas to obtain SiO2@Co-HCS/CNT；
(3) SiO obtained in the step (2)2@ Co-HCS/CNT is put into sodium hydroxide solution to be mixed and stood for treatment, and then the mixture is centrifuged, washed and dried to obtain Co-HCS/CNT;
(4) and (4) mixing the Co-HCS/CNT obtained in the step (3) with sulfur, grinding uniformly, and annealing in an inert atmosphere to obtain the Co-HCS/CNT/S composite lithium-sulfur battery positive electrode material, wherein the sulfur is uniformly loaded on the Co-HCS/CNT.
3. The method according to claim 2, wherein in the step (1), the synthesis of PPy is as follows:
methyl orange and FeCl3And magnetically stirring deionized water and pyrrole monomer at room temperature for 24 hours, centrifuging, washing and drying to obtain the compound.
4. The preparation method according to claim 2, wherein in the step (1), the mass fraction of ammonia water is 5wt%, the mass fraction of formaldehyde is 37wt%, the cobalt salt is cobalt nitrate hexahydrate, and the volume ratio of tetrapropyl orthosilicate to ethanol is (2-4): (46.6-93.3), the volume ratio of tetrapropyl orthosilicate to deionized water is (2-4): (6.66-13.33), and the volume ratio of tetrapropyl orthosilicate to ammonia water is (2-4): (2-4), the volume ratio of tetrapropyl orthosilicate to formaldehyde is (2-4): (0.37-0.74); the mass-volume ratio of the resorcinol to the tetrapropyl orthosilicate is (0.13-0.52): (2-4), the mass-to-volume ratio of PPy to tetrapropyl orthosilicate is 0.1: 3/0.2: 3, unit: g/mL; the molar volume ratio of cobalt nitrate hexahydrate to tetrapropyl orthosilicate is (0.45-0.9): (2-4), unit: mmoL/mL.
5. The method according to claim 4, wherein the volume ratio of tetrapropyl orthosilicate to ethanol is 3: 70, the volume ratio of tetrapropyl orthosilicate to deionized water is 3: 10, the volume ratio of tetrapropyl orthosilicate to ammonia water is 1: 1, the volume ratio of tetrapropyl orthosilicate to formaldehyde is 3: 0.56; the mass volume ratio of the resorcinol to the tetrapropyl orthosilicate is 0.2: 3, the mass-volume ratio of PPy to tetrapropyl orthosilicate is 0.15: 3, unit, g/mL; the molar volume ratio of the cobalt nitrate hexahydrate to the tetrapropyl orthosilicate is 0.68: 3, unit: mmoL/mL.
6. The method according to claim 2, wherein in the step (1), tetrapropyl orthosilicate, ethanol, and H are used2O and NH3·H2O, stirring for 15 minutes; adding resorcinol, formaldehyde, PPy, and Co (NO)3)2·6H2And O, stirring for 24 hours.
7. The preparation method of claim 2, wherein in the step (2), the calcining temperature is 650 ℃ to 750 ℃ and the calcining time is 3 to 5 hours.
8. The method according to claim 7, wherein the calcination temperature is 700 ℃ and the calcination time is 5 hours.
9. The preparation method according to claim 2, wherein in the step (3), the concentration of the sodium hydroxide is 2moL/mL, and the soaking time is 24-48 h.
10. The method of claim 9, wherein the soaking time is 36 hours.
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| CN109802124A (en) * | 2019-02-14 | 2019-05-24 | 西南大学 | Metal atom doped porous carbon nano-composite material of one kind and its preparation method and application |
| CN110380030A (en) * | 2019-07-18 | 2019-10-25 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN111540888A (en) * | 2020-04-29 | 2020-08-14 | 齐鲁工业大学 | CoSe2Hollow carbon nanosphere/S composite lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111661835A (en) * | 2020-06-08 | 2020-09-15 | 齐鲁工业大学 | Sulfur/carbon composite material and preparation method and application thereof |
| CN111675208A (en) * | 2020-06-08 | 2020-09-18 | 齐鲁工业大学 | Sulfur-nitrogen doped hollow carbon nanotube composite material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109802124A (en) * | 2019-02-14 | 2019-05-24 | 西南大学 | Metal atom doped porous carbon nano-composite material of one kind and its preparation method and application |
| CN110380030A (en) * | 2019-07-18 | 2019-10-25 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN111540888A (en) * | 2020-04-29 | 2020-08-14 | 齐鲁工业大学 | CoSe2Hollow carbon nanosphere/S composite lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111661835A (en) * | 2020-06-08 | 2020-09-15 | 齐鲁工业大学 | Sulfur/carbon composite material and preparation method and application thereof |
| CN111675208A (en) * | 2020-06-08 | 2020-09-18 | 齐鲁工业大学 | Sulfur-nitrogen doped hollow carbon nanotube composite material and preparation method and application thereof |
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