CN112786830A - Co-HCS/S composite lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents
Co-HCS/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/S composite lithium-sulfur battery positive electrode material and a preparation method thereof. The preparation method comprises (1) preparing a precursor doped with cobalt; (2) the precursor is inCalcining under inert gas to obtain SiO2@ Co-HCS; (3) sodium hydroxide to remove SiO2Obtaining Co-HCS; (4) mixing and calcining the mixture with sulfur powder under inert gas to obtain the Co-HCS/S composite lithium-sulfur battery anode material. The hollow carbon nanospheres are doped with Co, so that the hollow carbon nanospheres provide a conductive network to enhance the conductivity of the sulfur anode on the one hand, and the Co can be used as a catalyst to effectively enhance the conductivity of the lithium-sulfur battery anode, accelerate electron transmission and accelerate redox reaction, so that the lithium-sulfur battery anode has excellent cycling stability.
Description
Technical Field
The invention relates to a Co-HCS/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 energy crisis is considered as one of the most important problems facing modern society at present, and some energy sources cannot be supplemented from the nature in a short time after being consumed. Meanwhile, due to technical limitation, most energy sources can be obtained from primary energy sources (such as coal, natural gas and the like). The burning of a large amount of fossil energy also brings problems of resource shortage, environmental pollution and the like. The scientists are prompted to target new energy sources which can be developed sustainably and are good for the environment. Among them, the battery industry has become a new hot spot for the development of global economy as an important component in the field of new energy.
Lithium sulfur batteries are one of the most promising rechargeable batteries and have been considered as the next generation energy storage system to replace the current commercial lithium ion batteries. Since it has 1675 mAh g-1High theoretical specific capacity and 2600 Wh kg-1The method has the advantages of high energy density, low cost, environmental friendliness and the like, and attracts people's attention. However, lithium-sulfur batteries still face serious challenges in practical applications: (1) the reaction kinetics are slow due to the inherent insulating properties of sulfur, and the final discharge product coverage on the active material surface reduces the sulfur utilization. (2) Due to sulfur and Li during the circulation2The volume change due to the density difference of S is large (up to 80%), resulting in electrode cracking and active material consumption. (3) The shuttling effect caused by diffusion of highly soluble lithium polysulfides leads to rapid capacity fade and severe self-discharge.
Disclosure of Invention
Aiming at the problems, the invention provides the Co-HCS/S composite lithium-sulfur battery positive electrode material and the preparation method thereof, which effectively enhance the conductivity of the Co-HCS/S composite positive electrode material, accelerate electron transmission and the redox reaction, and ensure that the Co-HCS/S composite positive electrode material has excellent cycling stability; meanwhile, the preparation method is simple and easy to operate, and the preparation process is easy to control.
The technical scheme of the invention is as follows:
a Co-HCS/S composite lithium-sulfur battery cathode material is characterized in that hollow carbon nanospheres are doped with Co and are loaded with sulfur (S), and the S is loaded on the surface of the composite material. Co acts as a catalyst, not only to promote the redox reaction of polysulfides, but also to provide efficient chemisorption of polysulfides.
The preparation method of the Co-HCS/S composite lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) tetrapropyl orthosilicate, ethanol and H2O and NH3·H2Mixing and stirring uniformly; adding resorcinol, formaldehyde and cobalt salt into the solution, and stirring uniformly; centrifuging, washing 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；
(3) SiO obtained in the step (2)2@ Co-HCS is put into sodium hydroxide solution to be mixed and stood, centrifuged, washed and dried to obtain Co-HCS;
(4) and (4) mixing the Co-HCS obtained in the step (3) with sulfur, grinding uniformly, and annealing in an inert atmosphere to obtain the Co-HCS/S composite lithium-sulfur battery positive electrode material, wherein the sulfur is uniformly loaded on the Co-HCS.
The Co-HCS/S composite lithium-sulfur battery cathode material prepared by the invention has the characteristics of adsorption, catalysis and high conductivity.
According to the invention, in step (1), the ammonia water (NH) is preferably used in a mass fraction of 5wt%3·H2O) formaldehyde with the mass fraction of 37wt%, cobalt salt is nitre hexahydrateCobalt acid (Co (NO)3)2·6H2O); preferably tetrapropyl orthosilicate, ethanol, H2The volume ratio of O, ammonia water and formaldehyde is as follows: (2-4): (46.6-93.3): (6.66-13.33): (2-4): (0.37-0.74); the mass-volume ratio of the resorcinol to the tetrapropyl orthosilicate is (0.13-0.52): (2-4) unit of 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 tetrapropyl orthosilicate, ethanol, H2The volume ratio of O, ammonia water and formaldehyde is as follows: 3: 70: 10: 3: 0.56; the mass volume ratio of the resorcinol to the tetrapropyl orthosilicate is 0.2: 3, unit is g/mL; the molar volume ratio of the cobalt nitrate hexahydrate to the tetrapropyl orthosilicate is 0.6: 3, unit: mmoL/mL.
Preferably, according to the invention, in step (1), tetrapropyl orthosilicate, ethanol, H2O and NH3·H2O, stirring for 15 minutes; then adding resorcinol, formaldehyde 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/L, and the standing treatment time is 24-48 h; more preferably, the standing treatment time is 36 hours.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a Co-HCS/S composite material, and the hollow carbon nanospheres in the cathode material are doped with Co and loaded with sulfur, so that the conductivity of the composite cathode material is effectively enhanced, the electron transmission is accelerated, the redox reaction is accelerated, and the composite cathode material has excellent cycling stability.
2. The material prepared by the method is of a hollow structure. The composite material prepared by the method can effectively improve the conductivity of the lithium-sulfur battery cathode material, the adsorption effect on polysulfide and the catalytic effect, relieves the volume expansion in the charging and discharging process to a certain extent, and has good electrochemical performance.
3. The preparation method provided by the invention is simple and easy to obtain; compared with other metal (such as Ti, Ag and the like) compound raw materials, the material has low price and wide source; the preparation process does not generate waste liquid and waste materials which cannot be treated, and has low energy consumption, environmental friendliness and strong operability. Provides a new direction for preparing the anode material of the lithium-sulfur battery.
Drawings
Fig. 1 is an XRD pattern prepared in example 1.
FIG. 2 is a graph showing the cycle performance of the positive electrode material of the composite lithium-sulfur battery of comparative example 1 doped with cobalt
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/S composite lithium-sulfur battery positive electrode material and preparation method thereof
(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. Add 0.4 g resorcinol, 0.56 mL, 37% wt formaldehyde, 0.2 g Co (NO)3)2·6H2O, stirring for 24 hours; centrifuging, washing and drying to obtain a precursor;
(2) putting the precursor obtained in the step (1) into a tube furnace, and annealing for 5 hours at 700 ℃ in an argon atmosphere to obtain SiO2@Co-HCS；
(3) SiO obtained in the step (2)2Mixing and standing @ Co-HCS and 2mol/L sodium hydroxide solution for 36 hours, centrifuging, washing and drying to obtain Co-HCS;
(4) mixing sulfur and the Co-HCS obtained in the step (3) according to the mass ratio of 7:3, and grinding; keeping the temperature for 12 hours at the temperature of 155 ℃ under the argon atmosphere; preparing the Co-HCS/S composite lithium-sulfur battery anode material, and then preserving the heat of the Co-HCS/S composite lithium-sulfur battery anode material for 30min at 200 ℃.
Comparative example 1
A positive electrode material of HCS composite lithium-sulfur battery and a preparation method thereof are disclosed, the preparation method of the positive electrode material is as follows:
(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 stirring for 24 hours; centrifuging, washing and drying;
(2) annealing at 700 ℃ for 5 hours in argon atmosphere to obtain SiO2@HCS；
（3）SiO2@ HCS, 2mol/L sodium hydroxide solution mixed and left to stand for 36 hours. Drying after centrifugation;
(4) mixing sulfur powder and HCS 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.
The positive electrode material of comparative example 1 was prepared as a lithium sulfur battery according to the method provided in example 1 and tested for cycling stability on a novice test system. Through comparison of the electrical properties of the comparative example 1 and the example 1, it can be seen that the cycle performance of the lithium-sulfur battery prepared from the positive electrode material of the comparative example 1 is far smaller than the electrical properties of the invention, the Co in the example 1 is used as a catalyst to promote the oxidation-reduction reaction of polysulfide, so that high-efficiency polysulfide chemisorption is provided, fast and high-efficiency lithium ion and electron transmission can be realized, the sulfur utilization rate is improved, and the oxidation-reduction reaction is accelerated. The two components act synergistically to greatly improve the capacity and the cycle performance of the battery.
Example 2
Co-HCS/S composite lithium-sulfur battery positive electrode material and preparation method thereof
(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. Add 0.4 g resorcinol, 0.5 g6 mL, 37% wt% formaldehyde, 0.2 g Co (NO)3)2·6H2And O, stirring for 24 hours. Centrifuging, washing and drying to obtain a precursor;
(2) putting the precursor obtained in the step (1) into a tube furnace, and annealing for 5.5 hours at 700 ℃ in an argon atmosphere to obtain SiO2@Co-HCS；
(3) SiO obtained in the step (2)2Mixing and standing @ Co-HCS and 2.5 mol/L sodium hydroxide solution for 36 hours, centrifuging, washing and drying to obtain Co-HCS;
(4) mixing sulfur and the Co-HCS obtained in the step (3) according to the mass ratio of 7:3, and grinding; and (3) preserving the heat for 12 hours at 155 ℃ in an argon atmosphere to obtain the Co-HCS/S composite lithium-sulfur battery positive electrode material, and preserving the heat for 30 minutes at 200 ℃ for the Co-HCS/S composite lithium-sulfur battery positive electrode material.
Characterization of XRD
When the Co-HCS obtained in the step (2) of the present invention is analyzed, as shown in FIG. 1, it is found from the XRD pattern that the Co-HCS has a characteristic peak corresponding to PDF #07-0169 and has good crystallinity.
Electrical Performance testing
The prepared Co-HCS/S composite lithium-sulfur battery positive electrode is subjected to electrical performance test, the prepared Co-HCS/S composite material is used as a positive electrode material of the lithium-sulfur battery, the positive electrode material is mixed with acetylene black and PVDF according to a certain proportion, a certain amount of solvent (nitrogen methyl pyrrolidone) is dripped into the mixture to be uniformly mixed, then ball milling, drying, slicing and weighing are carried out, finally, the prepared electrode plate is utilized to carry out battery assembly, and finally, the battery used for testing is obtained. 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/S composite lithium-sulfur battery has a substantially stable capacity after 250 cycles, and the capacity is 600 mAh g after 250 cycles-1。
Claims (10)
1. The Co-HCS/S composite lithium-sulfur battery cathode material is characterized in that hollow carbon nanospheres in the cathode material are doped with Co and are loaded with sulfur (S), and the S is loaded on the surface of the composite material.
2. The method for preparing the Co-HCS/S composite lithium-sulfur battery cathode material according to claim 1, specifically comprising the following steps:
(1) tetrapropyl orthosilicate, ethanol and H2O and NH3·H2Mixing and stirring uniformly; adding resorcinol, formaldehyde and cobalt salt into the solution, and stirring uniformly; centrifuging, washing 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；
(3) SiO obtained in the step (2)2@ Co-HCS is put into sodium hydroxide solution to be mixed and stood, centrifuged, washed and dried to obtain Co-HCS;
(4) and (4) mixing the Co-HCS obtained in the step (3) with sulfur, grinding uniformly, and annealing in an inert atmosphere to obtain the Co-HCS/S composite lithium-sulfur battery positive electrode material, wherein the sulfur is uniformly loaded on the Co-HCS.
3. The production method according to claim 2, wherein in the step (1), the mass fraction of ammonia water (NH) is 5wt%3·H2O), 37wt% of formaldehyde and cobalt salt of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O）。
4. The method according to claim 2, wherein in the step (1), tetrapropyl orthosilicate, ethanol, and H are used2The volume ratio of O, ammonia water and formaldehyde is as follows: (2-4): (46.6-93.3): (6.66-13.33): (2-4): (0.37-0.74); the mass-volume ratio of the resorcinol to the tetrapropyl orthosilicate is (0.13-0.52): (2-4) unit of 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 in the step (1), tetrapropyl orthosilicate, ethanol, H2O、The volume ratio of ammonia water to formaldehyde is as follows: 3: 70: 10: 3: 0.56; the mass volume ratio of the resorcinol to the tetrapropyl orthosilicate is 0.2: 3, unit is g/mL; the molar volume ratio of the cobalt nitrate hexahydrate to the tetrapropyl orthosilicate is 0.6: 3, unit: mmoL/mL.
6. The method according to claim 2, wherein in the step (1), tetrapropyl orthosilicate, ethanol, H2O and NH3·H2O, stirring for 15 minutes; then adding resorcinol, formaldehyde and Co (NO)3)2·6H2And O, stirring for 24 hours.
7. The preparation method of claim 2, wherein in the step (2), the calcination temperature is 650 ℃ to 750 ℃ and the calcination 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 production method according to claim 2, wherein in the step (3), the concentration of sodium hydroxide is 2mol/L, and the standing treatment time is 24 to 48 hours.
10. The method according to claim 9, wherein the standing treatment time is 36 hours.
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