CN109065808B - Preparation method of functional interlayer for lithium-sulfur battery - Google Patents
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Abstract
The invention relates to a preparation method of a functional interlayer applied to a lithium-sulfur battery. The method comprises the steps of mixing metal cobalt salt with spinning solution, spinning, drying and calcining fibers spun by high-voltage electrospinning to obtain cobaltosic oxide nanofibers, and cutting to obtain the functional interlayer. The invention can improve the polysulfide shuttling effect in the lithium-sulfur battery in the prior art, and the defects of poor performance of the lithium-sulfur battery caused by low utilization rate of active substances in the anode material.
Description
Technical Field
The invention belongs to the technical field of battery interlayer preparation, and particularly relates to a preparation method of a functional interlayer applied to a lithium-sulfur battery.
Background
Lithium-sulfur batteries because of their high theoretical specific capacity (1675mAh g)-1) And theoretical energy density (2600Wh kg)-1) And the lithium ion battery has the advantages of high capacity, low cost and the like, is most hopeful to become a next generation battery after the lithium ion battery, and becomes one of novel high-energy chemical power systems with the most development potential. However, limitations of lithium sulfur batteries include the shuttle effect of lithium polysulfide during long-term cycling, inefficient use of sulfur, and severe volume expansion (80%). In addition, the diffusion of lithium polysulfide intermediate and redox reactions lead to severe self-discharge phenomena and low coulombic efficiency, resulting in poor reversibility of the battery reaction. In addition to the rapid development of sulfur anodes and lithium anodes, research into modified barrier materials has also received much attention. The common diaphragm plays roles of isolating the positive electrode and the negative electrode, avoiding short circuit and realizing the shuttle of ions and the infiltration of electrolyte in the lithium-sulfur battery. In addition to the above-described function of a common separator, the modified separator material can also improve the long cycle stability of the battery by physically confining or chemically adsorbing soluble polysulfides.
For example: singhal et al prepared carbon dioxide activated Polyacrylonitrile (PAN) nanofiber paper and carbonized PAN-Nafion nanofiber paper as the separator for lithium sulfur batteries. The carbon fiber paper interlayer not only can reduce electrochemical resistance, but also can limit the diffusion of polysulfide, and the first discharge capacity of the battery of the carbon fiber interlayer is 1549 mAh/g. Yang et al adopt high conductivity three-dimensional carbon fiber cloth as a spacer placed between the sulfur anode and the diaphragm to capture a soluble lithium polysulfide intermediate product, can obviously improve the capacity and the cycling stability of the battery, and the discharge capacity is still 560mAh/g after 1000 cycles under 5C multiplying power. CN106450104A discloses an interlayer applied to a lithium-sulfur battery and a preparation method thereof, wherein a metal oxide is attached to the fiber surface of bacterial cellulose for carbonization by the method, so as to obtain a novel anode interlayer. The interlayer can be used between the anode and the diaphragm of the lithium-sulfur battery, can well inhibit shuttle of polysulfide ions, and metal oxide in the interlayer can also adsorb the polysulfide ions; meanwhile, the metal oxide also has a certain catalytic action on the oxidation-reduction reaction of the lithium-sulfur battery, and plays an important role in improving the cycle performance of the lithium-sulfur battery. However, the above-mentioned techniques have disadvantages: the preparation process is complicated, the production cost is high, the production time is long, the consumption time is long, the large-scale production is difficult, the specific surface area of the prepared interlayer is small, the micro-morphology of the interlayer is difficult to control, and the wide application of the interlayer in the lithium-sulfur battery is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a functional interlayer applied to a lithium-sulfur battery, aiming at the defects in the prior art. According to the invention, the metal cobalt salt and the spinning solution are mixed and then spun, the fibers spun by the high-voltage electrospinning are dried and calcined to prepare the cobaltosic oxide nanofibers, and the functional interlayer is obtained by cutting.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a functional interlayer applied to a lithium-sulfur battery comprises the following steps:
the method comprises the following steps: preparing electrostatic spinning precursor solution: mixing cobalt nitrate hexahydrate, ethanol and N, N-dimethylformamide liquid, stirring for 5-20 min, adding polyvinylpyrrolidone (PVP), continuously stirring for 1-2 h, and then performing ultrasonic treatment for 1-2 h by using an ultrasonic machine to obtain an electrostatic spinning precursor solution;
wherein, 0.1-1 g of cobalt nitrate hexahydrate, 2-10 ml of N, N-dimethylformamide and 0.1-3 g of polyvinylpyrrolidone (PVP) are added into 2-10 ml of ethanol;
step two: preparing a metal cobalt salt nanofiber membrane: adding the precursor solution into an injector, controlling the working voltage to be 10-20 KV, adjusting the distance between a receiver and a spinning needle to be 5-20 cm, controlling the outflow speed of the solution to be 0.2-0.8 ml/h, and controlling the spinning time to be 3-5 h to obtain a metal cobalt salt nanofiber membrane;
step three: preparing cobaltosic oxide nano-fibers. Drying the spun metal cobalt salt fiber membrane in a vacuum drying oven (50-80 ℃) for 8 hours, and calcining at 300-500 ℃ for 3-5 hours; then naturally cooling to room temperature to obtain cobaltosic oxide nano-fibers;
step four: preparing an interlayer: mixing the cobaltosic oxide nano-fiber material obtained in the third step, a conductive agent and a binder polyvinylidene fluoride (PVDF) under the protection of argon atmosphere, dripping a N-methyl pyrrolidone solvent to prepare a slurry, coating the slurry on a diaphragm, airing and cutting to obtain a functional interlayer applied to the lithium-sulfur battery;
wherein the material ratio is that cobaltosic oxide nano-fiber material: conductive agent: 7-8.5 of binder: 0.5-2: 1, the conductive agent is acetylene black or Super P; the coating thickness of the sizing agent on the diaphragm is 0.01-0.1 mm.
The diaphragm is made of polypropylene microporous film.
The above functional Co for lithium-sulfur battery3O4The process for preparing the barrier, wherein the raw materials involved are commercially available, is well known to those skilled in the art.
The invention has the substantive characteristics that:
the invention prepares fiber nanometer cobaltosic oxide by an electrostatic spinning process, in particular to cobaltosic oxide in situ grows on a nano wire by heat treatment of cobalt nitrate and PVP blended fiber to form a net-shaped structure. The cobaltosic oxide fiber is used as an interlayer of the lithium-sulfur battery, so that lithium polysulfide can be effectively adsorbed in the charge-discharge cycle process, the shuttle effect in the lithium-sulfur battery is solved, and the volume expansion effect in the cycle process is relieved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention prepares Co by electrostatic spinning3O4The nanofiber membrane has abundant network structure morphology, and the calcined Co3O4The nanofiber well keeps a one-dimensional nano structure, and the nanofiber has a large specific surface area and rich pores. Co3O4The shuttling effect of polysulfides is prevented by the property of adsorbing polysulfides by themselves. In addition, electrostatic spinning is a new technology, which can prepare nano-sized filaments with the minimum diameter of 1 nm, and is the only method for directly and continuously preparing polymer nano-fibers at present3O4Friendly environment, low cost, rich resources, Co3O4The lithium-sulfur battery has good thermal stability and mechanical property, the absorption characteristic in electrolyte is improved, the diffusion of polysulfide is influenced, the electrochemical property of the lithium-sulfur battery is further improved, the charging and discharging efficiency is close to 100% under the current density of 0.1C, 0.2C and 0.5C, 1200mAh/g still exists after 100 cycles, the retention rate is 84%, and the lithium-sulfur battery has important reference value for realizing the industrialization of the lithium-sulfur battery.
Drawings
FIG. 1 shows Co obtained in example 13O4An X-ray diffraction (XRD) pattern of the fibrous functional barrier layer;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the metal cobalt salt fiber membrane prepared in example 1;
FIG. 3 shows Co obtained in example 13O4Multiplying power diagram of lithium-sulfur battery with fiber as interlayer
FIG. 4 shows a film obtained in example 1Co3O4And constant current charge and discharge diagram of the lithium-sulfur battery with the fiber as the interlayer under 0.1 ℃.
FIG. 5 shows Co obtained in example 13O4Cycle performance profile at 0.1C for lithium sulfur cells with fiber as the separator.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1:
step one, preparing electrostatic spinning precursor solution:
0.3g Co (NO) was added to the beaker3)2·6H2Stirring O, 5ml of ethanol and 5ml of N, N-Dimethylformamide (DMF) for 20min, adding 0.7g of PVP into the mixed solution, stirring for 1h, and finally performing ultrasonic treatment in an ultrasonic machine for 1h to obtain the electrostatic spinning precursor solution.
Step two, preparing the metal cobalt salt nanofiber membrane:
and adding the mixed solution into an injector, controlling the working voltage to be 20KV, adjusting the distance between a receiver and a spinning needle to be 15cm, and adjusting the outflow speed of the solution to be 0.5ml/h to obtain the metal cobalt salt nanofiber membrane.
Third step, Co3O4Preparing the nano-fibers:
the spun metal cobalt salt fiber membrane was dried in a vacuum drying oven (70 ℃ C.) for 10 hours and then calcined in a muffle furnace at 500 ℃ C. for 5 hours. Then naturally cooling to room temperature to obtain Co3O4And (3) nano fibers.
Fourthly, preparing an interlayer:
the obtained Co3O4The material, conductive agent and binder are placed in a mortar according to the mass ratio of 8: 1, ground and mixed into slurry, the slurry is evenly coated on a polypropylene microporous membrane (PP (Celgard-2400) diaphragm by scraping, and the coating thickness of the slurry is0.05mm), drying for 2h at 60 ℃, cutting to obtain an interlayer, taking sulfur as a positive electrode and a metal lithium sheet as a negative electrode, adding an electrolyte, and assembling in a glove box filled with argon to obtain a lithium-sulfur battery to obtain a button CR2032 half-battery.
Wherein, fig. 1 is an X-ray diffraction (XRD) pattern of the barrier material prepared in example 1, diffraction peaks are shown in the following relation to JCPDS: 42-1467 cards, all hkl peaks can be pointed to pure Co with spinel3O4A structure. This shows that Co obtained by the electrospinning process of this experiment was subjected to dry-firing3O4The material was very pure. FIG. 2 is a Scanning Electron Microscope (SEM) image of a cobalt salt obtained by electrospinning. It can be seen from fig. 2 that the metal cobalt salt fiber membrane obtained by electrostatic spinning has a large fiber width, an obvious mesh gap structure, a rich network structure and a good micro-morphology, so that the phenomenon of polysulfide shuttling during charging and discharging can be reduced to a great extent when the metal cobalt salt fiber membrane is used as a functional interlayer of a battery, and the electrochemical performance of the battery is improved.
FIGS. 3 and 4 are Co prepared in example 13O4A rate plot for a lithium sulfur battery with the fiber as the separator and a constant current charge discharge plot at 0.1C. From FIG. 3, it can be seen that Co3O4The lithium-sulfur battery with the fiber as the interlayer has excellent rate performance under the rate of 0.1C, 0.2C and 0.5C, and the charge-discharge efficiency is close to 100%. From fig. 4, it can be seen that there are two plateaus around 2.3V and 2.1V, which are two reduction peaks common in lithium sulfur batteries. From the figure, the maximum discharge capacity is 1420mAh/g, and the nanofiber structure has large specific surface area and abundant pores, so that the absorption characteristic in the electrolyte is improved, the diffusion of polysulfide is influenced, and the electrochemical performance of the lithium-sulfur battery is improved.
FIG. 5 is a graph of the cycling performance at 0.1C for the material made in example 1. It can be seen from fig. 5 that the cell with such fibers as the separator has good cycling performance. Under the multiplying power of 0.1C, the initial capacity reaches 1420mAh/g, the capacity remained after 100 cycles is 1200mAh/g, and on the premise of keeping higher discharge capacity, good cycle performance is also ensured.
Example 2:
step one, preparing electrostatic spinning precursor solution:
0.3g Co (NO) was added to the beaker3)2·6H2And stirring O, 10ml of ethanol and 5ml of N, N-Dimethylformamide (DMF) for 20min, adding 1g of PVP into the mixed solution, stirring for 2h, and finally performing ultrasonic treatment in an ultrasonic machine for 1h to obtain the electrostatic spinning precursor solution.
Step two, preparing the metal cobalt salt nanofiber membrane:
and adding the mixed solution into an injector, controlling the working voltage to be 20KV, adjusting the distance between a receiver and a spinning needle to be 15cm, and adjusting the outflow speed of the solution to be 0.5ml/h to obtain the metal salt nanofiber membrane.
Third step, Co3O4Preparing the nano-fibers:
the spun metal cobalt salt fiber membrane was dried in a vacuum drying oven (70 ℃ C.) for 10 hours and then calcined in a muffle furnace at 500 ℃ C. for 5 hours. Then naturally cooling to room temperature to obtain Co3O4And (3) nano fibers.
Fourthly, assembling the battery:
the obtained Co3O4The material, a conductive agent and a binder are placed in a mortar according to the mass ratio of 8: 1, the mixture is ground and mixed into slurry, the slurry is evenly spread on a polypropylene microporous membrane (PP (Celgard-2400) diaphragm) in a scraping way, the drying is carried out for 2 hours at the temperature of 60 ℃, a partition layer is obtained by cutting, sulfur is used as a positive electrode, a metal lithium sheet is used as a negative electrode, an electrolyte is added, and the lithium-sulfur battery is assembled in a glove box filled with argon gas to obtain the button type CR2032 half-battery.
The lithium-sulfur battery prepared by the embodiment is subjected to a test of the charge-discharge cycle performance of the battery through a Newcastle disease (BTS) -5V5mA channel, the first discharge specific capacity can reach 1236mAh/g under the multiplying power of 0.1C, and the discharge specific capacity can still keep 960mAh/g after 100 cycles.
Example 3:
step one, preparing electrostatic spinning precursor solution:
0.3g Co (NO) was added to the beaker3)2·6H2O and 5ml ethanol and 5ml N, N-dimethyl methylAnd (3) stirring amide (DMF) for 20min, adding 0.7g of PVP into the mixed solution, stirring for 2h, and finally performing ultrasonic treatment in an ultrasonic machine for 1h to obtain the electrostatic spinning precursor solution.
Step two, preparing the metal cobalt salt nanofiber membrane:
and adding the mixed solution into an injector, controlling the working voltage to be 10KV, adjusting the distance between a receiver and a spinning needle to be 25cm, and adjusting the outflow speed of the solution to be 0.1ml/h to obtain the metal salt nanofiber membrane.
Third step, Co3O4Preparing the nano-fibers:
the spun metal cobalt salt fiber membrane was dried in a vacuum drying oven (70 ℃ C.) for 10 hours and then calcined in a muffle furnace at 500 ℃ C. for 5 hours. Then naturally cooling to room temperature to obtain Co3O4And (3) nano fibers.
Fourthly, assembling the battery:
the obtained Co3O4The material, a conductive agent and a binder are placed in a mortar according to the mass ratio of 8: 1, the mixture is ground and mixed into slurry, the slurry is evenly spread on a polypropylene microporous membrane (PP (Celgard-2400) diaphragm) in a scraping way, the drying is carried out for 2 hours at the temperature of 60 ℃, a partition layer is obtained by cutting, sulfur is used as a positive electrode, a metal lithium sheet is used as a negative electrode, an electrolyte is added, and the lithium-sulfur battery is assembled in a glove box filled with argon gas to obtain the button type CR2032 half-battery.
The lithium-sulfur battery prepared by the embodiment is subjected to a test of the charge-discharge cycle performance of the battery through a Newcastle disease (BTS) -5V5mA channel, the first discharge specific capacity can reach 1196mAh/g under the multiplying power of 0.1C, and the discharge specific capacity can still keep 996mAh/g after 100 cycles.
Example 4:
step one, preparing electrostatic spinning precursor solution:
0.3g Co (NO) was added to the beaker3)2·6H2Stirring O, 5ml of ethanol and 5ml of N, N-Dimethylformamide (DMF) for 20min, adding 0.7g of PVP into the mixed solution, stirring for 1h, and finally performing ultrasonic treatment in an ultrasonic machine for 1h to obtain the electrostatic spinning precursor solution.
Step two, preparing the metal cobalt salt nanofiber membrane:
and adding the mixed solution into an injector, controlling the working voltage to be 20KV, adjusting the distance between a receiver and a spinning needle to be 15cm, and adjusting the outflow speed of the solution to be 0.5ml/h to obtain the metal salt nanofiber membrane.
Third step, Co3O4Preparing the nano-fibers:
the spun metal cobalt salt fiber membrane was dried in a vacuum drying oven (70 ℃) for 10 hours and then calcined in a muffle furnace at 800 ℃ for 5 hours. Then naturally cooling to room temperature to obtain Co3O4And (3) nano fibers.
Fourthly, assembling the battery:
the obtained Co3O4The material, a conductive agent and a binder are placed in a mortar according to the mass ratio of 8: 1, the mixture is ground and mixed into slurry, the slurry is evenly spread on a polypropylene microporous membrane (PP (Celgard-2400) diaphragm) in a scraping way, the drying is carried out for 2 hours at the temperature of 60 ℃, a partition layer is obtained by cutting, sulfur is used as a positive electrode, a metal lithium sheet is used as a negative electrode, an electrolyte is added, and the lithium-sulfur battery is assembled in a glove box filled with argon gas to obtain the button type CR2032 half-battery.
The lithium-sulfur battery prepared by the embodiment is subjected to a test of the charge-discharge cycle performance of the battery through a Newcastle disease Virus BTS-5V5mA channel, the first discharge specific capacity can reach 1293mAh/g under the multiplying power of 0.1C, and the discharge specific capacity can still keep 978mAh/g after 100 cycles.
The invention is not the best known technology.
Claims (1)
1. A preparation method of a functional interlayer applied to a lithium-sulfur battery is characterized by comprising the following steps:
the method comprises the following steps: preparing electrostatic spinning precursor solution: mixing cobalt nitrate hexahydrate, ethanol and an N, N-dimethylformamide solution, stirring for 5-20 min, adding polyvinylpyrrolidone (PVP), continuously stirring for 1-2 h, and then performing ultrasonic treatment for 1-2 h by using an ultrasonic machine to obtain an electrostatic spinning precursor solution;
wherein, 0.1-1 g of cobalt nitrate hexahydrate, 2-10 ml of N, N-dimethylformamide and 0.1-3 g of polyvinylpyrrolidone (PVP) are added into 2-10 ml of ethanol;
step two: preparing a metal cobalt salt nanofiber membrane: adding the precursor solution into an injector, controlling the working voltage to be 10-20 KV, adjusting the distance between a receiver and a spinning needle to be 5-20 cm, controlling the outflow speed of the solution to be 0.2-0.8 ml/h, and controlling the spinning time to be 3-5 h to obtain a metal cobalt salt nanofiber membrane;
step three: preparing cobaltosic oxide nano fibers: drying the spun metal cobalt salt fiber membrane in a vacuum drying oven for 8 hours, and calcining at 300-500 ℃ for 3-5 hours; then naturally cooling to room temperature to obtain cobaltosic oxide nano-fibers;
step four: preparing an interlayer: mixing the cobaltosic oxide nano-fiber material obtained in the third step, a conductive agent and a binder polyvinylidene fluoride (PVDF) under the protection of argon atmosphere, dripping a N-methyl pyrrolidone solvent to prepare a slurry, coating the slurry on a diaphragm, airing and cutting to obtain a functional interlayer applied to the lithium-sulfur battery;
wherein the material ratio is cobaltosic oxide nano-fiber material: conductive agent: 7-8.5 of binder: 0.5-2: 1, the conductive agent is acetylene black or Super P; the coating thickness of the sizing agent on the diaphragm is 0.01-0.1 mm;
the diaphragm is made of a polypropylene microporous membrane.
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| CN109768284A (en) * | 2019-03-11 | 2019-05-17 | 江南大学 | A kind of lithium-sulfur cell standalone functionality interlayer and preparation method thereof |
| CN111416092B (en) * | 2020-03-13 | 2022-08-23 | 上海电力大学 | Lithium-sulfur battery diaphragm and preparation method and application thereof |
| CN113594415B (en) * | 2021-07-28 | 2022-06-17 | 贵州大学 | Sandwich independent positive electrode for inhibiting shuttle effect of lithium-sulfur battery and preparation method thereof |
| CN115425363A (en) * | 2022-07-04 | 2022-12-02 | 东华大学 | Preparation method and application of metal sulfur battery interlayer material |
| CN115602997A (en) * | 2022-10-13 | 2023-01-13 | 河北工业大学（Cn） | Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm |
| CN117334849B (en) * | 2023-11-20 | 2024-05-28 | 浙江大学 | Red phosphorus anode, preparation method thereof and application thereof in lithium ion battery |
| CN117895190A (en) * | 2024-03-12 | 2024-04-16 | 山东海化集团有限公司 | Lithium-sulfur battery interlayer material and preparation method and application thereof |
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| CN106848156A (en) * | 2017-03-07 | 2017-06-13 | 南京航空航天大学 | Lithium-sulfur cell diaphragm material and its application |
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| KR101618218B1 (en) * | 2014-09-26 | 2016-05-09 | 대한민국 | An Electrochemical Device Comprising The Nano-Fiber Membrane Cellulose And Preparation Method Thereof |
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| US20140093790A1 (en) * | 2012-09-28 | 2014-04-03 | Di-Jia Liu | Nanofibrous electrocatalysts |
| CN105332097A (en) * | 2015-10-23 | 2016-02-17 | 济南大学 | Preparation method for Co3O4-nanoparticle-loaded carbon fiber composite material and obtained product |
| CN106848156A (en) * | 2017-03-07 | 2017-06-13 | 南京航空航天大学 | Lithium-sulfur cell diaphragm material and its application |
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