CN110158200B - Porous carbon nanofiber, preparation method thereof and lithium-sulfur battery - Google Patents

Porous carbon nanofiber, preparation method thereof and lithium-sulfur battery Download PDF

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CN110158200B
CN110158200B CN201810290249.9A CN201810290249A CN110158200B CN 110158200 B CN110158200 B CN 110158200B CN 201810290249 A CN201810290249 A CN 201810290249A CN 110158200 B CN110158200 B CN 110158200B
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porous carbon
carbon nanofiber
pore
thousand
lithium
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CN110158200A (en
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李梦
胡卫国
蒲雄
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Beijing Institute of Nanoenergy and Nanosystems
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Beijing Institute of Nanoenergy and Nanosystems
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
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    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
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    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • 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 the field of lithium-sulfur batteries, and discloses porous carbon nanofiber, a preparation method thereof and a lithium-sulfur battery. A preparation method of porous carbon nanofiber comprises the following steps: (1) mixing a pore-forming agent, a surface dispersant, a carbon source and an organic solvent to obtain a spinning solution; (2) carrying out electrostatic spinning on the spinning solution to obtain carbon fibers; (3) carbonizing the carbon fiber, removing the pore-forming agent, washing and drying. The porous carbon nanofiber prepared by the method has good mechanical strength, high conductivity and a criss-cross network structure, and can be directly used as a good carrier of sulfur without a conductive agent and a binder. Meanwhile, the porous carbon nanofiber has a large specific surface area and strong adsorption capacity, and can relieve the dissolution of polysulfide in electrolyte. The lithium-sulfur battery prepared from the porous carbon nanofiber has excellent cycle performance and rate capability.

Description

Porous carbon nanofiber, preparation method thereof and lithium-sulfur battery
Technical Field
The invention relates to the field of lithium-sulfur battery materials, in particular to porous carbon nanofiber and a preparation method thereof, and a lithium-sulfur battery prepared from the porous carbon nanofiber.
Background
With the consumption of a large amount of fossil energy and the pollution to the environment, batteries play an important role as sustainable clean energy. At present, the lithium ion battery anode material cannot meet the practical requirement due to low capacity, and the theoretical specific capacity of the lithium sulfur battery anode material is up to 1675mAh/g, so the lithium sulfur battery anode material is a promising anode material. However, lithium sulfur batteries also face several problems: (1) an intermediate product, namely polysulfide, generated in the charging and discharging process is easily dissolved in the organic electrolyte, so that the utilization rate of the sulfur of the positive active material is reduced, and the cycle performance of the battery is attenuated; (2) the ionic and electronic conductivity of sulfur is extremely low; (3) the volume change of sulfur in the ion extraction process causes the structural damage of the electrode material and the capacity decline. The traditional lithium-sulfur battery anode material has complex manufacturing process and needs to be accurately controlled. Inactive materials such as conductive agents and binders required in the coating process reduce the relative content of sulfur as an active material, and thus the energy density is reduced. Meanwhile, the binder is easy to lose efficacy in the charging and discharging processes of the battery, so that the active substance is separated from the current collector, the multiplying power performance of the battery is poor, and the development of the lithium-sulfur battery is limited.
Disclosure of Invention
The porous carbon nanofiber prepared by the method has good mechanical strength, high conductivity and a criss-cross network structure, and can be directly used as a good carrier of sulfur without a conductive agent and a binder. Meanwhile, the porous carbon nanofiber has a large specific surface area and strong adsorption capacity, and can relieve the dissolution of polysulfide in electrolyte. The lithium-sulfur battery prepared from the porous carbon nanofiber has excellent cycle performance and rate capability.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a porous carbon nanofiber, the method comprising the steps of:
(1) mixing a pore-forming agent, a surface dispersant, a carbon source and an organic solvent to obtain a spinning solution;
(2) carrying out electrostatic spinning on the spinning solution to obtain carbon fibers;
(3) carbonizing the carbon fiber, removing the pore-forming agent, washing and drying.
Preferably, the pore-forming agent is silica microspheres, zinc oxide or calcium carbonate; preferably, the particle size of the pore-forming agent is 7-30 nm.
Preferably, the surface dispersant is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate and polyoxyethylene polyoxypropylene ether block copolymer.
Preferably, the carbon source is one or more of polyacrylonitrile, polyvinylpyrrolidone, polyimide and phenolic resin.
Preferably, the organic solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide and dimethylsulfoxide.
Preferably, the feeding weight ratio of the pore-forming agent, the surface dispersant, the carbon source and the organic solvent is (0.3-0.9): (0.9-2.7): 1: (5-15).
Preferably, the mixing conditions include: the mixing temperature is 40-80 ℃, and the mixing time is 2-16 h.
Preferably, the electrospinning conditions include: the voltage is 15-30kV, the distance between the collecting plate and the needle is 15-25cm, and the advancing speed of the propulsion pump is 0.8-1.2 mL/h.
Preferably, the carbonization conditions include: the carbonization gas is argon or nitrogen, the carbonization temperature is 800-1200 ℃, the heating rate is 2-5 ℃/min, and the carbonization time is 6-14 h.
Preferably, the pore-forming agent is removed by soaking the carbonized carbon fiber in a hydrofluoric acid solution or a sodium hydroxide solution.
Preferably, after step (2) and before step (3), pre-oxidation is also performed.
Preferably, the pre-oxidation conditions include: the temperature is 200 ℃ and 220 ℃, the heating rate is 2-5 ℃/min, and the time is 1-2 h.
The second aspect of the invention provides the porous carbon nanofiber prepared by the method, wherein the porous carbon nanofiber has an average diameter of 500nm-2 μm, a porous structure and a specific surface area of 150-350m2(ii)/g, the average pore diameter is 8-35 nm.
In a third aspect, the invention provides a lithium-sulfur battery, wherein the battery comprises a positive electrode, a negative electrode and a separator, wherein the positive electrode contains the porous carbon nanofiber.
According to the invention, the pore-forming agent, the surface dispersant, the carbon source and the organic solvent are used in a combined manner, and the content relationship between the pore-forming agent, the surface dispersant, the carbon source and the organic solvent is limited, so that the prepared porous carbon nanofiber has the advantages of uniform distribution, criss-cross network structure and no agglomeration phenomenon as shown in fig. 1 and fig. 2; each carbon nanofiber has a porous structure, the average pore diameter is 8-35nm, and the average pore diameter can reach 150-350m2Specific surface area in g. Therefore, the carbon nanofiber has better mechanical property and high conductivity, can be directly used as a good carrier of sulfur, does not need a conductive agent and a binding agent, does not need a coating process, has high mechanical strength, and has low cost and simple and convenient preparation method compared with the lithium sulfur battery anode material using the binding agent, the conductive agent and a current collector, and can be industrially produced in a large scale.
Meanwhile, the porous carbon nanofiber has a large specific surface area and strong adsorption capacity, can adsorb polysulfide, inhibit shuttle effect of polysulfide, can relieve dissolution of polysulfide in electrolyte, can be used as a good carrier of sulfur, and the prepared flexible porous carbon fiber can be used as a carrier of a positive active substance of a lithium-sulfur battery, and shows excellent electrochemical properties, such as excellent cycle performance, rate capability and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a porous carbon nanofiber according to the present invention;
FIG. 2 is an enlarged scanning electron micrograph of a porous carbon nanofiber according to the present invention;
FIG. 3 is a nitrogen adsorption/desorption curve of the porous carbon fiber of the present invention;
FIG. 4 is a scanning electron micrograph of a carbon nanofiber according to comparative example 1;
fig. 5 is a graph of 100 cycles performance of a lithium sulfur battery assembled with a porous carbon nanofiber flexible positive electrode material at a current density of 0.25C (1C 1672 mA/g);
fig. 6 is a graph of 100 cycles of cycling performance of a lithium sulfur battery assembled with a porous carbon nanofiber flexible positive electrode material at a current density of 1C (1672 mA/g);
fig. 7 is a graph of rate performance of a lithium sulfur battery assembled with a porous carbon nanofiber flexible positive electrode material.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of porous carbon nanofiber, which comprises the following steps:
(1) mixing a pore-forming agent, a surface dispersant, a carbon source and an organic solvent to obtain a spinning solution;
(2) carrying out electrostatic spinning on the spinning solution to obtain carbon fibers;
(3) carbonizing the carbon fiber, removing the pore-forming agent, washing and drying.
According to the method of the invention, the pore-forming agent can be silica microspheres, zinc oxide or calcium carbonate. The particle size of the pore-forming agent can be 7-30nm, and the porous carbon nanofiber prepared from the pore-forming agent in the particle size range has a good porous structure and uniform pore diameter.
According to the method of the present invention, the silica microspheres may be commercially available monodisperse amino silica microspheres or core-shell silica magnetic microspheres, or the like.
According to the method of the present invention, the surface dispersant may be one or more of sodium dodecylbenzene sulfonate, sodium dodecylsulfate, and polyoxyethylene polyoxypropylene ether block copolymer. The surface dispersing agent, the pore-forming agent, the carbon source and the organic solvent have synergistic effect, so that the prepared porous carbon nanofiber is uniformly distributed and has a criss-cross network structure.
According to the method of the present invention, the carbon source may be one or more of polyacrylonitrile, polyvinylpyrrolidone, polyimide, and phenol resin. Wherein the polyacrylonitrile has a number average molecular weight of 50 to 300 ten thousand, preferably 150 to 200 ten thousand; the polyvinylpyrrolidone has a number average molecular weight of 50 to 300 ten thousand, preferably 150 to 200 ten thousand; the number average molecular weight of the polyimide is 50 to 300 ten thousand, preferably 150 to 200 ten thousand; the number average molecular weight of the phenolic resin is 50 to 300 ten thousand, preferably 150 to 200 ten thousand.
According to the method of the present invention, the organic solvent may be one or more of N, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, and dimethylsulfoxide.
According to the method, the feeding weight ratio of the pore-forming agent, the surface dispersant, the carbon source and the organic solvent is (0.3-0.9): (0.9-2.7): 1: (5-15), the porous carbon nanofiber prepared in the feeding proportion range has large specific surface area and strong adsorption capacity, and the porous carbon nanofiber is uniformly distributed.
According to the method of the present invention, the mixing conditions are for the purpose of sufficiently contacting the pore-forming agent, the surface dispersant, the carbon source and the organic solvent, for example, the mixing conditions may include, but are not limited to: the mixing temperature is 40-80 ℃, and the mixing time is 2-16 h.
According to the process of the invention, the conditions of electrospinning, which are aimed at causing final solidification into fibers, include, but are not limited to: the voltage is 15-30kV, the distance between the collecting plate and the needle is 15-25cm, and the advancing speed of the propulsion pump is 0.8-1.2 mL/h. In the invention, the electrostatic spinning method is convenient for industrial large-scale production, and the prepared carbon fiber has large area and good flexibility and can be used as an unsupported electrode carrier for a lithium-sulfur battery.
According to the process of the invention, the carbonization conditions include, but are not limited to: the carbonization gas is argon or nitrogen, the carbonization temperature is 800-1200 ℃, the heating rate is 2-5 ℃/min, and the carbonization time is 6-14 h. In the present invention, if pre-oxidation is performed before carbonization, the temperature rise rate at the time of carbonization is preferably 4 to 5 ℃/min; if pre-oxidation is not performed before carbonization, the temperature increase rate during carbonization is preferably 2 to 3 ℃/min.
According to the method of the present invention, the pore-forming agent may be removed by immersing the carbonized carbon fiber in a hydrofluoric acid solution or a sodium hydroxide solution. The conditions of the soaking, such as soaking time, are not particularly limited, and the pore-forming agent can be removed.
According to the method of the present invention, after step (2) and before step (3), pre-oxidation may also be performed. Preferably, the conditions of the pre-oxidation may include, but are not limited to: the temperature is 200 ℃ and 220 ℃, the heating rate is 2-5 ℃/min, and the time is 1-2 h. In the present invention, the pre-oxidation step can stabilize the structure of the collected carbon fibers.
According to the method of the present invention, the drying conditions are aimed at obtaining porous carbon nanofibers, and the drying conditions may include, but are not limited to: the drying temperature is 100-120 ℃, and the drying time is 8-16 h.
According to the method of the present invention, the preparation method of the porous carbon nanofiber may include the steps of:
(1) mixing a pore-forming agent and a surface dispersant in an organic solvent, stirring, performing ultrasonic treatment by using a cell crusher, repeating the steps for multiple times, adding a carbon source, and stirring to obtain a spinning solution;
(2) carrying out electrostatic spinning on the spinning solution to obtain carbon fibers;
(3) carbonizing the carbon fiber, removing pore-forming agent, washing and drying, wherein before carbonizing, pre-oxidation is optionally carried out.
The second aspect of the invention provides the porous carbon nanofiber prepared by the method, wherein the porous carbon nanofiber has an average diameter of 500nm-2 μm, a porous structure and a specific surface area of 150-350m2(ii)/g, the average pore diameter is 8-35 nm.
In the invention, the porous carbon nanofiber is shown in fig. 1 and fig. 2, and it can be seen from the drawings that the porous carbon nanofiber has uniform diameter and rough surface, can be used as a three-dimensional conductive carrier of sulfur, is beneficial to the transmission of lithium ions and electrons in the electrochemical reaction process, and can better absorb liquid sulfur electrolyte and increase the quality of active substances due to the large three-dimensional space. In addition, the porous carbon nanofiber disclosed by the invention has excellent flexibility, can be used for a soft package battery cathode material carrier, and is a good choice as a lithium liquid sulfur battery cathode carrier.
In a third aspect, the invention provides a lithium-sulfur battery, wherein the battery comprises a positive electrode, a negative electrode and a separator, wherein the positive electrode contains the porous carbon nanofiber.
Specifically, the porous carbon nanofiber provided by the invention is used as a carrier of a cathode material.
The present invention will be described in detail below by way of examples.
In the examples below, silica microspheres were purchased from sigma aldrich trade ltd, lot SLBP 7956V;
sodium dodecylbenzenesulfonate was purchased from Beijing Taize Jia industries science and technology development Co., Ltd, and its batch was D1401036;
n, N-dimethylformamide was purchased from Beijing chemical reagent works, batch E1514039;
the cell crusher is purchased from Ningbo Xinzhi Biotechnology Co., Ltd, and has a model of SCIENTZ-IID;
polyacrylonitrile is purchased from Beijing Bailingwei science and technology Limited, and has the batch of LH80Q67 and the number average molecular weight of 150 ten thousand;
zinc oxide was purchased from shanghai teng quasisomic co ltd, and the batch was W12a 051;
the polyoxyethylene polyoxypropylene ether block copolymer was purchased from sigma aldrich trade ltd, and was manufactured in batch SLBL 1780V;
n-methyl pyrrolidone is purchased from chemical reagents of national drug group, Inc., with the batch number of 20170803;
the polyvinylpyrrolidone is purchased from Shanghai Aladdin Biotechnology GmbH, with the batch D1613027 and the number average molecular weight and the weight average molecular weight of 150 ten thousand;
the spinning machine is purchased from Beijing Jetpurren Biotech Co., Ltd, and has the model of ET-1334H;
the scanning electron microscope is purchased from Hitachi high and new technology Co., Ltd, and the model is Hitachi SU 8020;
the specific surface area analyzer was purchased from macrmericek instruments ltd under model ASAP 2020.
Example 1
(1) Preparation of porous carbon nanofibers
Mixing 0.69g of silicon dioxide microspheres with the particle size of 7nm and 2.07g of sodium dodecyl benzene sulfonate in 18mL of N, N-dimethylformamide organic solvent, stirring the solution for 10min, performing ultrasonic treatment for 30min by using a cell crusher, and performing ultrasonic treatment for 30min after the solution is uniformly dispersed twice, namely stirring again for 10 min. Then, 1.8g of polyacrylonitrile was added, and the mixture was heated and stirred at 70 ℃ for 12 hours until the solution became a viscous spinning solution which was homogeneous and free from insoluble matter.
The spinning solution was transferred to a 20mL disposable syringe, the type of the spinning needle of the spinning machine was 21, and the syringe needle was connected to the positive high pressure of the spinning machine. The aluminum foil is a spinning collecting plate and is connected with negative high pressure. The distance between the collecting plate and the needle head is 20cm, the spinning voltage is 15kV, and the advancing speed of the propulsion pump is 1.0mL/h, so that the carbon fiber is obtained.
And (3) stripping the carbon fibers collected by spinning from the collecting plate, transferring the carbon fibers into a muffle furnace for pre-oxidation, raising the temperature to 200 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 1 h. Carrying out high-temperature carbonization treatment on the pre-oxidized carbon fiber, wherein the carbonization treatment conditions comprise: the flow rate of argon is 100sccm, then the temperature is raised to 1100 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 12h and then the temperature is naturally reduced. And finally, soaking the carbonized carbon fibers into 10 wt% of hydrofluoric acid to remove the silicon dioxide pore forming agent, washing the carbon fibers with deionized water by a suction filtration method, and drying for 12 hours at 110 ℃ under a vacuum condition to obtain the porous carbon nanofiber.
(2) And (3) performing characterization and nitrogen adsorption and desorption tests on the obtained porous carbon nanofiber:
the obtained porous carbon nanofiber is observed under a scanning electron microscope to obtain a scanning electron microscope image as shown in fig. 1 and an enlarged scanning electron microscope image as shown in fig. 2. As can be seen from FIG. 1, the porous carbon nanofibers are distributed in a layered, staggered and interlaced manner, and the carbon fibers have uniform diameters and rough surfaces. As can be seen from fig. 2, the average diameter of the carbon nanofibers is 900nm, and the fibers have a porous structure.
Carrying out nitrogen adsorption and desorption curves on the porous carbon nanofibers: after weighing the mass of the sample, it was degassed by heating under vacuum at 250 ℃ for 4h, and the lost mass was again weighed, under vacuum conditions of 500. mu. mHg (about 0.67bar), and during the analytical test the sample was placed in a liquid nitrogen atmosphere. The specific surface area analyzer was used to calculate the specific surface area, and a nitrogen adsorption/desorption curve as shown in fig. 3 was obtained, and as can be seen from fig. 3, the nitrogen adsorption/desorption curve of the prepared porous carbon fiber belongs to a typical iv-type curve. There is a clear H3 hysteresis loop indicating the presence of mesopores (2-50nm) within the hierarchical porous carbon (IUPAC classification) and at a higher relative pressure range (P/P)00.7-1.0), the adsorption-desorption curve has a clear upward trend, which is caused by capillary condensation. According to the calculation of the pore size distribution of BJH (the Barrett-Joyner-Halenda), the specific surface area of the porous carbon fiber is 275.5m2In terms of/g, the mean pore diameter is 8.8 nm.
Example 2
(1) Preparation of porous carbon nanofibers
0.69g of zinc oxide with the particle size of 7nm and 2.07g of polyoxyethylene polyoxypropylene ether block copolymer are mixed in 18mL of N-methylpyrrolidone organic solvent, the solution is stirred for 10min, then ultrasonic treatment is carried out for 30min by using a cell crusher, the solution is uniformly dispersed by carrying out the ultrasonic treatment twice, namely stirring is carried out again for 10min, and the ultrasonic treatment is carried out for 30 min. Then, 1.8g of polyvinylpyrrolidone was added, and the mixture was heated and stirred at 70 ℃ for 12 hours until the solution became a uniform and insoluble viscous spinning solution.
The spinning solution was transferred to a 20mL disposable syringe, the type of the spinning needle of the spinning machine was 21, and the syringe needle was connected to the positive high pressure of the spinning machine. The aluminum foil is a spinning collecting plate and is connected with negative high pressure. The distance between the collecting plate and the needle head is 25cm, the spinning voltage is 30kV, and the advancing speed of the propulsion pump is 1.2mL/h, so that the carbon fiber is obtained.
And (3) stripping the carbon fibers collected by spinning from the collecting plate, transferring the carbon fibers into a muffle furnace for pre-oxidation, raising the temperature to 200 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 1 h. Carrying out high-temperature carbonization treatment on the pre-oxidized carbon fiber, wherein the carbonization treatment conditions comprise: the flow rate of argon is 100sccm, then the temperature is raised to 1100 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 12h and then the temperature is naturally reduced. And finally, soaking the carbonized carbon fiber into a hydrochloric acid solution to remove a zinc oxide pore-forming agent, washing the carbon fiber with deionized water by a suction filtration method, and drying for 12 hours at 110 ℃ under a vacuum condition to obtain the porous carbon nanofiber.
(2) And (3) performing characterization and nitrogen adsorption and desorption tests on the obtained porous carbon nanofiber:
characterization was performed according to the method of example 1 to obtain porous carbon nanofibers similar to those shown in fig. 1 and 2, the porous carbon nanofibers having an average diameter of 900 nm.
The nitrogen adsorption and desorption test was carried out in accordance with the method of example 1, and the specific surface area of the porous carbon fiber was calculated to be 190.3m2In terms of/g, the mean pore diameter is 8.2 nm.
Example 3
Mixing 0.3g of silicon dioxide microspheres with the particle size of 7nm and 0.9g of sodium dodecyl benzene sulfonate in 5mL of N, N-dimethylformamide organic solvent, stirring the solution for 10min, performing ultrasonic treatment for 30min by using a cell crusher, and performing ultrasonic treatment for 30min after the solution is uniformly dispersed twice, namely stirring again for 10 min. Then 1g of polyacrylonitrile was added, and the mixture was heated and stirred at 70 ℃ for 12 hours until the solution became a uniform and insoluble viscous spinning solution.
The spinning solution was transferred to a 20mL disposable syringe, the type of the spinning needle of the spinning machine was 21, and the syringe needle was connected to the positive high pressure of the spinning machine. The aluminum foil is a spinning collecting plate and is connected with negative high pressure. The distance between the collecting plate and the needle head is 15cm, the spinning voltage is 25kV, and the advancing speed of the propulsion pump is 0.8mL/h, so that the carbon fiber is obtained.
And (3) stripping the carbon fibers collected by spinning from the collecting plate, transferring the carbon fibers into a muffle furnace for pre-oxidation, raising the temperature to 200 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 1 h. Carrying out high-temperature carbonization treatment on the pre-oxidized carbon fiber, wherein the carbonization treatment conditions comprise: the flow rate of nitrogen is 100sccm, then the temperature is raised to 1100 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 12h and then the temperature is naturally reduced. And finally, soaking the carbonized carbon fibers into 10 wt% of hydrofluoric acid to remove the silicon dioxide pore forming agent, washing the carbon fibers with deionized water by a suction filtration method, and drying for 12 hours at 110 ℃ under a vacuum condition to obtain the porous carbon nanofiber.
(2) And (3) performing characterization and nitrogen adsorption and desorption tests on the obtained porous carbon nanofiber:
characterization was performed according to the method of example 1 to obtain a structure similar to that shown in fig. 1 and 2, with the porous carbon nanofibers having an average diameter of 500 nm.
The nitrogen adsorption and desorption test was carried out in accordance with the method of example 1, and the specific surface area of the porous carbon fiber was calculated to be 166.7m2In terms of/g, the mean pore diameter is 8.2 nm.
Example 4
Mixing 0.9g of silicon dioxide microspheres with the particle size of 7nm and 2.7g of sodium dodecyl benzene sulfonate in 15mL of N, N-dimethylformamide organic solvent, stirring the solution for 10min, performing ultrasonic treatment for 30min by using a cell crusher, and performing ultrasonic treatment for 30min after the solution is uniformly dispersed twice, namely stirring again for 10 min. Then 1g of polyacrylonitrile was added, and the mixture was heated and stirred at 70 ℃ for 12 hours until the solution became a uniform and insoluble viscous spinning solution.
The spinning solution was transferred to a 20mL disposable syringe, the type of the spinning needle of the spinning machine was 21, and the syringe needle was connected to the positive high pressure of the spinning machine. The aluminum foil is a spinning collecting plate and is connected with negative high pressure. The distance between the collecting plate and the needle head is 20cm, the spinning voltage is 15kV, and the advancing speed of the propulsion pump is 1.0mL/h, so that the carbon fiber is obtained.
Stripping the carbon fibers collected by spinning from the collecting plate, and carrying out high-temperature carbonization treatment, wherein the carbonization treatment conditions comprise: the flow rate of argon is 100sccm, then the temperature is raised to 1100 ℃ at the heating rate of 2 ℃/min, and the temperature is preserved for 12h and then the temperature is naturally reduced. And finally, soaking the carbonized carbon fibers into 10 wt% of hydrofluoric acid to remove the silicon dioxide pore forming agent, washing the carbon fibers with deionized water by a suction filtration method, and drying for 12 hours at 110 ℃ under a vacuum condition to obtain the porous carbon nanofiber.
(2) And (3) performing characterization and nitrogen adsorption and desorption tests on the obtained porous carbon nanofiber:
characterization was performed according to the method of example 1 to obtain a structure similar to that shown in fig. 1 and 2, with the porous carbon nanofibers having an average diameter of 1 μm.
The nitrogen adsorption and desorption test was carried out in accordance with the method of example 1, and the specific surface area of the porous carbon fiber was calculated to be 189.6m2In terms of/g, the mean pore diameter is 8.8 nm.
Comparative example 1
According to the method of the embodiment, different from the method that sodium dodecyl benzene sulfonate is not used, agglomeration phenomenon is easy to occur in a solvent, so that a needle head is easy to block during solution spinning, spinning can not be carried out for a long time, and blocks are easy to occur on the surface of the obtained carbon fiber.
The characterization was performed according to the method of example 1, and the results are shown in FIG. 4. it can be seen from FIG. 4 that the pore structure distribution on the carbon fiber is very uneven and the diameter is not uniform.
Comparative example 2
Mixing 0.2g of silicon dioxide microspheres with the particle size of 7nm and 0.9g of sodium dodecyl benzene sulfonate in 5mL of N, N-dimethylformamide organic solvent, stirring the solution for 10min, performing ultrasonic treatment for 30min by using a cell crusher, and performing ultrasonic treatment for 30min after the solution is uniformly dispersed twice, namely stirring again for 10 min. Then 1g of polyacrylonitrile was added, and the mixture was heated and stirred at 70 ℃ for 12 hours until the solution became a uniform and insoluble viscous spinning solution.
The spinning solution was transferred to a 20mL disposable syringe, the type of the spinning needle of the spinning machine was 21, and the syringe needle was connected to the positive high pressure of the spinning machine. The aluminum foil is a spinning collecting plate and is connected with negative high pressure. The distance between the collecting plate and the needle head is 20cm, the spinning voltage is 15kV, and the advancing speed of the propulsion pump is 1.0mL/h, so that the carbon fiber is obtained.
And (3) stripping the carbon fibers collected by spinning from the collecting plate, transferring the carbon fibers into a muffle furnace for pre-oxidation, raising the temperature to 200 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 1 h. Carrying out high-temperature carbonization treatment on the pre-oxidized carbon fiber, wherein the carbonization treatment conditions comprise: the flow rate of argon is 100sccm, then the temperature is raised to 1100 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 12h and then the temperature is naturally reduced. And finally, soaking the carbonized carbon fibers into 10 wt% of hydrofluoric acid to remove the silicon dioxide pore forming agent, washing the carbon fibers with deionized water by a suction filtration method, and drying for 12 hours at 110 ℃ under a vacuum condition to obtain the porous carbon nanofiber.
(2) And (3) performing characterization and nitrogen adsorption and desorption tests on the obtained porous carbon nanofiber:
characterization was performed according to the method of example 1, with the porous carbon nanofibers having an average diameter of 400 nm.
The nitrogen adsorption and desorption test was carried out in accordance with the method of example 1, and the specific surface area of the porous carbon fiber was calculated to be 66.7m2In terms of/g, the mean pore diameter is 8.5 nm.
Comparative example 3
1g of silicon dioxide microspheres with the particle size of 7nm and 2.7g of sodium dodecyl benzene sulfonate are mixed in 15mL of N, N-dimethylformamide organic solvent, the solution is stirred for 10min, then the ultrasonic treatment is carried out for 30min by using a cell crusher, the solution is uniformly dispersed by carrying out the ultrasonic treatment twice, namely, the stirring is carried out again for 10min, and the ultrasonic treatment is carried out for 30 min. Then 1g of polyacrylonitrile was added, and the mixture was heated and stirred at 70 ℃ for 12 hours until the solution became a uniform and insoluble viscous spinning solution.
The spinning solution was transferred to a 20mL disposable syringe, the type of the spinning needle of the spinning machine was 21, and the syringe needle was connected to the positive high pressure of the spinning machine. The aluminum foil is a spinning collecting plate and is connected with negative high pressure. The distance between the collecting plate and the needle head is 20cm, the spinning voltage is 15kV, and the advancing speed of the propulsion pump is 1.0mL/h, so that the carbon fiber is obtained. The yarn blockage of the needle head is easy to occur during spinning.
And (3) stripping the carbon fibers collected by spinning from the collecting plate, transferring the carbon fibers into a muffle furnace for pre-oxidation, raising the temperature to 200 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 1 h. Carrying out high-temperature carbonization treatment on the pre-oxidized carbon fiber, wherein the carbonization treatment conditions comprise: the flow rate of argon is 100sccm, then the temperature is raised to 1100 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 12h and then the temperature is naturally reduced. And finally, soaking the carbonized carbon fibers into 10 wt% of hydrofluoric acid to remove the silicon dioxide pore forming agent, washing the carbon fibers with deionized water by a suction filtration method, and drying for 12 hours at 110 ℃ under a vacuum condition to obtain the porous carbon nanofiber.
(2) And (3) performing characterization and nitrogen adsorption and desorption tests on the obtained porous carbon nanofiber:
the porous carbon nanofibers are characterized by the method of example 1, the diameters of the porous carbon nanofibers are not uniform, the diameters are distributed in the range of 300nm-1 μm, and the surfaces of the carbon fibers are not smooth and are easy to form raised blocks.
The nitrogen adsorption and desorption test was carried out in accordance with the method of example 1, and the specific surface area of the porous carbon fiber was calculated to be 50.8m2In terms of/g, the mean pore diameter is 8.9 nm.
Test example 1
(1) Preparation of polysulfide electrolyte
1mol/L of lithium bis (trifluoromethanesulfonyl) imide and 0.5mol of lithium nitrate are added to a mixed solution of 1, 3-dioxolane and ethylene glycol dimethyl ether (volume ratio is 1: 1). Pouring sulfur and lithium sulfide with a molar ratio of 5:1 into the solution, then stirring in an oil bath for 24 hours at the temperature of 60 ℃ until the solution is uniformly stirred to obtain Li with the sulfur concentration of 2mol/L2S6Polysulfide electrolyte.
(2) Assembled lithium-sulfur button battery
A C2032 button cell was assembled in a glove box filled with argon, having a water content and an oxygen content of less than 0.1 ppm. The porous carbon nanofibers obtained in example 1 were punched into disks with a diameter of 1.2cm and a mass of 2mg, and the polysulfide electrolyte was dropped onto the disks at a ratio of 15 μ L/mg as a positive electrode of a lithium-sulfur battery, a porous membrane Celgard 2400 as a separator, and metal lithium as a battery negative electrode, to assemble a lithium-sulfur button battery.
(3) Charge and discharge cycle test
The lithium-sulfur button cell is discharged to 1.6V, and then is charged and discharged circularly between 1.6V and 2.8V. The specific discharge capacity calculation for lithium sulfur batteries is based on the mass of the positive electrode active material, sulfur.
(a) The first specific discharge capacity and the specific discharge capacity after 100 cycles of the battery were measured at a current density of 0.25C (1C: 1672mA/g), and the results are shown in fig. 5, and it can be seen from fig. 5 that the first specific discharge capacity was 924.6mAh/g, the specific discharge capacity after 100 cycles was 709.5mAh/g, and the capacity retention rate was 84.3% (compared with the second specific discharge capacity).
(b) Under the current density of 1C (1C is 1672mA/g), the first discharge specific capacity and the discharge specific capacity after 100 cycles of the battery are detected, and the result is shown in FIG. 6, and as can be seen from FIG. 6, the first discharge specific capacity is 715.6mAh/g, the specific capacity after 100 cycles of the battery is 510.2mAh/g, and the capacity retention rate is 82% (compared with the second cycle discharge specific capacity).
(c) After 24 times of rate discharge at room temperature, the capacity is kept at 641.1mAh/g at a large rate of 1C, after 30 times of rate discharge, the capacity is kept at 572.8mAh/g at a large rate of 2C, and when the current density returns to a small rate of 0.25C again, the capacity is 761.5mAh/g, as shown in FIG. 7.
Test examples 2 to 4
The procedure of test example 1 was followed except that the porous carbon nanofibers of example 1 were replaced with the porous carbon nanofibers of examples 2 to 4, and the results were similar to those of test example 1.
Test comparative example 1
The method of test example 1 was followed except that the porous carbon nanofiber of example 1 was replaced with the porous carbon nanofiber of comparative example 1.
Under the current density of 0.25C (1C: 1672mA/g), the initial discharge specific capacity is 734.7mAh/g, the specific capacity after 100 cycles is 513.5mAh/g, and the capacity retention rate is 89% (compared with the second cycle discharge specific capacity).
Under the current density of 1C (1C: 1672mA/g), the initial discharge specific capacity is 583.8mAh/g, the specific capacity after 100 cycles is 412.4mAh/g, and the capacity retention rate is 73.4% (compared with the second cycle discharge specific capacity).
Test comparative example 2
The method of test example 1 was followed except that the porous carbon nanofiber of example 1 was replaced with the porous carbon nanofiber of comparative example 2.
Under the current density of 0.25C (1C: 1672mA/g), the initial discharge specific capacity is 741.7mAh/g, the specific capacity after 100 cycles is 534.9mAh/g, and the capacity retention rate is 90.6% (compared with the second cycle discharge specific capacity).
Under the current density of 1C (1C: 1672mA/g), the initial discharge specific capacity is 608.2mAh/g, the specific capacity after 100 cycles is 440.8mAh/g, and the capacity retention rate is 76.3% (compared with the second cycle discharge specific capacity).
Test comparative example 3
The method of test example 1 was followed except that the porous carbon nanofiber of example 1 was replaced with the porous carbon nanofiber of comparative example 3.
Under the current density of 0.25C (1C: 1672mA/g), the initial discharge specific capacity is 820.4mAh/g, the specific capacity after 100 cycles is 618.5mAh/g, and the capacity retention rate is 81.2% (compared with the second cycle discharge specific capacity).
Under the current density of 1C (1C is 1672mA/g), the initial discharge specific capacity is 663.9mAh/g, the specific capacity after 100 cycles is 406.2mAh/g, and the capacity retention rate is 73.3% (compared with the second cycle discharge specific capacity).
As can be seen from examples 1 to 4 and comparative examples 1 to 3, the porous carbon nanofibers are uniformly distributed, have a criss-cross network structure, and are free of agglomeration; each carbon nanofiber has a porous structure, the average pore diameter is 8-35nm, and the average pore diameter can reach 150-350m2The specific surface area per gram, namely the porous carbon nanofiber has larger specific surface area and strong adsorption capacity. In contrast, in the reference 1 (without using a surfactant), agglomeration phenomenon is likely to occur in a solvent, so that a needle is easily blocked during solution spinning, spinning cannot be performed for a long time, lumps are likely to occur on the surface of the obtained carbon fiber, and the pore structure distribution on the carbon fiber is very uneven. Comparative examples 2 and 3 (the feeding weight ratio of pore-forming agent, surface dispersant, carbon source and organic solvent is not in the range defined by the invention) have the problems that the yarn blocking is easy to occur on the head during spinning, the diameter of the porous carbon nanofiber is uneven, the surface is not smooth and is easy to generate convex blocks, and the specific surface area is small.
As can be seen from test examples 1 to 4 and test comparative examples 1 to 3, the lithium sulfur battery prepared from the porous carbon nanofiber of the present invention has a first discharge specific capacity of 924.6mAh/g and a specific capacity of 709.5mAh/g after 100 cycles at a current density of 0.25C (1C: 1672 mA/g). Under the current density of 1C (1C: 1672mA/g) with large multiplying power, the first discharge specific capacity is 715.6mAh/g, and the specific capacity is 510.2mAh/g after 100 cycles of circulation. After 24 times of multiplying power discharge at room temperature, the capacity is kept at 641.1mAh/g at a large multiplying power of 1C, after 30 times of multiplying power discharge, the capacity is kept at 572.8mAh/g at a large multiplying power of 2C, and when the current density returns to a small multiplying power of 0.25C again, the capacity is 761.5mAh/g, and the excellent multiplying power performance is shown. Therefore, the lithium sulfur battery prepared by the porous carbon nanofiber has obviously excellent cycle performance and rate performance compared with the lithium sulfur battery prepared by the porous carbon nanofiber in the comparative examples 1-3.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. A preparation method of porous carbon nanofiber comprises the following steps:
(1) mixing a pore-forming agent, a surface dispersant, a carbon source and an organic solvent to obtain a spinning solution;
(2) carrying out electrostatic spinning on the spinning solution to obtain carbon fibers;
(3) carbonizing the carbon fiber, removing a pore-forming agent, washing and drying;
wherein the charging weight ratio of the pore-forming agent, the surface dispersant, the carbon source and the organic solvent is (0.3-0.9): (0.9-2.7): 1: (5-15);
wherein the pore-forming agent is silicon dioxide microspheres, zinc oxide or calcium carbonate;
the surface dispersant is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and polyoxyethylene polyoxypropylene ether block copolymer;
the organic solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide and dimethyl sulfoxide;
the carbon source is one or more of polyacrylonitrile, polyvinylpyrrolidone, polyimide and phenolic resin.
2. The method of claim 1, wherein the pore former has a particle size of 7-30 nm.
3. The method according to claim 1, wherein the polyacrylonitrile has a number average molecular weight of 50 to 300 ten thousand, and the polyvinylpyrrolidone has a number average molecular weight of 50 to 300 ten thousand; the number average molecular weight of the polyimide is 50 to 300 ten thousand; the phenolic resin has a number average molecular weight of 50 to 300 ten thousand.
4. The method according to claim 3, wherein the polyacrylonitrile has a number average molecular weight of 150 to 200 ten thousand, and the polyvinylpyrrolidone has a number average molecular weight of 150 to 200 ten thousand; the number average molecular weight of the polyimide is 150 to 200 ten thousand; the phenolic resin has a number average molecular weight of 150 to 200 ten thousand.
5. The method of claim 1, wherein the conditions of mixing comprise: the mixing temperature is 40-80 ℃, and the mixing time is 2-16 h.
6. The method of claim 1, wherein the electrospinning conditions comprise: the voltage is 15-30kV, the distance between the collecting plate and the needle is 15-25cm, and the advancing speed of the propulsion pump is 0.8-1.2 mL/h.
7. The method of claim 1, wherein the carbonizing conditions comprise: the carbonization gas is argon or nitrogen, the carbonization temperature is 800-1200 ℃, the heating rate is 2-5 ℃/min, and the carbonization time is 6-14 h.
8. The method according to claim 1, wherein the pore former is removed by immersing the carbonized carbon fiber in a hydrofluoric acid solution or a sodium hydroxide solution.
9. The method of claim 1, wherein after step (2) and before step (3), further performing a pre-oxidation.
10. The method of claim 9, wherein the pre-oxidation conditions comprise: the temperature is 200 ℃ and 220 ℃, the heating rate is 2-5 ℃/min, and the time is 1-2 h.
11. Porous carbon nanofiber prepared by the method as claimed in any one of claims 1 to 10, wherein the porous carbon nanofiber has an average diameter of 500nm to 2 μm, a porous structure, a specific surface area of 150-350m2(ii)/g, the average pore diameter is 8-35 nm.
12. A lithium-sulfur battery comprising a positive electrode, a negative electrode and a separator, wherein the positive electrode contains the porous carbon nanofiber according to claim 11.
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