CN110158200A - Porous carbon nanofiber and preparation method thereof and lithium-sulfur cell - Google Patents

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

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Publication number
CN110158200A
CN110158200A CN201810290249.9A CN201810290249A CN110158200A CN 110158200 A CN110158200 A CN 110158200A CN 201810290249 A CN201810290249 A CN 201810290249A CN 110158200 A CN110158200 A CN 110158200A
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porous carbon
carbon nanofiber
lithium
creating material
spinning
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CN110158200B (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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    • D—TEXTILES; PAPER
    • 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
    • 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
    • D—TEXTILES; PAPER
    • 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
    • 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
    • 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
    • D—TEXTILES; PAPER
    • 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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 present invention relates to lithium-sulfur cell fields, disclose porous carbon nanofiber and preparation method thereof and lithium-sulfur cell.A kind of preparation method of porous carbon nanofiber obtains spinning solution method includes the following steps: (1) mixes pore creating material, surface dispersant, carbon source and organic solvent；(2) spinning solution is subjected to electrostatic spinning, obtains carbon fiber；(3) carbon fiber is carbonized, removes pore creating material, washing and drying.Porous carbon nanofiber prepared by the present invention has good mechanical strength, high conductivity and criss-cross network structure, can be directly as the good carrier of sulphur, without conductive agent and binder.Meanwhile porous carbon nanofiber has biggish specific surface area and strong adsorption capacity, can alleviate the dissolution of polysulfide in the electrolytic solution.There is excellent cycle performance and high rate performance using lithium-sulfur cell prepared by porous carbon nanofiber of the invention.

Description

Porous carbon nanofiber and preparation method thereof and lithium-sulfur cell
Technical field
The present invention relates to lithium-sulfur cell Material Fields, and in particular to porous carbon nanofiber and preparation method thereof, and adopt The lithium-sulfur cell being prepared with above-mentioned porous carbon nanofiber.
Background technique
Consumption and pollution on the environment with a large amount of fossil energies, battery are played the part of as sustainable clean energy resource Drill critically important role.Currently, anode material for lithium-ion batteries is unable to satisfy real needs due to its low capacity, lithium sulphur Cell positive material theoretical specific capacity is up to 1675mAh/g, thus is a kind of very promising positive electrode.However, lithium sulphur electricity Pond equally faces Railway Project: (1) intermediate product generated in charge and discharge process, i.e. polysulfide are soluble in organic electrolyte, This reduces the utilization rate of positive active material sulphur, cycle performance of battery decaying；(2) ionic conductivity and electronic conduction of sulphur Rate is extremely low；(3) volume change that sulphur occurs during ion deinsertion causes electrode material structure to destroy, inducing capacity fading.Tradition Lithium sulfur battery anode material production process it is complicated, need to be precisely controlled.Conductive agent, binder for being needed in coating process etc. Inert matter reduces the relative amount of active material sulphur, thus energy density reduces.Binder is in battery charging and discharging simultaneously It is easy failure in the process, is detached from active material and collector, causes battery high rate performance to be deteriorated, limit the hair of lithium-sulfur cell Exhibition.
Summary of the invention
The purpose of the invention is to overcome the problems, such as that lithium-sulfur cell performance of the existing technology is bad, porous carbon is provided Nanofiber and preparation method thereof, and the lithium-sulfur cell being prepared using the porous carbon nanofiber, it is prepared by the present invention Porous carbon nanofiber has good mechanical strength, high conductivity and criss-cross network structure, can be directly as sulphur Good carrier, without conductive agent and binder.Meanwhile porous carbon nanofiber has biggish specific surface area and strong suction Attached ability can alleviate the dissolution of polysulfide in the electrolytic solution.The lithium sulphur prepared using porous carbon nanofiber of the invention Battery has excellent cycle performance and high rate performance.
To achieve the goals above, first aspect present invention provides a kind of preparation method of porous carbon nanofiber, should Method the following steps are included:
(1) pore creating material, surface dispersant, carbon source and organic solvent are mixed, obtains spinning solution；
(2) spinning solution is subjected to electrostatic spinning, obtains carbon fiber；
(3) carbon fiber is carbonized, removes pore creating material, washing and drying.
Preferably, the pore creating material is silicon dioxide microsphere, zinc oxide or calcium carbonate；Preferably, the grain of the pore creating material Diameter is 7-30nm.
Preferably, the surface dispersant is neopelex, lauryl sodium sulfate and polyoxyethylene polyoxy One of propylene ether block copolymers are a variety of.
Preferably, the carbon source be one of polyacrylonitrile, polyvinylpyrrolidone, polyimides and phenolic resin or It is a variety of.
Preferably, the organic solvent is n,N-Dimethylformamide, N-Methyl pyrrolidone, n,N-dimethylacetamide With one of dimethyl sulfoxide or a variety of.
Preferably, the feed weight ratio of the pore creating material, surface dispersant, carbon source and organic solvent is (0.3-0.9): (0.9-2.7): 1:(5-15).
Preferably, it is 40-80 DEG C that the mixed condition, which includes: mixing temperature, incorporation time 2-16h.
Preferably, it is 15-30kV that the condition of the electrostatic spinning, which includes: voltage, and the distance between collecting board and syringe needle is 15- 25cm, promoting the advanced speed of pump is 0.8-1.2mL/h.
Preferably, it is argon gas or nitrogen, carburizing temperature 800-1200 that the condition of the carbonization, which includes: the gas of carbonization, DEG C, heating rate is 2-5 DEG C/min, carbonization time 6-14h.
Preferably, the method for removing pore creating material is that the carbon fiber after carbonization is immersed in hydrofluoric acid solution or hydroxide In sodium solution.
Preferably, it after step (2) and before step (3), is also pre-oxidized.
Preferably, it is 200-220 DEG C that the condition of the pre-oxidation, which includes: temperature, and heating rate is 2-5 DEG C/min, time For 1-2h.
Second aspect of the present invention is provided by the porous carbon nanofiber of above-mentioned method preparation, wherein the porous carbon is received The average diameter of rice fiber is 500nm-2 μm, has porous structure, specific surface area 150-350m2/ g, average pore size 8- 35nm。
Third aspect present invention provides a kind of lithium-sulfur cell, wherein the battery includes the positive electrode, the negative electrode and the separator, wherein The anode contains above-mentioned porous carbon nanofiber.
The present invention limits containing between them by the way that pore creating material, surface dispersant, carbon source and organic solvent is applied in combination Magnitude relation is evenly distributed so that the porous carbon nanofiber of preparation is as depicted in figs. 1 and 2, has criss-cross network knot Structure, and the advantages of soilless sticking phenomenon；Each carbon nano-fiber all has porous structure, and average pore size 8-35nm can reach 150-350m2The specific surface area of/g.So that carbon nano-fiber has preferable mechanical performance, high conductivity, can directly make For the good carrier of sulphur, without conductive agent and binder, there is no need to coating process, high mechanical strength, relative to using The lithium sulfur battery anode material of binder, conductive agent and collector, lithium sulfur battery anode material of the invention is at low cost, preparation side Method is easy, can large-scale industrial production.
Meanwhile porous carbon nanofiber has biggish specific surface area and strong adsorption capacity, adsorbable polysulfide, suppression The shuttle effect of polysulfide processed can alleviate the dissolution of polysulfide in the electrolytic solution, can be used as the good carrier of sulphur, preparation Flexible, porous carbon fiber can be used for the carrier of lithium-sulphur cell positive electrode active material, show excellent chemical property, such as Excellent cycle performance and high rate performance etc..
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of porous carbon nanofiber of the invention；
Fig. 2 is the porous carbon nanofiber scanning electron microscope (SEM) photograph of amplification of the invention；
Fig. 3 is the nitrogen adsorption desorption curve of porous carbon fiber of the invention；
Fig. 4 is the scanning electron microscope (SEM) photograph of the carbon nano-fiber of comparative example 1；
Fig. 5 is the lithium-sulfur cell of porous carbon nanofiber flexibility positive electrode assembling in 0.25C (1C=1672mA/g) electricity 100 circle cycle performance figures under current density；
Fig. 6 is that the lithium-sulfur cell of porous carbon nanofiber flexibility positive electrode assembling is close in 1C (1C=1672mA/g) electric current 100 circle cycle performance figures under degree；
Fig. 7 is the high rate performance curve graph of the lithium-sulfur cell of porous carbon nanofiber flexibility positive electrode assembling.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention provides a kind of preparation method of porous carbon nanofiber, method includes the following steps:
(1) pore creating material, surface dispersant, carbon source and organic solvent are mixed, obtains spinning solution；
(2) spinning solution is subjected to electrostatic spinning, obtains carbon fiber；
(3) carbon fiber is carbonized, removes pore creating material, washing and drying.
According to the method for the present invention, the pore creating material can be silicon dioxide microsphere, zinc oxide or calcium carbonate.Wherein, institute The partial size for stating pore creating material can be 7-30nm, and the porous carbon nanofiber of the pore creating material preparation in the particle size range has preferable Porous structure, and aperture is more uniform.
According to the method for the present invention, silicon dioxide microsphere can be commercially available monodisperse aminosilica microballoon or nucleocapsid Formula silicone dioxide magnetic microsphere etc..
According to the method for the present invention, the surface dispersant can be neopelex, lauryl sodium sulfate With one of polyoxyethylene poly-oxygen propylene aether block copolymer or a variety of.Surface dispersant and pore creating material, carbon source and organic molten Agent synergistic effect has criss-cross network structure so that the porous carbon nanofiber of preparation is evenly distributed.
According to the method for the present invention, the carbon source can be polyacrylonitrile, polyvinylpyrrolidone, polyimides and phenolic aldehyde One of resin is a variety of.Wherein, the number-average molecular weight of the polyacrylonitrile be 500,000 to 3,000,000, preferably 1,500,000 to 2000000；The number-average molecular weight of the polyvinylpyrrolidone is 500,000 to 3,000,000, preferably 1,500,000 to 2,000,000；The polyamides The number-average molecular weight of imines is 500,000 to 3,000,000, preferably 1,500,000 to 2,000,000；The number-average molecular weight of the phenolic resin is 50 Ten thousand to 3,000,000, preferably 1,500,000 to 2,000,000.
According to the method for the present invention, the organic solvent can be n,N-Dimethylformamide, N-Methyl pyrrolidone, N, One of N- dimethyl acetamide and dimethyl sulfoxide are a variety of.
According to the method for the present invention, the feed weight ratio of the pore creating material, surface dispersant, carbon source and organic solvent is (0.3-0.9): (0.9-2.7): 1:(5-15), the porous carbon nanofiber being prepared within the scope of the ingredient proportion have compared with Big specific surface area and strong adsorption capacity, and porous carbon nanofiber is evenly distributed.
According to the method for the present invention, the mixed condition is so that pore creating material, surface dispersant, carbon source and organic solvent For the purpose of coming into full contact with, such as mixed condition can include but is not limited to: mixing temperature is 40-80 DEG C, incorporation time 2- 16h。
According to the method for the present invention, the condition of the electrostatic spinning is so that be finally solidified into for the purpose of fiber, Static Spinning The condition of silk includes but is not limited to: voltage 15-30kV, and the distance between collecting board and syringe needle is 15-25cm, promotes the advance of pump Rate is 0.8-1.2mL/h.In the present invention, the method for electrostatic spinning is convenient for industrialization large-scale production, the carbon fiber of preparation Area is big, and flexibility is good, can be used as without support electrode holder for lithium-sulfur cell.
According to the method for the present invention, the condition of the carbonization includes but is not limited to: the gas of carbonization is argon gas or nitrogen, carbon Changing temperature is 800-1200 DEG C, and heating rate is 2-5 DEG C/min, carbonization time 6-14h.In the present invention, if being carbonized Before pre-oxidized, heating rate when carbonization is preferably 4-5 DEG C/min；If before carbonization without pre-oxidation, when carbonization Heating rate be preferably 2-3 DEG C/min.
According to the method for the present invention, the method for removing pore creating material can be that the carbon fiber after carbonization is immersed in hydrogen fluorine In acid solution or sodium hydroxide solution.The condition of immersion, such as soaking time limit without special, are can remove pore creating material Purpose.
According to the method for the present invention, it after step (2) and before step (3), can also be pre-oxidized.Preferably, The condition of the pre-oxidation can include but is not limited to: temperature is 200-220 DEG C, and heating rate is 2-5 DEG C/min, time 1- 2h.In the present invention, pre-oxidation step can stablize the carbon fiber structural that spinning is collected into.
According to the method for the present invention, the condition of the drying is for the purpose of obtaining porous carbon nanofiber, the condition of drying Can include but is not limited to: the temperature of drying is 100-120 DEG C, and the time of drying is 8-16h.
According to the method for the present invention, the preparation method of porous carbon nanofiber may comprise steps of:
(1) pore creating material, surface dispersant are mixed in organic solvent, with biomixer ultrasound after stirring, are repeated more It is secondary, carbon source is added later, stirs to get spinning solution；
(2) spinning solution is subjected to electrostatic spinning, obtains carbon fiber；
(3) carbon fiber is carbonized, removes pore creating material, washing and drying, wherein, can before being carbonized Choosing pre-oxidize.
Second aspect of the present invention is provided by the porous carbon nanofiber of above-mentioned method preparation, wherein the porous carbon is received The average diameter of rice fiber is 500nm-2 μm, has porous structure, specific surface area 150-350m2/ g, average pore size 8- 35nm。
In the present invention, porous carbon nanofiber can be as depicted in figs. 1 and 2, it can be seen from the figure that of the invention is more Hole carbon nano-fiber diameter is more uniform, surface is rougher, can be used as the three-dimensional conductive carrier of sulphur, is conducive to lithium ion and electronics exists Transmission in electrochemical reaction process, and since three-dimensional space is larger, poly- molten sulfur electrolyte can be preferably absorbed, increases and lives The quality of property substance.Moreover, porous carbon nanofiber of the invention has excellent flexibility, it can be used for soft-package battery anode Material support is the good selection as lithium molten sulfur anode carrier.
Third aspect present invention provides a kind of lithium-sulfur cell, wherein the battery includes the positive electrode, the negative electrode and the separator, wherein The anode contains above-mentioned porous carbon nanofiber.
Specifically, the carrier of porous carbon nanofiber of the invention as positive electrode.
The present invention will be described in detail by way of examples below.
In the examples below, silicon dioxide microsphere is purchased from Sigma-Aldrich (Shanghai) trade Co., Ltd, batch For SLBP7956V；
Neopelex is purchased from Beijing Tai Zejia industry development in science and technology Co., Ltd, batch D1401036；
N,N-Dimethylformamide is purchased from Beijing chemical reagent factory, batch E1514039；
Biomixer is purchased from Xin Zhi bio tech ltd, Ningbo, model SCIENTZ-IID；
Polyacrylonitrile is purchased from Beijing lark prestige Science and Technology Ltd., batch LH80Q67, number-average molecular weight 1,500,000；
Zinc oxide is purchased from company, Shanghai Teng Zhun Biotechnology Co., Ltd, batch W12A051；
Polyoxyethylene poly-oxygen propylene aether block copolymer is purchased from Sigma-Aldrich (Shanghai) trade Co., Ltd, batch For SLBL1780V；
N-Methyl pyrrolidone is purchased from Sinopharm Chemical Reagent Co., Ltd., batch 20170803；
Polyvinylpyrrolidone is purchased from Shanghai Aladdin biochemical technology limited liability company, and batch D1613027, number is Molecular weight weight average molecular weight is 1,500,000；
Spinning machine is purchased from Beijing Ji Tepulun Biotechnology Co., Ltd, model ET-1334H；
Scanning electron microscope is purchased from Hitachi Hi-tech Technology Corp., model Hitachi SU8020；
Specific surface area analysis instrument is purchased from Mike Mo Ruitike equipment Co., Ltd, model ASAP2020.
Embodiment 1
(1) porous carbon nanofiber is prepared
The neopelex of silicon dioxide microsphere and 2.07g that the partial size of 0.69g is 7nm is mixed in 18mL's In n,N-Dimethylformamide organic solvent, after solution is stirred 10min, with biomixer ultrasound 30min, two are so carried out It is secondary that solution is made to be uniformly dispersed, that is, it is again stirring for 10min, ultrasonic 30min.The polyacrylonitrile of 1.8g is added later, is heated at 70 DEG C Stirring 12h becomes uniform state to solution, and the thick spinning solution without insoluble matter.
Above-mentioned spinning solution is transferred in the disposable syringe of 20mL, the spinning syringe needle model of spinning machine is 21, injection Device syringe needle is connected with the positive high voltage of spinning machine.Aluminium foil is spinning collecting board, and aluminium foil is connected with negative high voltage.Between collecting board and syringe needle Distance 20cm, spinning voltage 15kV, promote the advanced speed 1.0mL/h of pump, obtain carbon fiber.
The carbon fiber that spinning is collected into is stripped down from collecting board, is transferred in Muffle furnace and is pre-oxidized, with 5 DEG C/heating rate of min is raised to 200 DEG C, keep the temperature 1h.Carbon fiber after pre-oxidation is subjected to high temperature cabonization processing, carbonization treatment Condition includes: that argon stream amount is 100sccm, rises to 1100 DEG C later with the heating rate of 5 DEG C/min, keeps the temperature nature after 12h Cooling.Carbon fiber after carbonization is finally dipped to removing silica pore creating material in the hydrofluoric acid of 10 weight %, passes through suction filtration Method rinses carbon fiber with deionized water, dries 12h at 110 DEG C under vacuum condition, obtains porous carbon nanofiber.
(2) obtained porous carbon nanofiber is subjected to characterization and nitrogen adsorption desorption is tested:
Obtained porous carbon nanofiber is observed under scanning electron microscope, obtains scanning electron microscope (SEM) photograph as shown in Figure 1, And the scanning electron microscope (SEM) photograph of amplification as shown in Figure 2.By Fig. 1, it can be seen that porous carbon nanofiber of the invention is layered mistake Disorderly interweave distribution, and carbon fiber diameter is more uniform, and surface is rougher.By Fig. 2, it can be seen that the average diameter of carbon nano-fiber For 900nm, and there is porous structure on fiber.
Nitrogen adsorption desorption curve is carried out to porous carbon nanofiber: after the quality for weighing sample, the heating in vacuum at 250 DEG C Degasification 4h, weighing determines the quality of loss again, and vacuum condition is 500 μm of Hg (about 0.67bar), analyzes in test process, Sample is placed in liquid nitrogen environment.Specific surface area calculating is carried out using specific surface area analysis instrument, it is de- to obtain nitrogen suction as shown in Figure 3 Attached curve, from Fig. 3, it can be seen that the nitrogen adsorption desorption curve of prepared porous carbon fiber, belongs to typical IV type curve. There is apparent H3 to lag back-shaped ring in figure, illustrates that there are mesoporous (2-50nm) (IUPAC classification) in multi-stage porous carbon, and higher Opposite pressure range (P/P0=0.7-1.0) in, adsorption desorption curve has apparent ascendant trend, this is caused by capillary condensation. It is calculated according to BJH (the Barrett-Joyner-Halenda) pore-size distribution it is found that the specific surface area of porous carbon fiber is 275.5m2/ g, average pore size 8.8nm.
Embodiment 2
(1) porous carbon nanofiber is prepared
The polyoxyethylene poly-oxygen propylene aether block copolymer of zinc oxide and 2.07g that the partial size of 0.69g is 7nm is mixed in In the N-Methyl pyrrolidone organic solvent of 18mL, after solution is stirred 10min, with biomixer ultrasound 30min, so into Row makes solution be uniformly dispersed twice, that is, is again stirring for 10min, ultrasonic 30min.The polyvinylpyrrolidone of 1.8g is added later, Become uniform state in 70 DEG C of heating stirring 12h to solution, and the thick spinning solution without insoluble matter.
Above-mentioned spinning solution is transferred in the disposable syringe of 20mL, the spinning syringe needle model of spinning machine is 21, injection Device syringe needle is connected with the positive high voltage of spinning machine.Aluminium foil is spinning collecting board, and aluminium foil is connected with negative high voltage.Between collecting board and syringe needle Distance 25cm, spinning voltage 30kV, promote the advanced speed 1.2mL/h of pump, obtain carbon fiber.
The carbon fiber that spinning is collected into is stripped down from collecting board, is transferred in Muffle furnace and is pre-oxidized, with 5 DEG C/heating rate of min is raised to 200 DEG C, keep the temperature 1h.Carbon fiber after pre-oxidation is subjected to high temperature cabonization processing, carbonization treatment Condition includes: that argon stream amount is 100sccm, rises to 1100 DEG C later with the heating rate of 5 DEG C/min, keeps the temperature nature after 12h Cooling.The carbon fiber after carbonization is finally dipped in hydrochloric acid solution removing zinc oxide pore creating material, by suction filtration method spend from Sub- water rinses carbon fiber, dries 12h at 110 DEG C under vacuum condition, obtains porous carbon nanofiber.
(2) obtained porous carbon nanofiber is subjected to characterization and nitrogen adsorption desorption is tested:
It is characterized according to the method for embodiment 1, obtains similar Fig. 1 and porous carbon nanofiber shown in Fig. 2, porous carbon The average diameter of nanofiber is 900nm.
The test of nitrogen adsorption desorption is carried out according to the method for embodiment 1, is calculated, the specific surface area of porous carbon fiber is 190.3m2/ g, average pore size 8.2nm.
Embodiment 3
The neopelex of silicon dioxide microsphere and 0.9g that the partial size of 0.3g is 7nm is mixed in the N of 5mL, In dinethylformamide organic solvent, after solution is stirred 10min, with biomixer ultrasound 30min, so carry out twice So that solution is uniformly dispersed, that is, is again stirring for 10min, ultrasonic 30min.The polyacrylonitrile of 1g is added later, in 70 DEG C of heating stirrings 12h becomes uniform state to solution, and the thick spinning solution without insoluble matter.
Above-mentioned spinning solution is transferred in the disposable syringe of 20mL, the spinning syringe needle model of spinning machine is 21, injection Device syringe needle is connected with the positive high voltage of spinning machine.Aluminium foil is spinning collecting board, and aluminium foil is connected with negative high voltage.Between collecting board and syringe needle Distance 15cm, spinning voltage 25kV, promote the advanced speed 0.8mL/h of pump, obtain carbon fiber.
The carbon fiber that spinning is collected into is stripped down from collecting board, is transferred in Muffle furnace and is pre-oxidized, with 5 DEG C/heating rate of min is raised to 200 DEG C, keep the temperature 1h.Carbon fiber after pre-oxidation is subjected to high temperature cabonization processing, carbonization treatment Condition includes: that stream of nitrogen gas amount is 100sccm, rises to 1100 DEG C later with the heating rate of 5 DEG C/min, keeps the temperature nature after 12h Cooling.Carbon fiber after carbonization is finally dipped to removing silica pore creating material in the hydrofluoric acid of 10 weight %, passes through suction filtration Method rinses carbon fiber with deionized water, dries 12h at 110 DEG C under vacuum condition, obtains porous carbon nanofiber.
(2) obtained porous carbon nanofiber is subjected to characterization and nitrogen adsorption desorption is tested:
It is characterized according to the method for embodiment 1, obtains similar Fig. 1 and structure shown in Fig. 2, porous carbon nanofiber Average diameter is 500nm.
The test of nitrogen adsorption desorption is carried out according to the method for embodiment 1, is calculated, the specific surface area of porous carbon fiber is 166.7m2/ g, average pore size 8.2nm.
Embodiment 4
The neopelex of silicon dioxide microsphere and 2.7g that the partial size of 0.9g is 7nm is mixed in the N of 15mL, In dinethylformamide organic solvent, after solution is stirred 10min, with biomixer ultrasound 30min, so carry out twice So that solution is uniformly dispersed, that is, is again stirring for 10min, ultrasonic 30min.The polyacrylonitrile of 1g is added later, in 70 DEG C of heating stirrings 12h becomes uniform state to solution, and the thick spinning solution without insoluble matter.
Above-mentioned spinning solution is transferred in the disposable syringe of 20mL, the spinning syringe needle model of spinning machine is 21, injection Device syringe needle is connected with the positive high voltage of spinning machine.Aluminium foil is spinning collecting board, and aluminium foil is connected with negative high voltage.Between collecting board and syringe needle Distance 20cm, spinning voltage 15kV, promote the advanced speed 1.0mL/h of pump, obtain carbon fiber.
The carbon fiber that spinning is collected into is stripped down from collecting board, carries out high temperature cabonization processing, carbonization treatment condition Include: argon stream amount it is 100sccm, rises to 1100 DEG C later with the heating rate of 2 DEG C/min, keep the temperature Temperature fall after 12h. Carbon fiber after carbonization is finally dipped to removing silica pore creating material in the hydrofluoric acid of 10 weight %, is used by filtering method Deionized water rinses carbon fiber, dries 12h at 110 DEG C under vacuum condition, obtains porous carbon nanofiber.
(2) obtained porous carbon nanofiber is subjected to characterization and nitrogen adsorption desorption is tested:
It is characterized according to the method for embodiment 1, obtains similar Fig. 1 and structure shown in Fig. 2, porous carbon nanofiber Average diameter is 1 μm.
The test of nitrogen adsorption desorption is carried out according to the method for embodiment 1, is calculated, the specific surface area of porous carbon fiber is 189.6m2/ g, average pore size 8.8nm.
Comparative example 1
According to the method for embodiment, the difference is that, neopelex is not used, easily occurs reuniting now in a solvent As blocking up syringe needle when solution-polymerized SBR easily, spinning can not be carried out for a long time, and bulk easily occurs in the surface in obtained carbon fiber Object.
It is characterized according to the method for embodiment 1, as a result sees Fig. 4, from Fig. 4, it can be seen that the pore structure on carbon fiber is divided Cloth is very uneven, and diameter is inhomogenous.
Comparative example 2
The neopelex of silicon dioxide microsphere and 0.9g that the partial size of 0.2g is 7nm is mixed in the N of 5mL, In dinethylformamide organic solvent, after solution is stirred 10min, with biomixer ultrasound 30min, so carry out twice So that solution is uniformly dispersed, that is, is again stirring for 10min, ultrasonic 30min.The polyacrylonitrile of 1g is added later, in 70 DEG C of heating stirrings 12h becomes uniform state to solution, and the thick spinning solution without insoluble matter.
Above-mentioned spinning solution is transferred in the disposable syringe of 20mL, the spinning syringe needle model of spinning machine is 21, injection Device syringe needle is connected with the positive high voltage of spinning machine.Aluminium foil is spinning collecting board, and aluminium foil is connected with negative high voltage.Between collecting board and syringe needle Distance 20cm, spinning voltage 15kV, promote the advanced speed 1.0mL/h of pump, obtain carbon fiber.
The carbon fiber that spinning is collected into is stripped down from collecting board, is transferred in Muffle furnace and is pre-oxidized, with 5 DEG C/heating rate of min is raised to 200 DEG C, keep the temperature 1h.Carbon fiber after pre-oxidation is subjected to high temperature cabonization processing, carbonization treatment Condition includes: that argon stream amount is 100sccm, rises to 1100 DEG C later with the heating rate of 5 DEG C/min, keeps the temperature nature after 12h Cooling.Carbon fiber after carbonization is finally dipped to removing silica pore creating material in the hydrofluoric acid of 10 weight %, passes through suction filtration Method rinses carbon fiber with deionized water, dries 12h at 110 DEG C under vacuum condition, obtains porous carbon nanofiber.
(2) obtained porous carbon nanofiber is subjected to characterization and nitrogen adsorption desorption is tested:
It is characterized according to the method for embodiment 1, the average diameter of porous carbon nanofiber is 400nm.
The test of nitrogen adsorption desorption is carried out according to the method for embodiment 1, is calculated, the specific surface area of porous carbon fiber is 66.7m2/ g, average pore size 8.5nm.
Comparative example 3
The neopelex of silicon dioxide microsphere and 2.7g that the partial size of 1g is 7nm is mixed in the N, N- of 15mL In dimethylformamide organic solvents, after solution is stirred 10min, with biomixer ultrasound 30min, so made twice Solution is uniformly dispersed, that is, is again stirring for 10min, ultrasonic 30min.The polyacrylonitrile of 1g is added later, in 70 DEG C of heating stirring 12h Become uniform state to solution, and the thick spinning solution without insoluble matter.
Above-mentioned spinning solution is transferred in the disposable syringe of 20mL, the spinning syringe needle model of spinning machine is 21, injection Device syringe needle is connected with the positive high voltage of spinning machine.Aluminium foil is spinning collecting board, and aluminium foil is connected with negative high voltage.Between collecting board and syringe needle Distance 20cm, spinning voltage 15kV, promote the advanced speed 1.0mL/h of pump, obtain carbon fiber.In spinning, syringe needle is easy The case where existing plug wire.
The carbon fiber that spinning is collected into is stripped down from collecting board, is transferred in Muffle furnace and is pre-oxidized, with 5 DEG C/heating rate of min is raised to 200 DEG C, keep the temperature 1h.Carbon fiber after pre-oxidation is subjected to high temperature cabonization processing, carbonization treatment Condition includes: that argon stream amount is 100sccm, rises to 1100 DEG C later with the heating rate of 5 DEG C/min, keeps the temperature nature after 12h Cooling.Carbon fiber after carbonization is finally dipped to removing silica pore creating material in the hydrofluoric acid of 10 weight %, passes through suction filtration Method rinses carbon fiber with deionized water, dries 12h at 110 DEG C under vacuum condition, obtains porous carbon nanofiber.
(2) obtained porous carbon nanofiber is subjected to characterization and nitrogen adsorption desorption is tested:
It is characterized according to the method for embodiment 1, the diameter of porous carbon nanofiber is inhomogenous, and diameter is distributed in 300nm- 1 μm, the rough easy bulk for protrusion occur of carbon fiber surface.
The test of nitrogen adsorption desorption is carried out according to the method for embodiment 1, is calculated, the specific surface area of porous carbon fiber is 50.8m2/ g, average pore size 8.9nm.
Test case 1
(1) polysulfide electrolyte is prepared
Bis- (trifluoro methylsulfonyl) imine lithiums of 1mol/L and 0.5mol lithium nitrate are added to 1,3- dioxolanes and ethylene glycol In the mixed liquor of dimethyl ether (volume ratio 1:1).Sulphur and lithium sulfide that molar ratio is 5:1 are poured into above-mentioned solution, oil bath later For 24 hours, temperature is 60 DEG C for stirring, until solution stirs evenly, obtains the Li that sulphur concentration is 2mol/L2S6Polysulfide electrolyte.
(2) lithium sulphur button cell is assembled
It is being full of argon gas, water content and oxygen content assemble C2032 model button electricity all in 0.1ppm glove box below Pond.The porous carbon nanofiber that embodiment 1 obtains is washed into the disk of diameter 1.2cm, quality 2mg, above with 15 μ L/mg's Anode of the above-mentioned polysulfide electrolyte as lithium-sulfur cell is added dropwise in ratio, and perforated membrane Celgard 2400 is used as diaphragm, and lithium metal is Battery cathode, assembling obtain lithium sulphur button cell.
(3) charge and discharge cycles are tested
Lithium sulphur button cell is first discharged into 1.6V, then in 1.6V to cycle charge-discharge between 2.8V.Lithium-sulfur cell Specific discharge capacity calculating is the quality based on positive active material sulphur.
(a) under 0.25C (1C=1672mA/g) current density, the first discharge specific capacity and circulation 100 of battery are detected Specific discharge capacity after week, is as a result shown in Fig. 5, it can be seen from figure 5 that first discharge specific capacity is 924.6mAh/g, 100 circle of circulation Specific capacity is 709.5mAh/g afterwards, and capacity retention ratio is 84.3% (compared with the second circle specific discharge capacity).
(b) under big multiplying power 1C (1C=1672mA/g) current density, the first discharge specific capacity and circulation of battery are detected Specific discharge capacity after 100 weeks, is as a result shown in Fig. 6, from Fig. 6, it can be seen that first discharge specific capacity is 715.6mAh/g, circulation Specific capacity is 510.2mAh/g after 100 circles, and capacity retention ratio is 82% (compared with the second circle specific discharge capacity).
(c) after multiplying power discharging 24 encloses at room temperature, capacity is maintained at 641.1mAh/g at big multiplying power 1C, and multiplying power discharging 30 encloses Afterwards, capacity is maintained at 572.8mAh/g at big multiplying power 2C, and when current density turns again to small multiplying power 0.25C, capacity is 761.5mAh/g, as shown in Figure 7.
Test case 2-4
According to the method for test case 1, the difference is that, the porous carbon nanofiber of embodiment 1 is replaced with embodiment 2-4's Porous carbon nanofiber, it is as a result similar with test case 1.
Test comparison example 1
According to the method for test case 1, the difference is that, the porous carbon nanofiber of embodiment 1 is replaced with into the more of comparative example 1 Hole carbon nano-fiber.
Under 0.25C (1C=1672mA/g) current density, first discharge specific capacity 734.7mAh/g, 100 circle of circulation Specific capacity is 513.5mAh/g afterwards, and capacity retention ratio is 89% (compared with the second circle specific discharge capacity).
Under big multiplying power 1C (1C=1672mA/g) current density, first discharge specific capacity 583.8mAh/g, circulation 100 Specific capacity is 412.4mAh/g after circle, and capacity retention ratio is 73.4% (compared with the second circle specific discharge capacity).
Test comparison example 2
According to the method for test case 1, the difference is that, the porous carbon nanofiber of embodiment 1 is replaced with into the more of comparative example 2 Hole carbon nano-fiber.
Under 0.25C (1C=1672mA/g) current density, first discharge specific capacity 741.7mAh/g, 100 circle of circulation Specific capacity is 534.9mAh/g afterwards, and capacity retention ratio is 90.6% (compared with the second circle specific discharge capacity).
Under big multiplying power 1C (1C=1672mA/g) current density, first discharge specific capacity 608.2mAh/g, circulation 100 Specific capacity is 440.8mAh/g after circle, and capacity retention ratio is 76.3% (compared with the second circle specific discharge capacity).
Test comparison example 3
According to the method for test case 1, the difference is that, the porous carbon nanofiber of embodiment 1 is replaced with into the more of comparative example 3 Hole carbon nano-fiber.
Under 0.25C (1C=1672mA/g) current density, first discharge specific capacity 820.4mAh/g, 100 circle of circulation Specific capacity is 618.5mAh/g afterwards, and capacity retention ratio is 81.2% (compared with the second circle specific discharge capacity).
Under big multiplying power 1C (1C=1672mA/g) current density, first discharge specific capacity 663.9mAh/g, circulation 100 Specific capacity is 406.2mAh/g after circle, and capacity retention ratio is 73.3% (compared with the second circle specific discharge capacity).
By embodiment 1-4 and comparative example 1-3, it can be seen that porous carbon nanofiber of the invention is evenly distributed, have Criss-cross network structure, and soilless sticking phenomenon；Each carbon nano-fiber all has porous structure, average pore size 8- 35nm can reach 150-350m2The specific surface area of/g, i.e., porous carbon nanofiber of the invention have biggish specific surface area And strong adsorption capacity.And easily there is agglomeration in a solvent in documents 1 (not using surfactant), make solution-polymerized SBR When syringe needle it is easily stifled, spinning can not be carried out for a long time, and block, the hole on carbon fiber easily occurs in the surface in obtained carbon fiber Structure distribution is very uneven.Comparative example 2 and 3 (pore creating material, surface dispersant, carbon source and organic solvent feed weight ratio do not exist In the framework of the present definition) there are more uneven, the tables that is easy to appear plug wire, the diameter of porous carbon nanofiber of syringe needle when spinning The rough easy bulk for protrusion occur in face, the lesser problem of specific surface area.
By test case 1-4 and test comparison example 1-3, it can be seen that using porous carbon nanofiber preparation of the invention Lithium-sulfur cell, under 0.25C (1C=1672mA/g) current density, first discharge specific capacity 924.6mAh/g, 100 circle of circulation Specific capacity is 709.5mAh/g afterwards.Under big multiplying power 1C (1C=1672mA/g) current density, first discharge specific capacity is 715.6mAh/g, specific capacity is 510.2mAh/g after circulation 100 is enclosed.After multiplying power discharging 24 encloses at room temperature, hold at big multiplying power 1C Amount is maintained at 641.1mAh/g, and after multiplying power discharging 30 encloses, capacity is maintained at 572.8mAh/g at big multiplying power 2C, works as current density When turning again to small multiplying power 0.25C, capacity 761.5mAh/g shows excellent high rate performance.It can thus be seen that adopting The lithium-sulfur cell prepared with porous carbon nanofiber of the invention, compared to the porous carbon nanofiber system using comparative example 1-3 Standby lithium-sulfur cell, hence it is evident that there is excellent cycle performance and high rate performance.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited thereto.At this , can be with various simple variants of the technical solution of the present invention are made in the range of the technology design of invention, including each technical characteristic It is combined with any other suitable method, these simple variants and combination equally should be considered as in disclosed in this invention Hold, all belongs to the scope of protection of the present invention.

Claims (10)

1. a kind of preparation method of porous carbon nanofiber, method includes the following steps:
(1) pore creating material, surface dispersant, carbon source and organic solvent are mixed, obtains spinning solution；
(2) spinning solution is subjected to electrostatic spinning, obtains carbon fiber；
(3) carbon fiber is carbonized, removes pore creating material, washing and drying.
2. according to the method described in claim 1, wherein, the pore creating material is silicon dioxide microsphere, zinc oxide or calcium carbonate；It is excellent Selection of land, the partial size of the pore creating material are 7-30nm；
Preferably, the surface dispersant is neopelex, lauryl sodium sulfate and polyoxyethylene polyoxypropylene One of ether block copolymers are a variety of；
Preferably, the carbon source is one of polyacrylonitrile, polyvinylpyrrolidone, polyimides and phenolic resin or more Kind；Preferably, the number-average molecular weight of the polyacrylonitrile is 500,000 to 3,000,000, preferably 1,500,000 to 2,000,000, the polyethylene The number-average molecular weight of pyrrolidones is 500,000 to 3,000,000, preferably 1,500,000 to 2,000,000；The number-average molecular weight of the polyimides It is 500,000 to 3,000,000, preferably 1,500,000 to 2,000,000；The number-average molecular weight of the phenolic resin is 500,000 to 3,000,000, preferably 1500000 to 2,000,000；
Preferably, the organic solvent is n,N-Dimethylformamide, N-Methyl pyrrolidone, n,N-dimethylacetamide and two One of methyl sulfoxide is a variety of.
3. according to the method described in claim 1, wherein, the pore creating material, surface dispersant, carbon source and organic solvent feed intake Weight ratio is (0.3-0.9): (0.9-2.7): 1:(5-15).
4. according to the method described in claim 1, wherein, the mixed condition includes: that mixing temperature is 40-80 DEG C, mixing Time is 2-16h.
5. being collected according to the method described in claim 1, wherein, the condition of the electrostatic spinning includes: that voltage is 15-30kV Distance between plate and syringe needle is 15-25cm, and promoting the advanced speed of pump is 0.8-1.2mL/h.
6. according to the method described in claim 1, wherein, the condition of the carbonization includes: that the gas of carbonization is argon gas or nitrogen, Carburizing temperature is 800-1200 DEG C, and heating rate is 2-5 DEG C/min, carbonization time 6-14h.
7. according to the method described in claim 1, wherein, the method for removing pore creating material is that the carbon fiber after being carbonized impregnates In hydrofluoric acid solution or sodium hydroxide solution.
8. according to the method described in claim 1, wherein, after step (2) and before step (3), also being pre-oxidized；
Preferably, it is 200-220 DEG C that the condition of the pre-oxidation, which includes: temperature, and heating rate is 2-5 DEG C/min, time 1- 2h。
9. the porous carbon nanofiber of the preparation of the method as described in any one of claim 1-8, wherein the porous carbon nanometer The average diameter of fiber is 500nm-2 μm, has porous structure, specific surface area 150-350m2/ g, average pore size 8- 35nm。
10. a kind of lithium-sulfur cell, wherein the battery includes the positive electrode, the negative electrode and the separator, wherein the anode contains claim 9 The porous carbon nanofiber.
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