CN111945252B - Method for preparing hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning and potassium storage application thereof - Google Patents

Method for preparing hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning and potassium storage application thereof Download PDF

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CN111945252B
CN111945252B CN202010835167.5A CN202010835167A CN111945252B CN 111945252 B CN111945252 B CN 111945252B CN 202010835167 A CN202010835167 A CN 202010835167A CN 111945252 B CN111945252 B CN 111945252B
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CN111945252A (en
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柳伟
周峻安
高翔
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Ocean University of China
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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
    • 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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
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    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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Abstract

The invention discloses a method for preparing a hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning and potassium storage application thereof. The method comprises the steps of taking PAN and PMMA as precursors, dissolving antimony trichloride and CNT respectively with nickel acetate, stannous chloride and cobalt chloride in DMF according to a certain proportion to form spinning solution, transferring the spinning solution into a disposable injector, and carrying out electrostatic spinning in electrostatic spinning equipment to obtain a nanofiber membrane. After vacuum drying, the fiber membrane is placed in a tube furnace, the temperature is raised to 230-300 ℃ at a slower heating rate for heat preservation for a certain time for pre-carbonization, then the temperature is raised to 600-800 ℃ at a faster heating rate for carbonization, and a sample after carbonization is marked as XSb (X = Ni, Sn, Co)/CNT/PC. The carbon skeleton provides a three-dimensional conductive network, PMMA is pyrolyzed to generate a hollow channel, alloy particles are embedded on the inner surface and the outer surface of the carbon fiber, and CNT improves the overall conductivity of the material in the carbon fiber, so that the CNT shows excellent comprehensive electrochemical performance when being used as an electrode material of a potassium ion battery.

Description

Method for preparing hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning and potassium storage application of hollow antimony-based binary alloy composite nanofiber material
Technical Field
The invention belongs to the field of electrochemical energy storage materials, and provides a method for preparing a hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning, and application of the hollow antimony-based binary alloy composite nanofiber material in a potassium ion battery cathode material.
Background
Energy is an important material basis for the progress of human civilization, and with the gradual depletion of non-renewable energy sources such as petroleum, people are always exploring alternative renewable energy sources. In recent years, lithium ion batteries have been developed rapidly, and research on electrode materials of lithium ion batteries has led to great results. Lithium ion batteries have been commercially developed, but the storage of lithium resources in the earth's crust is very limited and is not uniformly distributed in the world. Therefore, the application of the lithium ion energy storage device in large-scale energy storage is limited. Sodium and potassium are similar in chemical properties to lithium, and in energy storage systems, the energy storage of several alkali metal ion batteriesMechanism is similar, and the oxidation-reduction potential (K/K) of potassium ions + 2.93V) and lithium ion (Li/Li) + -3.04V). The potassium element is distributed in the sixth world and is far more than the lithium element. In addition, the potassium resource has low price and high cost performance, and the potassium ion battery has the advantages of low reaction potential, high energy density, small solvated ion and the like, is widely concerned by people and has a certain application prospect in the energy storage market.
At present, the potassium ion battery is in a starting development stage, the performance of the potassium ion battery is good and bad, and the negative electrode material plays a vital role. The potassium ion battery negative electrode material can be divided into: carbonaceous materials, alloy materials, transition materials, intercalation materials, organic materials, and the like. Antimony-based materials are one of the negative electrode materials of alkali metal batteries. The electronic conductivity of Sb is 0.026 mu S cm -1 Theoretical capacity of 660 mAh g -1 Therefore, Sb is an ideal negative electrode material in the potassium ion battery. However, there is a volume expansion of about 400% during the intercalation and deintercalation of potassium ions, which may result in pulverization of the Sb-based material. It is therefore important how to suppress the volume expansion. There are three main strategies to address the volume expansion of electrode materials. Firstly, the particle size is reduced, and the volume expansion is relieved by changing the microstructure; secondly, by introducing a buffer phase, the stress caused by volume change is reduced; thirdly, compounding with carbon to prevent the particles from falling off. The invention aims to solve the crushing problem caused by volume expansion under the double action of a carbon matrix and a buffer phase by introducing the buffer phase, and simultaneously, the volume expansion is inhibited to a certain degree while the overall conductivity of the material is improved by adding the carbon nano tubes. Through the representation of electrochemical performance, the electrode material obtained by the invention well solves the problems, and obtains high specific capacity and good cycling stability.
Disclosure of Invention
The invention provides a method for preparing a hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning, which is characterized in that PAN and PMMA are used as precursors to carry out electrostatic spinning to obtain a hollow porous carbon nanofiber template, and on the basis of the carbon nanofiber template, different metal salts are dissolved into spinning solution to obtain antimony-based binary alloy particles embedded on the inner surface and the outer surface of a hollow carbon nanofiber. Meanwhile, the hydroxylated multi-wall carbon nano-tube is added, so that the overall conductivity of the material can be improved while the carbon nano-fiber is compounded, and the hollow antimony-based binary alloy composite nano-fiber material is obtained. When the hollow composite nanofiber material with good conductivity is used as a potassium ion energy storage electrode material, excellent electrochemical performance is shown.
In summary, the technical scheme adopted by the invention is as follows: dissolving a certain amount of PAN, PMMA and CNT in a DMF solution by ultrasonic stirring, and then dissolving antimony trichloride, nickel acetate, stannous chloride and cobalt chloride in the solution according to a certain molar ratio to obtain a spinning solution. And after the fiber membrane is fully dissolved, transferring the fiber membrane into electrostatic spinning equipment for electrostatic spinning, and then drying the obtained fiber membrane in vacuum. After drying, the fiber membrane is subjected to the steps of pre-carbonization, carbonization and the like in sequence to obtain the hollow antimony-based binary alloy composite nanofiber material.
Compared with the prior art, the invention has the beneficial effects that: (1) the synthetic route of the electrostatic spinning method can realize the mass and large-scale production of the composite nanofiber material, the electrostatic spinning can shorten the process flow, and the method has good market application prospect. In addition, the electrostatic spinning method is a low-cost environment-friendly synthesis process route. The method has obvious advantages in the field of energy storage, particularly in the preparation of electrode materials.
(2) The hydroxylated multi-wall carbon nano tube is rich in-OH, has certain surface defects, can be combined with positively charged metal ions through electrostatic adsorption, has certain anchoring effect on alloy particles, is interwoven with carbon fibers, improves the overall conductivity of the material, and can realize stable and high-capacity potassium storage performance.
(3) Polymethyl methacrylate can be decomposed by heating during calcination to produce CO 2 And CO and other gases are carbonized, hollow channels are left in the nano fibers, the nano fiber framework obtained by carbonizing polyacrylonitrile keeps a complete structure, the existence of the hollow channels can shorten the ion diffusion distance in the ion shuttling process,the specific surface area of the material is increased, so that the material has good cycle life when used for a potassium ion energy storage device.
(4) The molecular formula of polyacrylonitrile is (C) 3 H 3 N) n And has abundant N-containing functional groups. The introduction of the surface functional group provides an active site for ion reaction, reduces the reaction internal resistance of the electrode material, improves the ion conductivity and the electronic conductivity of the whole carbon nanofiber, and ensures that the carbon nanofiber has good potassium storage performance when being applied to a potassium ion battery cathode material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of the NiSb/CNT/PC composite nanofiber material obtained in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the SnSb/CNT/PC composite nanofiber material obtained in example 2.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the CoSb/CNT/PC composite nanofiber material obtained in example 3.
FIG. 4 is a comparison of XRD of the composite nanofiber materials obtained in examples 1-3 with a standard card.
FIG. 5 shows that when the hollow antimony-based binary alloy composite nanofiber materials prepared in examples 1 to 3 of the present invention are used as the negative electrode material of a potassium ion battery, the voltage ranges from 0.005V to 3V, and the current density ranges from 0.05V to 5A g in a blue battery testing system -1 The multiplying power performance chart of the charge and discharge test is shown below.
FIG. 6 shows that when the hollow antimony-based binary alloy composite nanofiber material prepared in examples 1-3 of the present invention is used as a negative electrode material of a potassium ion battery, the voltage is in the range of 0.005-3V, and the voltage is 1A g in a blue battery testing system -1 And (4) a cycle performance chart of a charge and discharge test is carried out on the current density.
Detailed Description
The invention will now be illustrated by reference to the following specific examples, which are not intended to be limiting.
Example 1
20mg of hydroxylated multiwalled carbon nanotubes are weighed out and dissolved in 10ml of DMF and sonicated for 3 hours to form a black solution, 2mmol of SbCl are added to the solution 3 And Ni (CH) 3 COO) 2 ・4H 2 After O, the mixture was stirred at room temperature for 4 hours, and then a mixture of 0.7g of polyacrylonitrile and 0.3g of polymethyl methacrylate was added, and the mixture was heated at 60 ℃ overnight with stirring. The spinning solution was transferred to a 10ml disposable syringe and then used for electrospinning. The propulsion speed is 50ul min -1 The sample is collected in an aluminum foil at the working voltage of 15KV, the model of a needle is 21G, and the distance from the needle to the collector is 18 cm. After spinning for 8 hours, the fiber membrane was dried overnight under vacuum at 80 ℃ to fully evaporate the solvent. Drying, and then putting the nanofiber membrane in Ar/H 2 First 2 under atmosphere o C min -1 Is increased to 280 oC Preserving heat for 3h for pre-carbonization, keeping the original shape of the fiber, and then adding 5 h o C min -1 Continues to heat up to 700 deg.f o C, preserving the heat for 2 hours for carbonization. The collected sample is a NiSb/CNT/PC composite nanofiber material. As shown in the SEM of FIG. 1, the diameter of the nanofiber is about 500nm, the diameter of the NiSb nanoparticle is 10-20nm, and the NiSb nanoparticle can be clearly seen to be uniformly distributed on the inner surface and the outer surface of the carbon fiber.
Example 2
The method of this example is substantially the same as example 1, except that: mixing Ni (CH) 3 COO) 2 ・4H 2 Conversion of O to SnCl 2 ，SnCl 2 And SbCl 3 Likewise in a molar ratio of 1: 1. the collected sample is the SnSb/CNT/PC composite nanofiber material. As shown by the SEM picture of FIG. 2, the diameter of the nanofiber is 200-300nm, and the surface is very smooth. SnSb alloy particles are about 50nm, and an agglomeration phenomenon exists. The SnSb alloy particles are in hollow channels inside the fiber. The presence of CNTs was not observed by SEM images, since CNTs were well confined inside the carbon nanofibers.
Example 3
The method of this example is substantially the same as example 1, except that: mixing Ni (CH) 3 COO) 2 ・4H 2 O is replaced by CoCl 2 ，CoCl 2 And SbCl 3 Likewise in a molar ratio of 1: 1. the collected sample is CoSb/CNT/PC composite nanofiber material. Shown by SEM picture of FIG. 3, nanofibersThe dimensional diameter is several hundred nanometers, the diameter of the CoSb nanoparticles is several nanometers, the CoSb nanoparticles can be clearly seen to be uniformly distributed on the inner and outer surfaces of the carbon fiber, and the interior of the fiber can be seen to be a hollow structure, because PMMA is produced by pyrolysis in the calcination process. The CNTs are exposed outside the hollow channels to form a good conductive network.
The crystal structure of the XSb (X = Ni, Sn, Co)/CNT/PC composite nanofiber material is characterized by using XRD technology, as shown in figure 4, as can be seen from figure 4, NiSb/CNT/PC, SnSb/CNT/PC and CoSb/CNT/PC respectively obtained in examples 1-3 have good diffraction peaks, and are completely consistent with the comparison of JCPDS (No. 41-1439), JCPDS (No. 33-0118) and JCPDS (No. 33-0097) of a standard sample card, which shows that the crystal form obtained by the hollow antimony-based binary alloy composite nanofiber material obtained in the embodiment is good. Meanwhile, the carbon in NiSb/CNT/PC, SnSb/CNT/PC and CoSb/CNT/PC obtained in the examples 1 to 3 is amorphous, and the peak shape is obvious around 23 degrees.
Application example 1
The hollow antimony-based binary alloy composite nanofiber material obtained in example 1-3, a conductive agent (conductive acetylene black) and a binder (polyvinylidene fluoride) are mixed in a mass ratio of 80:10:10, added into 1-methyl-2-pyrrolidone (NMP) and fully ground to prepare slurry, the slurry is uniformly coated on a current collector (stainless steel sheet) to prepare an electrode sheet, and the electrode sheet is dried in vacuum at 80 ℃ overnight. The battery takes metal potassium as a counter electrode, electrolyte is 1.0M KFSI in EC: DEC =1:1 Vol%, the diaphragm is a glass fiber diaphragm, the potassium ion battery is assembled in a glove box filled with argon, and a blue battery testing system is used for testing the electrochemical performance of the battery. The test results are shown in fig. 5-6.
FIG. 5 is a graph of rate capability of the hollow antimony-based binary alloy composite nanofiber material obtained in examples 1-3 at different current densities. As can be seen from FIG. 5, at 50mA g -1 The first-turn coulombic efficiencies of NiSb/CNT/PC, SnSb/CNT/PC and CoSb/CNT/PC were 48.1%, 35.1% and 17.9%, respectively. NiSb/CNT/PC electrode at 50mA g -1 Specific discharge capacity per hour is 297 mAh g -1 And has high specific discharge capacity. When electricity is generatedThe stream density was further increased to 0.1, 0.2, 0.5, 1, 2 and 5A g -1 The specific discharge capacity is respectively kept at 270, 256, 214, 184, 152 and 109 mAh g -1 When the current density is recovered to 50mA g -1 The specific capacity is kept at 294 mAh g -1 Thus, it can be seen that good rate performance is exhibited.
FIG. 6 shows that the hollow antimony-based binary alloy composite nanofiber material obtained in example 1-3 is 1A g -1 Cycling performance plot at current density. As shown in fig. 6, the capacity retention rate of NiSb/CNT/PC obtained in example 1 was 88.2%, the capacity retention rate of SnSb/CNT/PC obtained in example 2 was 64.9%, and the capacity retention rate of CoSb/CNT/PC obtained in example 3 was 87.3%, all showing good cycle stability. In particular, NiSb/CNT/PC electrode is at 1A g -1 Current density of 161.4 mAh g after 500 cycles -1 The high specific discharge capacity of the material is a sample with optimal performance in the material obtained by the invention. XSb (X = Ni, Sn, Co)/CNT/PC composite nano-fiber material as the anode material of the potassium ion battery has excellent electrochemical performance which can be attributed to the following reasons: (1) ni, Sn, Co and the like are taken as buffer phases, so that the large volume expansion of Sb can be relieved in the process of inserting/extracting potassium ions; (2) the hollow channel generated by PMMA pyrolysis can provide a buffer space for the volume expansion of the alloy nanoparticles; (3) the hydroxylated multi-walled carbon nanotube prevents the agglomeration of alloy particles inside the carbon nanofiber; (4) the compounding of the hydroxylated multi-walled carbon nanotubes and the carbon nanofibers improves the overall conductivity of the material.

Claims (3)

1. A method for preparing a hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning is characterized by comprising the following steps: (a) dissolving: respectively ultrasonically stirring and dissolving a proper amount of antimony trichloride and CNT with nickel acetate, stannous chloride and cobalt chloride in a certain proportion in a DMF (dimethyl formamide) solution, then dissolving PAN (Polymethylacetamide) and PMMA (polymethyl methacrylate) in the solution, and heating and violently stirring to obtain a black spinning solution; (b) electrostatic spinning: transferring the black spinning solution into a disposable injector, and carrying out electrostatic spinning in electrostatic spinning equipment, wherein the parameters of the electrostatic spinning to be adjusted comprise: spinningThe distance between the needle head and the metal collecting substrate, spinning time, the type of the needle head, spinning voltage, liquid feeding speed, environmental temperature and environmental humidity, collecting the nano-fibers obtained by spinning on an aluminum foil substrate, and waiting for the next step of treatment after vacuum drying for several hours; (c) and (3) calcining: placing the electrospun sample in a corundum porcelain boat, transferring the corundum porcelain boat into a tube furnace, drying, and then firstly adding 2 parts of nano-fiber film in Ar/H2 atmosphere o C min -1 Is increased to 280 o C, preserving heat for 3 hours for pre-carbonization, keeping the original shape of the fiber, and then preserving heat by 5 o C min -1 Continues to heat up to 700 deg.f o C, preserving heat for 2 hours for carbonization; in the step a, antimony trichloride is respectively mixed with stannous chloride, cobalt chloride and nickel acetate, the total amount is controlled to be 4mmol, the molar ratio of antimony trichloride to nickel acetate is controlled to be 1:1-1:3, the molar ratio of antimony trichloride to stannous chloride is controlled to be 1:1-1:3, and the molar ratio of antimony trichloride to cobalt chloride is controlled to be 1:1-1: 3; the addition of the hydroxylated multi-walled carbon nano-tube introduces a large amount of conductive networks in the carbon nano-fiber, and the existence of the hydroxylated multi-walled carbon nano-tube enables alloy particles to be adsorbed on the surface of the carbon nano-tube through electrostatic adsorption, so that the falling of the alloy particles is avoided; the mass fraction ratio of PAN to PMMA is 7: 3, the PMMA can generate CO2 and CO in the pyrolysis process by reasonable proportion, the volatilization of the gas can form a hollow channel in the carbon nanofiber, and the hollow carbon nanofiber matrix is obtained, wherein the diameter of the channel is within the range of 20-100 nm.
2. The method for preparing the hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning as claimed in claim 1, wherein: in step b, the distance between the spinning needle and the metal collecting substrate is set to be 18cm, and the liquid feeding speed is 50ul min -1 Setting the spinning working voltage at 15KV, the spinning time at 8-12h, the ambient temperature at 27 +/-2 ℃ and the ambient humidity at 40% -50%, collecting the nanofibers obtained by spinning on an aluminum foil substrate, and then drying in vacuum.
3. The potassium storage application of the hollow antimony-based binary alloy composite nanofiber material prepared by the method according to claims 1-2 and based on electrostatic spinning is characterized in that: the hollow XSb (X = Ni, Sn, Co)/CNT/C nanofiber material is used as a negative electrode material of a potassium ion battery, is beneficial to the intercalation and deintercalation of potassium ions due to the unique morphology and good conductivity, and shows excellent potassium storage performance.
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