CN114023957B - Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof - Google Patents

Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof Download PDF

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CN114023957B
CN114023957B CN202111295190.0A CN202111295190A CN114023957B CN 114023957 B CN114023957 B CN 114023957B CN 202111295190 A CN202111295190 A CN 202111295190A CN 114023957 B CN114023957 B CN 114023957B
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selenium
energy storage
storage material
carbon fiber
calcination
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CN114023957A (en
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张明瑜
周鹏
苏哲安
黄启忠
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Hunan Jinyue New Materials Co ltd
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Hunan Jinyue New Materials Co ltd
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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
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 invention provides a selenium-containing compound/carbon fiber energy storage material, a preparation method and application thereof, comprising carbon fibers and selenium-containing compounds loaded in the carbon fibers, wherein the selenium-containing compounds are copper selenide or manganese selenide-zinc; the preparation method comprises the following steps: (1) Dissolving divalent metal salt and high molecular polymer in an organic solvent to obtain a mixed solution; preparing precursor fibers by an electrostatic spinning method; (2) Drying the precursor fiber, transferring the precursor fiber into a tube furnace, heating to 200-300 ℃ in air, and calcining to obtain a pre-oxidized precursor fiber; (3) Mixing the pre-oxidized precursor fiber with selenium powder, calcining in vacuum, cooling, grinding, and sieving. According to the invention, the selenium-containing compound is modified by introducing the carbon material, and the optimized process is combined, so that the conductivity of the material and the diffusion rate of lithium ions in the material can be effectively improved, the pulverization phenomenon of the material caused by volume change is slowed down, and the aim of improving the electrochemical performance is fulfilled.

Description

Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a selenium-containing compound/carbon fiber energy storage material, and a preparation method and application thereof.
Background
The current commercial graphite-based lithium ion battery negative electrode material has low mass specific capacity, and lithium dendrites are easy to generate in the high-current charge and discharge process to cause safety problems, so that the development of the lithium ion battery negative electrode material which can replace a graphite base and has good safety performance, high mass specific capacity and low price is urgently needed. The manganese selenide, the zinc selenide and the copper selenide have the advantages of higher theoretical mass specific capacity, environmental friendliness, low cost, low discharge platform and the like, so that the manganese selenide and the zinc selenide and the copper selenide are hopeful to replace graphite to become novel anode materials of lithium ion batteries.
However, due to the low electron conductivity and lithium ion diffusion rate and the large volume change in the charge and discharge process, the electrode material is pulverized, so that the capacity is rapidly attenuated, the cycle performance and the rate performance are poor, and the defects restrict the application of the single-phase selenium-containing compound material in the field of lithium ion battery anode materials.
Disclosure of Invention
In order to solve the technical problems of poor circulation stability, poor multiplying power performance and the like when a simple selenium-containing compound is used as an energy storage material in the prior art, the invention provides the selenium-containing compound/carbon fiber energy storage material, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a selenium-containing compound/carbon fiber energy storage material comprises carbon fiber and selenium-containing compound loaded in the carbon fiber, wherein the selenium-containing compound is copper selenide or manganese selenide-zinc, and the chemical formula of the manganese selenide-zinc is Mn x Zn (1-x) Se, wherein x is more than or equal to 0.05 and less than or equal to 0.4.
When the selenium compound is copper selenide, the synergistic effect of the copper selenide and carbon provides a large number of lithium ion interface storage sites, so that the specific capacity, the circulation stability and the rate capability of the energy storage material are improved.
When the selenium compound is manganese selenide-zinc, the grain growth of the selenium compound and the zinc can be effectively limited by introducing the manganese selenide and the zinc selenide at the same time, so that the grain size of the selenide in the material can be effectively maintained at the nanometer scale; meanwhile, more phase interfaces are provided, so that the interface lithium storage effect of the material in the charge and discharge process is effectively improved, the capacity of the material is effectively improved, and the rate capability of the material is improved.
Preferably, the selenium-containing compound accounts for 30-70% of the mass of the selenium-containing compound/carbon fiber energy storage material.
As a general inventive concept, the present invention provides a method for preparing a selenium-containing compound/carbon fiber energy storage material, comprising the steps of:
(1) Dissolving divalent metal salt and high molecular polymer with viscosity in an organic solvent to obtain a mixed solution; preparing precursor fibers from the mixed solution by an electrostatic spinning method;
(2) Drying the precursor fiber, transferring the precursor fiber into a tube furnace, heating to 200-300 ℃ in air, and calcining for 120-240min at 200-300 ℃ to obtain a pre-oxidized precursor fiber;
(3) And uniformly mixing the pre-oxidized precursor fiber and selenium powder, then carrying out vacuum calcination, and then cooling, grinding and sieving to obtain the selenium-enriched fiber.
The preparation method provided by the invention is used for performing pre-oxidation treatment in the process of preparing the energy storage material, and can effectively prevent the problems of 'fusion adhesion' and the like of fibers in the pre-oxidation process, so that the morphology is kept undamaged to the greatest extent in the subsequent calcination process, the microstructure stability and conductivity of the material are ensured, and the selenium-containing compound/carbon fiber energy storage material plays a better role when being applied to a lithium ion battery.
Preferably, in the step (1), the divalent metal salt is a divalent manganese salt and a divalent zinc salt, the divalent manganese salt is one or two of manganese oxalate and manganese nitrate, and the divalent zinc salt is one or two of zinc oxalate and zinc nitrate; in the mixed solution, the concentration of the divalent manganese salt is 0.1-0.5mol/L, and the concentration of the divalent zinc salt is 0.1-0.5mol/L. The manganese selenide-zinc/carbon fiber energy storage material is prepared by limiting divalent metal salts to divalent manganese salts and divalent zinc salts.
Preferably, in the step (1), the divalent metal salt is copper oxalate, and the concentration of the copper oxalate in the mixed solution is 0.1-0.5mol/L. The divalent metal salt is limited to copper oxalate, and the selenium powder is converted from a solid state to a gas state during calcination, permeates into the pre-oxidized precursor fiber and forms copper selenide with copper ions; the high polymer is pyrolyzed in situ to become carbon to wrap the copper selenide nano particles, and the copper selenide/carbon fiber energy storage material is prepared.
In the above step, the concentration of each divalent metal salt is strictly controlled, and if the concentration of the metal salt exceeds the above range, large particle agglomeration easily occurs in step (3); if the content is less than this range, the content of selenium compound in the carbon fiber is too low to provide a certain capacity.
When the mixed solution is prepared, the condition is specifically that the mixed solution is stirred in a water bath at about 60 ℃, and the dissolving treatment time is 30-60min. The stirring is slow, usually 20-100 rpm.
Preferably, in the step (1), the high molecular polymer is one or two of polyacrylonitrile and polyvinylpyrrolidone; the number average molecular weight of the polyacrylonitrile is 100-200 ten thousand, and the number average molecular weight of the polyvinylpyrrolidone is 100-200 ten thousand; the organic solvent is N, N-dimethylformamide.
Preferably, in the step (1), the mass ratio of the high molecular polymer to the organic solvent is 0.06-0.12:1; if the mass ratio of the high molecular polymer to the organic solvent is outside this range, a continuous fibrous precursor cannot be formed at the time of electrospinning.
The voltage during electrostatic spinning is 8-18kV, and the distance between the spray head and the receiver is 8-30cm. Further preferably, the voltage during electrostatic spinning is 11-13kV, and the distance between the spray head and the receiver is 15-20cm. At this voltage and distance, a stable taylor cone may be formed, ensuring that a continuous nanofiber precursor is produced.
Preferably, in the step (2), the precursor fiber is dried by adopting a blast oven, wherein the drying temperature is 50-80 ℃ and the drying time is 10-15h; heating to 200-300 ℃ in air at a heating rate of 1-10 ℃/min. The invention controls the temperature rising rate to be 1-10 ℃/min, and can better ensure the microstructure stability and conductivity of the material.
Preferably, in the step (3), the mass ratio of the pre-oxidized precursor fiber to the selenium powder is 1-10:1, and the particle size of the selenium powder is 200-500 meshes; within this mass and particle size range, the selenium powder can just penetrate into the pre-oxidized precursor fiber during calcination to react with the metal salt without excessive residue on the sample surface.
The vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 450-1000 ℃, the calcination time is 30-180min, and the temperature rising rate is 3-15 ℃/min. In the temperature rising rate range, the sample can keep continuous fibrous morphology well, and no obvious particle or agglomeration phenomenon exists.
The invention also provides an application of the selenium-containing compound/carbon fiber energy storage material or the selenium-containing compound/carbon fiber energy storage material prepared by the preparation method in a lithium ion battery anode material.
Compared with the prior art, the invention has the beneficial effects that:
1) The selenium-containing compound/carbon fiber energy storage material is prepared by pre-oxidation and vacuum calcination in sequence. The selenium-containing compound has higher theoretical capacity but poor stability, and the product prepared by the method provided by the invention is a selenium-containing compound/carbon fiber energy storage material with uniform morphology, and selenide crystals are completely wrapped in carbon fibers. The one-dimensional fibrous structure can shorten the migration distance of lithium ions and improve the transfer rate of electrons; the synergistic effect of selenide and carbon provides a large number of lithium ion interface storage sites, so that the specific capacity, the cycling stability and the rate capability of the material are improved.
2) The energy storage material prepared by the method has lower production cost and much higher capacity than the graphite carbon material which is commercially applied at present, and has good application prospect in the aspect of lithium ion battery cathode materials.
3) The invention adopts divalent metal salt and the like as raw materials, has low price, can effectively control the production cost, and has simple and environment-friendly whole method and little environmental pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of the manganese selenide-zinc/carbon fiber energy storage material of example 1;
FIG. 2 is a scanning electron micrograph of the manganese selenide-zinc/carbon fiber energy storage material of example 1;
FIG. 3 is a transmission electron micrograph of the manganese selenide-zinc/carbon fiber energy storage material of example 1;
FIG. 4 is a scanning electron micrograph of the manganese selenide-zinc/carbon fiber energy storage material of comparative example 2;
FIG. 5 is a graph showing the specific capacities of the assembled button cell of the manganese selenide-zinc/carbon fiber energy storage material of example 1 at different currents;
fig. 6 is a graph showing the specific discharge capacity and efficiency of the button cell assembled from the manganese selenide-zinc/carbon fiber energy storage material of example 1 as a function of the number of cycles.
FIG. 7 is an X-ray diffraction pattern of the copper selenide/carbon fiber energy storage material of example 5;
FIG. 8 is a scanning electron micrograph of the copper selenide/carbon fiber energy storage material of example 5;
FIG. 9 is a transmission electron micrograph of the copper selenide/carbon fiber energy storage material of example 5;
FIG. 10 is a scanning electron micrograph of the copper selenide/carbon fiber energy storage material of comparative example 4;
FIG. 11 is a graph showing the specific capacities of the assembled button cell of example 5 for various currents;
fig. 12 is a graph showing the specific discharge capacity and efficiency of the assembled button cell of example 5 with respect to cycle number.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a preparation method of a manganese selenide-zinc/carbon fiber energy storage material comprises the following steps:
(1) Manganese oxalate, zinc oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1, the concentration of the manganese oxalate in the obtained mixed solution is 0.12mol/L, the concentration of the zinc oxalate is 0.24mol/L, and the dissolution condition is water bath stirring for 30min at 60 ℃. Precursor fibers are prepared by an electrostatic spinning method, the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
In the manganese selenide-zinc/carbon fiber energy storage material of the embodiment, the manganese selenide-zinc is formed by Mn 0.303 Zn 0.697 Se and Mn 0.29 Zn 0.71 Se composition. Wherein FIG. 1 is an energy storage material according to the embodimentThe X-ray diffraction diagram of the energy storage material can be seen from the diagram, and the energy storage material contains two phases of manganese selenide-zinc, and no obvious other phases are generated in the reaction process. Fig. 2 is a scanning electron micrograph of the energy storage material obtained in this example, and it can be seen from fig. 2 that the energy storage material obtained is composed of nano-sized fibers with uniform morphology. Fig. 3 is a transmission electron micrograph of the energy storage material obtained in this example, and it can be seen from the figure that the obtained composite material has a fibrous structure with a diameter of about 100 nm, and the manganese selenide-zinc nanoparticles are well-encapsulated in carbon fibers.
Example 2:
a preparation method of a manganese selenide-zinc/carbon fiber energy storage material comprises the following steps:
(1) Manganese oxalate, zinc oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.1:1, the concentration of the manganese oxalate in the obtained mixed solution is 0.24mol/L, the concentration of the zinc oxalate is 0.12mol/L, and the dissolution condition is water bath stirring for 30min at 60 ℃. Precursor fibers are prepared by an electrostatic spinning method, the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 300 ℃ in air at a heating rate of 5 ℃/min, and calcining at 300 ℃ for 120 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 90min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
Example 3:
a preparation method of a manganese selenide-zinc/carbon fiber energy storage material comprises the following steps:
(1) Manganese oxalate, zinc oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1, the concentration of the manganese oxalate in the obtained mixed solution is 0.12mol/L, the concentration of the zinc oxalate is 0.24mol/L, and the dissolution condition is water bath stirring for 30min at 60 ℃. Precursor fibers are prepared by an electrostatic spinning method, the voltage during the electrostatic spinning is 15kV, and the distance between a spray head and a receiver is 15cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
Example 4:
a preparation method of a manganese selenide-zinc/carbon fiber energy storage material comprises the following steps:
(1) Manganese oxalate, zinc oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1, the concentration of the manganese oxalate in the obtained mixed solution is 0.12mol/L, the concentration of the zinc oxalate is 0.24mol/L, and the dissolution condition is water bath stirring for 30min at 60 ℃. Precursor fibers are prepared by an electrostatic spinning method, the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 2:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 500 ℃, the calcination time is 120min, and the heating rate is 5 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
Comparative example 1:
the preparation method of the energy storage material comprises the following steps:
(1) Polyacrylonitrile (number average molecular weight 150 ten thousand) was dissolved in N, N-dimethylformamide, and the total mass ratio of polyacrylonitrile (number average molecular weight 150 ten thousand) to the solution was 0.08:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. Precursor fibers are prepared by an electrostatic spinning method, the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the pure carbon fiber without metal selenide, wherein the fiber keeps good fibrous morphology, but does not have excellent lithium storage performance due to the fact that the fiber has no capacity beyond that provided by the metal selenide.
Comparative example 2:
a preparation method of a manganese selenide-zinc/carbon fiber energy storage material comprises the following steps:
(1) Manganese oxalate, zinc oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1, the concentration of the manganese oxalate in the obtained mixed solution is 0.12mol/L, the concentration of the zinc oxalate is 0.24mol/L, and the dissolution condition is water bath stirring for 30min at 60 ℃. Precursor fibers are prepared by an electrostatic spinning method, the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) Uniformly mixing precursor fibers and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
Among them, fig. 4 is a scanning electron micrograph of the energy storage material obtained in comparative example 2. It is evident from fig. 4 that the sample without the pre-oxidation treatment, while marginally maintaining the carbon fiber-like structure, showed significant fiber-to-fiber adhesion and a large number of particles, indicating that the carbon fiber without the pre-oxidation treatment did not seal the metal selenide within the carbon fiber well.
Performance test of manganese selenide-zinc/carbon fiber energy storage material:
in order to test that the manganese selenide-zinc/carbon fiber energy storage material has energy storage characteristics and can be used as a lithium battery anode material, the manganese selenide-zinc/carbon fiber energy storage material obtained in the embodiment 1 is adopted as a lithium ion battery anode material, and specifically comprises the following steps:
preparation of button cell: 10wt% of adhesive (CMC), 10wt% of conductive agent (carbon black) and 80wt% of active substance (energy storage material of example 1) are dissolved in a mixed solvent of deionized water and ethanol (volume ratio: deionized water: ethanol=3:2), uniformly stirred, coated on a copper foil, and put into a blast drying box to be dried for 12 hours at 80 ℃; and (3) drying, and punching the electrode into a pole piece (phi 12 mm) by using a punch to obtain the required electrode. The loading capacity of active substances on the pole piece is 0.6-1.2mg/cm 2 . A metal lithium sheet was used as a counter electrode, a porous polypropylene film was used as a separator, and 1mol/L lithium hexafluorophosphate (LiPF 6 ) The mixed solution of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) was used as an electrolyte (EC: DMC volume ratio 1:1), and a button cell (O) was assembled in a glove box filled with argon gas 2 Content of H less than 0.1ppm 2 O content is less than 0.1 ppm).
And then, testing items such as charge and discharge curves and the like of the assembled button cell.
The test results are shown in particular in figures 5 to 6. Wherein, fig. 5 is a graph of specific capacity and efficiency of assembled button cell at different current densities, and the specific discharge capacities are 1055.6, 865.1, 758.9, 674.9, 673.2, 580.1, 514.0 and 436.1mAh/g at current densities of 0.1, 0.2, 0.5, 1, 1.5, 2, 3 and 5A/g, respectively, and 954.2 and 1215.2mAh/g still exist after the current densities are restored to 0.2 and 0.1A/g.
Fig. 6 is a graph of specific capacity versus cycle number for various currents for assembled coin cells, from which it can be seen that the specific discharge capacity of the energy storage material of example 1 is extremely high, and is 1082.8mAh/g after 300 cycles at a current density of 0.2A/g.
Example 5:
the preparation method of the copper selenide/carbon fiber energy storage material comprises the following steps:
(1) Copper oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the concentration of the copper oxalate in the obtained mixed solution is 0.3mol/L, and the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. And preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material, wherein the mass of the copper selenide accounts for 55.29% of the total mass of the obtained copper selenide/carbon fiber energy storage material.
Wherein, fig. 7 is an X-ray diffraction diagram of the copper selenide/carbon fiber energy storage material obtained in example 5, and it can be seen from the figure that the energy storage material contains one phase of copper selenide, and no obvious other phase is generated in the reaction process.
Fig. 8 is a scanning electron micrograph of the copper selenide/carbon fiber energy storage material obtained in example 5, and it can be seen from fig. 2 that the obtained composite material has a uniform morphology of nano-sized fibers.
Fig. 9 is a transmission electron micrograph of the copper selenide/carbon fiber energy storage material of example 5, showing that the resulting composite material has a fibrous structure with a diameter of about 150 nm, and the copper selenide nanoparticles are well encapsulated in the carbon fibers.
Example 6:
the preparation method of the copper selenide/carbon fiber energy storage material comprises the following steps:
(1) Copper oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the concentration of the copper oxalate in the obtained mixed solution is 0.4mol/L, and the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.1:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. And preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 300 ℃ in air at a heating rate of 5 ℃/min, and calcining at 300 ℃ for 120 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 90min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material.
Example 7:
the preparation method of the copper selenide/carbon fiber energy storage material comprises the following steps:
(1) Copper oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the concentration of the copper oxalate in the obtained mixed solution is 0.3mol/L, and the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. And preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 15kV, and the distance between a spray head and a receiver is 15cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material.
Example 8:
the preparation method of the copper selenide/carbon fiber energy storage material comprises the following steps:
(1) Copper oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the concentration of the copper oxalate in the obtained mixed solution is 0.3mol/L, and the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. And preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 2:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 500 ℃, the calcination time is 120min, and the heating rate is 5 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material.
Comparative example 3:
a preparation method of a carbon fiber energy storage material comprises the following steps:
(1) Polyacrylonitrile (number average molecular weight 150 ten thousand) was dissolved in N, N-dimethylformamide, and the total mass ratio of polyacrylonitrile to the solution in the obtained mixed solution was 0.08:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. And preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) And (3) drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180 minutes to obtain the pre-oxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the pure carbon fiber without metal selenide, wherein the fiber keeps good fibrous morphology, but does not have excellent lithium storage performance due to the fact that the fiber has no capacity beyond that provided by the metal selenide.
Comparative example 4:
the preparation method of the copper selenide/carbon fiber energy storage material comprises the following steps:
(1) Copper oxalate and polyacrylonitrile (with the number average molecular weight of 150 ten thousand) are dissolved in N, N-dimethylformamide, the concentration of the copper oxalate in the obtained mixed solution is 0.3mol/L, and the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1. The dissolution condition is water bath stirring at 60 ℃ for 30min. And preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm.
(2) Uniformly mixing precursor fibers and selenium powder (200-500 meshes) according to a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material.
Wherein fig. 10 is a scanning electron micrograph of the copper selenide/carbon fiber energy storage material obtained in comparative example 4. In comparison with the copper selenide/carbon fiber energy storage material of example 1, it is apparent that the sample of comparative example 4, which was not subjected to the pre-oxidation treatment, had a fibrous structure which was barely maintained, but significant adhesion between fibers occurred, and a large amount of particles occurred, indicating that the carbon fiber, which was not subjected to the pre-oxidation treatment, did not seal the metal selenide within the carbon fiber well.
Performance test of manganese selenide-zinc/carbon fiber energy storage material:
in order to test that the copper selenide/carbon fiber energy storage material provided by the invention has energy storage characteristics and can be used as a lithium battery anode material, the copper selenide/carbon fiber energy storage material obtained in the embodiment 5 is adopted as the lithium ion battery anode material, and specifically comprises the following steps:
preparation of button cell: 10wt% of adhesive (CMC), 10wt% of conductive agent (carbon black) and 80wt% of active substance (energy storage material of example 5) are dissolved in a mixed solvent of deionized water and ethanol (volume ratio: deionized water: ethanol=3:2), uniformly stirred, coated on a copper foil, and put into a blast drying box to be dried for 12 hours at 80 ℃; and (3) drying, and punching the electrode into a pole piece (phi 12 mm) by using a punch to obtain the required electrode. The loading capacity of active substances on the pole piece is 0.6-1.2mg/cm 2 . A metal lithium sheet was used as a counter electrode, a porous polypropylene film was used as a separator, and 1mol/L lithium hexafluorophosphate (LiPF 6 ) The mixed solution of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) was used as an electrolyte (EC: DMC volume ratio 1:1), and a button cell (O) was assembled in a glove box filled with argon gas 2 Content of H less than 0.1ppm 2 O content is less than 0.1 ppm).
And then, testing items such as charge and discharge curves and the like of the assembled button cell.
The test results are shown in particular in fig. 11 to 12. Wherein, fig. 11 is a graph of specific capacity and efficiency obtained at different current densities of assembled button cell, and the discharge capacities are 756.9, 790.4, 748.1, 711.1, 670.5, 621.6, 553.5 and 461.1mAh/g at current densities of 0.1, 0.2, 0.5, 1, 1.5, 2, 3 and 5A/g, respectively, and the discharge specific capacities remain 869.0 and 947.5mAh/g after the current densities are restored to 0.2 and 0.1A/g.
Fig. 12 is a graph of specific capacity versus cycle number for various currents for assembled coin cells, from which it can be seen that the specific capacity of the energy storage material of example 5 is extremely high, with a discharge specific capacity of 1079.1mAh/g after 100 cycles at a current density of 0.1A/g.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (2)

1. The preparation method of the selenium-containing compound/carbon fiber energy storage material is characterized in that the selenium-containing compound/carbon fiber energy storage material comprises carbon fibers and selenium-containing compounds loaded in the carbon fibers, and the selenium-containing compounds are copper selenide;
the preparation method of the selenium-containing compound/carbon fiber energy storage material comprises the following steps:
(1) Copper oxalate and polyacrylonitrile are dissolved in N, N-dimethylformamide, the concentration of the copper oxalate in the obtained mixed solution is 0.3mol/L, and the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1; the dissolution condition is water bath stirring for 30min at 60 ℃; preparing precursor fibers from the mixed solution by an electrostatic spinning method, wherein the voltage during the electrospinning is 13kV, and the distance between a spray head and a receiver is 20cm;
the number average molecular weight of the polyacrylonitrile is 150 ten thousand;
(2) Drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, then transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining for 180 minutes at 280 ℃ to obtain a pre-oxidized precursor fiber;
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder in a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min; cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material;
the particle size of the selenium powder is 200-500 meshes.
2. A preparation method of a selenium-containing compound/carbon fiber energy storage material is characterized in that the selenium-containing compound/carbon fiber energy storage material comprises carbon fibers and selenium-containing compounds loaded in the carbon fibers, wherein the selenium-containing compounds are manganese selenide-zinc, and the manganese selenide-zinc is prepared from Mn 0.303 Zn 0.697 Se and Mn 0.29 Zn 0.71 Se composition;
the preparation method of the selenium-containing compound/carbon fiber energy storage material comprises the following steps:
(1) Dissolving manganese oxalate, zinc oxalate and polyacrylonitrile in N, N-dimethylformamide, wherein the mass ratio of the polyacrylonitrile to the N, N-dimethylformamide is 0.08:1, the concentration of the manganese oxalate in the obtained mixed solution is 0.12mol/L, the concentration of the zinc oxalate is 0.24mol/L, and stirring in a water bath at 60 ℃ for 30min; preparing precursor fibers by an electrostatic spinning method, wherein the voltage is 13kV during the electrospinning, and the distance between a nozzle and a receiver is 20cm;
the number average molecular weight of the polyacrylonitrile is 150 ten thousand;
(2) Drying the precursor fiber by adopting a blast oven, wherein the drying temperature is 60 ℃ and the drying time is 12 hours, then transferring the precursor fiber into a tube furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining for 180 minutes at 280 ℃ to obtain a pre-oxidized precursor fiber;
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder in a mass ratio of 3:1, and then carrying out vacuum calcination, wherein the vacuum degree of the vacuum calcination is less than or equal to 0.1MPa, the calcination temperature is 650 ℃, the calcination time is 120min, and the heating rate is 10 ℃/min;
cooling, grinding and sieving to obtain the energy storage material;
the particle size of the selenium powder is 200-500 meshes.
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