CN114023957A - 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

Info

Publication number
CN114023957A
CN114023957A CN202111295190.0A CN202111295190A CN114023957A CN 114023957 A CN114023957 A CN 114023957A CN 202111295190 A CN202111295190 A CN 202111295190A CN 114023957 A CN114023957 A CN 114023957A
Authority
CN
China
Prior art keywords
selenium
energy storage
containing compound
storage material
precursor fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111295190.0A
Other languages
Chinese (zh)
Other versions
CN114023957B (en
Inventor
张明瑜
周鹏
苏哲安
黄启忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Jinyue New Materials Co ltd
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN202111295190.0A priority Critical patent/CN114023957B/en
Publication of CN114023957A publication Critical patent/CN114023957A/en
Application granted granted Critical
Publication of CN114023957B publication Critical patent/CN114023957B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a selenium-containing compound/carbon fiber energy storage material and a preparation method and application thereof, wherein the selenium-containing compound/carbon fiber energy storage material comprises carbon fibers and a selenium-containing compound loaded in the carbon fibers, and the selenium-containing compound is 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 fiber by an electrostatic spinning method; (2) drying the precursor fiber, transferring the dried precursor fiber to a tubular furnace, heating the dried precursor fiber to 200-300 ℃ in air, and calcining the dried precursor fiber to obtain pre-oxidized precursor fiber; (3) and (3) uniformly mixing the preoxidized precursor fiber and selenium powder, calcining in vacuum, cooling, grinding and sieving to obtain the nano-composite material. According to the invention, the selenium-containing compound is modified by introducing the carbon material, and an 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 purpose of improving the electrochemical performance is achieved.

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 as well as a preparation method and application thereof.
Background
The negative electrode material of the graphite-based lithium ion battery which is commercially applied at present has low mass-to-capacity ratio, and lithium dendrite is easily generated in the process of large-current charging and discharging to cause safety problems, so that the development of the negative electrode material of the lithium ion battery which can replace the graphite base and has good safety performance, high mass-to-capacity ratio and low price is urgently needed. Manganese selenide, zinc selenide and copper selenide have the advantages of high theoretical mass specific capacity, environmental friendliness, low cost, low discharge platform and the like, so that the manganese selenide and the zinc selenide and copper selenide are hopefully substituted for graphite to become novel negative electrode materials of lithium ion batteries.
However, the electronic conductivity and the lithium ion diffusion rate of the material are low, and the volume change is large in the charging and discharging process, so that the electrode material is pulverized, the capacity is rapidly attenuated, and the cycle performance and the rate performance are poor, so that the application of the single-phase selenium-containing compound material in the field of lithium ion battery cathode materials is limited.
Disclosure of Invention
In order to solve the technical problems of poor cycle stability, poor rate performance and the like when a pure selenium-containing compound is used as an energy storage material in the prior art, the invention provides a 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:
the selenium-containing compound/carbon fiber energy storage material comprises carbon fibers and a selenium-containing compound loaded in the carbon fibers, wherein the selenium-containing compound is copper selenide or manganese selenide-zinc, and the manganese selenide-zincHas the chemical formula of MnxZn(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 cycling stability and the rate capability of the energy storage material are improved.
When the selenium compound is manganese selenide-zinc, the growth of mutual crystal grains can be effectively limited by simultaneously introducing selenides of manganese and zinc, so that the crystal grain size of the selenides in the material is effectively maintained at a nano scale; meanwhile, more phase interfaces effectively improve the interface lithium storage effect of the material in the charging and discharging process, so that 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 fiber from the mixed solution by an electrostatic spinning method;
(2) drying the precursor fiber, transferring the dried precursor fiber to a tubular furnace, heating the precursor fiber to the temperature of 200-;
(3) and uniformly mixing the preoxidized precursor fiber and selenium powder, then carrying out vacuum calcination, cooling, grinding and sieving to obtain the nano-composite material.
The invention carries out preoxidation treatment in the process of preparing the energy storage material, can effectively prevent the fiber from generating the problems of fusion adhesion and the like in the preoxidation process, keeps the appearance from being damaged in the subsequent calcination process to the maximum extent, ensures the microstructure stability and the conductivity of the material, and ensures that the selenium-containing compound/carbon fiber energy storage material can play 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 0.1-0.5 mol/L. The manganese selenide-zinc/carbon fiber energy storage material is prepared by limiting divalent metal salts into 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 0.1-0.5 mol/L. Defining a divalent metal salt as copper oxalate, converting selenium powder from a solid state to a gaseous state during calcination, and infiltrating into a preoxidized precursor fiber to form copper selenide with copper ions; and carrying out in-situ pyrolysis on the high molecular polymer to obtain carbon to wrap the copper selenide nano-particles, thus preparing the copper selenide/carbon fiber energy storage material.
In the above step, the concentration of each divalent metal salt is strictly controlled, and if the concentration of the metal salt is out of the above range, the agglomeration of large particles is easily caused in the step (3); if the content is less than this range, the content of the selenium compound in the carbon fiber is too low to provide a certain capacity.
When the mixed solution is prepared, the water bath stirring is carried out under the condition of about 60 ℃, and the dissolving treatment time is 30-60 min. The stirring is carried out at a slow speed, usually 20 to 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-; 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 weight polymer to the organic solvent is outside this range, a continuous fibrous precursor cannot be formed during electrospinning.
The voltage during electrostatic spinning is 8-18kV, and the distance between the spray head and the receiver is 8-30 cm. Further preferably, the voltage during electrostatic spinning is 11-13kV, and the distance between the spray head and the receiver is 15-20 cm. Under the voltage and the distance, a stable Taylor cone can be formed, and the generation of continuous nanofiber precursor materials is guaranteed.
Preferably, in the step (2), a blast oven is adopted to dry the precursor fiber, the drying temperature is 50-80 ℃, and the drying time is 10-15 h; the temperature is raised to 200-300 ℃ in the air at the temperature raising rate of 1-10 ℃/min. The invention controls the heating rate to be 1-10 ℃/min, and can better ensure the microstructure stability and the 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 the mass and particle size range, the selenium powder can just permeate into the pre-oxidized precursor fiber to react with the metal salt in the calcining process, and the selenium powder cannot be excessively remained on the surface of the sample.
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 rise rate is 3-15 ℃/min. Within the temperature rise rate range, the sample can keep the continuous fibrous morphology without obvious particle or agglomeration.
As a general inventive concept, 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 cathode 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 preoxidation and vacuum calcination in sequence. The product prepared by the method is a selenium-containing compound/carbon fiber energy storage material with uniform appearance, 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, thereby improving the specific capacity, the cycling stability and the rate capability of the material.
2) The energy storage material prepared by the invention has lower production cost and capacity far higher than that of 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 integral method and small 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 used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of manganese-zinc selenide/carbon fiber energy storage material of example 1;
FIG. 2 is a scanning electron micrograph of a manganese-zinc selenide/carbon fiber energy storage material of example 1;
FIG. 3 is a photograph of a TEM image of the manganese-zinc selenide/carbon fiber energy storage material of example 1;
FIG. 4 is a scanning electron micrograph of the manganese-zinc selenide/carbon fiber energy storage material of comparative example 2;
fig. 5 is a specific capacity diagram of a button cell assembled by manganese selenide-zinc/carbon fiber energy storage material in example 1 under different currents;
fig. 6 is a graph showing the change of the specific discharge capacity and efficiency of the button cell assembled from the manganese selenide-zinc/carbon fiber energy storage material in example 1 with the cycle number.
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 a copper selenide/carbon fiber energy storage material of example 5;
FIG. 9 is a photograph of a TEM image of the copper selenide/carbon fiber energy storage material in 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 specific capacity diagram of a button cell assembled from copper selenide/carbon fiber energy storage material in example 5 at different currents;
fig. 12 is a graph showing the specific discharge capacity and efficiency of the button cell assembled from the copper selenide/carbon fiber energy storage material in example 5 as a function of cycle number.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art 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 limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can 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 (the number average molecular weight is 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 dissolving condition is that the mixed solution is stirred for 30min in a water bath at 60 ℃. The precursor fiber is prepared by an electrostatic spinning method, the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise 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 in the embodiment, manganese selenide-zinc is made of Mn0.303Zn0.697Se and Mn0.29Zn0.71Se composition. Fig. 1 is an X-ray diffraction diagram of the energy storage material obtained in this embodiment, and it can be seen from the diagram that the energy storage material contains two phases of manganese selenide-zinc, and no other phases are obviously generated in the reaction process. Fig. 2 is a scanning electron microscope photograph of the energy storage material obtained in this embodiment, and it can be seen from fig. 2 that the prepared energy storage material is composed of nano-scale fibers with uniform morphology. Fig. 3 is a transmission electron microscope photograph of the energy storage material obtained in this example, and it can be seen from the figure that the prepared composite material is a fibrous structure with a diameter of about 100 nm, and the manganese selenide-zinc nanoparticles are perfectly encapsulated in the 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 (the number average molecular weight is 150 ten thousand) are dissolved in N, N-dimethylformamide, the mass ratio of polyacrylonitrile to N, N-dimethylformamide is 0.1:1, the concentration of manganese oxalate in the obtained mixed solution is 0.24mol/L, the concentration of zinc oxalate is 0.12mol/L, and the dissolving condition is that the mixed solution is stirred for 30min in a water bath at 60 ℃. The precursor fiber is prepared by an electrostatic spinning method, the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 300 ℃ in air at a heating rate of 5 ℃/min, and calcining at 300 ℃ for 120min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise 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 (the number average molecular weight is 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 dissolving condition is that the mixed solution is stirred for 30min in a water bath at 60 ℃. The precursor fiber is prepared by an electrostatic spinning method, the voltage is 15kV during electrospinning, and the distance between a spray head and a receiver is 15 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise 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 (the number average molecular weight is 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 dissolving condition is that the mixed solution is stirred for 30min in a water bath at 60 ℃. The precursor fiber is prepared by an electrostatic spinning method, the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 2:1, and then performing 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 temperature rise rate is 5 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
Comparative example 1:
a preparation method of an energy storage material comprises the following steps:
(1) polyacrylonitrile (number average molecular weight of 150 ten thousand) was dissolved in N, N-dimethylformamide, and the ratio of polyacrylonitrile (number average molecular weight of 150 ten thousand) to the total mass of the solution was 0.08: 1. The dissolution condition was water bath stirring at 60 ℃ for 30 min. The precursor fiber is prepared by an electrostatic spinning method, the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise rate is 10 ℃/min; and then cooling, grinding and sieving are carried out to obtain the pure carbon fiber without the metal selenide, the fiber keeps good fibrous appearance, but does not have excellent lithium storage performance because no metal selenide provides external capacity.
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 (the number average molecular weight is 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 dissolving condition is that the mixed solution is stirred for 30min in a water bath at 60 ℃. The precursor fiber is prepared by an electrostatic spinning method, the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Uniformly mixing the precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise rate is 10 ℃/min; and cooling, grinding and sieving to obtain the energy storage material.
Wherein, fig. 4 is a scanning electron microscope photograph of the energy storage material obtained in comparative example 2. It is apparent from fig. 4 that the sample without the pre-oxidation treatment did not maintain the carbon fiber-like structure, but significant adhesion occurred between the fibers and a large number of particles were present, indicating that the carbon fiber without the pre-oxidation treatment did not seal the metal selenide well within the carbon fiber.
And (3) testing the performance of the 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 cathode material, the manganese selenide-zinc/carbon fiber energy storage material obtained in the embodiment 1 is used as a lithium ion battery cathode material, and the method specifically comprises the following steps:
preparing a button cell: dissolving 10 wt% of a bonding agent (CMC), 10 wt% of a conductive agent (carbon black) and 80 wt% of an active substance (the energy storage material in the embodiment 1) in a mixed solvent of deionized water and ethanol (volume ratio: deionized water: ethanol: 3:2), uniformly stirring, coating on a copper foil, and drying for 12 hours at 80 ℃ in a blast drying oven; after drying, the electrode is punched into a pole piece (phi 12mm) by a punch, and the required electrode is prepared. The loading capacity of the active substance on the pole piece is 0.6-1.2mg/cm2. Using a metal lithium sheet as a counter electrode, a porous polypropylene film as a diaphragm, and 1mol/L lithium hexafluorophosphate (LiPF)6) The mixed solution of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte (EC: DMC volume ratio is 1:1), and a button cell (O) is assembled in a glove box filled with argon2Content less than 0.1ppm, H2O content less than 0.1 ppm).
And then testing items such as charge and discharge curves of the button cell obtained by assembling.
The test results are shown in detail in fig. 5 to 6. Wherein, fig. 5 is a graph of specific capacity and efficiency of the assembled button cell under different current densities, the specific discharge capacity is 1055.6, 865.1, 758.9, 674.9, 673.2, 580.1, 514.0 and 436.1mAh/g under the current densities of 0.1, 0.2, 0.5, 1, 1.5, 2, 3 and 5A/g, respectively, and the specific discharge capacity of 954.2 and 1215.2mAh/g still exists after the current densities are restored to 0.2 and 0.1A/g.
Fig. 6 is a graph of specific capacity and cycle number of the assembled button cell under different currents, and it can be seen from the graph that the specific discharge capacity of the energy storage material of example 1 is extremely high, and the specific discharge capacity is 1082.8mAh/g after 300 cycles at a current density of 0.2A/g.
Example 5:
a preparation method of a copper selenide/carbon fiber energy storage material comprises the following steps:
(1) copper oxalate and polyacrylonitrile (number average molecular weight is 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 was water bath stirring at 60 ℃ for 30 min. And preparing precursor fiber from the mixed solution by an electrostatic spinning method, wherein the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise 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 percent of the total mass of the obtained copper selenide/carbon fiber energy storage material.
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 diagram that the energy storage material contains a phase of copper selenide, and no other phases are obviously generated in the reaction process.
Fig. 8 is a scanning electron microscope photograph of the copper selenide/carbon fiber energy storage material obtained in example 5, and it can be seen from fig. 2 that the prepared composite material is composed of nano-scale fibers with uniform morphology.
Fig. 9 is a transmission electron micrograph of the copper selenide/carbon fiber energy storage material obtained in example 5, and it can be seen that the prepared composite material is a fibrous structure with a diameter of about 150 nm, and copper selenide nanoparticles are perfectly encapsulated in carbon fibers.
Example 6:
a preparation method of a copper selenide/carbon fiber energy storage material comprises the following steps:
(1) copper oxalate and polyacrylonitrile (number average molecular weight is 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 was water bath stirring at 60 ℃ for 30 min. And preparing precursor fiber from the mixed solution by an electrostatic spinning method, wherein the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 300 ℃ in air at a heating rate of 5 ℃/min, and calcining at 300 ℃ for 120min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise rate is 10 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material.
Example 7:
a preparation method of a copper selenide/carbon fiber energy storage material comprises the following steps:
(1) copper oxalate and polyacrylonitrile (number average molecular weight is 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 was water bath stirring at 60 ℃ for 30 min. And preparing precursor fiber from the mixed solution by an electrostatic spinning method, wherein the voltage during electrospinning is 15kV, and the distance between a spray head and a receiver is 15 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise rate is 10 ℃/min; and cooling, grinding and sieving to obtain the copper selenide/carbon fiber energy storage material.
Example 8:
a preparation method of a copper selenide/carbon fiber energy storage material comprises the following steps:
(1) copper oxalate and polyacrylonitrile (number average molecular weight is 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 was water bath stirring at 60 ℃ for 30 min. And preparing precursor fiber from the mixed solution by an electrostatic spinning method, wherein the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 2:1, and then performing 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 temperature rise 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 was water bath stirring at 60 ℃ for 30 min. And preparing precursor fiber from the mixed solution by an electrostatic spinning method, wherein the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Drying the precursor fiber by a blast oven at 60 ℃ for 12h, transferring the precursor fiber to a tubular furnace, heating to 280 ℃ in air at a heating rate of 2 ℃/min, and calcining at 280 ℃ for 180min to obtain the preoxidized precursor fiber.
(3) Uniformly mixing the pre-oxidized precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise rate is 10 ℃/min; and then cooling, grinding and sieving are carried out to obtain the pure carbon fiber without the metal selenide, the fiber keeps good fibrous appearance, but does not have excellent lithium storage performance because no metal selenide provides external capacity.
Comparative example 4:
a preparation method of a copper selenide/carbon fiber energy storage material comprises the following steps:
(1) copper oxalate and polyacrylonitrile (number average molecular weight is 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 was water bath stirring at 60 ℃ for 30 min. And preparing precursor fiber from the mixed solution by an electrostatic spinning method, wherein the voltage during electrospinning is 13kV, and the distance between a spray head and a receiver is 20 cm.
(2) Uniformly mixing the precursor fiber and selenium powder (200-500 meshes) in a mass ratio of 3:1, and then performing 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 temperature rise 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 microscope photograph of the copper selenide/carbon fiber energy storage material obtained in comparative example 4. Compared with the copper selenide/carbon fiber energy storage material in example 1, it is obvious that the sample which is not subjected to the pre-oxidation treatment in comparative example 4 has a fiber-shaped structure, but obvious adhesion occurs between fibers and a large number of particles occur, which indicates that the carbon fiber which is not subjected to the pre-oxidation treatment cannot well seal the metal selenide in the carbon fiber.
And (3) testing the performance of the 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 cathode material, the copper selenide/carbon fiber energy storage material obtained in the embodiment 5 is used as a lithium ion battery cathode material, and the method specifically comprises the following steps:
preparing a button cell: dissolving 10 wt% of a bonding agent (CMC), 10 wt% of a conductive agent (carbon black) and 80 wt% of an active substance (the energy storage material in example 5) in a mixed solvent of deionized water and ethanol (volume ratio: deionized water: ethanol: 3:2), uniformly stirring, coating on a copper foil, and drying for 12 hours at 80 ℃ in a blast drying oven; after drying, the electrode is punched into a pole piece (phi 12mm) by a punch, and the required electrode is prepared. The loading capacity of the active substance on the pole piece is 0.6-1.2mg/cm2. Using a metal lithium sheet as a counter electrode, a porous polypropylene film as a diaphragm, and 1mol/L lithium hexafluorophosphate (LiPF)6) The mixed solution of Ethyl Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte (EC: DMC volume ratio is 1:1), and argon is filled in the electrolyteAssembled button cell (O) in glove box2Content less than 0.1ppm, H2O content less than 0.1 ppm).
And then testing items such as charge and discharge curves of the button cell obtained by assembling.
The test results are shown in detail in fig. 11 to 12. Wherein, fig. 11 is a graph of specific capacity and efficiency of the button cell obtained by assembling under different current densities, the discharge capacity is 756.9, 790.4, 748.1, 711.1, 670.5, 621.6, 553.5 and 461.1mAh/g under the current densities of 0.1, 0.2, 0.5, 1, 1.5, 2, 3 and 5A/g, and the discharge specific capacity is 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 at different currents for the assembled button cell, and it can be seen from the graph that the specific capacity of the energy storage material of example 5 is very high, and the specific discharge capacity is 1079.1mAh/g after 100 cycles at a current density of 0.1A/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The selenium-containing compound/carbon fiber energy storage material is characterized by comprising carbon fibers and a selenium-containing compound loaded in the carbon fibers, wherein the selenium-containing compound is copper selenide or manganese selenide-zinc, and the chemical general formula of the manganese selenide-zinc is MnxZn(1-x)Se, wherein x is more than or equal to 0.05 and less than or equal to 0.4.
2. The selenium-containing compound/carbon fiber energy storage material as claimed in claim 1, wherein the selenium-containing compound accounts for 30-70% of the mass of the selenium-containing compound/carbon fiber energy storage material.
3. A preparation method of a selenium-containing compound/carbon fiber energy storage material is characterized by comprising the following steps:
(1) dissolving divalent metal salt and high molecular polymer with viscosity in an organic solvent to obtain a mixed solution; preparing precursor fiber from the mixed solution by an electrostatic spinning method;
(2) drying the precursor fiber, transferring the dried precursor fiber to a tubular furnace, heating the precursor fiber to the temperature of 200-;
(3) and uniformly mixing the preoxidized precursor fiber and selenium powder, then carrying out vacuum calcination, cooling, grinding and sieving to obtain the nano-composite material.
4. The preparation method according to claim 3, wherein 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 both of manganese oxalate and manganese nitrate, and the divalent zinc salt is one or both 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 0.1-0.5 mol/L.
5. The method according to claim 3, wherein in the step (1), the divalent metal salt is copper oxalate, and the concentration of copper oxalate in the mixed solution is 0.1 to 0.5 mol/L.
6. The preparation method according to any one of claims 3 to 5, wherein 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-; the organic solvent is N, N-dimethylformamide.
7. The production method according to any one of claims 3 to 5, wherein in the step (1), the mass ratio of the high molecular polymer to the organic solvent is 0.06 to 0.12: 1; the voltage during electrostatic spinning is 8-18kV, and the distance between the spray head and the receiver is 8-30 cm.
8. The preparation method according to any one of claims 3 to 5, characterized in that in the step (2), a blast oven is adopted to dry the precursor fiber, the drying temperature is 50-80 ℃, and the drying time is 10-15 h; the temperature is raised to 200-300 ℃ in the air at the temperature raising rate of 1-10 ℃/min.
9. The preparation method according to any one of claims 3 to 5, wherein 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; 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 rise rate is 3-15 ℃/min.
10. Use of the selenium-containing compound/carbon fiber energy storage material according to claim 1 or 2 or the selenium-containing compound/carbon fiber energy storage material prepared by the preparation method according to any one of claims 3 to 9 in a negative electrode material of a lithium ion battery.
CN202111295190.0A 2021-11-03 2021-11-03 Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof Active CN114023957B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111295190.0A CN114023957B (en) 2021-11-03 2021-11-03 Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111295190.0A CN114023957B (en) 2021-11-03 2021-11-03 Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114023957A true CN114023957A (en) 2022-02-08
CN114023957B CN114023957B (en) 2023-10-20

Family

ID=80060445

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111295190.0A Active CN114023957B (en) 2021-11-03 2021-11-03 Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114023957B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114725334A (en) * 2022-03-10 2022-07-08 中南大学 Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof
CN116314771A (en) * 2023-05-12 2023-06-23 湖南镓睿科技有限公司 High-surface-capacity potassium ion battery anode material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106920874A (en) * 2017-04-15 2017-07-04 苏州思创源博电子科技有限公司 A kind of preparation method of copper selenide base thermoelectricity material
CN108532029A (en) * 2018-04-17 2018-09-14 浙江理工大学 Using taking or the discarded method taken acrylic fibers and prepare carbon nano-fiber
CN109755528A (en) * 2019-01-04 2019-05-14 中南大学 A kind of preparation method and applications of manganese selenide/carbon fiber energy storage material
CN109755527A (en) * 2019-01-04 2019-05-14 中南大学 A kind of preparation method and applications of zinc selenide/carbon fiber energy storage material
CN111640944A (en) * 2020-06-11 2020-09-08 重庆文理学院 (Zn, Mn) Se/C composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106920874A (en) * 2017-04-15 2017-07-04 苏州思创源博电子科技有限公司 A kind of preparation method of copper selenide base thermoelectricity material
CN108532029A (en) * 2018-04-17 2018-09-14 浙江理工大学 Using taking or the discarded method taken acrylic fibers and prepare carbon nano-fiber
CN109755528A (en) * 2019-01-04 2019-05-14 中南大学 A kind of preparation method and applications of manganese selenide/carbon fiber energy storage material
CN109755527A (en) * 2019-01-04 2019-05-14 中南大学 A kind of preparation method and applications of zinc selenide/carbon fiber energy storage material
CN111640944A (en) * 2020-06-11 2020-09-08 重庆文理学院 (Zn, Mn) Se/C composite material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李云杰等: "溶剂热制备CuSe纳米片及其储钠性能研究", 《中国科学：化学》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114725334A (en) * 2022-03-10 2022-07-08 中南大学 Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof
CN114725334B (en) * 2022-03-10 2024-02-06 湖南金钺新材料有限责任公司 Flower-like zinc selenide-manganese/carbon composite material and preparation method and application thereof
CN116314771A (en) * 2023-05-12 2023-06-23 湖南镓睿科技有限公司 High-surface-capacity potassium ion battery anode material and preparation method thereof
CN116314771B (en) * 2023-05-12 2023-10-31 湖南镓睿科技有限公司 High-surface-capacity potassium ion battery anode material and preparation method thereof

Also Published As

Publication number Publication date
CN114023957B (en) 2023-10-20

Similar Documents

Publication Publication Date Title
CN111193019B (en) Lithium supplement additive, preparation method thereof and lithium ion battery
CN109860534B (en) Carbon quantum dot modified ternary cathode material and preparation method thereof
CN111180714B (en) Carbon/molybdenum dioxide/silicon/carbon composite material, battery cathode comprising same and lithium ion battery
CN105810914A (en) Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN114023957B (en) Selenium-containing compound/carbon fiber energy storage material and preparation method and application thereof
CN108987683A (en) A kind of preparation method of carbon coating tertiary cathode material
CN111769272A (en) Bi @ C hollow nanosphere composite material and preparation method and application thereof
CN111900407B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN111564612A (en) High-thermal-conductivity and high-electrical-conductivity lithium battery positive electrode material and preparation method thereof
CN108400296B (en) Heterogeneous element doped ferroferric oxide/graphene negative electrode material
CN112054174A (en) Potassium ion battery negative electrode material and preparation method and application thereof
CN110635116A (en) Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery
CN110311111B (en) N-doped CNT in-situ coated Co nanoparticle composite material and preparation and application thereof
CN114300671A (en) Graphite composite negative electrode material and preparation method and application thereof
CN111554905B (en) Preparation method, product and application of zinc oxide-based carbon composite nano material
CN110600710B (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN116845191A (en) Self-supplementing lithium ternary material, preparation method and application
CN115425209A (en) Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material
CN115249799A (en) Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material
CN113666411B (en) Method for preparing ultra-small oxide and carbon composite lithium battery anode material by microwave method
CN114203994A (en) Preparation method and application of lithium-sulfur battery positive electrode material
CN111509188A (en) Anode material, anode, lithium ion battery and preparation method
CN113206247A (en) Core-shell structure negative electrode material, preparation method thereof and lithium ion battery
CN114262955B (en) Size-controllable Ni-NiO heterojunction nanoparticle doped carbon fiber, preparation method and application thereof in lithium-sulfur battery diaphragm

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20230905

Address after: 414022, 1st to 2nd floors, Building 16, Science and Technology Innovation Industrial Park, Xinyuan Community, Muligang Management Office, Yueyang Economic and Technological Development Zone, Yueyang City, Hunan Province

Applicant after: Hunan Jinyue New Materials Co.,Ltd.

Address before: 410083 Hunan province Changsha Lushan Road No. 932

Applicant before: CENTRAL SOUTH University

GR01 Patent grant
GR01 Patent grant