CN111088562B - Composite micro-nano hollow fiber material and preparation method and application thereof - Google Patents

Composite micro-nano hollow fiber material and preparation method and application thereof Download PDF

Info

Publication number
CN111088562B
CN111088562B CN201911347006.5A CN201911347006A CN111088562B CN 111088562 B CN111088562 B CN 111088562B CN 201911347006 A CN201911347006 A CN 201911347006A CN 111088562 B CN111088562 B CN 111088562B
Authority
CN
China
Prior art keywords
metal
nano
nickel
composite micro
cobalt
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.)
Active
Application number
CN201911347006.5A
Other languages
Chinese (zh)
Other versions
CN111088562A (en
Inventor
于乐
李念武
陈晨
何心
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.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
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 Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201911347006.5A priority Critical patent/CN111088562B/en
Publication of CN111088562A publication Critical patent/CN111088562A/en
Application granted granted Critical
Publication of CN111088562B publication Critical patent/CN111088562B/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Textile Engineering (AREA)
  • Nanotechnology (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a composite micro-nano hollow fiber material and a preparation method and application thereof. The composite micro-nano hollow fiber material is a carbon nanofiber with a metal simple substance, or alloy, or a metal compound porous hollow nano prism wrapped inside, the metal compound is at least one of metal sulfide, phosphide and selenide, the metal compound contains at least one metal element of iron, nickel and cobalt, and the alloy contains at least two metal elements of iron, nickel and cobalt. When the composite micro-nano fiber is used as a lithium metal negative electrode carrier, the multistage hollow structure in the composite micro-nano fiber is beneficial to permeation and diffusion of electrolyte in the fiber, and a space is provided for deposition of lithium in the fiber. Secondly, metal sulfide, phosphide, selenide or metal simple substance or alloy in the carrier has better lithium affinity, which is beneficial to the deposition of metal lithium in the carbon fiber.

Description

Composite micro-nano hollow fiber material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy and nano material preparation, and particularly relates to a composite micro-nano hollow fiber material and a preparation method and application thereof.
Background
The demand for next-generation lithium ion batteries with high energy density and good safety performance is very urgent in the fields of energy storage, new energy automobiles and consumer electronics. The metallic lithium has excellent theoretical specific capacity (3860mAh g-1) And lowest electrochemical potential as lithiumMetal battery negative electrode materials have natural advantages and are considered as the final solution for high energy density batteries. However, the practical application of lithium metal batteries still faces great challenges, for example, dendritic lithium dendrites are easily generated in the lithium metal negative electrode during repeated charge and discharge processes, and the performance of the batteries is greatly damaged. On one hand, the lithium dendrite reacts with the electrolyte to consume the lithium metal and the electrolyte, and on the other hand, the lithium dendrite separated from the lithium metal negative electrode substrate cuts off the electronic channel and cannot participate in the electrochemical reaction to form 'dead lithium', so that the cycle efficiency of the lithium metal negative electrode is reduced. In addition, the continuous growth of the metal lithium dendrites can pierce through the diaphragm, so that the short circuit of the anode and the cathode of the battery is caused, the battery explosion can be seriously caused, and the coulomb efficiency and the cycle performance of the battery are further influenced.
Disclosure of Invention
In order to solve the problems, the invention provides a composite micro-nano hollow fiber material which is a carbon nanofiber internally wrapped with a metal simple substance, an alloy or a metal compound-based porous hollow nano prism, wherein the metal compound is at least one of a metal sulfide, a metal phosphide and a metal selenide.
In one embodiment, the metal compound contains at least one metal element of iron, nickel and cobalt, the alloy contains at least two metal elements of iron, nickel and cobalt, or the metal simple substance is any one of iron, nickel and cobalt.
According to an embodiment of the present invention, when two metal elements are contained in the metal compound or alloy, the molar ratio is 1:9 to 9:1, for example, nickel cobalt metal elements are contained in a molar ratio of 1:9 to 9: 1.
According to an embodiment of the present invention, the carbon nanofiber comprises a porous hollow nanoprism of at least one of a metal sulfide, a metal phosphide, and a metal selenide, or a simple metal porous hollow nanoprism, or an alloy porous hollow nanoprism inside.
According to an embodiment of the present invention, the porous hollow nanoprisms have a length of 0.5 to 3 μm and a width of 0.1 to 1 μm; for example, the length is 0.8 to 2.5 μm and the width is 0.2 to 0.8 μm.
According to an embodiment of the present invention, the carbon nanofibers have a diameter of 0.001 to 3 μm, for example 0.1 to 2 μm.
According to an exemplary embodiment of the invention, the composite micro-nano hollow fiber material is a carbon nanofiber internally wrapped with at least one of nickel-cobalt sulfide, nickel-cobalt phosphide and nickel-cobalt selenide, or a nickel metal simple substance, or a cobalt metal simple substance, or a nickel-cobalt alloy porous hollow nanoprism.
According to an embodiment of the invention, the alloy has the meaning known in the art and refers to a substance having metallic properties synthesized by a certain method from two or more metals and non-metals, for example, herein refers to a substance obtained by directly annealing acetate hydroxide precursors of two or more metals at high temperature in an inert gas atmosphere. The invention also provides a preparation method of the composite micro-nano hollow fiber material, which comprises the following steps:
s1) dissolving polyvinylpyrrolidone and metal acetate in an alcohol solvent to form a mixed solution, and heating for reaction to obtain a metal-based acetate hydroxide precursor;
s2) respectively dispersing the metal-based acetate hydroxide precursor obtained in the step S1) and a fiber-forming polymer in an amide solvent to respectively form two precursor solutions, mixing the two precursor solutions to obtain a spinning solution, and preparing the spinning solution into a film material consisting of micro-nano fibers through electrostatic spinning;
s3) carrying out high-temperature annealing treatment on the film material obtained in the step S2) and at least one of a sulfur source, a phosphorus source and a selenium source under inert atmosphere, or directly carrying out high-temperature annealing treatment on the obtained film material under inert atmosphere, so as to obtain the composite micro-nano hollow fiber material formed by hollow nano prisms, wherein the interior of the composite micro-nano hollow fiber material is wrapped with at least one of metal sulfide, metal phosphide and metal selenide, or a metal simple substance or an alloy.
According to an embodiment of the present invention, the metal acetate in step S1) is at least one of acetate of iron, nickel and cobalt.
According to an embodiment of the invention, the polyvinylpyrrolidone in step S1) has a number average molecular weight of 10000 to 58000, such as 20000 to 30000.
According to an embodiment of the invention, when acetates of any two metals are used in step S1), the molar ratio of the two acetates is 1:9 to 9:1, such as 1:5 to 5: 1.
According to an embodiment of the present invention, the temperature of heating in step S1) is 30 to 95 ℃; the heating time is 30 min-24 hours.
According to an embodiment of the present invention, the alcoholic solvent in step S1) is selected from methanol, ethanol or propanol.
According to an embodiment of the present invention, the mass fraction of the polyvinylpyrrolidone in the mixed solution in step S1) is 0.5% to 5%, preferably 1 to 4%.
According to an embodiment of the present invention, the mass fraction of the metal acetate in the mixed solution in step S1) is 0.1% to 3%, preferably 0.5% to 2%.
According to an embodiment of the present invention, the particle length of the precursor obtained in step S1) is 0.5 to 3 μm, and the width is 0.1 to 1 μm; for example, the length is 0.8 to 2.5 μm and the width is 0.2 to 0.8 μm.
According to an embodiment of the present invention, the mass fractions of the metal-based acetate hydroxide precursor and the fiber-forming polymer in the spinning solution in step S2) are the same or different, and are 5% to 30% independently of each other; preferably, the two are independent of each other 10-30%; also preferably, the two are independently 15 to 25% of each other.
According to an embodiment of the present invention, the amide-based solvent of step S2) is at least one selected from N, N-dimethylformamide or N, N-dimethylacetamide.
According to an embodiment of the present invention, the fiber-forming polymer in step S2) is at least one of polyacrylonitrile or polyvinylpyrrolidone.
According to the embodiment of the present invention, the working voltage applied during the electrostatic spinning process in the step S2) is 10 to 25 kV.
According to an embodiment of the present invention, the temperature of the electrospinning in the step S2) is 20 to 70 ℃.
According to an embodiment of the present invention, the collecting distance of the electrospinning in the step S2) is 10 to 30 cm.
According to the embodiment of the invention, in the step S2), the spinning solution is prepared into a film material consisting of micro-nano fibers with the diameter of 0.2-2 μm.
According to an embodiment of the present invention, the temperature of the high temperature annealing treatment in the step S3) is 300 to 900 ℃, for example 300 to 550 ℃.
According to an embodiment of the present invention, the inert atmosphere in the high temperature annealing process in step S3) is provided by nitrogen or argon.
According to an embodiment of the present invention, the sulfur source in step S3) is sulfur powder; the phosphorus source is NaH2PO2(ii) a The selenium source is selenium powder.
According to an embodiment of the present invention, the mass ratio of the thin film material to the sulfur source, the phosphorus source, or the selenium source in step S3) is 1:1 to 1:10, for example 1:2 to 1: 8.
According to the embodiment of the invention, when only acetate of one metal is used in the step S1), the porous hollow nanoprisms formed by metal simple substances are wrapped in the composite micro-nano hollow fiber material obtained by the direct high-temperature annealing treatment in the step S3); when acetates of more than two metals are used in the step S1), the composite micro-nano hollow fiber material obtained through the direct high-temperature annealing treatment in the step S3) is wrapped by an alloy hollow nano prism; when the film material obtained in the step S2) and at least one of a sulfur source, a phosphorus source and a selenium source are subjected to high-temperature annealing treatment, at least one of a metal sulfide hollow nano prism, a metal phosphide hollow nano prism and a metal selenide hollow nano prism is wrapped in the obtained composite micro-nano hollow fiber material.
The invention also provides the composite micro-nano hollow fiber material prepared by the method.
The invention also provides application of the composite micro-nano hollow fiber material as a metal battery negative electrode protection material, for example, as a lithium metal negative electrode carrier.
The invention provides a lithium metal negative electrode carrier which comprises the composite micro-nano hollow fiber material.
Advantageous effects
When the composite micro-nano fiber prepared by the invention is used as a lithium metal negative electrode carrier, the multi-stage hollow structure in the composite micro-nano fiber is beneficial to permeation and diffusion of electrolyte in the fiber, and a space is provided for deposition of lithium in the fiber. And secondly, the metal sulfide, metal phosphide, metal selenide, or metal simple substance or alloy in the carrier has better lithium affinity, and is beneficial to the deposition of metal lithium in the carbon fiber. And because of the existence of the carbon fiber skeleton of the smooth pipe wall, the transmission of ions and electrons is facilitated, and the local excessive deposition of lithium on the surface of the fiber is prevented. The advantages can ensure that the metal lithium is uniformly deposited and nucleated in each fiber, effectively inhibit the growth of lithium dendrites in the circulation process, and enhance the quick charging capacity, the circulation stability and the safety performance of the lithium metal battery.
Drawings
FIG. 1 shows a scanning electron micrograph of nickel cobalt based acetate hydroxide (molar ratio of nickel cobalt element 1: 2) in example 1 of the present invention.
Fig. 2 shows (a) a field emission scanning electron micrograph and (b) a transmission electron micrograph of a fibrous thin film material comprising nickel cobalt acetate hydroxide nanoprisms encapsulated in example 1 of the present invention.
Fig. 3 shows a transmission electron micrograph of a fiber thin film material in which nickel-cobalt alloy hollow nanoprisms are wrapped in example 1 of the present invention.
Fig. 4 shows an XRD pattern of a fibrous film material coated with nickel-cobalt alloy hollow nanoprisms in example 1 of the present invention.
FIG. 5 shows that (a) the composite micro-nano hollow fiber prepared in example 1 and (b) a copper sheet are respectively used as lithium metal negative electrode carriers to assemble a half cell, and the current density of the half cell is 0.5mA cm-2Scanning electron microscope photograph of field emission after 6 hours of lithium deposition.
FIG. 6 shows that the current density of a half-cell assembled by the composite micro-nano hollow fiber and the copper sheet prepared in example 1 respectively serving as lithium metal negative electrode carriers is 1mA cm-2Voltage profile after 4 hours of first lithium deposition.
FIG. 7 shows a sample prepared in example 1The composite micro-nano hollow fiber and the copper sheet are respectively used as lithium metal cathodes to assemble a half-cell with the current density of 3mA cm-2Then, a polarization voltage curve of 80 cycles of charge and discharge was cyclically performed.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1: preparation of carbon micro-nano hollow fiber material wrapped with nickel-cobalt alloy hollow nanoprism
Dissolving polyvinylpyrrolidone (number average molecular weight: 40000) and a mixture of nickel acetate and cobalt acetate with the molar ratio of nickel cobalt element being 1:2 in ethanol at 25 ℃, wherein the mass fraction of polyvinylpyrrolidone and the mass fraction of nickel cobalt acetate in the mixed solution are 1.5% and 1%, heating the mixed solution to 65 ℃, and reacting for 1 hour to obtain the nickel cobalt base acetate hydroxide precursor. The scanning electron micrograph of the nickel-cobalt based acetate hydroxide precursor is shown in FIG. 1. the length dimension of the nickel-cobalt based acetate hydroxide precursor particles is about 1.3 μm, and the width dimension thereof is about 0.3. mu.m;
respectively dispersing the nickel-cobalt-based acetate hydroxide precursor and polyacrylonitrile in N, N-dimethylformamide, and mixing the two precursor solutions to obtain a spinning solution, wherein the mass fractions of the nickel-cobalt-based acetate hydroxide precursor and the polyacrylonitrile are both 15%; the working voltage applied in the electrostatic spinning process is 17kV, the temperature is 35 ℃, the collection distance is 20cm, namely, the spinning solution is prepared into a thin film material consisting of micro-nano fibers with the diameter of 0.5-1.2 mu m, the field emission scanning electron microscope photo is shown in figure 2(a), and the transmission electron microscope photo is shown in figure 2 (b).
And (3) placing the film material in a tube furnace, heating to 450 ℃ in a nitrogen atmosphere, and carrying out high-temperature annealing treatment to obtain the composite micro-nano hollow fiber wrapped with the nickel-cobalt alloy hollow nano prism, wherein a transmission electron microscope photo of the composite micro-nano hollow fiber is shown in fig. 3. The width of the hollow nanoprisms is about 1 μm. The XRD pattern is shown in figure 4.
Example 2: is wrapped with Ni5CoS4Preparation of carbon micro-nano hollow fiber material of hollow nano prism
Dissolving polyvinylpyrrolidone (number average molecular weight: 40000) and a mixture of nickel acetate and cobalt acetate with a nickel-cobalt element molar ratio of 5:1 in ethanol at 22 ℃, heating the mixed solution to 85 ℃ to react for 1 hour, wherein the mass fraction of the polyvinylpyrrolidone and the mass fraction of the nickel-cobalt acetate in the mixed solution are 2% and 1.5%, and the product is the nickel-cobalt-based acetate hydroxide precursor. The product particles had a length dimension of about 1 μm and a width dimension of about 0.5. mu.m;
respectively dispersing the nickel-cobalt-based acetate hydroxide precursor and polyacrylonitrile in N, N-dimethylformamide, and mixing the two precursor solutions to obtain a spinning solution, wherein the mass fractions of the nickel-cobalt-based acetate hydroxide precursor and the polyacrylonitrile are both 18%; the working voltage applied in the electrostatic spinning process is 18kV, the temperature is 40 ℃, the collection distance is 17cm, namely, the spinning solution is prepared into a film material consisting of micro-nano fibers with the diameter of 0.8-1.5 mu m;
placing the film material and sulfur powder in a mass ratio of 1:4 in a tube furnace, heating to 350 ℃ in a nitrogen atmosphere, and carrying out high-temperature annealing treatment to obtain the composite micro-nano hollow fiber material internally wrapped with the nickel-cobalt-based sulfide hollow nano prism with the width of about 0.45 mu m.
Example 3: wrapped with NiCo2Preparation of P hollow nanoprism carbon micro-nano hollow fiber material
Dissolving polyvinylpyrrolidone (number average molecular weight: 40000) and a mixture of nickel acetate and cobalt acetate with the molar ratio of nickel cobalt element being 1:2 in ethanol at 21 ℃, wherein the mass fraction of polyvinylpyrrolidone and the mass fraction of nickel cobalt acetate in the mixed solution are 1.5%, and the mass fraction of nickel cobalt acetate is 1.5%, heating the obtained mixed solution to 45 ℃ for reacting for 4 hours to obtain the nickel cobalt base acetate hydroxide precursor. The product particles had a length dimension of about 1.2 μm and a width dimension of about 0.2 μm;
respectively dispersing the nickel-cobalt-based acetate hydroxide precursor and polyacrylonitrile in N, N-dimethylformamide, and mixing the two precursor solutions to obtain a spinning solution, wherein the mass fractions of the nickel-cobalt-based acetate hydroxide precursor and the polyacrylonitrile are both 20%; the working voltage applied in the electrostatic spinning process is 20kV, the temperature is 40 ℃, the collection distance is 18cm, namely, the spinning solution is prepared into a film material consisting of micro-nano fibers with the diameter of 1-2 mu m;
mixing a film material and NaH in a mass ratio of 1:62PO2And placing the composite micro-nano hollow fiber material in a tubular furnace, heating the composite micro-nano hollow fiber material to 400 ℃ in an argon atmosphere, and carrying out high-temperature annealing treatment to obtain the composite micro-nano hollow fiber material, wherein the nickel-cobalt-based phosphide hollow nanoprism with the width of about 0.18 mu m is wrapped in the composite micro-nano hollow fiber material.
Example 4: wrapped with NiCo5Se4Preparation of carbon micro-nano hollow fiber material of hollow nano prism
Dissolving polyvinylpyrrolidone (number average molecular weight: 40000) and a mixture of nickel acetate and cobalt acetate with the molar ratio of nickel cobalt element being 1:5 in ethanol at 23 ℃, wherein the mass fraction of polyvinylpyrrolidone and the mass fraction of nickel cobalt acetate in the mixed solution are 2.5% and 0.8%, heating the mixed solution to 65 ℃, and reacting for 4 hours to obtain the nickel cobalt base acetate hydroxide precursor. The product particles had a length dimension of about 1.5 μm and a width dimension of about 0.5. mu.m;
respectively dispersing the nickel-cobalt-based acetate hydroxide precursor and polyacrylonitrile in N, N-dimethylformamide, and mixing the two precursor solutions to obtain a spinning solution, wherein the mass fractions of the nickel-cobalt-based acetate hydroxide precursor and the polyacrylonitrile are both 25%; the working voltage applied in the electrostatic spinning process is 15kV, the temperature is 30 ℃, the collection distance is 20cm, namely, the spinning solution is prepared into a film material consisting of micro-nano fibers with the diameter of 0.5-1 mu m;
placing the film material and selenium powder in a mass ratio of 1:4 in a tube furnace, heating to 300 ℃ in an argon atmosphere, and carrying out high-temperature annealing treatment to obtain the composite micro-nano hollow fiber material internally wrapped with the nickel-cobalt-based selenide hollow nano prism with the width of about 0.4 mu m.
Test example 1
The composite micro-nano hollow fiber material and the copper sheet prepared in the example 1 are respectively used as a carrier of a lithium metal negative electrode to assemble a half cell, wherein an electrolyte used by the half cell is a mixed solution composed of ethylene carbonate, ethylmethyl carbonate, vinylene carbonate and lithium hexafluorophosphate. At a current density of 0.5mA cm-2The scanning electron micrograph of the field emission image 6 hours after lithium deposition is shown in FIG. 5. As can be seen from fig. 5, metal lithium is uniformly deposited on the composite micro-nano hollow fiber carrier without changing the morphology of the fiber. But the metallic lithium is deposited on the carrier copper sheet unevenly and is agglomerated in island shape. As can be seen from fig. 5, compared with the copper sheet, due to the existence of the porous nanoprisms in the composite micro-nano hollow fiber material prepared in example 1, a space is provided for deposition of lithium in the fiber, and the composite micro-nano hollow fiber material has good lithium affinity, which is beneficial to inhibiting growth of lithium dendrites in a circulation process.
The composite micro-nano hollow fiber material and the copper sheet prepared in the embodiment 1 are respectively used as negative electrode carriers of lithium metal to assemble a half-cell with the current density of 1mA cm-2The voltage profile after 4 hours of the first lithium deposition cycle is shown in fig. 6 (in which the half-cell electrolyte is a mixed solution of ethylene carbonate, ethylmethyl carbonate, vinylene carbonate and lithium hexafluorophosphate). As can be seen from fig. 6, the electrode nucleation overpotential formed by using the composite micro-nano hollow fiber material prepared in example 1 as a carrier of a lithium metal negative electrode is significantly lower than that of a copper sheet, which means that the composite micro-nano hollow fiber material has more excellent lithium affinity and smaller lithium nucleation barrier compared with the copper sheet, and is beneficial to uniform deposition of metal lithium and growth of a dendrite-free form.
The composite micro-nano hollow fiber material and the copper sheet prepared in the embodiment 1 are respectively used as negative electrode carriers of lithium metal to assemble a half-cell with the current density of 3mA cm-2In the case where the electrolyte used in the half cell is composed of ethylene carbonate, ethylmethyl carbonate, vinylene carbonate and lithium hexafluorophosphateThe mixed solution of (2), the polarization voltage curve of 80 cycles of the cyclic charge and discharge (1 hour each of the discharge and charge processes) is shown in fig. 7. As can be seen from fig. 7, the electrode voltage platform of the composite micro-nano hollow fiber material prepared in example 1 as the carrier is maintained to be stable, and the overpotential is relatively stably maintained at a lower level, which is much lower than the electrode with the copper sheet as the carrier, so that the lithium metal electrode obtained by using the composite micro-nano hollow fiber material as the carrier has better negative electrode cycling stability than the electrode with the copper sheet as the carrier.
Therefore, the composite micro-nano hollow fiber material prepared by the invention has good lithium affinity, can effectively inhibit the growth of lithium dendrites in the circulation process, is beneficial to uniform deposition of metal lithium, can effectively improve the circulation stability of the lithium battery cathode, has excellent performance and has good application prospect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (21)

1. The composite micro-nano hollow fiber material is characterized in that the material is a carbon nanofiber internally wrapped with a metal simple substance, an alloy or a metal compound-based porous hollow nano prism, and the metal compound is at least one of a metal sulfide, a metal phosphide and a metal selenide;
the metal compound contains at least one metal element of iron, nickel and cobalt; the alloy contains at least two metal elements of iron, nickel and cobalt; the metal simple substance is any one of iron, nickel and cobalt;
the length of the porous hollow nanoprism is 0.5-3 mu m, and the width of the porous hollow nanoprism is 0.1-1 mu m.
2. The composite micro-nano hollow fiber material according to claim 1, wherein when two metal elements are contained in the metal compound or the alloy, the molar ratio of the two metal elements is 1: 9-9: 1.
3. The composite micro-nano hollow fiber material according to claim 1, wherein the carbon nanofibers internally comprise at least one porous hollow nanoprism of nickel-cobalt based sulfide, nickel-cobalt based phosphide or nickel-cobalt based selenide, or nickel/cobalt elemental metal porous hollow nanoprism, or nickel-cobalt alloy porous hollow nanoprism.
4. The composite micro-nano hollow fiber material according to any one of claims 1 to 3, wherein the diameter of the fiber is 2 to 3 μm.
5. The preparation method of the composite micro-nano hollow fiber material according to any one of claims 1 to 4, characterized by comprising the following steps:
s1) dissolving polyvinylpyrrolidone and metal acetate in an alcohol solvent to form a mixed solution, and heating for reaction to obtain a metal-based acetate hydroxide precursor;
s2) respectively dispersing the metal-based acetate hydroxide precursor obtained in the step S1) and a fiber-forming polymer in an amide solvent to respectively form two precursor solutions, mixing the two precursor solutions to obtain a spinning solution, and preparing the spinning solution into a film material consisting of micro-nano fibers through electrostatic spinning;
s3) respectively carrying out high-temperature annealing treatment on the film material obtained in the step S2) and at least one of a sulfur source, a phosphorus source and a selenium source under an inert atmosphere, or directly carrying out high-temperature annealing treatment on the obtained film material under the inert atmosphere, so as to prepare the composite micro-nano hollow fiber material with at least one of a metal sulfide porous hollow nano prism, a phosphide porous hollow nano prism or a selenide porous hollow nano prism wrapped inside, or a metal simple substance porous hollow nano prism or an alloy porous hollow nano prism.
6. The method according to claim 5, wherein in step S1), the metal acetate is selected from at least one acetate of Fe, Ni and Co.
7. The method according to claim 5, wherein the polyvinylpyrrolidone in step S1) has a number average molecular weight of 10000 to 58000.
8. The method according to claim 5, wherein the alcoholic solvent in step S1) is selected from methanol, ethanol, and propanol.
9. The method according to claim 5, wherein the mass fraction of polyvinylpyrrolidone in the mixed solution in step S1) is 0.5 to 5%.
10. The method according to claim 5, wherein the mass fraction of metal acetate in the mixed solution in step S1) is 0.1-3%.
11. The production method according to claim 5, wherein the mass fractions of the metal-based acetate hydroxide precursor and the fiber-forming polymer in the spinning solution in step S2) are the same or different and are 5% to 30% independently of each other.
12. The method of any one of claims 5-11, wherein the fiber-forming polymer in step S2) is at least one of polyacrylonitrile or polyvinylpyrrolidone.
13. The method according to any one of claims 5 to 11, wherein the working voltage applied during the electrospinning in step S2) is 10 to 25 kV.
14. The method according to any one of claims 5 to 11, wherein the temperature of the electrospinning in the step S2) is 20 to 70 ℃.
15. The method according to any one of claims 5 to 11, wherein the collecting distance of the electrospinning in step S2) is 10 to 30 cm.
16. The production method according to any one of claims 5 to 11, wherein the temperature of the high-temperature annealing treatment in step S3) is 300 to 900 ℃.
17. The production method according to any one of claims 5 to 11, wherein the sulfur source in step S3) is sulfur powder; the phosphorus source is NaH2PO2(ii) a The selenium source is selenium powder.
18. The preparation method according to any one of claims 5 to 11, wherein the mass ratio of the thin film material to the sulfur source, the phosphorus source or the selenium source in step S3) is 1:1 to 1: 10.
19. The composite micro-nano hollow fiber material prepared by the method according to any one of claims 5 to 18.
20. The use of the composite micro-nano hollow fiber material according to any one of claims 1 to 4 as a metal battery negative electrode protection material.
21. The use of the composite micro-nano hollow fiber material according to any one of claims 1 to 4 as a negative electrode carrier of a lithium battery.
CN201911347006.5A 2019-12-24 2019-12-24 Composite micro-nano hollow fiber material and preparation method and application thereof Active CN111088562B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911347006.5A CN111088562B (en) 2019-12-24 2019-12-24 Composite micro-nano hollow fiber material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911347006.5A CN111088562B (en) 2019-12-24 2019-12-24 Composite micro-nano hollow fiber material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111088562A CN111088562A (en) 2020-05-01
CN111088562B true CN111088562B (en) 2021-07-23

Family

ID=70396838

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911347006.5A Active CN111088562B (en) 2019-12-24 2019-12-24 Composite micro-nano hollow fiber material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111088562B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111799469B (en) * 2020-08-26 2022-01-18 中南大学 CoP @ carbon nanotube composite material and preparation and application thereof
CN113540403B (en) * 2020-08-30 2023-04-28 中南大学 High-stability three-dimensional porous lithium metal anode and preparation method and application thereof
CN113540454B (en) * 2020-08-30 2022-10-14 中南大学 Lithium-philic porous composite carbon skeleton of 3D lithium metal negative electrode and preparation method and application thereof
CN112201782B (en) * 2020-10-16 2022-09-30 西南大学 Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof
CN112877812B (en) * 2021-01-21 2022-04-19 西北大学 Bimetal-doped metal phosphide nanofiber and preparation method thereof
CN113097496B (en) * 2021-02-25 2022-04-29 东华大学 Zinc cathode with composite nanofiber protective layer and preparation and application thereof
CN114678508A (en) * 2022-04-13 2022-06-28 电子科技大学长三角研究院(湖州) Carbon-based supported metal sulfide composite material and preparation method and application thereof
CN115838521A (en) * 2022-06-20 2023-03-24 宁德时代新能源科技股份有限公司 Hollow fiber composite, method for producing same, electrode sheet, battery module, battery pack, and device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102668194B (en) * 2009-12-04 2015-05-20 路透Jj股份有限公司 Anode active material precursor and active material for a rechargeable lithium battery comprising hollow nanofibrous carbon, and a production method therefor
CN103337641A (en) * 2013-03-12 2013-10-02 上海中聚佳华电池科技有限公司 Oxygen electrode composite catalyst used for lithium-air batteries and preparation method of the oxygen electrode composite catalyst

Also Published As

Publication number Publication date
CN111088562A (en) 2020-05-01

Similar Documents

Publication Publication Date Title
CN111088562B (en) Composite micro-nano hollow fiber material and preparation method and application thereof
Xue et al. Porous Co 3 O 4 nanoneedle arrays growing directly on copper foils and their ultrafast charging/discharging as lithium-ion battery anodes
CN108649190A (en) Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application
CN112928238B (en) Ultrathin metal lithium electrode, preparation thereof and application of ultrathin metal lithium electrode as negative electrode of secondary lithium battery
KR101997968B1 (en) Spider network structure composition of N-doped carbon nanofibers containing MnCoOx nanoparticles, the preparation method, and application to anode material for secondary battery
CN112467200B (en) Lithium fluoride/lithium lanthanum titanate nanofiber solid electrolyte interface material and preparation method and application thereof
CN112615009A (en) Flexible self-supporting lithium-tin alloy composite nanofiber lithium metal battery cathode material
KR101392388B1 (en) Carbon nanofibers composite and method for preparing the same and anode active materials for lithium secondary batteries comprising the same
CN107634206A (en) A kind of lithium ion battery flexibility negative material and preparation method thereof
CN110854381B (en) Preparation method of carbon-doped tin-manganese composite oxide nanofiber modified by cobalt oxide
US20150287980A1 (en) Method of producing porous electrodes for batteries and fuel cells
CN113699687B (en) Double-needle electrostatic spinning Li 3 VO 4 Preparation method of/C fiber lithium ion battery cathode material
CN110592807B (en) Thin film material for inhibiting growth of lithium dendrite and preparation method thereof
CN112538692B (en) Co-Mn bimetallic organic framework derived porous carbon fiber and preparation method and application thereof
CN110474023B (en) Fibrous nickel-bismuth battery and preparation method thereof
CN113488656A (en) 3D lithium-philic composite porous metal alloy current collector and preparation method and application thereof
CN106920961B (en) Modification method of ternary material for lithium ion battery
CN115148956A (en) Electrode based on sub-nanometer tellurium @ graded porous carbon fiber and preparation method thereof
CN115101725A (en) Preparation method of silicon nanowire electrode and application of silicon nanowire electrode in lithium ion battery
CN113753962A (en) Cobalt sulfide/carbon composite negative electrode material for sodium ion battery and preparation method thereof
CN109301201A (en) The compound Ga of the double carbon structures of self-supporting2O3Negative electrode of lithium ion battery preparation method
CN114262955B (en) Size-controllable Ni-NiO heterojunction nanoparticle doped carbon fiber, preparation method and application thereof in lithium-sulfur battery diaphragm
CN111564619B (en) Preparation method of carbon-coated nano nickel lithium battery material
CN115360026B (en) Preparation method of carbon-based composite high-entropy alloy CuAgCoCdZn lithium electrode material
CN116254624A (en) Porous transition metal-based composite fiber membrane, and in-situ preparation method and application thereof

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
GR01 Patent grant
GR01 Patent grant