CN110735232A - fiber materials, and preparation method and application thereof - Google Patents

fiber materials, and preparation method and application thereof Download PDF

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Publication number
CN110735232A
CN110735232A CN201810791508.6A CN201810791508A CN110735232A CN 110735232 A CN110735232 A CN 110735232A CN 201810791508 A CN201810791508 A CN 201810791508A CN 110735232 A CN110735232 A CN 110735232A
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sodium alginate
sintering
based composite
spinning
lithium
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CN110735232B (en
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何海勇
王德宇
潘林海
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application discloses fiber materials and a preparation method and application thereof, wherein the materials are prepared by sintering a sodium alginate-based composite fiber membrane, the materials can be used as a negative electrode current collector of a lithium metal secondary battery, and a porous structure among fibers can effectively relieve the volume change in the process of lithium intercalation and deintercalation.

Description

fiber materials, and preparation method and application thereof
Technical Field
The application relates to fiber materials and a preparation method and application thereof, belonging to the field of material preparation.
Background
The lithium metal negative electrode has very high theoretical specific capacity (3860mA h g)-1) And a lower reduction potential (-3.04V, relative to standard hydrogen electrodes), are the most promising negative electrode materials for high energy density lithium secondary battery systems. However, the charging and discharging processThe growth of the lithium dendrites can cause repeated fracture and regeneration of SEI, and potential safety hazards are brought; unstable deposition and dissolution of lithium metal in the circulation process are easy to form 'dead lithium', and the coulombic efficiency of the battery is reduced. These problems hinder practical application of lithium metal negative electrodes.
Sodium alginate (figure 1 is a sodium alginate structure diagram) is derived from algae plants such as brown algae in the sea and is renewable resources, the sodium alginate is easily dissolved in water to form viscous liquid, and the sodium alginate is natural polysaccharide carbohydrates, has carboxyl, has the characteristics of excellent biocompatibility, no toxic or side effect, controllable biodegradability, no antibiotics and the like, and can be used as food additives, thickening agents, stabilizing agents, textile dyeing assistants, hemostatic agents, medical stent materials and other fields due to the excellent performances.
Disclosure of Invention
According to aspects of the application, fiber materials are provided, the fiber materials can be used as a negative current collector of a lithium metal secondary battery, and the porous structure among fibers can effectively relieve the volume change in the process of lithium intercalation and deintercalation.
The fiber material is characterized in that the material is prepared by sintering a sodium alginate-based composite fiber membrane.
Optionally, the sodium alginate-based composite fiber membrane is a sodium alginate-based composite nanofiber membrane.
Optionally, the material has a porous structure among fibers, and the specific surface area of the material is 0.3-0.36 m2(ii)/g; the fiber diameter is 100nm &1000nm。
Optionally, an additive is included in the sodium alginate-based composite fiber membrane.
Optionally, the additive comprises at least of polyethylene oxide, gelatin, chitosan, chitin, polyvinyl alcohol.
Optionally, the thickness of the sodium alginate-based composite nanofiber membrane is 10-300 μm, and the fiber diameter is 100-1000 nm.
In another aspect of the present application, there is provided a method for preparing the fiber material of any , comprising:
and (3) carrying out electrostatic spinning on the solution containing the sodium alginate, and sintering to obtain the fiber material.
Optionally, the solution containing sodium alginate is subjected to electrostatic spinning after air bubbles are removed.
Optionally, the solution containing sodium alginate further comprises an additive;
the mass fraction of the additive in the solution containing sodium alginate is 0.1-50%.
Optionally, the mass fraction of sodium alginate in the solution containing sodium alginate is 0.1-10%.
Optionally, the upper limit of the mass fraction of the additive in the sodium alginate containing solution is selected from 0.2%, 0.5%, 1%, 1.5%, 2%, 2.8%, 5%, 5.3%, 6.5%, 7.6%, 10%, 15%, 20%, 21%, 28%, 31%, 32%, 35%, 40%, 45% or 50%; the lower limit is selected from 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.8%, 5%, 5.3%, 6.5%, 7.6%, 10%, 15%, 20%, 21%, 28%, 31%, 32%, 35%, 40% or 45%.
Optionally, the upper limit of the mass fraction of sodium alginate in the sodium alginate containing solution is selected from 0.2%, 0.5%, 0.9%, 1%, 1.4%, 2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 4%, 4.5%, 5%, 5.3%, 6.25%, 7%, 7.6%, 8%, 9% or 10%; the lower limit is selected from 0.1%, 0.2%, 0.5%, 0.9%, 1%, 1.4%, 2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 4%, 4.5%, 5%, 5.3%, 6.25%, 7%, 7.6%, 8%, or 9%.
Optionally, the solvent in the solution containing sodium alginate is selected from water or a mixed solvent of water.
Optionally, the mixed solvent further comprises at least of methanol, ethanol, glycerol, formic acid and acetic acid.
Optionally, the ratio of the solvent to the water in the mixed solvent of water is 0.1% to 99%.
Optionally, the sodium alginate-containing solution is obtained in a manner comprising: adding sodium alginate and additive into solvent, stirring to obtain the solution containing sodium alginate.
Optionally, the stirring time is 6-24 h.
Optionally, the stirring is magnetic stirring.
Optionally, the electrospinning conditions are: the inner diameter of the spinning needle is 0.16-2.20 mm, the voltage is 8-15 KV, the distance between the needle and the receiving device is 8-20 cm, the spinning temperature is 25-60 ℃, the spinning flow is 0.5-3 mL/h, and the rotating speed of the receiving roller is 15-35 m/h.
Optionally, the electrospinning conditions are: the inner diameter of the spinning needle is 0.6mm, the voltage is 15KV, the distance between the needle and the receiving device is 10cm, the spinning temperature is 25-60 ℃, the spinning flow is 0.5-3 mL/h, and the rotating speed of the receiving roller is 15-35 m/h.
Optionally, the receiving means is an aluminum foil.
Optionally, the sintering is performed under an inert atmosphere.
Optionally, the sintering conditions are: and (3) preserving the heat for 2-4 hours at 650-850 ℃ in an inert atmosphere.
Optionally, the inert atmosphere comprises at least of nitrogen and inert gas.
Optionally, the inert atmosphere is selected from N2Atmosphere or Ar atmosphere.
Optionally, the upper temperature limit of the sintering is selected from 700 ℃, 750 ℃, 800 ℃ or 850 ℃; the lower limit is selected from 650 deg.C, 700 deg.C, 750 deg.C or 800 deg.C.
Optionally, the upper time limit of the sintering is selected from 2.5h, 3h, 3.5h or 4 h; the lower limit is selected from 2.5h, 3h or 3.5 h.
Optionally, the temperature rise rate in the sintering process is 3-5 ℃/min.
Optionally, the temperature rise rate of the sintering process is 2 ℃/min.
Optionally, the method comprises:
(1) preparing sodium alginate, an additive and a solvent into a polymer solution and removing bubbles in the polymer solution;
(2) performing electrostatic spinning on the polymer solution prepared in the step (1) to obtain a sodium alginate-based composite nanofiber membrane;
(3) and (3) sintering the sodium alginate-based composite nanofiber membrane obtained in the step (2), and obtaining the nanofiber material after the sintering treatment is finished.
Optionally, the thickness of the sodium alginate-based composite nanofiber membrane in the step (2) is 10-300 μm, and the fiber diameter is 100-1000 nm.
The fibrous current collector has a large specific surface area, and can reduce the local current density in the lithium deposition process, which is beneficial to uniform deposition of lithium. In addition, the porous structure formed between the fibers can effectively relieve the volume change in the lithium intercalation and deintercalation process. The material used as the negative current collector of the lithium metal secondary battery can obviously inhibit the formation of lithium dendrites and effectively prolong the service life of the lithium metal secondary battery.
In yet another aspect of the present application, there are provided lithium metal secondary battery negative electrode current collectors, comprising at least of the fibrous material of any above, prepared according to any above.
Optionally, the lithium metal secondary battery negative electrode current collector is the fiber material.
Optionally, the negative electrode current collector of the lithium metal secondary battery is applied to a lithium air battery and/or a lithium sulfur battery.
The application discloses a preparation method of lithium metal secondary battery negative electrode current collectors, which comprises the following steps:
step 1, preparing sodium alginate, an additive and a solvent into polymer solution with constant concentration and removing bubbles in the polymer solution;
step 2, performing electrostatic spinning on the polymer solution prepared in the step 1 to obtain a sodium alginate composite nanofiber membrane;
and 3, sintering the sodium alginate composite nanofiber membrane obtained in the step 2, wherein the material obtained after sintering can be used as a negative current collector of the lithium metal secondary battery.
The beneficial effects that this application can produce include:
the sodium alginate composite nanofiber material in the application is used as a current collector material of a negative electrode of a lithium metal secondary battery, and the porous structure between fibers can effectively relieve the volume change of lithium insertion and separation processes. In addition, the larger specific surface area of the material can reduce local current density, and is beneficial to uniform deposition of lithium. The material used as a lithium metal negative electrode current collector can obviously inhibit the formation of lithium dendrites and effectively prolong the service life of the lithium metal secondary battery. Meanwhile, the preparation process provided by the invention is simple and easy to implement, has low production cost, and has a great application prospect in actual production.
Drawings
FIG. 1 is a diagram showing the structure of sodium alginate;
fig. 2 is an SEM image of negative electrode current collector 1# of the lithium metal secondary battery prepared in example 1;
fig. 3 is a time-voltage diagram of a half-cell assembled with a lithium sheet and a negative electrode current collector 1# of the lithium metal secondary battery prepared in example 1.
Fig. 4 is a cycle performance test chart of a half cell assembled with a lithium sheet and a negative electrode current collector 1# of the lithium metal secondary battery prepared in example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials such as sodium alginate, chitosan, polyvinyl alcohol, gelatin, polyethylene oxide, etc. in the examples of the present application are purchased from alatin reagent (shanghai) co.
The sodium alginate is purchased from chemical reagents of national drug group, ltd.
The chitosan was purchased from national drug group chemical agents, ltd.
The polyvinyl alcohol is purchased from national pharmaceutical group chemical agents, ltd.
The gelatin was purchased from alatin reagent (shanghai) ltd.
The polyethylene oxide was purchased from national pharmaceutical group chemical agents, ltd.
The analysis method in the examples of the present application is as follows:
SEM analysis was performed using a field emission scanning electron microscope thermal field from Sirion200, FEI, USA.
Electrochemical performance analysis was performed using the wuhan blue electricity company CT2001A blue cell test system.
Specific surface area test analysis was performed using a Coulter Ommishop 100CX specific surface and porosity Analyzer (BET) instrument.
Example 1
0.2g of sodium alginate and 1.4g of polyvinyl alcohol are weighed and put into a beaker filled with 20g of deionized water, and stirred for 6 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 15m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 25 micrometers.
And (3) putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, keeping the temperature of 650 ℃ for 4h (the heating rate is 2 ℃/min) in an argon atmosphere, and obtaining a required sample after sintering and marking as # 1.
Example 2
0.4g of sodium alginate and 8g of gelatin are weighed and put into a beaker filled with 20g of deionized water, and stirred for 6 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 20m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 40 microns.
And (3) putting the sodium alginate-based composite fiber membrane into a tubular furnace, keeping the temperature of 650 ℃ for 4h (the heating rate is 2 ℃/min) in an argon atmosphere, and obtaining a required sample after sintering and marking as # 2.
Example 3
0.6g of sodium alginate and 0.6g of polyoxyethylene are weighed into a beaker filled with 20g of deionized water, and stirred on a magnetic stirrer for 6 hours to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 20m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 30 microns.
And (3) putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, keeping the temperature of 650 ℃ for 4h (the heating rate is 2 ℃/min) in an argon atmosphere, and obtaining a required sample after sintering and marking the sample as # 3.
Example 4
0.8g of sodium alginate and 5.6g of chitosan are weighed and put into a beaker filled with 20g of deionized water, and stirred for 6 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 25m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 50 microns.
And (3) putting the sodium alginate-based composite fiber membrane into a tubular furnace, preserving the heat for 4 hours at 750 ℃ in a nitrogen atmosphere (the heating rate is 2 ℃/min), and obtaining a required sample after sintering and marking as # 4.
Example 5
1g of sodium alginate and 10g of gelatin are weighed and put into a beaker filled with 20g of deionized water, and stirred for 6 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 25m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 55 microns.
And (3) putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, preserving the heat for 4 hours at 750 ℃ in a nitrogen atmosphere (the heating rate is 2 ℃/min), and obtaining a required sample after sintering and marking as # 5.
Example 6
1.2g of sodium alginate and 1.2g of polyoxyethylene are weighed and put into a beaker filled with 20g of deionized water, and stirred on a magnetic stirrer for 6 hours to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 30m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 70 microns.
And (3) putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, preserving the heat for 4 hours at 750 ℃ in a nitrogen atmosphere (the heating rate is 2 ℃/min), and obtaining a required sample after sintering and marking as 6 #.
Example 7
1.4g of sodium alginate and 9.8g of polyvinyl alcohol are weighed and put into a beaker filled with 20g of deionized water, and stirred for 6 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 30m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 78 micrometers.
And (3) putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, keeping the temperature at 850 ℃ for 4h (the heating rate is 2 ℃/min) under the argon atmosphere, and obtaining a required sample after sintering and marking the sample as 7 #.
Example 8
1.6g of sodium alginate and 10g of gelatin are weighed and put into a beaker filled with 20g of deionized water, and stirred for 6 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 35m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 90 microns.
And (3) putting the sodium alginate-based fiber membrane into a tubular furnace, keeping the temperature at 850 ℃ for 4h (the heating rate is 2 ℃/min) under the argon atmosphere, and obtaining a required sample after sintering and marking as # 8.
Example 9
1.8g of sodium alginate and 1.8g of polyoxyethylene are weighed and put into a beaker filled with 20g of deionized water, and stirred on a magnetic stirrer for 6 hours to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: 2ml of the solution is taken out and placed in an injector, the inner diameter of a needle head is 0.6mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 10cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 35m/h, and the flow of the fixed solution is 0.5 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 110 microns.
And putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, keeping the temperature at 850 ℃ for 4h (the heating rate is 2 ℃/min) under the argon atmosphere, and obtaining a required sample after sintering and marking the sample as 9 #.
Example 10
0.2g of sodium alginate and 1.4g of polyvinyl alcohol are weighed and put into a beaker filled with 20g of deionized water, and stirred for 24 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: taking out 2ml of the above solution, placing the solution in an injector, wherein the inner diameter of a needle head is 0.16mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 8kV, the fixed distance (the distance between a needle head and a receiving device) is 8cm, the spinning temperature is 25 ℃, the rotating speed of a receiving roller is 15m/h, and the flow of the fixed solution is 3 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 25 micrometers.
And (3) putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, keeping the temperature of 650 ℃ for 2h (the heating rate is 5 ℃/min) in an argon atmosphere, and obtaining a required sample after sintering and marking as No. 10.
Example 11
2g of sodium alginate and 10g of polyvinyl alcohol are weighed and put into a beaker filled with 20g of deionized water, and stirred for 12 hours on a magnetic stirrer to remove bubbles.
Carrying out electrostatic spinning on the solution obtained in the step: taking out 2ml of the above solution, placing the solution in an injector, wherein the inner diameter of a needle head is 2.20mm, aluminum foil paper is used as a receiving device, and the preset spinning conditions are as follows: the fixed voltage is 15kV, the fixed distance (the distance between a needle head and a receiving device) is 20cm, the spinning temperature is 60 ℃, the rotating speed of a receiving roller is 35m/h, and the flow of the fixed solution is 2 mL/h. And after spinning is finished, the sodium alginate-based composite nanofiber membrane is taken off from the aluminum foil. The thickness of the sodium alginate-based composite nanofiber membrane is 130 microns.
And putting the sodium alginate-based composite nanofiber membrane into a tubular furnace, keeping the temperature at 650 ℃ for 3h (the heating rate is 1 ℃/min) in an argon atmosphere, and obtaining a required sample after sintering and marking as # 11.
Example 12
The procedure for preparing the sample in this example is similar to that of example 1, except that the spinning temperature is 45 deg.C, the other conditions are the same as those of example 1, and the sintered sample is numbered 12 #.
Samples 1# to 12# prepared in examples 1 to 12 were all used as negative electrode current collectors of lithium metal secondary batteries as they were.
Example 13 topography characterization
The morphologies of sample # 1 to sample # 12 of examples 1 to 12 were characterized, as shown typically in fig. 2.
Fig. 2 is an SEM image of a negative electrode current collector (sample # 1) of the lithium metal secondary battery prepared in example 1, and it can be seen from the image that the sample fibers have a porous structure therebetween, and the porous structure between the fibers can effectively alleviate the volume change during the lithium intercalation and deintercalation processes.
The test results of other samples are similar to the above, the sample fibers have porous structures, and the fiber diameter is 100 nm-1000 nm.
Example 14 specific surface area test
The specific surface area test was carried out for samples # 1 to # 12 in examples 1 to 12The specific surface area of the material is 0.3-0.36 m2The specific surface area of the conventional carbon cloth is 0.35-0.4 m2The material has a large specific surface area.
Example 15 electrochemical Performance test
The electrochemical performance of the half cell is tested on samples 1# to 12# in examples 1 to 12, and the half cell assembled with the lithium sheet after the samples are cut into 14mm pole pieces specifically comprises the following steps:
the material is used as a positive electrode of a half cell, a lithium sheet is used as a counter electrode, and an electrolyte is DME solvent added with 1MLiTFSI and 1 wt.% LiNO3。
FIGS. 3 and 4 are graphs showing electrochemical properties of a half-cell assembled with a lithium plate after a negative electrode current collector (sample # 1) of a lithium metal secondary battery prepared in example 1 was cut into a 14mm pole piece (FIG. 3 is a time-voltage graph of the half-cell; FIG. 4 is a cycle performance test graph of the half-cell) at a current density of 1mA/cm2And the loading capacity is 4mAh/cm2The coulombic efficiency is kept above 95% after 30 cycles of circulation under the test condition. As can be seen from fig. 4: at 4mAh/cm2The material has better cycling stability as the material is cycled for 30 cycles under the condition of large loading without large capacity attenuation. From fig. 3, it can be seen that there is a small overpotential and nucleation overpotential during the deposition of lithium on the material, which indicates that the material can induce the uniform deposition of lithium on the surface of the material, which will effectively inhibit the generation of lithium dendrites during the lithium deposition process, and greatly improve the service life of the lithium metal battery.
The results for the other samples were similar to those described above, and both better cycling stability and smaller nucleation overpotentials were obtained.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1, kinds of fiber material, characterized by that, the said material is prepared from sodium alginate based composite fiber membrane through sintering.
2. The material according to claim 1, wherein the material has a porous structure among fibers, and the specific surface area of the material is 0.3-0.36 m2/g；
The diameter of the fiber is 100 nm-1000 nm.
3. The material according to claim 1, wherein the sodium alginate-based composite fiber membrane comprises an additive therein;
preferably, the additive comprises at least of polyethylene oxide, gelatin, chitosan, chitin and polyvinyl alcohol.
4. The material of , wherein the thickness of the film is 10-300 μm and the diameter of the fiber is 100-1000 nm.
5. A method of making a fibrous material according to any of claims 1 to 4 and , comprising:
and (3) carrying out electrostatic spinning on the solution containing the sodium alginate, and sintering to obtain the fiber material.
6. The method as claimed in claim 5, wherein the solution containing sodium alginate comprises additives;
the mass fraction of the additive in the solution containing sodium alginate is 0.1-50%;
preferably, the mass fraction of the sodium alginate in the solution containing the sodium alginate is 0.1-10%;
preferably, the solvent in the solution containing sodium alginate is selected from water or a mixed solvent of water;
preferably, the mixed solvent further comprises at least of methanol, ethanol, glycerol, formic acid and acetic acid.
7. The method according to claim 5, characterized in that the electrospinning conditions are: the inner diameter of a spinning needle head is 0.16-2.20 mm, the voltage is 8-15 KV, the distance between the needle head and a receiving device is 8-20 cm, the spinning temperature is 25-60 ℃, the spinning flow is 0.5-3 mL/h, and the rotating speed of a receiving roller is 15-35 m/h;
preferably, the sintering conditions are: preserving heat for 2-4 h at 650-850 ℃ in an inactive atmosphere;
preferably, the temperature rise rate in the sintering process is 3-5 ℃/min;
preferably, the temperature rise rate of the sintering process is 2 deg.C/min.
8. The method of claim 5, wherein the method comprises:
(1) preparing sodium alginate, an additive and a solvent into a polymer solution and removing bubbles in the polymer solution;
(2) performing electrostatic spinning on the polymer solution prepared in the step (1) to obtain a sodium alginate-based composite nanofiber membrane;
(3) and (3) sintering the sodium alginate-based composite nanofiber membrane obtained in the step (2), and obtaining the nanofiber material after the sintering treatment is finished.
9, lithium metal secondary battery negative electrode current collectors, characterized by comprising at least of the fibrous materials of claims 1-4- , prepared according to the method of claims 5-8- .
10. The negative electrode current collector of a lithium metal secondary battery according to claim 9 is applied to a lithium air battery and/or a lithium sulfur battery.
CN201810791508.6A 2018-07-18 2018-07-18 Fiber material and preparation method and application thereof Active CN110735232B (en)

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CN103022413A (en) * 2012-12-28 2013-04-03 东莞新能源科技有限公司 Negative pole piece for lithium battery, preparation method of negative pole piece and lithium battery with negative pole piece
CN103346281A (en) * 2013-07-17 2013-10-09 中国科学院青岛生物能源与过程研究所 Sodium alginate-based lithium battery diaphragm and preparation method thereof
CN104178929A (en) * 2014-08-19 2014-12-03 中信大锰矿业有限责任公司 Method for preparing LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning
CN106033813A (en) * 2016-06-08 2016-10-19 陕西科技大学 Method for preparing sodium-ion battery negative electrode material with sodium alga acid as carbon source
CN106898778A (en) * 2017-04-17 2017-06-27 中国科学院化学研究所 A kind of metal secondary batteries negative pole three-dimensional collector and its production and use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009041117A (en) * 2007-08-06 2009-02-26 Nisshinbo Ind Inc Polysaccharide nanofibers
CN103022413A (en) * 2012-12-28 2013-04-03 东莞新能源科技有限公司 Negative pole piece for lithium battery, preparation method of negative pole piece and lithium battery with negative pole piece
CN103346281A (en) * 2013-07-17 2013-10-09 中国科学院青岛生物能源与过程研究所 Sodium alginate-based lithium battery diaphragm and preparation method thereof
CN104178929A (en) * 2014-08-19 2014-12-03 中信大锰矿业有限责任公司 Method for preparing LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning
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