CN110854343B - Preparation method of skin-core structure cellulose modified nanofiber lithium battery diaphragm - Google Patents
Preparation method of skin-core structure cellulose modified nanofiber lithium battery diaphragm Download PDFInfo
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- CN110854343B CN110854343B CN201911173452.9A CN201911173452A CN110854343B CN 110854343 B CN110854343 B CN 110854343B CN 201911173452 A CN201911173452 A CN 201911173452A CN 110854343 B CN110854343 B CN 110854343B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
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- 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
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- 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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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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
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a skin-core structure cellulose modified nanofiber lithium battery diaphragm. Adding cellulose and a flame retardant into a solvent, uniformly stirring and mixing to prepare a mixed solution of the cellulose and the flame retardant, wherein the mixed solution is used as a cortex spinning solution; dissolving the high polymer in a solvent, and stirring by magnetic force to uniformly dissolve the high polymer to prepare a core layer spinning solution; respectively injecting the solution into two different injectors, controlling the two injectors to carry out electrostatic spinning through two different micro-injection pumps, and collecting on the surface of a collecting device to obtain a jet-cured skin-core structure fiber membrane; finally, vacuum drying is carried out to obtain the product. The novel skin-core structure nanofiber diaphragm with a good flame retardant effect is prepared, and the nanofiber lithium battery diaphragm with good electrolyte lyophilic property, thermal stability and flame retardant effect is formed.
Description
Technical Field
The invention relates to the technical field of liquid lithium battery manufacturing, in particular to a preparation method of a skin-core structure cellulose modified nanofiber lithium battery diaphragm with a flame retardant effect.
Background
Currently, the problem of energy shortage is increasingly prominent, and the demand for new energy is increasing. The development of electrochemical energy storage devices is an important way to break the energy bottleneck restriction. The lithium battery is used as a green high-performance power supply, and has the advantages of high energy density, long cycle life, low memory effect and the like, so that great attention and application are paid. However, some accidents caused by explosion of electronic products such as notebook computers and mobile phones due to lithium battery failure have attracted attention to the safety performance of the batteries, and corresponding solutions are required to be adopted for dealing with the accidents. The main components of the liquid lithium battery include a positive electrode, a negative electrode, a separator and an electrolyte. The separator functions to retain an electrolyte, provide a passage for lithium ion transport, prevent short circuit between electrodes, and perform safe deactivation of a lithium battery in the event of overcharge, abnormal heating, or mechanical rupture. Meanwhile, the performance of the separator, such as ionic conductivity, affects the ohmic polarization of the battery, which is very important for the battery to be used under severe charging and discharging conditions such as high voltage or high current density. In addition, porosity, tensile strength, electrolyte absorption capacity, thermal stability, etc., all can also directly affect the cycle life and safety performance of the battery. At present, polyolefin separators, such as Polyethylene (PE), polypropylene (PP) and composite separators thereof, which are commercially widely used, have low production cost, high strength and excellent chemical stability, but due to the hydrophobic property of the non-polar polyolefin separator, in an electrolyte containing a high content of polar solvent, poor wettability and electrolyte liquid absorption and retention capability are exhibited, so that the performance of a lithium ion battery is limited; in addition, because the stretching process is involved in the production of the diaphragm, the diaphragm shrinks due to the recombination of polymer chains at high temperature, once the diaphragm shrinks, the positive electrode and the negative electrode are in contact with short circuit, and safety accidents are easy to happen, so that the safety problem and the performance optimization problem of the lithium battery are still full of challenges.
The electrostatic spinning method is a spinning method for obtaining polymer nano-fibers by carrying out jet drawing on a polymer solution or a melt under the action of a strong electric field force. The electrostatic spinning has the advantages of simple device, simple and convenient operation, controllable process and the like, and is widely used for preparing nano fiber materials.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a preparation method of a skin-core structure cellulose modified nanofiber lithium battery diaphragm with a flame retardant effect.
The technical scheme adopted by the invention is as follows:
1) adding cellulose and a flame retardant into a solvent for dissolving cellulose, wherein the mass ratio of the cellulose to the flame retardant is 3:1, magnetically stirring for 12 hours, and the mass percentage of the cellulose in the mixed solution is 10-20%, continuously stirring for 8 hours, uniformly mixing to prepare the mixed solution of the cellulose and the flame retardant, and taking the mixed solution as a cortex spinning solution;
2) dissolving a high polymer with the mass percentage of 10-30% in a solvent for dissolving the high polymer, and magnetically stirring for at least 8 hours to uniformly dissolve the high polymer to prepare a core layer spinning solution;
3) as shown in fig. 1, the solutions prepared in the steps 1) and 2) are respectively injected into two different injectors (1) and (2), then the two injectors (1) and (2) are controlled to work by two different micro-injection pumps, the advancing rates of the spinning solutions of the skin layer and the core layer are regulated, the spinning solutions of the skin layer and the core layer are extruded to a coaxial spinneret (3) for electrostatic spinning, then the spinning solutions overcome the surface tension thereof under the action of an electrostatic field applied by a high-voltage device (4) to form jet flows, and finally, the jet-cured skin-core structure fiber membranes are collected on the surface of a collecting device (5);
4) and (4) placing the skin-core structure fiber membrane with a certain thickness collected in the step 3) in a vacuum drying oven for vacuum drying to promote the spinning solvent to better volatilize, thereby preparing the nanofiber membrane applied to the lithium battery.
The propulsion speed of the spinning solution of the skin layer and the core layer in the steps 1) and 2) needs to be reasonably configured and accurately controlled, and the thickness of the skin layer is suitable and not suitable to be too thick through regulation and control. In the step 3), spinning of the core layer
The liquid advancing speed is 0.2-0.6ml/h, the spinning solution advancing speed of the skin layer is 0.2-0.6ml/h, and finally the thickness of the skin layer does not exceed 1/3 of the diameter of the core layer.
The vacuum drying oven treatment of the step 4) comprises the following steps: vacuum-drying at 60 deg.C for 12 h.
The high-voltage device (4) is a voltage circuit which is connected with the coaxial spinneret (3) and applies voltage of 10-23 KV.
The collecting device (5) is of a cylindrical structure.
The flame retardant is triphenyl phosphate (TPP).
The high polymer is PVDF, and the corresponding solvent is a DMF/acetone mixed solution; or polyisophthaloyl metaphenylene diamine (PMIA) in a solvent such as N, N-dimethylacetamide (DMAc).
The nanofiber membrane is arranged between two electrodes in the lithium battery and used for isolating the two electrodes. In one embodiment, the nanofiber separator may be pressed into a thin sheet, such as an 18mm disk, to be placed between the two electrodes of a CR2032 lithium battery. Without being limited thereto, assembly into a button cell is only one aspect of the membrane performance characterization of the present invention.
The cellulose is Cellulose Acetate (CA), and the corresponding solvent is a DMF/acetone mixed solution; or Ethyl Cellulose (EC), corresponding to absolute ethanol.
The skin layer of the invention mainly adopts cellulose spinning solution, and flame retardant is added in the cellulose spinning solution, so that the outer layer of the fiber has flame retardant effect. The core layer mainly adopts high polymer with electrostatic spinning spinnability and strong mechanical property of the obtained fiber, and the melting point of the high polymer must exceed 140 ℃.
The fiber membrane prepared by electrospinning nano has a mutually communicated porous structure, has the characteristics of high porosity, controllable fiber appearance and structure, flexible selection of polymer raw materials and the like, can absorb more electrolyte and provide a quick ion transmission channel, and is favorable for improving the cycle performance and the rate capability of the lithium battery. The prepared skin-core structure fiber diaphragm has more advantages, not only has the advantages of an electrostatic spinning diaphragm, but also can play the synergistic effect between different high polymers of the inner skin-core layer and the outer skin-core layer. The core layer is typically a high polymer with excellent mechanical strength and some thermal stability, which serves as a support. The high polymer of the skin layer has better electrochemical stability and good wettability to electrolyte. The cooperation of the inner layer and the outer layer enables the whole diaphragm to have certain mechanical strength and heat resistance, and also has strong liquid absorption and retention capacity, so that the performance of the assembled lithium battery is greatly improved.
The invention has the beneficial effects that:
in the invention, the skin-core structure nanofiber membrane prepared by coaxial electrostatic spinning can exert the synergistic effect formed by different high polymers of the inner layer and the outer layer.
In the invention, the skin layer is made of green environment-friendly natural high polymer, namely cellulose, the initial melting temperature of the skin layer is higher, and a proper amount of flame retardant is added into the skin layer, so that the fiber outer layer not only has good thermal stability, but also has a flame retardant effect. Meanwhile, because of the lyophilic property of the cortical cellulose, the liquid contact angle of the coaxial electrospinning diaphragm is far smaller than that of a commercial PE diaphragm, and the instantaneous infiltration effect of the electrolyte is better.
In addition, the coaxial diaphragm has excellent liquid absorption and retention capacity and lower bulk resistance, so that the ion conductivity of the coaxial diaphragm is greatly superior to that of a PE diaphragm. In addition, the skin-core structure nanofiber diaphragm has advantages in the aspects of stability and cycle performance of the battery, has excellent comprehensive performance and has good application prospect.
Drawings
Fig. 1 is a schematic of an electrospinning process.
FIG. 2 is an SEM (scanning electron microscope) image of the CA/TPP @ PVDF skin-core structure nanofiber membrane prepared in example 1.
FIG. 3 is a TEM (Transmission Electron microscope) image of the CA/TPP @ PVDF skin-core structured nanofiber membrane prepared in example 1.
FIG. 4 is a comparison graph of the flame retardant effect of the CA/TPP @ PVDF skin-core structured nanofiber membrane prepared in example 1 and a commercial PE membrane infiltrated electrolyte: CA/TPP @ PVDF (a-d); PE (e-h).
FIG. 5 is a graph showing the comparison between the contact angle and the soaking effect of the CA/TPP @ PVDF skin-core structure nanofiber membrane solution prepared in example 1 and the pure PVDF nanofiber membrane and the commercial PE membrane prepared in the comparative example: CA/TPP @ PVDF (c, f); PVDF (b, e); PE (a, d).
Table 1 shows the porosity, liquid absorption rate, bulk resistance and ionic conductivity of the CA/TPP @ PVDF skin-core structured nanofiber membrane prepared in example 1, and the porosity, liquid absorption rate, bulk resistance and ionic conductivity of a pure PVDF nanofiber membrane and a commercial PE membrane which are used in comparison.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1:
preparing a skin layer spinning solution, adding Cellulose Acetate (CA) and triphenyl phosphate (TPP) in a mass ratio of 3:1 into a mixed solution of DMF/acetone for dissolving, wherein the concentration of the solution is 18%; then preparing a core layer spinning solution of pure PVDF, wherein the PVDF is dissolved in DMF/acetone, and the concentration of the solution is 12%. The two solutions are respectively filled into different syringes after being uniformly stirred, the syringes are connected by adopting coaxial needles, a high-voltage power supply chuck is clamped on the coaxial needles, the voltage adopts 10KV, the advancing speed of a core layer is 0.6ml/h, the advancing speed of a skin layer is 0.6ml/h, and the spinning time is regulated and controlled so as to obtain the fiber membrane with the corresponding thickness. The collected CA/TPP @ PVDF skin-core structure nanofiber membrane needs to be placed in a vacuum drying oven and subjected to vacuum drying for 12 hours at the temperature of 60 ℃ so as to enable the solvent to be fully volatilized, and thus the nanofiber membrane with a stable form is prepared. FIG. 2 is a completely coated CA/TPP @ PVDF sheath-core structured nanofiber; FIG. 3 demonstrates the sheath-core structure; FIG. 4 is a graph showing that the wettability of the nanofiber membrane with the sheath-core structure is measured, and compared with a PE membrane, the liquid contact angle is obviously reduced, and the instantaneous wetting effect on electrolyte is better than that of the PE membrane; FIG. 5 is a schematic view showing that the fiber membrane is completely soaked in the electrolyte and then ignited by open fire, and due to the flame-retardant effect, no continuous fire source appears, and the membrane is instantly extinguished; table 1 shows the comparison of the porosity, the liquid absorption rate, the bulk resistance, the ionic conductivity and other parameters of the diaphragm of the invention and the PE diaphragm, and all the numerical values are greatly improved, and the comprehensive performance is good.
Comparative example: as a comparison in example 1
Preparing a PVDF pure spinning solution with the concentration of 12%, loading the PVDF pure spinning solution into an injector, clamping a high-voltage power supply chuck on a pillow, controlling the spinning time by adopting 10KV voltage and the advancing speed of the spinning solution to be 0.6ml/h, taking down a fiber membrane with the same thickness from a collector, placing the fiber membrane in a vacuum drying oven, and vacuumizing and drying at 60 ℃ for 12h to fully volatilize a solvent, thereby preparing the nano-fiber membrane with stable form.
TABLE 1 comparison of porosity, liquid absorption, bulk resistance, ionic conductivity, etc. of inventive membranes with commercial PE membranes
Example 2:
preparing a sheath spinning solution, adding CA and triphenyl phosphate (TPP) with the mass ratio of 3:1 into a mixed solution of DMF/acetone for dissolving, wherein the concentration of the solution is 18%; then preparing a core layer spinning solution of pure PVDF, wherein the PVDF is dissolved in a DMF/acetone solution, and the concentration of the solution is 14%. The two solutions are respectively filled into different syringes after being uniformly stirred, the syringes are connected by adopting coaxial needles, a high-voltage power supply chuck is clamped on the coaxial needles, the voltage adopts 14KV, the advancing speed of a core layer is 0.5ml/h, the advancing speed of a skin layer is 0.3ml/h, and the spinning time is regulated and controlled so as to obtain the fiber membrane with the corresponding thickness. The collected CA/TPP @ PVDF skin-core structure nanofiber membrane needs to be placed in a vacuum drying oven and subjected to vacuum drying at 60 ℃ for 12 hours, so that the solvent is fully volatilized. The characterization and test results of the performance of the nanofiber membrane with the sheath-core structure prepared in the example are similar to those of the example 1, and relevant data and pictures are not listed.
Example 3:
preparing a sheath spinning solution, adding CA and triphenyl phosphate (TPP) with the mass ratio of 3:1 into a mixed solution of DMF/acetone for dissolving, wherein the concentration of the solution is 18%; then preparing pure PVDF core layer spinning solution, wherein PVDF is dissolved in DMF/acetone, and the concentration of the prepared solution is 16%. The two solutions are respectively filled into different injectors after being uniformly stirred, the two solutions are connected by adopting a coaxial needle, a high-voltage power supply chuck is clamped on the coaxial needle, the voltage adopts 16KV, the advancing speed of a core layer is 0.4ml/h, the advancing speed of a skin layer is 0.3ml/h, and the spinning time is regulated and controlled so as to obtain the fiber membrane with corresponding thickness. The collected CA/TPP @ PVDF skin-core structure nanofiber membrane needs to be placed in a vacuum drying oven and subjected to vacuum drying at 60 ℃ for 12 hours, so that the solvent is fully volatilized. The performance characterization and test results of the sheath-core structured nanofiber membrane prepared in this example are similar to those of example 1, and the relevant data and pictures are not shown.
Example 4:
preparing a sheath spinning solution, adding CA and triphenyl phosphate (TPP) with the mass ratio of 3:1 into a mixed solution of DMF/acetone for dissolving, wherein the concentration of the solution is 18%; then, a core spinning solution of pure PMIA was prepared, and PMIA was dissolved in DMAc at a solution concentration of 12%. The two solutions are respectively filled into different injectors after being uniformly stirred, the two solutions are connected by adopting a coaxial needle, a high-voltage power supply chuck is clamped on the coaxial needle, the voltage adopts 23KV, the advancing speed of a core layer is 0.2ml/h, the advancing speed of a skin layer is 0.2ml/h, and the spinning time is regulated and controlled so as to obtain the fiber membrane with corresponding thickness. The collected CA/TPP @ PMIA skin-core structure nanofiber membrane needs to be placed in a vacuum drying oven and subjected to vacuum drying at 60 ℃ for 12 hours, so that the solvent is fully volatilized. The performance characterization and test results of the sheath-core structured nanofiber membrane prepared in this example are similar to those of example 1, and the relevant data and pictures are not shown.
Example 5:
preparing a sheath spinning solution, wherein the mass ratio of Ethyl Cellulose (EC) to triphenyl phosphate (TPP) is 3:1, and adding the solution into absolute ethyl alcohol for dissolving, wherein the concentration of the solution is 25%; then preparing a core layer spinning solution of pure PVDF, wherein PVDF is dissolved in DMF/acetone, and the concentration of the prepared solution is 16%. The two solutions are respectively filled into different syringes after being uniformly stirred, the syringes are connected by adopting coaxial needles, a high-voltage power supply chuck is clamped on the coaxial needles, the voltage adopts 16KV, the advancing speed of a core layer is 0.4ml/h, the advancing speed of a skin layer is 0.3ml/h, and the spinning time is regulated and controlled so as to obtain the fiber membrane with the corresponding thickness. The collected EC/TPP @ PVDF skin-core structure nanofiber membrane needs to be placed in a vacuum drying oven and subjected to vacuum drying at 60 ℃ for 12 hours, so that the solvent is fully volatilized. The characterization and test results of the performance of the nanofiber membrane with the sheath-core structure prepared in the example are similar to those of the example 1, and relevant data and pictures are not listed.
Therefore, the novel skin-core structure nanofiber diaphragm with a good flame retardant effect is prepared by utilizing a coaxial electrostatic spinning technology and through process innovation. The skin layer adopts cellulose, and a certain proportion of flame retardant is added, so that the diaphragm has better electrolyte lyophilic, thermal stability and flame retardant effect; the core layer adopts high polymer with good mechanical property to play a supporting effect, and the nanofiber lithium battery diaphragm with excellent performance is formed through the synergistic effect of the inner layer and the outer layer, so that the nanofiber lithium battery diaphragm has good commercial prospect.
Claims (5)
1. A preparation method of a skin-core structure cellulose modified nanofiber lithium battery diaphragm is characterized by comprising the following steps: the method comprises the following steps:
1) adding cellulose and a flame retardant into a solvent for dissolving cellulose, wherein the mass ratio of the cellulose to the flame retardant is 3:1, magnetically stirring for 12 hours, and the cellulose accounts for 10-20% of the mass percentage of the mixed solution, continuously stirring to uniformly mix the cellulose and the flame retardant to prepare the mixed solution of the cellulose and the flame retardant, and taking the mixed solution as a cortex spinning solution;
2) dissolving a high polymer with the mass percentage of 10-30% in a solvent for dissolving the high polymer, and stirring by magnetic force to uniformly dissolve the high polymer to prepare a core layer spinning solution;
the high polymer is PVDF, and the corresponding solvent is a DMF/acetone mixed solution; or polyisophthaloyl metaphenylene diamine (PMIA) in N, N-dimethylacetamide (DMAc);
the cellulose is Cellulose Acetate (CA), and the corresponding solvent is DMF/acetone mixed solution; or Ethyl Cellulose (EC), with the corresponding solvent being absolute ethanol;
3) respectively injecting the solutions prepared in the steps 1) and 2) into two different injectors (1) and (2), controlling the work of the two injectors (1) and (2) through two different micro injection pumps, regulating and controlling the propelling speed of the spinning solution of the skin layer and the core layer, extruding the spinning solution of the skin layer and the core layer to a coaxial spinneret (3) for electrostatic spinning, overcoming the surface tension of the spinning solution under the action of an electrostatic field applied by a high-voltage device (4) to form jet flow, and finally collecting the jet-cured skin-core structure fiber membrane on the surface of a collecting device (5);
4) and (4) placing the skin-core structure fiber membrane collected in the step 3) in a vacuum drying oven for vacuum drying, thereby preparing the nanofiber membrane applied to the lithium battery.
2. The method for preparing the skin-core structure cellulose modified nanofiber lithium battery separator as claimed in claim 1, wherein the method comprises the following steps: in the step 3), the advancing speed of the spinning solution of the core layer is 0.2-0.6ml/h, and the advancing speed of the spinning solution of the skin layer is 0.2-0.6 ml/h.
3. The method for preparing the skin-core structure cellulose modified nanofiber lithium battery separator as claimed in claim 1, wherein the method comprises the following steps: the vacuum drying oven treatment of the step 4) comprises the following steps: vacuum drying at 60 deg.C for 12 h.
4. The method for preparing the skin-core structure cellulose modified nanofiber lithium battery separator as claimed in claim 1, wherein the method comprises the following steps: the flame retardant is triphenyl phosphate (TPP).
5. The method for preparing the skin-core structure cellulose modified nano-fiber lithium battery diaphragm according to claim 1, characterized in that: the nanofiber membrane is arranged between two electrodes in the lithium battery and used for isolating the two electrodes.
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| CN111987275B (en) * | 2020-09-01 | 2022-04-19 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
| CN112928389A (en) * | 2021-03-03 | 2021-06-08 | 华中科技大学 | Phase-change temperature-regulating diaphragm and preparation method and application thereof |
| CN114024096A (en) * | 2021-06-17 | 2022-02-08 | 四川启睿克科技有限公司 | Preparation method of battery diaphragm and battery diaphragm |
| CN114649637A (en) * | 2022-03-22 | 2022-06-21 | 赣南师范大学 | Co-jet spinning lithium ion battery diaphragm and preparation method thereof |
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| US9818998B2 (en) * | 2013-03-13 | 2017-11-14 | Freya Energy, Inc. | Separator for electrochemical cell with overcharge protection and method of making same |
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