CN110144726B - Heat crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of realizing rapid lithium ion transmission and preparation and application thereof - Google Patents
Heat crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of realizing rapid lithium ion transmission and preparation and application thereof Download PDFInfo
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- CN110144726B CN110144726B CN201910408672.9A CN201910408672A CN110144726B CN 110144726 B CN110144726 B CN 110144726B CN 201910408672 A CN201910408672 A CN 201910408672A CN 110144726 B CN110144726 B CN 110144726B
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 90
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 90
- 239000000835 fiber Substances 0.000 title claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004132 cross linking Methods 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000005540 biological transmission Effects 0.000 title claims description 15
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 57
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 56
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000002121 nanofiber Substances 0.000 claims description 24
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 230000037427 ion transport Effects 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 238000006138 lithiation reaction Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001523 electrospinning Methods 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 16
- 239000000243 solution Substances 0.000 abstract description 16
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 229920001021 polysulfide Polymers 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 5
- 150000008117 polysulfides Polymers 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 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
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- 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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
The invention discloses a heat crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing an electrostatic spinning polyvinyl alcohol/polyacrylic acid composite fiber membrane by adopting an electrostatic spinning method; obtaining a thermal crosslinking polyvinyl alcohol/polyacrylic acid composite fiber diaphragm through heat treatment; and finally, lithiating by using LiOH aqueous solution to obtain the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions. The invention adopts a thermal crosslinking method to treat the electrostatic spinning polyvinyl alcohol/polyacrylic acid composite fiber diaphragm, so that the mechanical strength and the stability of the composite diaphragm in an aqueous solution are greatly enhanced. And then, treating the composite fiber diaphragm by using LiOH solution to change unreacted polyacrylic acid in the fiber surface into lithium polyacrylate, so that the lithium ion conductivity of the composite fiber diaphragm is greatly improved while the electrostatic repulsion effect on lithium polysulfide is ensured.
Description
Technical Field
The invention belongs to the technical field of composite fiber diaphragms, and particularly relates to preparation of a thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of realizing rapid lithium ion transmission and application of the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm in a lithium-sulfur battery.
Background
Lithium-sulfur (Li-S) batteries are due to their ultra-high theoretical specific energy (2600W h kg)-1) And theoretical specific capacity (1672mA h g)-1) The sulfur has the advantages of abundant reserves, low cost, no environmental pollution and the like, and becomes one of the novel rechargeable battery systems with the most development potential. In the charging and discharging process of the lithium-sulfur battery, the high specific capacity characteristic of the sulfur cathode material is brought about due to the multi-stage electrochemical reaction characteristic of sulfur, but more complexity exists in the lithium-sulfur battery system. On one hand, the sulfur positive electrode can generate soluble lithium polysulfide in the electrochemical reaction process, and the lithium polysulfide can directly react with the lithium metal negative electrode by penetrating through a traditional battery diaphragm, so that continuous loss of active substances and reduction of coulombic efficiency are caused, and the shuttle effect is realized. On the other hand, since the lithium metal negative electrode material has a process of continuously depositing lithium ions during the cycle process, uneven growth of lithium dendrites is easily caused, which raises a great safety problem.
The separator is one of the key components of the battery system, and serves as an electronic insulator to isolate the positive and negative electrode materials; secondly, the separator itself needs to have ion conductivity or to be able to contain a certain amount of electrolyte, so as to ensure the normal transmission of ions inside the battery. At present, commercial battery separators in the market are mainly polyolefin separators, the chemical properties of the separators are stable, but the problems of shuttle effect, lithium dendrite and the like in the lithium-sulfur battery cannot be effectively inhibited, so that a plurality of defects still exist in practical application.
Disclosure of Invention
The invention aims to provide a thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm for rapid lithium ion transmission, which has the advantages of low cost, simple process and excellent electrochemical performance, and a preparation method and application thereof.
In order to achieve the aim, the invention provides a preparation method of a thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions, which is characterized in that an electrostatic spinning polyvinyl alcohol/polyacrylic acid composite fiber membrane is prepared by an electrostatic spinning method; obtaining a thermal crosslinking polyvinyl alcohol/polyacrylic acid composite fiber diaphragm through heat treatment; and finally, lithiating by using LiOH aqueous solution to obtain the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions.
Preferably, the preparation method of the rapid lithium ion-transporting thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber membrane specifically comprises the following steps:
step 1: preparing the polyvinyl alcohol/polyacrylic acid composite fiber by adopting an electrostatic spinning method:
firstly, dissolving polyvinyl alcohol in deionized water by a heating and stirring method, and cooling to room temperature after the solution becomes clear and transparent; adding polyacrylic acid, stirring and dissolving at room temperature, and standing to obtain uniform mixed spinning solution; carrying out electrostatic spinning, and receiving the spun nanofiber by using a rotating aluminum foil to obtain an electrostatic spinning polyvinyl alcohol/polyacrylic acid composite nanofiber membrane;
step 2: carrying out heat treatment:
placing the electrostatic spinning polyvinyl alcohol/polyacrylic acid fiber membrane in a blast oven for heating treatment to obtain a thermal crosslinking polyvinyl alcohol/polyacrylic acid fiber membrane;
and step 3: treatment with aqueous LiOH solution:
and soaking the thermal crosslinking polyvinyl alcohol/polyacrylic acid fiber diaphragm in LiOH solution for lithiation treatment, then washing with deionized water, and finally drying to obtain the thermal crosslinking polyvinyl alcohol/polyacrylic acid lithium fiber diaphragm capable of realizing rapid lithium ion transmission.
Preferably, the mass ratio of the polyvinyl alcohol to the polyacrylic acid to the deionized water in the step 1 is 3-7: 5.5-9.5: 83.5-91.5.
More preferably, the mass ratio of the polyvinyl alcohol, the polyacrylic acid and the deionized water in the step 1 is 5:7.5: 87.5.
Preferably, the dissolving temperature of the polyvinyl alcohol in the step 1 is 95-100 ℃, and the stirring and dissolving time is 2-8 hours; adding polyacrylic acid, and dissolving at room temperature for 12-24 h; the standing time is 4-10 h.
More preferably, the dissolving temperature of the polyvinyl alcohol in the step 1 is 97 ℃, and the stirring dissolving time is 6 hours; adding polyacrylic acid, and dissolving at room temperature for 18 h; the standing time is 6 h.
Preferably, the electrospinning in step 1 comprises: 3-5 mL of mixed spinning solution is poured into a 5mL injector to control the amount of the spun fiber; the spinning parameters are set as follows: the propelling speed is 0.07-0.1 mm/min, the voltage between the needle head and the receiving aluminum foil is 15-18 KV, the environmental temperature is 25 +/-2 ℃, and the air humidity is 35 +/-3%.
More preferably, the electrostatic spinning parameters in the step 1 are set as follows: the advancing speed is 0.08mm/min, and the voltage between the needle head and the receiving aluminum foil is 17 KV.
Preferably, the fiber diameter of the electrostatic spinning polyvinyl alcohol/polyacrylic acid composite nanofiber membrane obtained in the step 1 is 0.4-0.7 μm, the porosity is 85-92%, and the pore size distribution of the fiber membrane is 0.4-2.0 μm.
Preferably, the temperature of the heat treatment in the step 2 is 100-140 ℃, and the treatment time is 2-4 h.
More preferably, the heat treatment temperature in the step 2 is 120 ℃ and the treatment time is 3 h.
Preferably, the fiber diameter of the thermal crosslinking polyvinyl alcohol/polyacrylic acid fiber diaphragm obtained in the step 2 is 0.4-0.7 μm, the porosity is 84-92%, and the pore size distribution of the fiber diaphragm is 0.4-2.0 μm.
Preferably, the concentration of the LiOH solution in the step 3 is 0.05-0.5 mol/L, and the treatment time is 5-30 min.
More preferably, the concentration of the LiOH solution in the step 3 is 0.2mol/L, and the treatment time is 15 min.
Preferably, the drying temperature in the step 3 is 50-80 ℃, and the time is 12-24 h.
More preferably, the drying temperature in the step 3 is 60 ℃ and the drying time is 18 h.
Preferably, the edge of the composite membrane is fixed during the drying process in step 3 to prevent the membrane from shrinking and deforming.
Preferably, the fiber diameter of the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm with rapid lithium ion transmission obtained in the step 3 is 0.5-0.8 μm, the porosity is 65-75%, and the pore size distribution of the fiber membrane is 0.3-1.4 μm.
The invention also provides the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions, which is prepared by the method.
Preferably, the fiber diameter of the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions is 0.5-0.8 μm, the porosity is 65-75%, and the pore size distribution of the fiber membrane is 0.3-1.4 μm.
The invention also provides application of the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm for rapid lithium ion transmission in a diaphragm material of a lithium-sulfur battery or a lithium ion battery.
Hydroxyl (-OH) in polyvinyl alcohol (PVA) molecules and carboxyl (-COOH) in polyacrylic acid (PAA) molecular chains can undergo esterification reaction under the condition of heat treatment, one molecule of water is removed, and ester groups are generated between molecular chains, so that the stability and mechanical properties of the composite material can be greatly enhanced. Based on this background, we proposed a thermally crosslinked polyvinyl alcohol/lithium polyacrylate fibrous membrane with fast lithium ion transport using electrostatic spinning, thermal crosslinking and lithium hydroxide (LiOH) solution treatment: the mechanical strength of the electrostatic spinning polyvinyl alcohol/polyacrylic acid composite fiber which is thermally crosslinked at high temperature is greatly improved; and subsequent LiOH solution treatment enables unreacted-COOH on the surface of the composite fiber to be replaced by-COOLi, namely, lithium polyacrylate is formed through reaction, so that the electrostatic repulsion effect on lithium polysulfide is ensured, and the lithium ion conductivity of the composite fiber diaphragm is greatly improved. The thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm with rapid lithium ion transmission has great development potential in the aspects of improving the cycle performance of the battery, inhibiting the growth of lithium dendrite and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polyvinyl alcohol/polyacrylic acid composite nanofiber is prepared by adopting an electrostatic spinning method, the composite nanofiber has uniform diameter and complete fiber appearance, and polyvinyl alcohol and polyacrylic acid are uniformly distributed on a single fiber without any phase separation phenomenon; the mechanical strength and modulus of the composite diaphragm are greatly improved by adopting a thermal crosslinking method of polyvinyl alcohol and polyacrylic acid; the treatment of the LiOH solution enables the unreacted polyacrylic acid on the surface of the fiber to be changed into lithium polyacrylate, so that the lithium ion conductivity is greatly enhanced.
(2) The preparation process is simple and easy to implement, is very environment-friendly, is a quick and efficient preparation method, and is suitable for large-scale production.
(3) The thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions, prepared by the invention, has the advantages of stable physical and chemical properties, excellent mechanical properties and the like, and has a great application prospect in the energy field of lithium-sulfur batteries or lithium ion batteries and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a material of the present invention; wherein, (a) is polyvinyl alcohol/polyacrylic acid composite nanofiber of electrostatic spinning, (b) is heat cross-linked polyvinyl alcohol/polyacrylic acid composite nanofiber, (c) is the heat cross-linked polyvinyl alcohol/lithium polyacrylate fibrous diaphragm of the fast lithium ion transmission;
FIG. 2 is an infrared characterization and mechanical properties of the materials of the present invention; wherein, the chart (a) is the infrared spectrum of various materials in the invention, and the chart (b) is the mechanical performance chart of different fiber materials in the invention;
fig. 3 is a graph of electrochemical impedance spectra and rate capability of a lithium sulfur battery assembled from the materials of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions, which is prepared by the following specific steps:
step 1: preparing the polyvinyl alcohol/polyacrylic acid composite nanofiber by adopting an electrostatic spinning method:
taking deionized water as a solvent, and weighing 500G (sigma-aldrich, 341584-100G) and 100G (sigma-aldrich, 181285-100G) of polyvinyl alcohol and deionized water according to the mass ratio of 5:7.5: 87.5; firstly, adding polyvinyl alcohol into deionized water, and stirring the mixture for 6 hours on a stirring table at the rotating speed of 700r/min at 97 ℃ to obtain a polyvinyl alcohol solution; after cooling to room temperature, adding the weighed polyacrylic acid, stirring at the rotating speed of 700r/min for 18 hours at room temperature, and then standing for 6 hours to obtain a mixed spinning solution; pouring 5mL of mixed spinning solution into a 5mL injector to control the amount of spun fibers; setting the spinning parameters as the advancing speed of 0.08mm/min, receiving the nano-fibers by using a rotating aluminum foil, carrying out electrostatic spinning to obtain a polyvinyl alcohol/polyacrylic acid composite nano-fiber membrane, wherein the voltage between a needle head and the aluminum foil for receiving is 17KV, the environmental temperature is 25 +/-2 ℃, and the air humidity is 35 +/-3%;
step 2: and (3) heat treatment:
and (3) placing the electrostatic spinning polyvinyl alcohol/polyacrylic acid composite nanofiber membrane in a blast oven, and treating for 3h at 120 ℃ to obtain the thermal crosslinking polyvinyl alcohol/polyacrylic acid composite nanofiber membrane.
And step 3: treating with LiOH aqueous solution, preparing 50mL of 0.2mol/L LiOH aqueous solution, soaking a piece of thermal crosslinking polyvinyl alcohol/polyacrylic acid composite nanofiber membrane with the length and width of 4cm in the LiOH aqueous solution for lithiation treatment for 15min, and then washing with deionized water for 3 times; and finally, fixing the edges of the periphery of the treated composite diaphragm, and drying the composite diaphragm in a drying oven at 60 ℃ for 18h to obtain the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions.
The structural morphology and the chemical structure of the obtained rapid lithium ion-transporting thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm are characterized by using a Scanning Electron Microscope (SEM) and a Fourier infrared spectrum, and the diaphragm and a commercial Celgard diaphragm are assembled into a lithium-sulfur battery respectively to test the electrochemical performance, and the results are as follows:
(1) the SEM test results show that: the electrostatic spinning polyvinyl alcohol/polyacrylic acid composite nano-fiber has uniform thickness, diameter distribution of 0.4-0.7 micron, and continuous and uniform fiber appearance (figure 1 a). After the heat treatment (fig. 1b), the morphology of the composite membrane was not changed, and the fiber diameter and porosity were not substantially changed, indicating that the heat treatment method did not change the fiber structure of the composite membrane. However, after the treatment with the LiOH aqueous solution, as shown in fig. 1c, partial bonding between the composite fibers occurs because polyacrylic acid on the fiber surface in the LiOH aqueous solution is reacted into lithium polyacrylate, thereby causing changes in the chemical structure and physical morphology of the composite fiber material. See figure 1.
(2) The results of the Fourier infrared test and the mechanical property test show that: the characteristic functional group on the surface of the composite nanofiber of the electrostatic spinning polyvinyl alcohol/polyacrylic acid is the combination of polyacrylic acid and polyvinyl alcohol, which indicates the successful preparation of the composite nanofiber. Compared with the thermal crosslinking polyvinyl alcohol/polyacrylic acid nano fiber, the infrared characteristic spectrum of the thermal crosslinking polyvinyl alcohol/polyacrylic acid nano fiber is not changed, which shows that part of the polyacrylic acid and the polyvinyl alcohol exposed on the surface of the fiber do not participate in the reaction. After treatment with an aqueous LiOH solution, the wavelength was 1701cm-1The peak of-COOH group in polyacrylic acid disappears, and the wavelength is 1571cm-1Is a peak of-COO-Peaks of radicals, indicating successful preparation of lithium polyacrylate, seeFigure 2 a. The corresponding mechanical property test results show that the tensile strength (14.07MPa) and the Young modulus (755.17MPa) of the thermal crosslinking polyvinyl alcohol/polyacrylic acid nano-fiber after the heat treatment are obviously higher than those of the electrostatic spinning polyvinyl alcohol/polyacrylic acid nano-fiber (12.03MPa) and the Young modulus (70.76 MPa). After the LiOH aqueous solution is adopted for treatment, the tensile strength (26.45MPa) and the Young modulus (1274.90MPa) of the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions are greatly improved, and the treated composite fiber diaphragm has more excellent comprehensive mechanical properties.
(3) Impedance test and rate performance test of lithium-sulfur battery: the thermal crosslinking polyvinyl alcohol/polyacrylic acid lithium fiber, the thermal crosslinking polyvinyl alcohol/polyacrylic acid lithium fiber for rapid lithium ion transmission and a commercial Celgard diaphragm are respectively used as diaphragms of lithium-sulfur batteries to assemble the button type lithium-sulfur batteries. As shown in a of fig. 3, the charge transfer resistance of the lithium-sulfur battery assembled by the thermally crosslinked polyvinyl alcohol/lithium polyacrylate fiber membrane with rapid lithium ion transport is 40.1 ohm, which is significantly higher than that of the electrostatic spun polyvinyl alcohol/polyacrylic acid nanofiber membrane (58.0 ohm) and the commercial Celgard (76.8 ohm), indicating that the lithium ion conductivity of the composite fiber membrane treated by LiOH is significantly improved. As shown in b of fig. 3, in terms of rate performance of the lithium sulfur battery, the lithium sulfur battery assembled by the rapid lithium ion transport thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber membrane exhibits higher specific discharge capacity at a low current density of 0.1C and a high current density of 2C. 1646mA h g at 0.1C magnification-1The initial discharge specific capacity of the lithium ion battery is close to a theoretical value; respectively having 1071mA h g at 0.2C, 0.5C, 1C and 2C multiplying power-1、784mA h g-1、651mA h g-1And 487mA h g-1The reversible specific capacity of (a). This is due to the significant decrease in both porosity and pore size distribution of the composite nanofiber membrane upon treatment with aqueous LiOH solutions, thereby enhancing rejection of lithium polysulfide. In addition, polyacrylic acid on the surface of the fiber is reacted into lithium polyacrylate, so that the lithium ion transmission efficiency in the battery is improved, and the reduction of the pore structure is counteractedThe side effects of (1).
Example 2
A fast lithium ion transporting thermally crosslinked polyvinyl alcohol/lithium polyacrylate fibrous separator similar to that of example 1, except that: the ratio of polyvinyl alcohol, polyacrylic acid and deionized water in example 1 was changed to 4:8.5:87.5, and the resulting product was labeled as thermally crosslinked polyvinyl alcohol/lithium polyacrylate fibrous membrane-1 for rapid lithium ion transport.
Example 3
A fast lithium ion transporting thermally crosslinked polyvinyl alcohol/lithium polyacrylate fibrous separator similar to that of example 1, except that: and (3) performing heat treatment in the second step at 140 ℃ for 2 hours, and marking the obtained product as the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm-2 with rapid lithium ion transmission.
Claims (7)
1. A preparation method of a thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber diaphragm capable of rapidly transmitting lithium ions is characterized by comprising the following steps:
step 1: preparing the polyvinyl alcohol/polyacrylic acid composite fiber by adopting an electrostatic spinning method:
firstly, dissolving polyvinyl alcohol in deionized water by a heating and stirring method, and cooling to room temperature after the solution becomes clear and transparent; adding polyacrylic acid, stirring and dissolving at room temperature, and standing to obtain uniform mixed spinning solution; carrying out electrostatic spinning, and receiving the spun nanofiber by using a rotating aluminum foil to obtain an electrostatic spinning polyvinyl alcohol/polyacrylic acid composite nanofiber membrane; the mass ratio of the polyvinyl alcohol to the polyacrylic acid to the deionized water is 3-7: 5.5-9.5: 83.5-91.5; the dissolving temperature of the polyvinyl alcohol is 95-100 ℃, and the stirring and dissolving time is 2-8 h; adding polyacrylic acid, and dissolving at room temperature, wherein the stirring time is 12-24 hours, and the standing time is 4-10 hours;
step 2: carrying out heat treatment:
placing the electrostatic spinning polyvinyl alcohol/polyacrylic acid fiber membrane in a blast oven for heating treatment to obtain a thermal crosslinking polyvinyl alcohol/polyacrylic acid fiber membrane;
and step 3: treatment with aqueous LiOH solution:
and soaking the thermal crosslinking polyvinyl alcohol/polyacrylic acid fiber diaphragm in LiOH solution for lithiation treatment, then washing with deionized water, and finally drying to obtain the thermal crosslinking polyvinyl alcohol/polyacrylic acid lithium fiber diaphragm capable of realizing rapid lithium ion transmission.
2. The method of preparing a rapid lithium ion-transporting thermally crosslinked polyvinylalcohol/lithium polyacrylate fibrous separator as set forth in claim 1, wherein the electrospinning in step 1 comprises: 3-5 mL of mixed spinning solution is poured into a 5mL injector to control the amount of the spun fiber; the spinning parameters are set as follows: the propelling speed is 0.07-0.1 mm/min, the voltage between the needle head and the receiving aluminum foil is 15-18 KV, the environmental temperature is 25 +/-2 ℃, and the air humidity is 35 +/-3%.
3. The method for preparing the thermal crosslinking polyvinyl alcohol/lithium polyacrylate fiber membrane with rapid lithium ion transmission according to claim 1, wherein the temperature of the heat treatment in the step 2 is 100-140 ℃, and the treatment time is 2-4 h.
4. The method for preparing a rapid lithium ion-transporting thermally crosslinked polyvinyl alcohol/lithium polyacrylate fiber separator according to claim 1, wherein the concentration of the LiOH solution in the step 3 is 0.05 to 0.5mol/L, and the treatment time is 5 to 30 min; the drying temperature is 50-80 ℃, and the drying time is 12-24 h.
5. A thermally crosslinked polyvinyl alcohol/lithium polyacrylate fiber separator for rapid lithium ion transport prepared by the method of any one of claims 1 to 4.
6. The thermally crosslinked polyvinyl alcohol/lithium polyacrylate fiber membrane with rapid lithium ion transport according to claim 5, wherein the fiber diameter of the fiber membrane is 0.5 to 0.8 μm, the porosity is 65 to 75%, and the pore size distribution of the fiber membrane is 0.3 to 1.4 μm.
7. The use of the thermally crosslinked polyvinyl alcohol/lithium polyacrylate fibrous membrane for rapid lithium ion transport according to claim 5 or 6 in a lithium sulfur battery or lithium ion battery membrane material.
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