CN114164646A - Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity - Google Patents
Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity Download PDFInfo
- Publication number
- CN114164646A CN114164646A CN202111460181.2A CN202111460181A CN114164646A CN 114164646 A CN114164646 A CN 114164646A CN 202111460181 A CN202111460181 A CN 202111460181A CN 114164646 A CN114164646 A CN 114164646A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- membrane
- hfp
- mxene
- electrostatic spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 27
- 239000000835 fiber Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 68
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 41
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 28
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 22
- 239000007983 Tris buffer Substances 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000002121 nanofiber Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000013535 sea water Substances 0.000 abstract description 13
- 238000012986 modification Methods 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 229960003638 dopamine Drugs 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001523 electrospinning Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000005616 pyroelectricity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M11/73—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 with carbon or compounds thereof
- D06M11/74—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 with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- 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
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
-
- 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
- D04H1/43838—Ultrafine fibres, e.g. microfibres
-
- 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
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
Abstract
The invention provides a preparation method and application of an electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity, comprising the following stepsThe method comprises the following steps: preparing PVDF fiber membrane, coating heat conducting layer, coating hydrophilic layer, preparing PVDF-HFP electrostatic spinning membrane as base material by electric spinning technology, Ti3C2MXene is a two-dimensional material with high-efficiency photothermal conversion capacity, the photothermal conversion efficiency of the MXene can reach 100%, solar energy can be efficiently converted into heat energy, dopamine and polyethyleneimine can be fully polymerized under the condition of weak base to carry out hydrophilic modification on the single-side membrane surface of the PVDF-HFP electrostatic spinning membrane, the original hydrophobic property of the PVDF-HFP electrostatic spinning membrane is modified into hydrophilicity, then seawater enters the membrane along pores in the PVDF-HFP electrostatic spinning membrane, and the seawater passes through Ti and enters the membrane through the pores in the Ti3C2The MXene has high-efficiency photothermal conversion capability, absorbs and transfers heat irradiated by sunlight, evaporates seawater in a membrane, and further desalts seawater.
Description
Technical Field
The invention relates to the technical field of PVDF (polyvinylidene fluoride) fiber membranes, in particular to a preparation method and application of an electrospun PVDF fiber membrane with excellent thermal conductivity and hydrophilicity.
Background
PVDF, namely polyvinylidene fluoride, is a highly non-reactive thermoplastic fluorine-containing polymer, can be synthesized through the polymerization reaction of 1, 1-difluoroethylene, is a hydrophobic polymer, has the characteristics of both fluororesin and general resin, has special properties such as piezoelectric property, dielectric property, thermoelectric property and the like besides good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance and ray radiation resistance, is combined by fluorine-carbon bond in a chemical structure, and forms the most stable and firm combination with hydrogen ions by the structure with short bond property, so that the fluorocarbon coating has specific physicochemical properties, not only has strong wear resistance and impact resistance, but also has high fading resistance and ultraviolet resistance in extremely severe and harsh environments, and Ti3C2MXene is a two-dimensional material with high-efficiency photothermal conversion capacity, the photothermal conversion efficiency of MXene can reach 100%, solar energy can be efficiently converted into heat energy, and PVDF and Ti are combined3C2MXene and a PVDF fiber membrane are modified, and the electro-spinning PVDF fiber membrane with excellent thermal conductivity and hydrophilicity is provided and applied to the field of seawater desalination.
Disclosure of Invention
The embodiment of the invention provides a preparation method and application of an electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity, which aims to solve the problem of compatibility of a modified polystyrene composite material and straws, improve the mechanical property of the composite material, and improve the flame retardance of the modified polystyrene composite material by partially replacing a polluted halogen flame retardant with the modified straws.
In view of the above problems, the technical solution proposed by the present invention is:
a preparation method of an electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity comprises the following steps:
s1, preparation of PVDF fiber membrane:
(1) preparing PVDF-HFP electrostatic spinning solution;
(2) electrostatic spinning;
s2, covering the heat conduction layer:
(1) preparation of Ti3C2MXene dispersion or Ti3C2MXene suspension;
(2) evenly spraying Ti on one side surface of the PVDF-HFP electrostatic spinning film3C2MXene dispersion or Ti3C2The MXene suspension is uniformly dripped on one side of the PVDF-HFP electrostatic spinning film;
s3, covering a hydrophilic layer:
(1) preparing a Tris buffer solution;
(2) single-sided deposition of Tris buffer;
(3) the non-sprayed Ti obtained through the step S23C2One side of PVDF-HFP electrospun membrane of MXene was soaked in the solution obtained in step S3 (2).
In an embodiment of the present invention, the PVDF-HFP electrospinning solution described in step S1 is prepared by mixing acetone and N-Dimethylformamide (DMF) at a mass ratio of 1:1, mixing PVDF-HFP and a mixed solvent at a mass ratio of 1:5, and stirring them uniformly to obtain a PVDF-HFP solution with a mass fraction of 20%, and heating and stirring the obtained solution in a water bath at 50 ℃ to obtain a spinning solution.
In an embodiment of the present invention, the electrospinning according to step S1 is performed by electrospinning the PVDF-HFP electrospinning solution prepared in step S1 at a room temperature of 27 ℃ and a relative humidity of 40% to obtain a PVDF-HFP nanofiber membrane, wherein the PVDF-HFP electrospinning solution is input to a nozzle of an electrospinning device at a flow rate of 1.5ml/h, and is simultaneously electrospun by using a high voltage power supply of 15kV, a distance between a receiving device and the nozzle is 15cm, and a rotation speed of a receiving drum is 200 rpm.
In one embodiment of the present invention, Ti is added as described in step S23C2The MXene suspension was uniformly dropped on one side of the PVDF-HFP electrospun membrane, and the surface of the membrane was dried using a blower, and the Ti-coated membrane obtained in the step S2 was subjected to3C2The PVDF-HFP nano-fiber membrane of MXene needs to be stored in a low-temperature closed manner.
In one embodiment of the present invention, Tris buffer is prepared as described in step S3 by dissolving 100ml of deionized water in 0.121g of Tris (hydroxymethyl) aminomethane, stirring for 30min, and adjusting pH to 8.5 to make it weakly alkaline.
In one embodiment of the present invention, the single-side deposition Tris buffer of step S3 is added with 0.2g of polyethyleneimine and 0.2g of dopamine hydrochloride to the Tris buffer obtained in step S3(1) and stirred for 10S.
In one embodiment of the present invention, the step S3 includes spraying Ti to be coated in step S23C2One side of PVDF-HFP electrospun membrane of MXene is soaked in the solution obtained in step S3(2), wherein the soaking time is 4-6h and the ambient temperature needs to be maintained at 60 ℃.
The invention has the beneficial effects that:
the PVDF-HFP electrostatic spinning film obtained by using the electrospinning technology is used as a base material, and the surface of one side of the PVDF-HFP electrostatic spinning film is coated with Ti3C2MXene, and Ti3C2MXene is a two-dimensional material with high-efficiency photothermal conversion capacity, the photothermal conversion efficiency of the MXene can reach 100%, solar energy can be efficiently converted into heat energy, and therefore the PVDF-HFP electrostatic spinning film is coated with Ti3C2One side of MXene has excellent heat-conducting property and is coated with Ti3C2The other side surface of the PVDF-HFP electrostatic spinning membrane of MXene modifies the original hydrophobic property of the PVDF-HFP electrostatic spinning membrane into hydrophilicity through a Tris buffer solution, so when the combined membrane is applied to seawater desalination, the PVDF-HFP electrostatic spinning membrane is subjected to the Tris buffer solutionThe original hydrophobic property of the silk film is modified into hydrophilic property, so that seawater enters the film along the pores in the PVDF-HFP electrostatic spinning film and passes through Ti3C2MXene absorbs and transfers heat irradiated by sunlight, and is used for evaporating seawater inside a PVDF-HFP electrostatic spinning membrane to further realize seawater desalination, and the hydrophobic PVDF-HFP can block water from continuously spreading to the upper layer to prevent salt from being separated out on the surface, so that Ti is protected3C2The MXene film has the advantages that the structure is not damaged, the long-term stable work is facilitated, the PVDF-HFP polymer has good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance and ray radiation resistance, and has special performances such as piezoelectricity, dielectricity and pyroelectricity, so that the service life and the application environment of the combination are greatly prolonged.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing an electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity, which is disclosed by the embodiment of the invention;
FIG. 2 is an SEM scan of PVDF-HFP disclosed in the examples of the invention;
FIG. 3 is a contact angle graph of a PVDF-HFP fiber membrane before and after hydrophilic modification according to an embodiment of the present invention;
FIG. 4 shows Ti sprayed with different contents according to the embodiment of the present invention3C2Different temperature profiles that can be achieved by MXene;
FIG. 5 is an SEM scan of modified PVDF-HFP disclosed in the examples of the invention;
FIG. 6 shows Ti according to an embodiment of the present invention3C2XRD pattern of MXene.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Other embodiments of the invention may select all alternative reagents within the scope of the claims. Unless otherwise specified, the parts are parts by mass.
The invention discloses a preparation method of an electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity, which comprises the following steps:
s1, preparation of PVDF fiber membrane:
(1) preparing PVDF-HFP electrostatic spinning solution;
(2) electrostatic spinning;
s2, covering the heat conduction layer:
(1) preparation of Ti3C2MXene dispersion or Ti3C2MXene suspension;
(2) evenly spraying Ti on one side surface of the PVDF-HFP electrostatic spinning film3C2MXene dispersion or Ti3C2The MXene suspension is uniformly dripped on one side of the PVDF-HFP electrostatic spinning film;
s3, covering a hydrophilic layer:
(1) preparing a Tris buffer solution;
(2) single-sided deposition of Tris buffer;
(3) the non-sprayed Ti obtained through the step S23C2One side of PVDF-HFP electrospun membrane of MXene was soaked in the solution obtained in step S3 (2).
As an example of the present invention, further, the PVDF-HFP electrospinning solution described in step S1 is prepared by mixing acetone and N-Dimethylformamide (DMF) at a mass ratio of 1:1, mixing PVDF-HFP and a mixed solvent at a mass ratio of 1:5, and stirring them uniformly to obtain a PVDF-HFP solution with a mass fraction of 20%, and heating and stirring the obtained solution in a water bath at 50 ℃ to obtain a spinning solution.
In one embodiment of the present invention, the electrospinning according to step S1 comprises electrospinning the PVDF-HFP electrospinning solution prepared in step S1 at a room temperature of 27 ℃ and a relative humidity of 40% to obtain a PVDF-HFP nanofiber membrane, wherein PVDF-HFP electrostatic spinning solution is input to a nozzle of electrostatic spinning equipment at a flow rate of 1.5ml/h, simultaneously, a high-voltage power supply of 15kV is used for electrostatic spinning, the distance between a receiving device and a spray head is 15cm, the rotating speed of a receiving roller is 200rpm, as shown in fig. 2, which is an SEM scan of PVDF-HFP, it can be seen that the fibers are randomly arranged, many pores are formed in the middle, and the average diameter of the electrospun fibers is 0.6 to 0.8 μm by the particle size analysis, the spinning membrane has better ion filtering effect as the fiber diameter is smaller, so that the nano-grade electrostatic spinning membrane can be used as the base membrane.
As an embodiment of the present invention, further, Ti is added in step S23C2The MXene suspension was uniformly dropped on one side of the PVDF-HFP electrospun membrane, and the surface of the membrane was dried using a blower, and the Ti-coated membrane obtained in the step S2 was subjected to3C2The PVDF-HFP nano-fiber membrane of MXene needs to be stored in a low-temperature closed manner, and Ti with different contents is sprayed as shown in figure 43C2The temperature that can be reached by MXene. Thus Ti3C2The higher the MXene content, the more obvious the photothermal conversion effect, the higher the temperature can be raised, and the higher the temperature can be reached on the surface of the photothermal film.
As an example of the present invention, further, in the step S3, a Tris buffer is prepared, 100ml of deionized water is taken, 0.121g of Tris (hydroxymethyl) aminomethane is dissolved in the deionized water, the mixture is stirred for 30min, and the pH is adjusted to 8.5 to make the mixture weakly alkaline.
As an example of the present invention, further, the single-side deposition Tris buffer described in step S3 is added with 0.2g of polyethyleneimine and 0.2g of dopamine hydrochloride to the Tris buffer obtained in step S3(1) and stirred for 10 seconds.
As an embodiment of the present invention, further, the step S3 describes that the Ti non-sprayed coating obtained through the step S2 is not sprayed3C2Soaking one side of PVDF-HFP electrospun membrane of MXene in the solution obtained in the step S3(2), wherein the soaking time is 4-6h, the ambient temperature needs to be maintained at 60 ℃, and the contact angles of the PVDF-HFP electrospun membrane before and after hydrophilic modification are shown in FIG. 3According to the graph, the hydrophilic modification of the surface of the unilateral membrane is realized by the characteristic that dopamine and polyethyleneimine can be fully polymerized on the surface of the membrane under the condition of weak base, and the contact angle of the membrane before modification and the modified membrane is paired, wherein the average value of the contact angle is reduced from 125.46 degrees to 24.91 degrees, namely, the hydrophobic membrane is converted into the hydrophilic membrane.
In the embodiment of the invention, the PVDF-HFP electrostatic spinning film obtained by the electrospinning technology is used as a base material, and Ti is coated on the surface of one side of the PVDF-HFP electrostatic spinning film3C2MXene, and Ti3C2MXene is a two-dimensional material with high-efficiency photothermal conversion capacity, the photothermal conversion efficiency of the MXene can reach 100%, solar energy can be efficiently converted into heat energy, and therefore the PVDF-HFP electrostatic spinning film is coated with Ti3C2One side of MXene has excellent heat-conducting property and is coated with Ti3C2The original hydrophobic property of the PVDF-HFP electrostatic spinning membrane is modified into hydrophilicity through the Tris buffer solution on the other side of the PVDF-HFP electrostatic spinning membrane of MXene, so when the combined membrane is applied to seawater desalination, the original hydrophobic property of the PVDF-HFP electrostatic spinning membrane is modified into hydrophilicity through the Tris buffer solution, seawater enters the membrane along the pores in the PVDF-HFP electrostatic spinning membrane and passes through Ti3C2MXene absorbs and transfers heat irradiated by sunlight, and is used for evaporating seawater inside a PVDF-HFP electrostatic spinning membrane to further realize seawater desalination, and the hydrophobic PVDF-HFP can block water from continuously spreading to the upper layer to prevent salt from being separated out on the surface, so that Ti is protected3C2The MXene film has the advantages that the structure is not damaged, the long-term stable work is facilitated, the PVDF-HFP polymer has good chemical corrosion resistance, high temperature resistance, oxidation resistance, weather resistance and ray radiation resistance, and has special performances such as piezoelectricity, dielectricity and pyroelectricity, so that the service life and the application environment of the combination are greatly prolonged.
To better illustrate that the electrospun PVDF fiber membrane with excellent thermal conductivity and hydrophilicity prepared by the invention has excellent hydrophilicity, the comparison between the coating hydrophilic layer and the original substrate is carried out: according to contact angle graphs before and after hydrophilic modification of a PVDF-HFP fiber membrane shown in figure 3, the single-side membrane is subjected to hydrophilic modification by the characteristic that dopamine and polyethyleneimine can be fully polymerized on the surface of the membrane under the condition of weak alkali, the contact angle of the membrane before modification and the contact angle of the modified membrane are aligned, the average value of the contact angle is reduced to 24.91 degrees from 125.46 degrees, namely the hydrophilic membrane is converted from a hydrophobic membrane to a hydrophilic membrane, the hydrophilic modification of the surface of the single-side membrane is realized, scanning electron microscopy is performed on the membrane after treatment, and tests are shown in figure 5.
To better illustrate that the electrospun PVDF fiber membrane with excellent thermal conductivity and hydrophilicity prepared by the invention has excellent thermal conductivity, the ratio of the heat-conducting layer to the original substrate is now: to determine the crystal structure, the surface of the film is coated with a layer of Ti3C2MXene, para-film, Ti3C2MXene powder and coating Ti3C2X-ray diffraction analysis of MXene film to obtain XRD pattern shown in figure 6, wherein a is X-ray diffraction pattern of original film, and b is Ti-coated film3C2X-ray diffraction pattern of MXene film, c is Ti3C2X-ray diffraction pattern of MXene powder, d is XPS test pattern of photothermal film surface, and Ti content sprayed with different contents is shown in FIG. 43C2Different temperature profiles achievable with MXene, thus obtaining Ti3C2The higher the MXene content, the more obvious the photothermal conversion effect, the higher the temperature can be raised, and the higher the temperature can be reached on the surface of the photothermal film.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. A preparation method of an electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity is characterized by comprising the following steps: the method comprises the following steps:
s1, preparation of PVDF fiber membrane:
(1) preparing PVDF-HFP electrostatic spinning solution;
(2) electrostatic spinning;
s2, covering the heat conduction layer:
(1) preparation of Ti3C2MXene dispersion or Ti3C2MXene suspension;
(2) evenly spraying Ti on one side surface of the PVDF-HFP electrostatic spinning film3C2MXene dispersion or Ti3C2The MXene suspension is uniformly dripped on one side of the PVDF-HFP electrostatic spinning film;
s3, covering a hydrophilic layer:
(1) preparing a Tris buffer solution;
(2) single-sided deposition of Tris buffer;
(3) the non-sprayed Ti obtained through the step S23C2One side of PVDF-HFP electrospun membrane of MXene was soaked in the solution obtained in step S2 (2).
2. The method for preparing an electrospun PVDF fibrous membrane with excellent thermal conductivity and hydrophilicity according to claim 1, wherein: and S1, mixing acetone and N-Dimethylformamide (DMF) according to a mass ratio of 1:1, mixing PVDF-HFP and a mixed solvent according to a mass ratio of 1:5, uniformly stirring to obtain a PVDF-HFP solution with a mass fraction of 20%, and heating and uniformly stirring the obtained solution in a water bath at 50 ℃ to obtain a spinning solution.
3. The method for preparing an electrospun PVDF fibrous membrane with excellent thermal conductivity and hydrophilicity according to claim 1, wherein: and (S1) performing electrostatic spinning on the PVDF-HFP electrostatic spinning solution prepared in the step S1 at the room temperature of 27 ℃ and the relative humidity of 40% to obtain the PVDF-HFP nanofiber membrane, wherein the PVDF-HFP electrostatic spinning solution is input to a nozzle of electrostatic spinning equipment at the flow rate of 1.5ml/h, electrostatic spinning is performed by using a high-voltage power supply of 15kV, the distance between a receiving device and the nozzle is 15cm, and the rotating speed of a receiving roller is 200 rpm.
4. The method for preparing an electrospun PVDF fibrous membrane with excellent thermal conductivity and hydrophilicity according to claim 1, wherein: step S2 describes mixing Ti3C2The MXene suspension was uniformly dropped on one side of the PVDF-HFP electrospun membrane, and the surface of the membrane was dried using a blower, and the Ti-coated membrane obtained in the step S2 was subjected to3C2The PVDF-HFP nano-fiber membrane of MXene needs to be stored in a low-temperature closed manner.
5. The method for preparing an electrospun PVDF fibrous membrane with excellent thermal conductivity and hydrophilicity according to claim 1, wherein: the Tris buffer solution prepared in step S3 is prepared by dissolving 100ml of deionized water in 0.121g of Tris (hydroxymethyl) aminomethane, stirring for 30min, and adjusting the pH to 8.5 to make the solution weakly alkaline.
6. The method for preparing an electrospun PVDF fibrous membrane with excellent thermal conductivity and hydrophilicity according to claim 1, wherein: the single-side deposition Tris buffer described in step S3 was added with 0.2g of polyethyleneimine and 0.2g of dopamine hydrochloride to the Tris buffer obtained in step S3(1) and stirred for 10 seconds.
7. The method for preparing an electrospun PVDF fibrous membrane with excellent thermal conductivity and hydrophilicity according to claim 1, wherein: step S3 of spraying Ti to be coated in step S23C2One side of PVDF-HFP electrospun membrane of MXene is soaked in the solution obtained in step S3(2), wherein the soaking time is 4-6h and the ambient temperature needs to be maintained at 60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111460181.2A CN114164646A (en) | 2021-12-02 | 2021-12-02 | Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111460181.2A CN114164646A (en) | 2021-12-02 | 2021-12-02 | Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114164646A true CN114164646A (en) | 2022-03-11 |
Family
ID=80482422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111460181.2A Pending CN114164646A (en) | 2021-12-02 | 2021-12-02 | Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114164646A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106422809A (en) * | 2016-06-19 | 2017-02-22 | 贵州省材料产业技术研究院 | Fast and efficient boron removal hollow fiber composite membrane and preparation method thereof |
| CN108043238A (en) * | 2017-12-29 | 2018-05-18 | 上海海事大学 | A kind of composite semipermeable membrane containing Ti3C2, its preparation method and purposes for light evaporation water |
| US20180169591A1 (en) * | 2014-11-17 | 2018-06-21 | Khaled Ahmed Mahmoud | Two-dimensional metal carbide desalination membrane |
| CN108862478A (en) * | 2018-07-16 | 2018-11-23 | 梧州市兴能农业科技有限公司 | A kind of distillation device for desalinizing seawater |
| US20200156006A1 (en) * | 2018-11-16 | 2020-05-21 | National Taiwan University | Omniphobic Membranes and Application Thereof |
| CN111185103A (en) * | 2020-01-09 | 2020-05-22 | 东华大学 | Nanofiber-based organic/inorganic composite nanofiltration membrane and preparation method thereof |
| CN111760463A (en) * | 2020-07-28 | 2020-10-13 | 深圳大学 | Asymmetric membrane, preparation method thereof and application thereof in membrane distillation seawater desalination |
| CN113401959A (en) * | 2021-05-10 | 2021-09-17 | 北京化工大学 | Efficient photo-thermal evaporation material and preparation method thereof |
-
2021
- 2021-12-02 CN CN202111460181.2A patent/CN114164646A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180169591A1 (en) * | 2014-11-17 | 2018-06-21 | Khaled Ahmed Mahmoud | Two-dimensional metal carbide desalination membrane |
| CN106422809A (en) * | 2016-06-19 | 2017-02-22 | 贵州省材料产业技术研究院 | Fast and efficient boron removal hollow fiber composite membrane and preparation method thereof |
| CN108043238A (en) * | 2017-12-29 | 2018-05-18 | 上海海事大学 | A kind of composite semipermeable membrane containing Ti3C2, its preparation method and purposes for light evaporation water |
| CN108862478A (en) * | 2018-07-16 | 2018-11-23 | 梧州市兴能农业科技有限公司 | A kind of distillation device for desalinizing seawater |
| US20200156006A1 (en) * | 2018-11-16 | 2020-05-21 | National Taiwan University | Omniphobic Membranes and Application Thereof |
| CN111185103A (en) * | 2020-01-09 | 2020-05-22 | 东华大学 | Nanofiber-based organic/inorganic composite nanofiltration membrane and preparation method thereof |
| CN111760463A (en) * | 2020-07-28 | 2020-10-13 | 深圳大学 | Asymmetric membrane, preparation method thereof and application thereof in membrane distillation seawater desalination |
| CN113401959A (en) * | 2021-05-10 | 2021-09-17 | 北京化工大学 | Efficient photo-thermal evaporation material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 肖成伟: "《电动汽车工程手册 第4卷 动力蓄电池》", vol. 1, 北京：机械工业出版社, pages: 201 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103718360B (en) | Polymer dielectric film and the method preparing this polymer dielectric film for fuel cell | |
| CN111394892B (en) | Polyimide nanofiber membrane coaxially coated with nano zirconium dioxide inorganic layer and preparation method thereof | |
| CN108774808B (en) | Polyimide nanofiber membrane with cross-linked appearance and zirconium dioxide coated surface and preparation method thereof | |
| US20170362740A1 (en) | Flexible ceramic fibers and polymer composite and method of making the same | |
| CN111760463B (en) | Asymmetric membrane, preparation method thereof and application thereof in membrane distillation seawater desalination | |
| CN102691175A (en) | Composite fibre membrane with unidirectional water permeable performance and preparation method thereof | |
| CN105199137B (en) | A kind of preparation method of porous composite polymer electrolyte membrane material | |
| CN108914550B (en) | Preparation method of polyimide fiber membrane with surface coated with zirconium dioxide nano layer | |
| CN105568555B (en) | A kind of preparation method of air filtration graphene fiber film | |
| CN102417604A (en) | Preparation method of polyimide porous film | |
| CN109244324A (en) | The bacteria cellulose composite diaphragm of heat cross-linking poly propenoic acid vinyl alcohol filling | |
| CN110358135A (en) | A kind of flexible nano fiber composite aerogel material and preparation method thereof | |
| CN108755104B (en) | Preparation method of surface-modified titanium dioxide nanoparticle polyimide fibrous membrane | |
| CN104064712A (en) | Method for selecting lithium ion battery ceramic diaphragm bonding agent | |
| US20050048274A1 (en) | Production of nanowebs by an electrostatic spinning apparatus and method | |
| Kefan et al. | Controllable Coaxial Coating of Boehmite on the Surface of Polyimide Nanofiber Membrane and Its Application as a Separator for Lithium‐Ion Batteries | |
| CN113622089B (en) | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof | |
| CN114164646A (en) | Preparation method and application of electrospun PVDF (polyvinylidene fluoride) fiber membrane with excellent thermal conductivity and hydrophilicity | |
| CN107571586B (en) | A kind of laminated construction ferroelectric polymers based dielectric film, and its preparation method and application | |
| Li et al. | High‐performance nano‐TiO2@ polyvinylidene fluoride composite separators prepared by electrospinning for safe lithium‐ion battery | |
| CN110556496B (en) | High-safety composite diaphragm with high-temperature self-closing function and preparation method thereof | |
| CN109280993B (en) | Method for synthesizing lithium iron silicate nanofiber by electrostatic spinning technology | |
| WO2016167285A1 (en) | Metal halide crystal and perovskite compound crystal each having controlled structure | |
| CN110620253B (en) | Method for preparing non-aqueous proton exchange membrane based on sulfonated graphene oxide by utilizing spin coating technology | |
| CN113529404B (en) | Polyimide nanofiber membrane with surface uniformly coated with controllable nano zirconium dioxide inorganic layer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |