CN117328264A - Preparation method of polyphenylene sulfide alkaline electrolyzed water diaphragm - Google Patents
Preparation method of polyphenylene sulfide alkaline electrolyzed water diaphragm Download PDFInfo
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 133
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 133
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004744 fabric Substances 0.000 claims abstract description 76
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000011282 treatment Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical group CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 230000008595 infiltration Effects 0.000 abstract description 7
- 238000001764 infiltration Methods 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 125000000101 thioether group Chemical group 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- -1 hydroxyl ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/52—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 sulfur, selenium, tellurium, polonium or compounds thereof with selenium, tellurium, polonium or their compounds; with sulfur, dithionites or compounds containing sulfur and halogens, with or without oxygen; by sulfohalogenation with chlorosulfonic acid; by sulfohalogenation with a mixture of sulfur dioxide and free halogens
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- 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
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a preparation method of a polyphenylene sulfide alkaline electrolyzed water diaphragm, which comprises the following steps: (1) Washing and drying polyphenylene sulfide woven diaphragm cloth in deionized water and ethanol in sequence; (2) Soaking the polyphenylene sulfide woven membrane cloth obtained in the step (1) in an haloalkane solvent, taking out and drying for later use; (3) The polyphenylene sulfide woven diaphragm cloth obtained in the step (2) is soaked in a good organic solvent of the polyphenylene sulfide under the ultrasonic condition; (4) And (3) carrying out sulfonation reaction on the soaked polyphenylene sulfide woven diaphragm cloth obtained in the step (3), washing and drying to obtain the hydrophilically modified PPS alkaline electrolytic water diaphragm. According to the invention, the polyphenylene sulfide woven diaphragm cloth is subjected to two-step infiltration treatment and then is subjected to sulfonation reaction, so that the hydrophilicity of the PPS diaphragm is improved, and the surface resistance is reduced; and the resistance is still stable after being soaked in the high-temperature alkaline electrolyte environment for a long time.
Description
Technical Field
The invention belongs to the field of polyphenylene sulfide polymers, and particularly relates to a preparation method of a polyphenylene sulfide alkaline electrolytic water diaphragm.
Background
The existing technology for producing hydrogen by electrolyzing water mainly comprises four types of alkaline aqueous solution electrolysis (ALK), proton exchange membrane electrolysis (PEM), high-temperature Solid Oxide Electrolysis (SOEC) and solid polymer anion exchange membrane electrolysis (AEM). The proton exchange membrane electrolysis has the advantages of high electrolysis current density, high efficiency, high response speed and the like. However, in acidic media, the use of expensive noble metal catalysts (Pt and IrO 2 Etc.) and titanium-based bipolar plates, the high cost limits the large-scale utilization of the proton exchange membrane electrolyzed water. In contrast, in alkaline media, it can utilize inexpensive non-noble metals (e.g., fe, co, ni, etc.) as catalysts and avoid the use of expensive titanium-based components. High temperature solid oxide electrolysis and solid polymer anion exchange membrane electrolysis technologies are not mature, and the production scale is also to be improved. Therefore, the development of the alkaline water electrolysis hydrogen production technology is beneficial to remarkably reducing the large-scale hydrogen production cost.
The alkaline water electrolysis hydrogen production refers to a process of carrying out water electrolysis hydrogen production in an alkaline electrolyte environment, and the electrolyte is a KOH solution with the mass concentration of 30 percent. In the alkaline water electrolysis hydrogen production technology, a diaphragm is an important component of an alkaline electrolysis tank, and the main functions comprise 3 aspects: (1) the cathode and the anode are separated to form a cathode chamber and an anode chamber, so that short circuit is prevented; (2) the danger caused by mixing hydrogen and oxygen generated by two poles is avoided; (3) has high porosity, and is convenient for hydroxyl ions to be transferred from the cathode to the anode. Therefore, the ideal separator material should possess the following characteristics: 1. high porosity, which is beneficial to hydroxyl ion transfer; 2. high gas barrier properties, preventing hydrogen generated by electrolysis from mixing with oxygen; 3. high hydrophilicity, low resistivity; 4. high corrosion resistance, stable existence in electrolyte of 30% KOH solution; 5. the thickness is thin, the aperture is small, the mechanical strength is high, and the dimensional stability is good; 6. low cost and long service life.
Commercial separator materials for alkaline cells are mainly porous separators. The porous diaphragm has no conductivity, and ion conduction is realized mainly by electrolyte filled in gaps of the material. Asbestos diaphragm is the earliestCommercial alkaline separator materials, but because they are carcinogens, are being phased out. At present, polyphenylene sulfide (PPS) is mostly used as an alkaline electrolytic cell diaphragm instead of asbestos, and PPS is an amorphous thermoplastic resin prepared by polycondensation reaction of paradichlorobenzene and sodium sulfide, and has high temperature resistance, good mechanical strength and thermal stability and excellent physicochemical properties. However, the hydrophilicity of PPS fabric is too weak, and the use of PPS fabric alone as an alkaline water electrolysis separator causes excessive internal resistance of the electrolytic cell, and thus improvement of the hydrophilicity of PPS fabric is required. There are two main methods for PPS fabric modification: one is to coat the surface of PPS fabric with functional coating to improve the hydrophilicity, which forms a composite membrane similar to a sandwich structure, but the composite membrane can lead to the falling of inorganic deposition layer under long-term operation, thereby leading to performance reduction. Still another method is to chemically treat PPS, and the hydrophilic functional group (-SO) of the branch on the molecular chain of polyphenylene sulfide 3 H. -c=o, etc.).
CN115084611a discloses a sulfonated polyphenylene sulfide proton exchange membrane and a preparation method thereof, which is characterized in that polyphenylene sulfide and proton exchange resin are reacted in a polar solvent, redundant solvent and impurities are removed, sulfide is added for continuous reaction, and the sulfonated polyphenylene sulfide proton exchange resin is formed. But the quality of the synthesized sulfonated polyphenylene sulfide proton exchange resin is required to be evaluated, and the process is complicated.
CN113862821a discloses a polyphenylene sulfide fiber fabric type alkaline water electrolysis diaphragm, which is characterized in that zirconia modified polyphenylene sulfide fibers are subjected to spinning and weaving processes, and the polyphenylene sulfide fiber fabric type alkaline water electrolysis diaphragm has good hydrophilicity. However, the PPS membrane is woven by blending and granulating PPS resin and inorganic nano-particles of zirconia and then spinning, the physical blending is easy to generate phase separation, the blending is poor, the surface hydrophilicity of the PPS membrane is uneven after spinning and weaving, and the phenomenon can be avoided by chemical grafting.
CN11133130a discloses a hydrophilization treatment method of polyphenylene sulfide resin, which is to electrolyze sulfuric acid to generate persulfuric acid, treat the surface of PPS resin by strong oxidation of persulfuric acid, and adjust the hydrophilization degree of the surface of PPS resin by sulfuric acid concentration.
The surface of the polyphenylene sulfide is subjected to hydrophilic modification treatment after grafting, sulfonation and other treatments, but the inside of the polyphenylene sulfide is still in a hydrophobic state, and the polyphenylene sulfide is unstable under high-temperature alkaline electrolysis water conditions, is difficult to withstand the high-temperature alkaline electrolysis environment for a long time, and has gradually reduced barrier performance and shorter service life in use.
CN113201839a discloses a polyphenylene sulfide fabric for water electrolysers, which is obtained by preparing a fabric from polyphenylene sulfide yarns, then sulfonating the fabric in 300-1000g/L sulfuric acid and 150-500g/L chromic acid at different stages, and then cleaning. After the treatment of the patent, hydrophilic groups are arranged on the surface and the inside of the polyphenylene sulfide fabric, and a large amount of hydrophilic groups still exist after long-term use, so that the stability and the service life of the PPS diaphragm are improved. The mechanism is that chromic acid breaks down the macromolecular chain segment of polyphenylene sulfide into small molecular chain segments, and concentrated sulfuric acid can enter the PPS to sulfonate, so that the surface and the inside of PPS fiber are both introduced with sulfoxy groups. However, chromic acid with strong oxidizing property in the mixed solution can decompose the macromolecular chain segments of the polyphenylene sulfide into a plurality of small molecular chain segments, so that the original physical and chemical properties of the PPS are changed, and the mechanical strength of the PPS diaphragm is reduced.
Therefore, the PPS diaphragm for hydrogen production by alkaline water electrolysis needs to be hydrophilic modified, can keep the hydrophilic capacity for a long time, can withstand high-temperature alkaline electrolysis conditions, and has the mechanical property reaching the standard. There is also a need to develop a PPS membrane that can satisfy the combination of excellent properties for hydrogen production by alkaline electrolysis of water in the actual industry.
Disclosure of Invention
In order to solve the defect that the hydrophilia modified polyphenylene sulfide (PPS) diaphragm cloth cannot resist high-temperature alkaline electrolysis water for a long time, so that the service life is short, the invention provides the hydrophilia modification method of the polyphenylene sulfide woven diaphragm cloth, which can improve the hydrophilia of the PPS woven diaphragm cloth and reduce the internal resistance of the PPS woven diaphragm cloth applied in an electrolytic tank; meanwhile, the electrolyte can resist high-temperature alkaline water electrolysis conditions, plays a role for a long time, has long service life and meets the actual industrial requirements.
The invention realizes the aim through the following technical scheme:
a preparation method of a polyphenylene sulfide alkaline electrolyzed water diaphragm comprises the following steps:
(1) Washing and drying polyphenylene sulfide woven diaphragm cloth in deionized water and ethanol in sequence;
(2) Soaking the polyphenylene sulfide woven membrane cloth obtained in the step (1) in an haloalkane solvent, taking out and drying for later use;
(3) The polyphenylene sulfide woven diaphragm cloth obtained in the step (2) is soaked in a good organic solvent of the polyphenylene sulfide under the ultrasonic condition;
(4) And (3) carrying out sulfonation reaction on the soaked polyphenylene sulfide woven diaphragm cloth obtained in the step (3), washing and drying to obtain the hydrophilically modified PPS alkaline electrolytic water diaphragm.
Further, in the step (1), the polyphenylene sulfide woven membrane cloth has a thickness of 0.6 to 1.0mm, preferably 0.7 to 0.8mm, and a gram weight of 400 to 500g/m 2 The polyphenylene sulfide fiber diameter is 7-20 μm, preferably 10-15 μm; washing with deionized water and ethanol to remove water-soluble impurities and organic impurities in PPS woven membrane cloth.
Further, in the step (2), the halogenated hydrocarbon is selected from at least one of 1, 2-dichloroethane, dichloromethane, chloroform, tetrachloromethane, dichlorobenzene species, preferably 1, 2-dichloroethane; the purpose of the halogenated hydrocarbon infiltration is to make the PPS woven diaphragm cloth better contact with concentrated sulfuric acid, so that the sulfonation of the PPS woven diaphragm cloth is more uniform; of which 1, 2-dichloroethane is most effective. The soaking time in the halohydrocarbon solvent is 0.5-1h. The amount of the halogenated hydrocarbon solvent is not particularly limited as long as the polyphenylene sulfide woven membrane cloth can be sufficiently impregnated.
Further, in the step (3), the ultrasonic frequency is 30-60kHz, the soaking time under the ultrasonic condition is 1-3min, and the good solvent is at least one of amide solvents and imidazolidinone solvents; the amide solvent is at least one selected from dimethylacetamide and dimethylformamide, and the imidazolidone is 1, 3-dimethyl-2-imidazolidone. The applicant has found that the sulfonation modification effect on the PPS woven diaphragm cloth can be greatly improved by soaking the PPS woven diaphragm cloth with the haloalkane firstly and then soaking the polyphenylene sulfide with a good solvent of the polyphenylene sulfide in a short time under the ultrasonic condition. The PPS woven membrane cloth has the advantages that the hydrophilicity is improved, the alkaline electrolysis water condition can be resisted, and the good hydrophilicity is kept for a long time, so that the PPS woven membrane cloth has longer service life as an alkaline electrolysis water membrane, and the PPS membrane material plays a larger role in the electrolysis water field in industry, and has great industrial advantages and practical significance. The ultrasonic condition can not be excessively long, otherwise, the membrane structure is damaged, the mechanical property and the dimensional stability of the PPS membrane are reduced, and the service life of the PPS membrane in alkaline electrolyzed water is also not facilitated. The invention utilizes ultrasonic conditions to shorten the time for achieving full infiltration, and the soaking time is preferably 1-3 min.
Furthermore, the organic solvent is a mixed solvent of an amide solvent and an imidazolidinone solvent according to a volume ratio of 3-5:1. For example, a mixed solvent of dimethylacetamide and 1, 3-dimethyl-2-imidazolidone according to a volume ratio of 3-5:1, or a mixed solvent of dimethylformamide and 1, 3-dimethyl-2-imidazolidone according to a volume ratio of 3-5:1. The compounded solvent system is soaked under the ultrasonic condition, so that the optimal sulfonation effect can be achieved.
Further, in the step (4), after being soaked in a good solvent under the ultrasonic condition, the polyphenylene sulfide woven diaphragm cloth is taken out and directly subjected to sulfonation reaction without drying treatment; the sulfonation reaction is to contact the soaked polyphenylene sulfide woven membrane cloth with a sulfonation reagent for reaction, wherein the sulfonation reagent is at least one selected from concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and sulfur trioxide; the amount of the sulfonating agent is not particularly limited as long as the polyphenylene sulfide woven membrane cloth can be immersed; the sulfonation reaction temperature is 40-50 ℃ and the reaction time is 30-60min. In the step (2) and the step (3), the polyphenylene sulfide woven membrane cloth is soaked by the halogenated alkane and the organic good solvent in sequence, the sulfonation reaction in the step (4) is smoothly carried out, and the surface of the polyphenylene sulfide woven membrane cloth is subjected to the sulfonation reaction, and the inside of the polyphenylene sulfide woven membrane cloth is also subjected to the sulfonation reaction to a certain extent.
Further, in the step (4), the washing is sequentially water washing under ultrasonic conditions, 1, 2-dichloroethane washing and acetone washing.
Further, pressThe water absorption speed of the polyphenylene sulfide woven diaphragm cloth prepared by the method is less than 10s, such as 1-7s; the surface resistance is 0.25-0.34 Ω cm 2 。
The technical scheme of the invention provides the following beneficial effects:
(1) The invention carries out two-step infiltration treatment on the polyphenylene sulfide woven diaphragm cloth, namely long-time pre-infiltration of haloalkane and short-time infiltration of good polyphenylene sulfide solvent under ultrasonic condition, and then carries out sulfonation reaction, and introduces-SO on benzene ring of the polyphenylene sulfide woven diaphragm cloth 3 H, improving the hydrophilicity of the PPS diaphragm and reducing the surface resistance of the PPS diaphragm as an alkaline electrolytic water diaphragm; and the resistance is still stable after being soaked in the high-temperature alkaline electrolyte environment for a long time, thus providing possibility of industrialized mass production for preparing hydrogen by electrolyzing water under alkaline conditions.
(2) The PPS woven membrane cloth subjected to hydrophilic modification has good hydrophilic performance, can reduce the surface resistance, reduce the energy loss and reduce the hydrogen production cost in the use process; in addition, because the membrane has good hydrophilic performance, a layer of water film can be formed on the surface layer of the membrane in the use process, so that the aperture of the membrane is reduced, the generated hydrogen and oxygen can be effectively prevented from passing through each other, and the purity of the hydrogen and the oxygen is increased.
Drawings
Fig. 1 is a drawing of a polyphenylene sulfide woven cloth diaphragm Scanning Electron Microscope (SEM).
FIG. 2 is a photograph of a membrane of an unsulfonated pre-polyphenylene sulfide woven cloth.
FIG. 3 is a photograph of a membrane of polyphenylene sulfide woven cloth after sulfonation of example 1.
Fig. 4 is an XPS energy spectrum of sulfur element of a polyphenylene sulfide woven cloth diaphragm before and after sulfonation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention, but are not intended to limit the same. The experimental methods in the following examples are conventional methods unless otherwise specified.
Polyphenylene sulfide woven diaphragm cloth is purchased from Zhejiang Zhengben New material Co., ltd, and has the thickness of 0.76mm and the gram weight of 461g/m 2 The diameter of the polyphenylene sulfide fiber is 10-15 mu m.
Example 1
(1) Washing 10cm multiplied by 10cm newly added polyphenylene sulfide woven diaphragm cloth with deionized water for 30min, washing with ethanol for 30min, and drying;
(2) Soaking the dried polyphenylene sulfide woven diaphragm cloth in 1, 2-dichloroethane for 0.5h, taking out, and drying for later use;
(3) Soaking the dried polyphenylene sulfide woven diaphragm cloth obtained in the step (2) in dimethylformamide under the ultrasonic condition of 60kHz for 1min, and then taking out;
(4) Reacting the polyphenylene sulfide woven membrane cloth soaked in the step (3) with concentrated sulfuric acid at 40 ℃ for 0.5h, taking out the membrane cloth, sequentially washing with ultrasonic waves (30 kHz) in deionized water for 10min, washing with 1, 2-dichloroethane for 10min, washing with acetone for 10min, and drying after washing is finished to obtain the hydrophilically modified polyphenylene sulfide woven membrane cloth.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a membrane of an unsulfonated pre-polyphenylene sulfide woven cloth, and it can be seen that the fiber diameter is 7-20um. FIG. 2 is a photograph of a membrane of an unsulfonated pre-polyphenylene sulfide woven cloth. FIG. 3 is a photograph of a membrane of polyphenylene sulfide woven cloth after sulfonation of example 1. It can be seen that the hydrophilicity of the polyphenylene sulfide woven cloth diaphragm after sulfonation modification is obviously improved.
Example 2
Other conditions and operations were the same as in example 1, except that in step (3), the soaking time was 2min.
Example 3
Other conditions and operations were the same as in example 1, except that in step (3), the soaking time was 3min.
Example 4
Other conditions and operations were the same as in example 1, except that in step (3), the soaking time was 4min.
Example 5
Other conditions and operations were the same as in example 2 except that in step (3), 1, 3-dimethyl-2-imidazolidone was used as the soaking solvent.
Example 6
Other conditions and operations are the same as in example 2, except that in step (3), the immersed solvent is a mixed solvent of dimethylformamide and 1, 3-dimethyl-2-imidazolidone in a volume ratio of 3:1.
Example 7
Other conditions and operations are the same as in example 2, except that in step (3), the immersed solvent is a mixed solvent of dimethylacetamide and 1, 3-dimethyl-2-imidazolidone in a volume ratio of 5:1.
Comparative example 1
Other conditions and operations were the same as in example 2, except that step (3) was omitted, the polyphenylene sulfide woven membrane cloth impregnated with 1, 2-dichloroethane of step (2) was directly subjected to sulfonation reaction and post-treatment (washing, drying) of step (4).
Comparative example 2
Other conditions and operations were the same as in example 2, except that in step (3), the ultrasonic conditions were canceled.
Comparative example 3
Other conditions and operations were the same as in example 2, except that step (2) was omitted, the polyphenylene sulfide woven membrane cloth pretreated in step (1) was directly immersed in the PPS good solvent under ultrasonic conditions in step (3).
Effect example
The polyphenylene sulfide woven membrane cloths of the above examples and comparative examples were subjected to performance tests, test items and methods as follows:
morphology structure: and (3) bonding the PPS diaphragm fiber on the conductive adhesive, and performing morphology characterization by using a scanning electron microscope.
X-ray photoelectron spectroscopy (XPS): the distribution of the surface elements of the PPS diaphragm before and after sulfonation is analyzed by an X-ray photoelectron spectrometer. After the sample was cut to a size of 0.5cm by 0.5cm, it was fixed to a metal plate with a conductive tape for testing. The peaks of the unsulfonated PPS separator correspond to electron binding energies of 163.3eV and 164.5eV, corresponding to PPSBinding energy of S element in thioether group on benzene ring; whereas the sulfonated PPS membrane showed a distinct peak at 169.1eV, which corresponds to the binding energy of the S atom in the sulfonic acid group. This indicates that the surface of PPS diaphragm is successfully grafted with sulfonic acid group (-SO) 3 H)。
Surface resistance: according to the testing standard of the surface resistance of the diaphragm of the alkaline storage battery in the electronic industry standard SJ/T10171.5-1991 of the people's republic of China, the diaphragm is measured in a homemade surface resistance testing device.
Drip diffusion time: the water absorption and the water absorption time before and after the hydrophilic treatment are tested according to the GB/T21655.1-2008 standard.
Alkali resistance electrolytic water environment test: after the polyphenylene sulfide woven membrane cloths of the above examples and comparative examples were immersed in 30% wt KOH solution at 80℃for 300 hours, the surface resistance and the drip diffusion time were measured. The results are shown in Table 1 below.
TABLE 1 test results of PPS diaphragm cloth Performance
As can be seen from the data in Table 1, after the hydrophilic modified polyphenylene sulfide woven cloth is subjected to two-step infiltration and sulfonation treatment, the hydrophilicity of the polyphenylene sulfide woven membrane cloth is obviously improved, the surface resistance of the cloth is reduced, and the cloth can be stabilized in a high-temperature alkaline electrolyte environment for a long time, so that the lower surface resistance and the faster dripping diffusion time are maintained. However, the hydrophilically modified polyphenylene sulfide woven cloth of the comparative example is not sufficiently hydrophilically modified or cannot withstand high-temperature alkaline electrolytic water environment for a long time, and has reduced hydrophilism, thus causing energy loss and increasing hydrogen production cost.
Claims (10)
1. The preparation method of the polyphenylene sulfide alkaline electrolyzed water diaphragm is characterized by comprising the following steps:
(1) Washing and drying polyphenylene sulfide woven diaphragm cloth in deionized water and ethanol in sequence;
(2) Soaking the polyphenylene sulfide woven membrane cloth obtained in the step (1) in an haloalkane solvent, taking out and drying for later use;
(3) The polyphenylene sulfide woven diaphragm cloth obtained in the step (2) is soaked in a good organic solvent of the polyphenylene sulfide under the ultrasonic condition;
(4) And (3) carrying out sulfonation reaction on the soaked polyphenylene sulfide woven diaphragm cloth obtained in the step (3), washing and drying to obtain the hydrophilically modified PPS alkaline electrolytic water diaphragm.
2. The process according to claim 1, wherein in the step (1), the polyphenylene sulfide woven membrane cloth has a thickness of 0.6 to 1.0mm and a gram weight of 400 to 500g/m 2 The diameter of the polyphenylene sulfide fiber is 7-20um.
3. The method according to claim 2, wherein in the step (1), the polyphenylene sulfide woven membrane cloth has a thickness of 0.7 to 0.8mm and a diameter of 10 to 15 μm.
4. The process according to claim 1, wherein in step (2), the halogenated hydrocarbon is at least one selected from the group consisting of 1, 2-dichloroethane, dichloromethane, chloroform, tetrachloromethane, dichlorobenzene species; the soaking time in the halohydrocarbon solvent is 0.5-1h.
5. The process according to claim 4, wherein in step (2), the halogenated hydrocarbon is 1, 2-dichloroethane.
6. The preparation method according to claim 1, wherein in the step (3), the ultrasonic frequency is 30-60kHz, the soaking time under the ultrasonic condition is 1-3min, and the good solvent is at least one selected from amide solvents and imidazolidinone solvents; the amide solvent is at least one selected from dimethylacetamide and dimethylformamide, and the imidazolidone is 1, 3-dimethyl-2-imidazolidone.
7. The preparation method according to claim 6, wherein the organic solvent is a mixed solvent of an amide solvent and an imidazolidinone solvent in a volume ratio of 3-5:1.
8. The preparation method of claim 1, wherein in the step (4), after the polyphenylene sulfide woven membrane cloth is soaked in a good solvent under the ultrasonic condition, the polyphenylene sulfide woven membrane cloth is taken out and directly subjected to sulfonation reaction without drying treatment; the sulfonation reaction is to contact the soaked polyphenylene sulfide woven membrane cloth with a sulfonation reagent for reaction, wherein the sulfonation reagent is at least one selected from concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid and sulfur trioxide; the sulfonation reaction temperature is 40-50 ℃ and the reaction time is 30-60min.
9. The method according to claim 1, wherein in the step (4), the washing is sequentially washing with water, washing with 1, 2-dichloroethane and washing with acetone under ultrasonic conditions in the step (4).
10. A polyphenylene sulfide alkaline electrolyzed water membrane prepared by the preparation method of any one of claims 1 to 9; preferably, the water absorption speed of the polyphenylene sulfide woven diaphragm cloth is less than 10s, and the surface resistance is 0.25-0.34 omega cm 2 。
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