Classifications

• • 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
• • 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
  • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
  • C25B9/70—Assemblies comprising two or more cells
  • C25B9/73—Assemblies comprising two or more cells of the filter-press type
• • 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
  • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
• • 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
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

• This disclosure relates to a kind of diaphragm cloth for a water electrolyzer and a manufacturing method therefor.
• diaphragm cloth is disposed between an anode and a cathode of the water electrolyzer to prevent gas on the anode side from mixing with gas on the cathode side and thus to ensure the purity of gas.
• Diaphragm cloth has the following requirements on its properties: full wettability by the electrolyte; small average pore size and high gas-tightness; large porosity; certain mechanical strength and stiffness; corrosion resistance to alkaline electrolyte, high-temperature resistance, strong chemical stability and ease of production.
• CN101372752A discloses non-woven cloth made of common polyphenylene sulfide fiber, where the non-woven cloth is sulfonated with 90%-98% H 2 SO 4 at 70-130° C. for 20-40 min and then treated with 30% potassium hydroxide to finally obtain a high-temperature-resistant diaphragm for an alkaline water electrolyzer.
• the non-woven cloth has a relatively high liquid absorption rate
• the non-woven cloth after being treated by strong acid, needs to consume a large amount of valuable water resource and chemicals during a cleaning process and takes a long time to clean, and the technological operation is complicated and easily to pollute the environment. Meanwhile, such non-woven cloth is low in safety and not suitable for industrial production.
• CN101195944A discloses asbestos-free, environmental and energy-saving diaphragm cloth which is woven fabric made of one or more of poly(ether-ether-ketone) fiber, polyphenylene sulfide fiber and polypropylene fiber.
• the gas-tightness of this diaphragm cloth fulfills the standard requirements of an asbestos diaphragm, the hydrophilicity of the obtained diaphragm cloth is poor because the chemical fiber has poor water absorption, and thus is unable to actually fulfill the use requirements.
• a diaphragm cloth for a water electrolyzer including a woven fabric, non-woven cloth or knitted fabric composed of alkali-resistant fiber at a common use temperature of no less than 150° C.; an average pore size of the diaphragm cloth is less than 10 ⁇ m and, under conditions of pressure of 3 KPa, venting quality of the diaphragm cloth is 2 L/cm 2 /min or less.
• diaphragm cloth for a water electrolyzer, wherein the diaphragm cloth is woven fabric, non-woven cloth or knitted fabric composed of alkali-resistant fiber at a common use temperature of no less than 150° C.; the average pore size of the diaphragm cloth is smaller than 10 ⁇ m; and under the condition of a pressure at 3 KPa, the venting quality of the diaphragm cloth is 2 L/cm 2 /min or less.
• the average pore size and the venting quality of the diaphragm cloth are controlled within the above ranges, high gas-tightness of the diaphragm for a water electrolyzer can be ensured. In this way, gas molecules and bubbles are difficult to pass through. As a result, gas on the anode side can be prevented from mixing with gas on the cathode side, the purity of gas and good safety are ensured. From the perspective of ensuring the separator fabric to stably have high gas-tightness for a long term, preferably, the average pore size of the diaphragm cloth is less than 5 ⁇ m and the venting quality is 1.5 L/cm 2 /min or less.
• the average pore size is kept within a certain range and the weaving conditions are controlled to improve the uniformity of the pore size.
• the average pore size is less than 10 ⁇ m, and pores with a pore size of 0.2-10 ⁇ m in the diaphragm cloth take up no less than 60% of all pores; more preferably, pores with a pore size of 0.2-10 ⁇ m in the diaphragm cloth take up no less than 80% of all pores; and particularly preferably, the average pore size is less than 5 ⁇ m, and pores with a pore size of 0.2-5 ⁇ m in the diaphragm cloth take up above 60% of all pores.
• the diaphragm cloth for a water electrolyzer is formed from high-temperature-resistant and alkali-resistant fiber at a common use temperature of no less than 150° C.
• such fiber is usually at least one of polyphenylene sulfide (PPS) fiber, polytetrafluoroethylene (PTFE) fiber, poly(p-phenylene benzobisoxazole) (PBO) fiber and poly(ether-ether-ketone) (PEEK) fiber.
• PPS polyphenylene sulfide
• PTFE polytetrafluoroethylene
• PBO poly(p-phenylene benzobisoxazole)
• PEEK poly(ether-ether-ketone)
• the cover factor of the fabric is a parameter which characterizes the tightness of the fabric. The higher the cover factor is, the tighter the fabric is, and the smaller the venting quality and pore size are.
• the weave of the woven fabric is plain weave, twill weave, satin weave, derivative weave and multiple weave thereof, where the plain cloth has the most weaving points and the largest tightness. From the perspective of better fulfilling the gas-tightness requirement of the diaphragm cloth, the plain cloth is preferred of the above mentioned woven fabric plain cloth.
• the cover factor ranges from 2300 to 3000, preferably 2500 to 2900.
• the cover factor of the plain cloth is less than 2300, the gas-tightness of the fabric is low due to insufficient tightness of the fabric, thus the diaphragm cloth is difficult to prevent gas on the cathode side and gas on the anode side from passing through, and both the purity of gas and the safety thus can not be ensured.
• the cover factor of the plain cloth is more than 3000, the higher requirements are proposed for a weaving machine and the weaving is difficult.
• the diaphragm cloth is of multiple weave, for example, weft-backed, weft-tripled or multi-layer fabric
• the density of warps or wefts can be further improved under limited conditions of weaving tightness, thereby reducing the venting quality of the fabric and improving the gas-tightness.
• the cover factor of the knitted fabric is 0.7 to 1.5.
• the diaphragm cloth for a water electrolyzer When in practical operation, if the diaphragm cloth for a water electrolyzer can remain airtight for 2 min at a pressure of no less than 200 mm H 2 O (2 KPa), the use requirement of gas-tightness of the diaphragm cloth for a water electrolyzer can be basically fulfilled. From the perspective of ensuring the diaphragm cloth to have excellent gas-tightness, ion permeability and diaphragm cloth processability, the diaphragm cloth for a water electrolyzer preferably has gas-tightness remaining for 2 min at a pressure of 250-450 mm H 2 O (2.5-4.5 KPa).
• the gas-tightness is less than 250 mm H 2 O (2.5 KPa), the basic requirement on the diaphragm can not be fulfilled, and the purity of the generated gas will be influenced.
• the gas-tightness is more than 450 mm H 2 O (4.5 KPa), it is likely to result in difficult weaving and high cost; furthermore, the resistance of the separator will be increased and the energy consumption for a unit of gas generation is thus increased.
• the diaphragm cloth for a water electrolyzer has high stiffness.
• the high stiffness can make the separator difficultly wrinkled during the cutting and mounting process, so it is easier, more convenient and more efficient to mount.
• a size deviation caused in the cutting process and a thickness deviation caused by wrinkling in the mounting process of the diaphragm can be reduced.
• the uniformity of the diaphragm in use is improved.
• the stiffness of the diaphragm cloth in both warp and weft directions is no less than 3 N, preferably no less than 5N.
• the high-temperature-resistant and alkali-resistant fiber at a common use temperature of no less than 150° C. contains hydrophilic groups on its surface, and the content of oxygen element on the fiber surface is 12 wt % or more.
• the content of oxygen element on the fiber surface is less than 12 wt %, improvement in hydrophilicity of the diaphragm cloth is low, and the diaphragm cloth cannot be completely wetted by the electrolyte, resulting in poor ion permeability, large resistance of the diaphragm cloth, low electrolysis efficiency and large energy loss.
• the content of oxygen element on the fiber surface is preferably with 15-40 wt %, more preferably within 15-30 wt %.
• the type of hydrophilic groups and chemical bonds contained on the surface of the high-temperature-resistant and alkali-resistant fiber at a common use temperature of no less than 150° C. is related to a processing method and the type of processing gas.
• the hydrophilic groups are at least one of carboxyl groups (COOH), carbonyl groups (C ⁇ O), hydroxyl groups (—OH), formyl groups (CHO) or —SO x .
• the hydrophilic groups are at least one of carboxyl groups (COOH), carbonyl groups (C ⁇ O), hydroxyl groups (—OH) or formyl groups (CHO), and the total content of the hydrophilic groups takes up 10-60% of the total content (mol number) of the groups on the fabric surface.
• the total content of the hydrophilic groups takes up 20-50% of the total content (mol number) of the groups on the fabric surface.
• the diaphragm cloth for a water electrolyzer is composed of polyphenylene sulfide fiber
• no less than 20 wt % of the polyphenylene sulfide fiber is modified cross-section polyphenylene sulfide fiber.
• the modified cross-section polyphenylene sulfide fiber may improve water absorption and water conductivity of the fabric by wicking If the content of the modified cross-section polyphenylene sulfide fiber is less than 20 wt %, the specific surface area of fiber in yarns will be reduced so that improvement in water absorption and water conductivity of the prepared diaphragm cloth is not significant, hydrophilicity of the diaphragm cloth is poor, ion permeability and the effect of energy saving are influenced.
• the modified cross-section polyphenylene sulfide fiber may be crossed, latticed, polygonal, leaf-shaped, elliptic or flat cross-section polyphenylene sulfide fiber. From the perspective of preparing diaphragm cloth with excellent hydrophilicity, the modified cross-section polyphenylene sulfide fiber is preferably crossed or polygonal cross-section polyphenylene sulfide fiber. Among the polygonal cross-section polyphenylene sulfide fiber, hexagonal cross-section polyphenylene sulfide fiber is preferred.
• the knitted fabric may be warp-knitted fabric.
• the warp-knitted fabric is obtained from weaving polyphenylene sulfide yarns or filaments by warp knitting equipment via warp knitting processes.
• the number of yarns forming the warp-knitted fabric is brought to be lower than that of yarns forming the woven fabric, and the yarns are arranged in a same direction so that the water absorption and water conductivity of the diaphragm cloth may be improved.
• the warp-knitted fabric itself has a feature of shrinkage, and due to the shrinkage of the warp-knitted fabric, the diaphragm cloth may be allowed to have high density and high gas-tightness.
• the fabric for the diaphragm cloth for a water electrolyzer is subjected to hydrophilic treatment so that the water absorption of the diaphragm cloth for a water electrolyzer may be improved by no less than 15%, compared with the fabric before treatment. If the improvement rate of the water absorption is less than 15%, the improvement effect of the hydrophilicity is poor. Considering the balance between the hydrophilicity and the processability of the diaphragm cloth, the improvement rate of the water absorption is preferably 15-200%, more preferably 20-100%.
• high-temperature-resistant and alkali-resistant fiber at a common use temperature of no less than 150° C. are woven, non-woven or knitted to obtain high-temperature-resistant and alkali-resistant woven fabric, non-woven cloth or knitted fabric, the woven fabric or knitted fabric are refined and dried after weaving, and then the surface of the obtained woven fabric, non-woven cloth or knitted fabric is subjected to discharge modification to obtain the finished product.
• the raw material of the non-woven cloth is preferably polyphenylene sulfide fiber.
• the manufacturing method of non-woven cloth made of polyphenylene sulfide fiber is as fol-lows: stretched polyphenylene sulfide fiber is mixed with non-stretched polyphenylene sulfide fiber in water at a certain proportion by weight to form papermaking dispersion, then the wet-laid non-woven cloth of polyphenylene sulfide fiber wet-laid obtained by a wet-laid non-weaving process, then dried and calendered by a roll calendar consisting of a steel roll and a paper roll, and the surface (front side) of the non-woven cloth of polyphenylene sulfide fiber is brought into contact with the steel roll and then heated and pressurized to obtain single-side pressed non-woven cloth; then, the inner side of non-woven cloth is brought into contact with the steel roll and then heated and pressurized to obtain double-side pressed non-woven cloth
• the discharge modification increases the number of hydrophilic groups on the surface of fabric by a physical processing method and thus to further improve hydrophilicity of the diaphragm cloth.
• this method will not bring any burden to the environment and can generate durability which ordinarily will not be generated by the hydrophilic chemical reagent in the alkaline environment, and the hydrophilicity may be remained after long-term use in the alkaline environment.
• the discharge modification is plasma treatment or electric ironing treatment, preferably plasma treatment.
• the fiber surface of the fabric is etched so that the surface area is increased.
• active groups are generated on the fiber surface so that graft copolymerization of hydrophilic monomers on the material surface is caused. Accordingly, when applied in a water electrolyzer, the fabric is easily wet by the electrolyte so that the hydrophilicity of the diaphragm cloth is improved.
• the plasma treatment is preferably vacuum plasma surface treatment or atmospheric pressure plasma surface treatment.
• a gas (process gas) that forms plasma may be oxygen or argon, or a gas mixture of oxygen and argon, or may be carbon dioxide or air.
• the pressure of the used vacuum chamber is 5-100 Pa, and the treatment intensity is 50-500 KW ⁇ s/m 2 .
• oxygen-containing polar groups can be formed on the fiber surface.
• the diaphragm cloth has excellent hydrophilicity.
• the process gas is argon, as argon is an inert gas with high molecular energy and is easy to be ionized, the fiber on the surface of the fabric is easily activated to fully form polar groups.
• the process gas is a gas mixture of oxygen and argon
• the fiber on the surface of the plasma-ionized fabric is activated first, to be grafted more easily when meeting the oxygen component.
• the process gas is preferably a gas mixture of oxygen and argon.
• air contains oxygen, nitrogen and carbon dioxide, when air is used as the process gas, the plasma-treated fabric can also achieve excellent hydrophilicity.
• the pressure in the used vacuum chamber is generally 5-100 Pa. Considering treatment effect and energy consumption, the pressure is preferably 30-70 Pa.
• the treatment intensity is 50-500 KW ⁇ s/m 2 , preferably 80-300 KW ⁇ s/m 2 .
• the treatment intensity is calculated by the following formula:
• treatment intensity discharge power (KW) ⁇ treatment duration (s)/treatment area (m 2 ), or
• treatment intensity discharge power (KW)/treatment rate (m/s)/treatment breadth (m).
• the treatment intensity is less than 50 KW ⁇ s/m 2 , the energy of the charged particles of the plasma is low, thereby leading to a weak cross-linking action on the fiber surface and very few of hydrophilic groups generated on the fiber surface so the finally formed diaphragm cloth is difficult to be fully wetted by the electrolyte.
• the treatment intensity is more than 500 KW ⁇ s/m 2 , the treatment effect becomes stable when the treatment intensity reaches about 500 KW ⁇ s/m 2 so that further increasing the treatment intensity will increase the energy consumption rather than improving the treatment effect.
• the treatment intensity is preferably 80-300 KW ⁇ s/m 2 . In this case, the energy of the charged particles is increased, and the cross-linking action can play a full role.
• the treatment intensity is generally set as 50-500 KW ⁇ s/m 2 .
• the treatment intensity is calculated by the following formula:
• treatment intensity discharge power (KW)/treatment rate (m/s)/treatment breadth (m).
• the treatment intensity is less than 50 KW ⁇ s/m 2 , the energy of the charged particles of the plasma is low, thereby leading to a weak cross-linking action on the fiber surface and very few of hydrophilic groups generated on the fiber surface so the finally formed diaphragm cloth is difficult to be fully wetted by electrolyte.
• the treatment intensity is more than 500 KW ⁇ s/m 2 , the treatment effect becomes stable when the treatment intensity reaches about 500 KW ⁇ s/m 2 so that further increasing the treatment intensity will increase the energy consumption rather than improving the treatment effect.
• the treatment intensity is preferably 80-300 KW ⁇ s/m 2 . In this case, the energy of the charged particles is increased, and the cross-linking action can play a full role.
• the fabric surface can be subjected to graft modification with a graft modification chemical reagent.
• the fabric surface can be grafted with carboxyl groups, acrylic groups, sulfonic groups or the like.
• the diaphragm cloth for a water electrolyzer has the features of high gas-tightness and excellent ion permeability, also has low cost, safety, environmental friendliness and light weight; and the manufacturing method is rapid, high efficiency, no pollution, simple operation and energy saving.
• Alkali resistance, the common use temperature, the hydrophilic groups and the total content (mol number) of the hydrophilic groups are defined as follows:
• the percentage of the total content of hydrophilic groups in the total content (mol number) of groups on the fabric surface chemical components on the fiber surface are analyzed qualitatively and quantitatively by an X-ray photoelectron spectroscopy (XPS), then peak separation analysis is performed to Peak C, and the type and mol concentration content of groups are judged according to the result of peak separation, where oxygen-containing polar groups are hydrophilic groups, and the sum of mol concentration percentages of the hydrophilic groups is the percentage of the total content of hydrophilic groups in the total content of groups on the fabric surface.
• XPS X-ray photoelectron spectroscopy
• the physical properties of the fiber are measured by the following methods or calculated by the following formulae.
• N W denotes the warp density of the fabric (yarns/inch);
• D W denotes the fineness of warp filaments in the fabric (dtex);
• N f denotes the weft density of the fabric (yarns/inch);
• D f denotes the fineness of weft filaments in the fabric (dtex).
• the pore size of fabric is measured by a capillary flowing porosimeter (a product from PMI; Model: CFP-1100-AE), and the working mode is set as a wet-up/dry-down mode.
• the test environment is 20 ⁇ 2° C. and 65 ⁇ 4% RH.
• a fabric sample is placed into a sample chamber and then wetted with silwick silicone fluid with a surface tension of 19.1 dynes/cm.
• the bottom clamp of the sample chamber has a porous metal disc insert with a diameter of 2.54 cm and a thickness of 3.175 mm, while the top clamp of the sample chamber has a hole with a diameter of 3.175 mm, thus the value of the average pore size of the fabric can be directly read. An average value of two times of measurement is used as the final average pore size value.
• the distribution condition of pore size and the ratio of each pore size range can be directly read from the specific measurement results, and the pore size ratio within a certain range can be obtained by adding the measured values shown in the measurement results.
• the venting quality is measured by a high-pressure air permeability tester (a product from Technoworld; Model: WI70848) at 23° C. and 50% RH.
• the specific measurement methods are as follows: 17 circular samples each with a diameter of 10 cm are stretched in a breadth direction of the fabric, the venting quality of each sample is measured at 3 KPa, and an average value of 13 intermediate data is used as a final test result.
• the gas-tightness is measured in accordance with the Term 4.5.2 “Gas-tightness Measurement” of “Asbestos Diaphragm Cloth” of the Chinese building material industry standard JC/T211-2009.
• the water absorption of diaphragm cloth before or after hydrophilic treatment is measured in accordance with GB/T21655.1-2008.
• the water absorption rate is measured in accordance with the Term 7.1.1 “Falling-drop Method” of JIS L1907-2010 “Water Absorption Test Method of a Fiber Product.”
• the stiffness is measured by a fabric stiffness tester (SASD-672-1) (J.A. KING & COMPANY) in accordance with the ASTM D4032 stiffness test standard.
• SASD-672-1 fabric stiffness tester
• the specific method is as follows: warp and weft samples are prepared, and then tested on a stiffness tester after the pressure is regulated to 324 KPa.
• the test environment is 20 ⁇ 2° C. and 65 ⁇ 4% RH, and the humidification to the samples is performed for above 24 hours.
• Chemical components on the fiber surface are analyzed qualitatively and quantitatively by an X-ray photoelectron spectroscopy (“KRATOS” that is produced by SHIMAZU Co. Ltd.,; Model: AXIS ULTRA HAS).
• KRATOS X-ray photoelectron spectroscopy
• the content of oxygen element on the fiber surface is calculated according to the X-ray photoelectron energy spectrum.
• the bonding capacity of each carbon/oxygen peak can be apparently recognized according to the X-ray photoelectron energy spectrum, thus the hydrophilic group components are determined.
• Warps and wefts are both woven with 20 s/6 polyphenylene sulfide yarns to obtain plain cloth with a warp density of 39 yarns/inch and a weft density of 27 yarns/inch.
• the plain cloth is refined and dried, and then the surface of the polyphenylene sulfide plain cloth is subjected to vacuum plasma treatment, where the pressure in a vacuum chamber is 50 Pa, the process gas is a gas mixture of oxygen and argon, and the treatment intensity is 150 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with a cover factor of 2777.89 and an average pore size of 3 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 90% of all pores, and the breaking strength of the diaphragm cloth is 4008 N/5 cm and 3218 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polyphenylene sulfide fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 25 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O) and hydroxyl groups (—OH), and the total content of the oxygen-containing hydrophilic groups takes up 48% of the total content of groups on the fabric surface.
• the physical properties of the separator diaphragm cloth for a water electrolyzer in Example 1 are shown in Table 1.
• Warps and wefts are both woven with 20 s/4 polyphenylene sulfide yarns to obtain plain cloth with a warp density of 47 yarns/inch and a weft density of 32 yarns/inch.
• the plain cloth is refined and dried, and then the surface of the polyphenylene sulfide plain cloth is subjected to atmospheric pressure plasma surface treatment, where the process gas is air, and the treatment intensity is 150 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with a cover factor of 2705.82 and an average pore size of 4 ⁇ m is obtained, and wherein pores with a pore size of 0.2-10 ⁇ m take up 85% of all pores, and the breaking strength of the diaphragm cloth is 2247 N/5 cm and 2110 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polyphenylene sulfide fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 30 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O), hydroxyl groups (—OH) and formyl groups (CHO), and the total content of the oxygen-containing hydrophilic groups takes up 45% of the total content of surface groups of the fabric.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 2 are shown in Table 1.
• Crossed cross-section polyphenylene sulfide fiber is mixed with circular cross-section polyphenylene sulfide fiber at a proportion by weight of 20:80, and then 15 s/4 polyphenylene sulfide yarns are obtained by a spinning process. Then, the obtained polyphenylene sulfide yarns are used as warps and wefts for weaving to form plain cloth with a warp density of 39 yarns/inch and a weft density of 28 yarns/inch. After weaving, the polyphenylene sulfide plain cloth is refined and dried, and then the surface of the plain cloth is subjected to atmospheric pressure plasma surface treatment, where the process gas is air, and the treatment intensity is 130 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with a cover factor of 2658.70 and an average pore size of 5 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 80% of all pores, and the breaking strength of the diaphragm cloth is 2600 N/5 cm and 2216 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polyphenylene sulfide fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 20 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O), hydroxyl groups (—OH) and formyl groups (CHO), and the total content of the oxygen-containing hydrophilic groups takes up 43% of the total content of groups on the fabric surface.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 3 are shown in Table 1.
• Hexagonal cross-section polyphenylene sulfide fiber is mixed with circular cross-section polyphenylene sulfide fiber at a proportion by weight of 50:50, to obtain 220 dtex polyphenylene sulfide fiber-mixed filaments.
• the obtained filaments are warp-knitted to form knitted fabric with a longitudinal density of 89 rows/inch and a transverse density of 63 columns/inch.
• the polyphenylene sulfide knitted fabric is refined and dried, and then the surface of the fabric is subjected to vacuum plasma treatment, where the pressure in a vacuum chamber is 50 Pa, the process gas is a gas mixture of oxygen and argon, and the treatment intensity is 150 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with a cover factor of 1.3 and an average pore size of 7 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 60% of all pores, and the breaking strength of the diaphragm cloth is 2347 N/5 cm and 1540 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polyphenylene sulfide fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 11 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O) and hydroxyl groups (—OH), and the total content of the oxygen-containing hydrophilic groups takes up 21% of the total content of groups on the fabric surface.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 4 are shown in Table 1.
• Hexagonal cross-section polyphenylene sulfide fiber is mixed with circular cross-section polyphenylene sulfide fiber at a proportion by weight of 80:20, and then 20 s/6 polyphenylene sulfide yarns are obtained by a spinning process. Then, the obtained yarns are used as warps and wefts for weaving to form 3/3 twill-woven fabric with a warp density of 56 yarns/inch and a weft density of 40 yarns/inch.
• the 3/3 twill-woven fabric is refined and dried, and then the surface of the fabric is subjected to vacuum plasma treatment, where the pressure in a vacuum chamber is 50 Pa, the process gas is air, and the treatment intensity is 100 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with an average pore size of 8 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 70% of all pores, and the breaking strength of the diaphragm cloth is 4980 N/5 cm and 3600 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polyphenylene sulfide fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 26 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O) and hydroxyl groups (—OH), and the total content of the oxygen-containing hydrophilic groups takes up 40% of the total content of surface groups of the fabric.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 5 are shown in Table 1.
• Warps and wefts are both woven with 440 dtex-60 f polytetrafluoroethylene filaments to obtain plain cloth with a warp density of 76 yarns/inch and a weft density of 62 yarns/inch.
• the plain cloth is refined and dried, and then the surface of the plain cloth is subjected to vacuum plasma treatment, where the pressure in a vacuum chamber is 50 Pa, the process gas is a gas mixture of oxygen and argon, and the treatment intensity is 200 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with a cover factor of 2895 and an average pore size of 5 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 75% of all pores, and the breaking strength of the diaphragm cloth is 4008 N/5 cm and 3218 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polytetrafluoroethylene fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 20 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O) and hydroxyl groups (—OH), and the total content of the oxygen-containing hydrophilic groups takes up 38% of the total content of surface groups of the fabric.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 6 are shown in Table 1.
• Stretched polyphenylene sulfide fiber (“TORCON ®” from TORAY; Specification: S301) with a fineness of 1.0 dtex (10 ⁇ m in diameter) and a cutting length of 6 mm and non-stretched polyphenylene sulfide fiber (“TORCON®” from TORAY; Specification: S111) with a fineness of 3.0 dtex (17 ⁇ m in diameter) and a cutting length of 6 mm are dispersed in water at a proportion by weight of 60:40 to form papermaking dispersion.
• a 140-mesh papermaking net for handmade paper is provided on the bottom, and the dispersion is fed at a rate of 80 g/m 2 by a small paper machine (from KUMAGAI RIKI KOGYO Co., Ltd.) with a size of 25 cm ⁇ 25 cm and a height of 40 cm. Then, water is added into the dispersion to make the total amount of the dispersion to be 20 L, and the dispersion is fully stirred by a stirrer. Water in the small paper machine is drained, and the residual wet-laid paper on the papermaking net is transferred to a piece of filter paper.
• a small paper machine from KUMAGAI RIKI KOGYO Co., Ltd.
• the described wet-laid paper and the filter paper are put into a rotary dryer (ROTARY DRYER DR-200 from KUMAGAI RIKI KOGYO Co., Ltd.) together for drying (a temperature of 100° C., a rate of 0.5 m/min, a length of 1.25 m and a duration of 2.5 min) for one time to obtain wet-laid non-woven cloth of polyphenylene sulfide fiber.
• a rotary dryer ROTARY DRYER DR-200 from KUMAGAI RIKI KOGYO Co., Ltd.
• Calendering is performed under a steel roll temperature of 200° C., a line pressure of 490 N/cm and a roller rotation speed of 5 m/min by a hydraulic three-roll calender (from Ligun Company; Model: IH type H3RCM) consisting of a steel roll and a paper roll.
• the surface (front side) of the wet-laid non-woven cloth of polyphenylene sulfide fiber is brought into contact with the steel roll and then heated and pressurized to obtain single-side pressed non-woven cloth.
• the inner side of the wet-laid non-woven cloth is brought into contact with the steel roll and then heated and pressurized to obtain double-side pressed non-woven cloth.
• the surface of the double-side pressed non-woven cloth is subjected to vacuum plasma treatment, where the pressure in a vacuum chamber is 50 Pa, the process gas is a gas mixture of oxygen and argon, and the treatment intensity is 150 KW ⁇ s/m 2 .
• diaphragm cloth for a water electrolyzer with a volume density of 0.94 and an average pore size of 8 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 80% of all pores, and the breaking strength of the diaphragm cloth is 151 N/5 cm and 143 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polytetrafluoroethylene fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 25 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O) and hydroxyl groups (—OH), and the total content of the oxygen-containing hydrophilic groups takes up 48% of the total content of surface groups of the fabric.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 7 are shown in Table 1.
• Stretched polyphenylene sulfide fiber (“TORCON®” from TORAY; Specification: S301) with a fineness of 1.0 dtex (10 ⁇ m in diameter) and a cutting length of 6 mm and non-stretched polyphenylene sulfide fiber (“TORCON®” from TORAY; Specification: S111) with a fineness of 3.0 dtex (17 ⁇ m in diameter) and a cutting length of 6 mm are dispersed in water at a proportion by weight of 60:40 to form papermaking dispersion.
• a 140-mesh papermaking net for handmade paper is provided on the bottom, and the dispersion is fed at a rate of 100 g/m 2 by a small paper machine (from KUMAGAI RIKI KOGYO Co., Ltd.) with a size of 25 cm ⁇ 25 cm and a height of 40 cm.
• the other processing conditions are the same as Example 7.
• diaphragm cloth for a water electrolyzer with a volume density of 0.96 and an average pore size of 4 ⁇ m is obtained, wherein pores with a pore size of 0.2-10 ⁇ m take up 90% of all pores, and the breaking strength of the diaphragm cloth is 204 N/5 cm and 198 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polytetrafluoroethylene fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element is 25 wt %.
• the oxygen-containing hydrophilic groups include carbonyl groups (C ⁇ O) and hydroxyl groups (—OH), and the total content of the oxygen-containing hydrophilic groups takes up 48% of the total content of surface groups of the fabric.
• the physical properties of the diaphragm cloth for a water electrolyzer in Example 8 are shown in Table 1.
• Warps and wefts are both woven with 20 s/6 polyphenylene sulfide yarns to obtain plain cloth with a warp density of 36 yarns/inch and a weft density of 22 yarns/inch. After weaving, the plain cloth is refined, dried and shaped to finally obtain diaphragm cloth for a water electrolyzer with a cover factor of 2441.17 and an average pore size of 12 ⁇ m, wherein the breaking strength of the diaphragm cloth is 3800 N/5 cm and 2120 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the content of oxygen element on the polyphenylene sulfide fiber surface is 2 wt %.
• the physical properties of this diaphragm cloth for a water electrolyzer are shown in Table 1.
• Warps and wefts are both woven with 20 s/4 polyphenylene sulfide yarns to obtain plain cloth with a warp density of 42 yarns/inch and a weft density of 24 yarns/inch. After weaving, the plain cloth is refined, dried and shaped to finally obtain diaphragm cloth for a water electrolyzer with a cover factor of 2268.13 and an average pore size of 15 ⁇ m, wherein the breaking strength of the diaphragm cloth is 2100 N/5 cm and 1980 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the content of oxygen element in the polyphenylene sulfide fiber surface is 4 wt %.
• the physical properties of this diaphragm cloth for a water electrolyzer are shown in Table 1.
• Polyphenylene sulfide fiber with a fineness of 2.2 dtex and a length of 51 mm are successively subjected to opening, mixing, carding, web-forming and needle-punched to form non-woven cloth, and then the non-woven cloth is sulfonated in 98% H 2 SO 4 at 80° C. for 30 min and then treated with 30% KOH solution. Finally, diaphragm cloth for a water electrolyzer with an average pore size of 13 ⁇ m is obtained, wherein the breaking strength of the diaphragm cloth is 1180 N/5 cm and 1500 N/5 cm in warp and weft directions, respectively.
• the prepared diaphragm cloth is tested by an X-ray photoelectron spectroscopy. It is measured that the polytetrafluoroethylene fiber surface of the diaphragm cloth contains oxygen-containing hydrophilic groups, and the content of oxygen element on the polytetrafluoroethylene fiber surface is 12 wt %.
• the physical properties of the water electrolyzer are shown in Table 1.
• Example 1 Example 2
• Example 3 Example 4
• Example 5 Example 6 Content of modified 0 0 20 50 80 0 cross-section fiber (%)
• Type of modified — Crossed Hexagonal Hexagonal — cross-section fiber
• Form of fabric Woven Woven Woven Knitted Woven Woven Fabric fabric fabric fabric fabric fabric fabric fabric Thickness (mm) 1.0 0.8 0.8 1.2 1.4 0.5 Weight (g/m 2 ) 568 426 455 400 1130 275 Density Warp 39 47 39 89 56 76 direction (yarns/ inch) Weft 27 32 28 63 40 62 direction (yarns/ inch) Cover factor 2777.89 2705.82 2658.70 1.3 — 2895 (volume density) (g/cm 3 ) — — — — — Average pore sizes ( ⁇ m) 3 4 5 7 8 5 Gas-tightness (mmH 2 O) 300 370 380 240 320 350 Venting quality 0.68 0.79 1.06 1.59 1.

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