CN117362808A - Creep-resistant POE membrane for sealing flow battery and preparation method thereof - Google Patents

Creep-resistant POE membrane for sealing flow battery and preparation method thereof Download PDF

Info

Publication number
CN117362808A
CN117362808A CN202311382592.3A CN202311382592A CN117362808A CN 117362808 A CN117362808 A CN 117362808A CN 202311382592 A CN202311382592 A CN 202311382592A CN 117362808 A CN117362808 A CN 117362808A
Authority
CN
China
Prior art keywords
sealing
flow battery
film
creep
poe
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
Application number
CN202311382592.3A
Other languages
Chinese (zh)
Inventor
王宇
张超
姚建男
辛健
吴淑玥
樊静秋
姚忠
项瞻波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suqian Shidai Energy Storage Technology Co ltd
Original Assignee
Suqian Shidai Energy Storage Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suqian Shidai Energy Storage Technology Co ltd filed Critical Suqian Shidai Energy Storage Technology Co ltd
Priority to CN202311382592.3A priority Critical patent/CN117362808A/en
Publication of CN117362808A publication Critical patent/CN117362808A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/028—Sealing means characterised by their material
    • H01M8/0284—Organic resins; Organic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0276—Sealing means characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0286—Processes for forming seals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The invention provides a creep-resistant POE membrane for sealing a flow battery and a preparation method thereof; preparing the above sealing film by a blend containing a thermoplastic elastomer, other thermoplastic functional resins and necessary functional auxiliaries; the thermoplastic elastomer is an ethylene-olefin copolymer (POE); such other thermoplastic functional resins include amorphous alpha-olefin copolymers (APAO) and polypropylene waxes (PP waxes); the functional auxiliary agent is a size stabilizer, a compatilizer, a lubricant and an antioxidant; the composition is subjected to physical blending and pre-granulation, and then a thin elastic film is uniformly coated on one side of the PP plate frame through an encapsulation process, and the thin elastic film and the plate frame are formed into a whole, so that the thickness is uniform, and the thin elastic film can play a good role in sealing the flow battery.

Description

Creep-resistant POE membrane for sealing flow battery and preparation method thereof
Technical Field
The invention belongs to the field of flow battery sealing films and preparation thereof, and particularly relates to a sealing film for a flow battery, which is used for sealing each pile component of the flow battery, and a manufacturing method of the sealing film.
Background
In recent years, renewable energy power generation is rapidly developing, and solar energy and wind energy have intermittence and volatility compared with conventional fossil energy. In order to avoid the impact on the safety of the power grid, a large-scale energy storage technology is developed to realize peak clipping and valley filling of the power grid, and the organic flow battery is generated as novel energy storage equipment.
The flow battery is further a water-based organic flow battery, and has the characteristics of safety, environmental protection, long service life and the like. The electrolyte is dissolved in pure water by adopting an organic composition, the system has no strong acid and strong corrosiveness, does not depend on metal resources, and is relatively more environment-friendly.
The performance of the stack in the aqueous organic flow battery affects the charge and discharge performance of the overall battery system. The electric pile is formed by sequentially superposing and connecting a plurality of single cell elements in series, wherein the single cell elements generally comprise the following components: as shown in fig. 1, the cell element includes: a plate frame 1; a bipolar plate 2 disposed within the plate frame; a carbon felt electrode 3, a sealing gasket 4 is arranged between the plate frame 1 and the ion exchange membrane 5; an ion exchange membrane 5 is arranged between the bipolar plates and surrounds the plate frame to form a cavity, and electrolyte and carbon felt electrode 3 can be contained in the cavity. The single cell elements formed by the components are sequentially overlapped and are fastened through bolts and nuts to finally form the organic flow cell pile.
The pile is formed by superposing and combining a plurality of single cell elements, and the quality of sealing performance of the pile directly influences whether the water-based organic flow battery can run safely and stably. At present, most of traditional flow batteries are assembled by adopting a fastening mode of bolts and nuts, but due to the fact that the hardness of each sealing element in the electric pile and the structural accuracy of the sealing elements are different, the problem that the packaging pressure of each component in the electric pile is easily distributed unevenly under the packaging load cannot be solved, the long-term tightness of the electric pile cannot be maintained, and the stability of battery charging and discharging and the safety of operation are further affected.
Disclosure of Invention
In order to solve the problem that the sealing performance of a traditional galvanic pile is insufficient, the traditional sealing film is formed by punching a complete film, the actual utilization rate of the film is only about 30%, the rest about 70% of the film is recycled after being crushed, the recycled film is recycled after being subjected to punching, and the reciprocating circulation is performed, so that a great amount of manpower and material resources are consumed on one hand, and on the other hand, the processability and the sealing film performance of the film-forming resin are affected after being recycled for many times. The invention creatively adopts the encapsulation injection molding process, and directly coats a thin elastic film on one side of the plate frame. Meanwhile, the C-shaped short glass fiber is introduced into the sealing film composition, so that the sealing film composition has excellent dimensional stability and compression creep resistance, and the sealing performance and the safety of long-term operation of the flow battery stack are ensured.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a creep-resistant POE film for sealing a flow battery, which takes ethylene-olefin copolymer POE as a base material, and is blended with other thermoplastic functional resins except an elastomer, and meanwhile, necessary functional auxiliary agents are added. The MFR of POE is preferably 1 to 20g/10min, more preferably 2 to 10g/10min. Other thermoplastic functional resins are amorphous alpha-olefin copolymers (APAO) and polypropylene waxes (PP waxes), which are low molecular weight olefin resins. The necessary functional auxiliary agents comprise a dimensional stabilizer, a compatilizer, a lubricant and an antioxidant. The thickness of the sealing film is controlled to be 0.1-1mm according to the requirement.
The sealing film for the compression creep-resistant flow battery comprises, by weight, 70-85 parts of an ethylene-olefin copolymer, 5-15 parts of an amorphous alpha-olefin copolymer, 1-10 parts of polypropylene wax, 2-15 parts of a dimensional stabilizer, 0-10 parts of a compatilizer, 0-3 parts of a lubricant and 0-2 parts of an antioxidant.
Further, the ethylene-olefin copolymer is one or two of ethylene-butene copolymer and ethylene-octene copolymer.
Further, the size stabilizer is an extremely-short glass fiber of C-shaped short glass fiber which is ground and screened, the length is 60-100 mu m, and the alkali content is lower than 15%; the chemical stability, the electrical insulation performance and the strength are all good, and the purpose of adding the short glass fiber is to reduce the compression creep rate of the sealing film and improve the long-term dimensional stability of the sealing film.
Further, the compatilizer is maleic anhydride grafted POE resin (POE-g-MAH), and the compatilizer has the function of improving the dispersion effect and interfacial compatibility of glass fibers in the resin.
Further, the antioxidant is a hindered phenol antioxidant; preferably 0-2 parts of antioxidant.
Further, the lubricant is an organic-based lubricant, preferably, the lubricant is a fatty acid soap compound such as zinc stearate, calcium stearate, lead stearate, calcium montanate, etc., preferably, 0 to 3 parts of the lubricant.
The invention also provides a preparation method of the creep-resistant POE film for sealing the flow battery, which comprises the following steps: uniformly mixing an ethylene-olefin copolymer, an amorphous alpha-olefin copolymer, polypropylene wax, a size stabilizer, a compatilizer, a lubricant and an antioxidant, extruding and granulating by a screw extruder, and encapsulating, injecting and forming a film. Before the sealing film is finally produced, it is necessary to perform pre-granulation by a twin-screw extruder, and the purpose of the pre-granulation is to disperse the various components more uniformly by the kneading process.
Before mixing, the glass fibers are subjected to a high temperature treatment, i.e., 400 ℃ for 1 hour, to remove the bundled aids adhering to the surface and render them into bulk fibers for use.
POE, APAO, PP wax, dried at 80 ℃ for 5 hours for use.
Further, the temperature of the extrusion granulation is 180-210 ℃. In order to minimize the loss of material properties due to shear heat, a twin screw extruder is specified with an aspect ratio of 7-18:1.
Further, the encapsulation injection molding film is realized by secondary injection molding, one side of the plate frame is coated with a thin sealing film, and the sealing film and the plate frame are molded into a whole, so that the thickness is uniform. The temperature of the encapsulation and injection molding is 180-220 ℃.
The invention also provides a flow battery, which comprises the creep-resistant POE film for sealing the flow battery.
Further, the creep-resistant POE film for flow battery sealing described above is used to overmold a flow battery assembly into a film seal.
The beneficial effects of the invention are as follows:
the invention provides a composition, which comprises a sealing film for an organic flow battery, wherein the sealing film takes a thermoplastic elastomer POE as a main resin and comprises other thermoplastic functional resins and necessary functional auxiliary agents. The sealing film has certain strength, higher rebound resilience, excellent creep resistance, stable size and corrosion resistance. The organic flow battery using the sealing film solves the problem of electrolyte leakage caused by the difference of the hardness and the structural precision of each sealing element of the galvanic pile. Therefore, the organic flow battery with the sealing film structure operates more safely and smoothly.
Drawings
FIG. 1 is a schematic diagram of a cell stack structure of a typical organic flow battery;
FIG. 2 is a schematic diagram of a cell stack structure of an organic flow battery of the present invention;
list of drawing identifiers:
a plate frame 1; a bipolar plate 2; an electrode 3; a gasket 4; an ion exchange membrane 5; sealing film 6.
Detailed Description
The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.
The sealing film for the organic flow battery takes thermoplastic elastomer POE as main resin, and simultaneously comprises other thermoplastic functional resins and necessary functional auxiliary agents.
The thermoplastic elastomer provides necessary strength and rebound resilience for the sealing film, vulcanization is not needed, extrusion molding can be carried out after direct plasticizing, the molding process only involves physical change, and the process is simpler. The POE thermoplastic elastomer is of two types, namely ethylene-butene copolymer and ethylene-octene copolymer, preferably of ethylene-octene copolymer type.
For elastomer POE, namely thermoplastic elastomer prepared by in-situ polymerization of ethylene and octene by adopting a metallocene catalyst, the soft chain curled structure of the octene and the crystallized ethylene chain are used as physical crosslinking points, so that the elastomer POE has excellent toughness and good processability. The main chain does not contain double bonds, so that the heat stability and the aging resistance are better.
The sealing film for organic flow battery of the present invention uses a POE thermoplastic elastomer, and further uses an amorphous α -olefin copolymer (APAO) and a polypropylene wax (PP wax) in minor amounts.
The APAO is an amorphous plastic material with low molecular weight, is produced by polymerization reaction of a-olefin, and can improve the processability and compatibility of the material;
the PP wax is metallocene catalyzed polypropylene, is usually used as a raw material of hot melt adhesive, has excellent adhesive force and cohesive force, can reduce the solution viscosity, and the addition of nonpolar PP wax is beneficial to improving the bonding strength between a film forming matrix and a plate frame made of PP material after secondary injection molding.
Example 1
POE 8200:50kg, APAO 751:4.7kg, PP wax 6452:0.7kg, C-type short glass fiber: 3kg, POE-g-MAH GR216:1.5kg, zinc stearate: 0.18kg, antioxidant 1010:0.12kg.
Specific implementation steps
S1: drying the C-type short glass fiber in a drying oven at 400 ℃ for 1 hour, and grinding and sieving to obtain extremely short glass fiber with the length of 60-100 mu m for later use;
s2: drying the film-forming resin (POE, APAO, PP wax) in a drying oven at 80 ℃ for 5 hours for later use;
s3: fully and uniformly mixing all the compositions in a high-speed stirrer, granulating by a double-screw extruder, and controlling the double-screw extrusion temperature at 205 ℃;
s4: and (3) forming a film from the mixture after granulation through an encapsulation injection molding process, wherein the injection molding temperature is controlled between 180 ℃ and 220 ℃, and thus, the sealing film is prepared.
Example 2
POE 8200:50kg, APAO 751:4.4kg, PP wax 6452:0.8kg of C-shaped short glass fiber: 3.9kg, POE-g-MAH GR216:5.5kg, zinc stearate: 0.20kg, antioxidant 1010:0.13kg.
Specific implementation steps
S1: drying the C-type short glass fiber in a drying oven at 400 ℃ for 1 hour, and grinding and sieving to obtain extremely short glass fiber with the length of 60-100 mu m for later use;
s2: drying the film-forming resin (POE, APAO, PP wax) in a drying oven at 80 ℃ for 5 hours for later use;
s3: fully and uniformly mixing all the compositions in a high-speed stirrer, granulating by a double-screw extruder, and controlling the double-screw extrusion temperature at 205 ℃;
s4: and (3) forming a film from the mixture after granulation through an encapsulation injection molding process, wherein the injection molding temperature is controlled between 180 ℃ and 220 ℃, and thus, the sealing film is prepared.
Example 3
POE 8200:50kg, APAO 751:6.3kg, PP wax 6452:1.5kg, C-type short glass fiber: 5.3kg, POE-g-MAH GR216:6.9kg, calcium stearate: 0.21kg, antioxidant 1010:0.14kg.
Specific implementation steps
S1: drying the C-type short glass fiber in a drying oven at 400 ℃ for 1 hour, and grinding and sieving to obtain extremely short glass fiber with the length of 60-100 mu m for later use;
s2: drying the film-forming resin (POE, APAO, PP wax) in a drying oven at 80 ℃ for 5 hours for later use;
s3: fully and uniformly mixing all the compositions in a high-speed stirrer, granulating by a double-screw extruder, and controlling the double-screw extrusion temperature at 205 ℃;
s4: and (3) forming a film from the mixture after granulation through an encapsulation injection molding process, wherein the injection molding temperature is controlled between 180 ℃ and 220 ℃, and thus, the sealing film is prepared.
Comparative example 1
POE 8200:60kg, APAO 751:5.8kg, PP wax 6452:0.7kg, calcium stearate: 0.20kg, antioxidant 1010:0.13kg.
Specific implementation steps
S1: drying the film-forming resin (POE, APAO, PP wax) in a drying oven at 80 ℃ for 5 hours for later use;
s2: fully and uniformly mixing all the compositions in a high-speed stirrer, granulating by a double-screw extruder, and controlling the double-screw extrusion temperature to be 200 ℃;
s3: and (3) forming a film from the mixture after granulation through an encapsulation injection molding process, wherein the injection molding temperature is controlled between 180 ℃ and 220 ℃, and thus, the sealing film is prepared.
Comparative example 2
POE 8200:60kg, APAO 751:12.2kg, PP wax 6452:4.3kg, zinc stearate: 0.23kg, antioxidant 1010:0.15kg.
Specific implementation steps
S1: drying the film-forming resin (POE, APAO, PP wax) in a drying oven at 80 ℃ for 5 hours for later use;
s2: fully and uniformly mixing all the compositions in a high-speed stirrer, granulating by a double-screw extruder, and controlling the double-screw extrusion temperature to be 200 ℃;
s3: and (3) forming a film from the mixture after granulation through an encapsulation injection molding process, wherein the injection molding temperature is controlled between 180 ℃ and 220 ℃, and thus, the sealing film is prepared.
Comparative example 3
POE 8200:60kg, APAO 751:3.2kg, zinc stearate: 0.19kg, antioxidant 1010:0.13kg.
Specific implementation steps
S1: drying film-forming resin (POE, PP wax) in a drying oven at 80deg.C for 5 hr;
s2: fully and uniformly mixing all the compositions in a high-speed stirrer, granulating by a double-screw extruder, and controlling the double-screw extrusion temperature to be 200 ℃;
s3: and (3) forming a film from the mixture after granulation through an encapsulation injection molding process, wherein the injection molding temperature is controlled between 180 ℃ and 220 ℃, and thus, the sealing film is prepared.
The sealing film obtained in the above steps comprises an electrolyte flow outlet, an inflow port and a screw positioning and fastening hole, and is assembled into a flow battery according to the structure diagram shown in fig. 2; the sealing film 6 is coated on one side of the plate frame 1, wherein the bipolar plate 2 is embedded in the plate frame 1. The plate frame of the wrapping sealing film 6 and the ion exchange film 5 are surrounded to form a cavity, and the carbon felt electrode 3 is placed in the cavity, thereby combining into a single cell element. To ensure the sealing effect of the galvanic pile, the sealing film 6 needs to have a certain strength and elasticity and long-term dimensional stability, which requires a low compression creep rate. The technical effects of the present invention were examined by several examples and comparative examples, and the specific results are shown in table 1.
TABLE 1
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 Comparative example 3
Tensile Strength (MPa) 7.0 7.2 6.8 6.7 4.8 7.0
Hardness of 69 71 75 61 70 67
Creep index (%) 0.33 0.29 0.28 1.27 1.19 1.29
As can be seen from the data in table 1, the sealing films prepared according to examples 1 to 3 of the present invention have a certain strength and moderate hardness, and can be used as sealing films, and at the same time, the creep indexes are low, which indicates that the risk of leakage during long-term operation of the galvanic pile is low; the sealing films prepared according to comparative examples 1 to 3 have a higher creep index and the risk of leakage of the stack during long-term operation is higher. Therefore, it was further demonstrated that the sealing film prepared according to the present invention can exert a good sealing effect.
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.

Claims (10)

1. The creep-resistant POE film for sealing the flow battery is characterized by comprising, by weight, 70-85 parts of an ethylene-olefin copolymer, 5-15 parts of an amorphous alpha-olefin copolymer, 1-10 parts of polypropylene wax, 2-15 parts of a size stabilizer, 0-10 parts of a compatilizer, 0-3 parts of a lubricant and 0-2 parts of an antioxidant.
2. The creep-resistant POE film for sealing a flow battery according to claim 1, wherein the ethylene-olefin copolymer is one or both of an ethylene-butene copolymer and an ethylene-octene copolymer.
3. The creep-resistant POE membrane for sealing the flow battery according to claim 1, wherein the dimensional stabilizer is C-type short glass fiber, and the C-type short glass fiber is ground and screened to obtain extremely-short glass fiber with the length of 60-100 mu m, and the alkali content is lower than 15%.
4. The creep-resistant POE film for sealing a flow battery according to claim 1, wherein the compatibilizer is a maleic anhydride grafted POE resin.
5. The creep-resistant POE membrane for sealing a flow battery of claim 1, wherein the antioxidant is a hindered phenol antioxidant; the lubricant is an organic lubricant.
6. A method for preparing the creep-resistant POE film for sealing a flow battery as recited in any one of claims 1 to 5, comprising the steps of: uniformly mixing an ethylene-olefin copolymer, an amorphous alpha-olefin copolymer, polypropylene wax, a size stabilizer, a compatilizer, a lubricant and an antioxidant, extruding and granulating by a screw extruder, and encapsulating, injecting and forming a film.
7. The method for preparing the creep-resistant POE film for sealing the flow battery according to claim 6, wherein the extrusion granulation temperature is 180-210 ℃.
8. The method for preparing the creep-resistant POE film for sealing the flow battery according to claim 6, wherein the encapsulation injection molding is performed for forming the film by secondary injection molding, a thin sealing film is coated on one side of a plate frame, and the sealing film and the plate frame are integrally formed and have uniform thickness; the temperature of the encapsulation and injection molding is 180-220 ℃.
9. A flow battery comprising the creep-resistant POE membrane for sealing a flow battery as recited in any one of claims 1 to 5.
10. The flow battery of claim 9, wherein the creep-resistant POE membrane for flow battery sealing of any one of claims 1 to 5 is used to encapsulate the flow battery assembly by injection molding into a film seal.
CN202311382592.3A 2023-10-24 2023-10-24 Creep-resistant POE membrane for sealing flow battery and preparation method thereof Pending CN117362808A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311382592.3A CN117362808A (en) 2023-10-24 2023-10-24 Creep-resistant POE membrane for sealing flow battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311382592.3A CN117362808A (en) 2023-10-24 2023-10-24 Creep-resistant POE membrane for sealing flow battery and preparation method thereof

Publications (1)

Publication Number Publication Date
CN117362808A true CN117362808A (en) 2024-01-09

Family

ID=89392482

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311382592.3A Pending CN117362808A (en) 2023-10-24 2023-10-24 Creep-resistant POE membrane for sealing flow battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117362808A (en)

Similar Documents

Publication Publication Date Title
CN110591223B (en) High-filling thermoplastic resin composite material and preparation method thereof
CN100400574C (en) Method for raising fluidity of thermoplastic cross-linked rubber
CN109486473B (en) Multifunctional phase-change composite material and preparation method thereof
CN101531741B (en) Preparation method of glycidyl methacrylate graft polyisobutene copolymer
CN102558736A (en) Polypropylene composite material for automotive instrument panel and preparation method for polypropylene composite material
CN104672626A (en) High-elasticity thermoplastic elastomer material and preparation method thereof
CN1995124A (en) High tenacious polypropylene material for manufacturing central conditioner air-discharge hose and its preparation method
CN105255082B (en) Acrylate rubber/nylon thermoplastic vulcanized rubber and preparation method thereof
CN112759809A (en) Polyethylene composite material for injection molding and preparation method thereof
CN101525454A (en) High tenacity dynamic full-sulfuration thermoplastic elastomer and preparation method thereof
KR20200141475A (en) Rubber composition
CN117362808A (en) Creep-resistant POE membrane for sealing flow battery and preparation method thereof
CN111138754A (en) High-fluidity and high-rigidity alloy composite material and preparation method thereof
US11795313B2 (en) Rubber composition for fuel-cell cooling hose and fuel-cell cooling hose using same
CN113292810A (en) Non-crosslinked modified polypropylene-based graphene composite semiconductive shielding material for 6-220 kV high-voltage cable and preparation method thereof
JP6228134B2 (en) Resin composition for gasket and gasket for secondary battery
CN114437463B (en) Vulcanized composition, EPDM-based vulcanized rubber composition, vulcanized rubber, preparation method and application thereof
CN110041625A (en) A kind of ship shore electric cable insulation composite material and preparation method
CN112745581B (en) High-fluidity high-crystallization impact-resistant polypropylene material and preparation method thereof
CN116111129B (en) Packaging adhesive film for integrating electrode frame and diaphragm, and preparation method and application thereof
CN116218085B (en) High-melt-strength polypropylene material for foaming and preparation method thereof
CN114437407A (en) Vulcanized composition, EPDM-based vulcanized rubber composition, vulcanized rubber, and preparation method and application thereof
CN107090125A (en) A kind of high voltage direct current cable insulating materials and preparation method thereof
CN1145937A (en) Fireproof self-sticking insulating rubber tape
CN114045127A (en) Adhesive resin for soft package lithium ion battery aluminum plastic film and preparation method and application 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