WO2016036072A1 - 레독스 플로우 전지용 바이폴라 플레이트 제조 방법 - Google Patents

레독스 플로우 전지용 바이폴라 플레이트 제조 방법 Download PDF

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Publication number
WO2016036072A1
WO2016036072A1 PCT/KR2015/009088 KR2015009088W WO2016036072A1 WO 2016036072 A1 WO2016036072 A1 WO 2016036072A1 KR 2015009088 W KR2015009088 W KR 2015009088W WO 2016036072 A1 WO2016036072 A1 WO 2016036072A1
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Prior art keywords
bipolar plate
redox flow
flow battery
bipolar
manufacturing
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.)
Ceased
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PCT/KR2015/009088
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English (en)
French (fr)
Inventor
김호성
김민영
강병수
양선우
노희숙
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Korea Institute of Industrial Technology KITECH
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Korea Institute of Industrial Technology KITECH
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Priority to JP2017531437A priority Critical patent/JP6370494B2/ja
Priority to US15/506,406 priority patent/US10629916B2/en
Publication of WO2016036072A1 publication Critical patent/WO2016036072A1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0226—Composites in the form of mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/04—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles using movable moulds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/14—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/14—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps
    • B29C2043/141—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps for making single layer articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • B29C2043/525—Heating or cooling at predetermined points for local melting, curing or bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2505/00—Use of metals, their alloys or their compounds, as filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2507/00—Use of elements other than metals as filler
    • B29K2507/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
    • B29K2509/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • 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

Definitions

  • the present invention relates to a method for manufacturing a bipolar plate for a redox flow battery.
  • the present invention relates to a method for manufacturing a bipolar plate for a redox flow battery, which enables low-cost, high-efficiency compression molding without damage to the product without a separate ejection mechanism and system during molding.
  • the redox flow secondary battery is composed of porous electrodes (anode and cathode), bipolar plate, and frame on both sides of the ion exchange membrane (diaphragm).
  • the bipolar plate is a plate that separates each cell of the stack. In order to minimize the internal resistance of the conductive material, conductivity is required, and the electrolyte is required to be reliably cut off due to the leaking cell. In addition, the bipolar plate is highly mechanical due to the heat shrinkage due to the pressure and temperature change caused by the electrolyte.
  • the conventional bipolar plate is composed of a conductive filler (carbon material) or structure (carbon ingot), a binder resin (thermoplastic or thermosetting), and a functional additive.
  • a separator plate or bipolar plate hereinafter referred to as a 'bipolar plate'
  • the surface is polished to the required size by cutting and roughing.
  • the final required product standard is a precision cutting and surface polishing process.
  • these conventional processes are very expensive to manufacture and also have uniformity in quality and dimensions. There are characteristics that change according to wear of tool.
  • the conventional technology has the above configuration, and generally uses a product manufactured by a method of expensive cutting, and in order to solve the problem of product cost, graphite and extrusion methods are used. Attempts are being made to manufacture composite bipolar plates of resin.
  • the above-mentioned conventional technology is based on the small size of the bipolar plate, which is comparatively small in size for the fuel cell, compared to 100 crf, and has not yet been confirmed for more than 700 crf bipolar plates such as redox flow batteries.
  • the large-area bipolar plate also has extremely high defects in forming, and additional mold design and manufacturing costs are expected to maintain the mold's molding temperature and pressure uniformly. Due to its floating characteristics, there are problems of reworking the surface and poor formation of parts of the product.
  • the present invention can improve the electrical conductivity and the mechanical strength by increasing the content of the abbreviation in order to solve the problems of the prior art as described above, and can be molded at low cost without damage to the product without taking out the compression molding time. It is an object of the present invention to provide a method for manufacturing a bipolar plate for a redox flow battery.
  • step (b) may be performed by layering the mixture on a mold to heat and pressurize it.
  • the epoxy may have an epoxy equivalent weight (EEW) of 1 84 to 190 g / eq, a viscosity of 1 1,500 to 13,500 cps, and a specific gravity of 0.8 to 1.5.
  • EW epoxy equivalent weight
  • the conductive filler may be at least one selected from graphite, metal and ceramic materials.
  • the abbreviation may be needle or spherical.
  • the abbreviation may be a needle-shaped fluke.
  • the conductive filler has a particle resistivity of 100 to 150 mQ cm and an average particle diameter of 5 to 5
  • the mixture is 100 parts by weight of epoxy; 25 to 67 parts by weight of hardener; and conductive filler
  • the compression molding in step (b) includes the mixture between the two resin films.
  • the resin film may be polyester (PET) or polyimide (PI), and preferably polyester (PET).
  • the method may further include the step of passing the mixture through a sieve to homogenize the particles before step (b).
  • step (b) The compression molding failure in step (b) can be performed in two stages at one temperature.
  • step (b), (b-1) the mixture at a pressure of 80 to 200 kgf / orf, 50 to 70 ° C
  • steps (b-1) and (b-2) can be carried out for 30 minutes to 2 hours.
  • the bipolar plate manufactured using the mold may have a large area.
  • the bipolar plate may have an area of 600 crf or more.
  • the bipolar plate has a number of days the area 600 to '3,500 cnf.
  • a manufacturing method of a redox flow battery comprising the manufacturing method.
  • the present invention is based on the known technique of abyss or carbon mass (ingot).
  • bipolar plates are produced through a two-stage compression molding process using epoxy. It is easy to manufacture large-area bipolar plates of about 700cnf or more, and it is possible to reduce the manufacturing cost of bipolar plates by eliminating the need for a separate special thermal stirrer for complexing graphite and resin.
  • the present invention can easily increase the amount of graphite filler up to 90wt% of the entire bipolar plate without expensive additives for improving conductivity such as CNT, thereby easily increasing the electrical conductivity and mechanical strength of the bipolar plate.
  • the present invention manufactures bipolar plates by depositing a resin film on a mold and then deposits a mixture containing epoxy, hardener, and conductive filler, so that the bipolar plates can be manufactured at low cost without damage to the product without a separate extraction device.
  • FIG. 33 shows the shape of the conductive filler used in the examples in the present invention.
  • FIG. 2 is a view showing the powder state of a complex containing an epoxy, a hardener and a conductive filler for a bipolar plate according to the present invention.
  • FIG 3 is a view for explaining a method of manufacturing a bipolar plate according to the present invention.
  • FIG. 4 is a view showing a bipolar plate prototype manufactured by the method for manufacturing a bipolar plate for a redox flow battery according to the present invention.
  • FIG. 5 shows the surface and cross-sectioning of a bipolar plate prototype manufactured by the method for manufacturing a bipolar plate for a redox flow battery according to the present invention.
  • FIG. 6 is a result of EPMA analysis of the cross-sectional state of a bipolar plate prototype manufactured by the method of manufacturing a bipolar plate for a redox flow battery according to the present invention.
  • FIG. 7 is a graph showing electrical resistance measurement results of a bipolar plate manufactured by a method for manufacturing a bipolar plate for a redox flow battery according to the present invention.
  • FIG. 9 shows gas permeability measurement results of a bipolar plate manufactured by a method for manufacturing a bipolar plate for a redox flow battery according to the present invention.
  • component I may be named as a second component without departing from the scope of the present invention, and similarly, the second component may also be named as a first component. have.
  • the method for manufacturing a bipolar plate for a redox flow battery of the present invention prepares a conductive filler, a resin (epoxy and hardener), and an additive pillar as raw materials.
  • the epoxy may have an epoxy equivalent weight (EEW) of 184 to 190 g / eq, a viscosity of 1 to 1500 to 13,500 cps, and a specific gravity of 1.0 to 1.5.
  • EW epoxy equivalent weight
  • the conductive filler may be any metal, ceramic or ceramic material.
  • the conductive filler may have a particle resistivity of 100 to 150 mQ.cm, an average particle diameter of 5 to 30, a specific surface area of 0.3 to 3.0 n / g, and a density of 1.5 to 3.0 g / cirf. It has physical properties as shown in [Table I].
  • the following graphite 1. (Spherical graphite) and Abbreviation 2 (needle type graphite) are shown in FIG.
  • the mixture is prepared by mixing the epoxy, the hardener and the conductive filler (step a).
  • the mixture contains 100 parts by weight of epoxy, 25 to 67 parts by weight of hardener and conductive filler.
  • the hardening agent may be included in an amount of preferably 30 to 60 parts by weight, more preferably 35 to 55 parts by weight.
  • the conductive filler is preferably 500 to 1400 parts by weight, more preferably
  • the graphite of the mixture may be mixed and stirred at room temperature so that the graphite is uniformly distributed.
  • the mixture comprising epoxy, hardener and conductive filler has a diameter of a certain size (e.g., 1 mm) in order to make the particles of the mixture powder uniform with the powder state shown in FIG. Hit it with a sieve.
  • step b the mixture is compression molded to produce a bipolar plate.
  • the compression molding may be performed by layering the mixture on a mold to heat and pressurize it.
  • the mixture can be charged after the resin film is placed on the lower part of the mold so that the product can be molded without damage even without a separate ejection device.
  • PET polyimide
  • PI polyimide
  • compression molding can be carried out after placing the resin film on the mixture before the compression molding.
  • the compression molding can be performed in two steps (step b-1 and step b-2) at different temperatures.
  • the first compression molding is performed at a pressure of 80 to 200 kgf / crf and a pressure of 50 to 70 o C.
  • step b-1 This can be done for 30 minutes to 2 hours at temperature (step b-1).
  • [68] Preferably it can be carried out for 40 minutes to 1 hour 30 minutes at a pressure of 100 to 180 kgf / crf and a temperature of 52 to 68 ° C, more preferably a pressure of 1 10 to 160 kgf / crf and 55 to 65 It can be carried out for 45 minutes to 1 hour 15 minutes at a temperature of ° C.
  • the second compression molding can be performed for 30 minutes to 2 hours at a pressure of 80 to 200 kgf / cnf and a temperature of 100 to 160 ° C (step b-2).
  • [70] Preferably it can be carried out for 40 minutes to 1 hour 30 minutes at a pressure of 100 to 180 kgf / cn and a temperature of 1 10 to 150 ° C, more preferably 1 10 to 1.60 kgf / c'tn ' This can be done for 45 minutes to 1 hour and 15 minutes at pressure and temperatures from 120 to 140 ° C.
  • Step b-1 is a condition in which fluidity (flowability) is best due to epoxy properties (solubility), which increases the formation of resin between resins in the mold.
  • the curing reaction begins, and when the pressure is increased to a temperature of 100 ° C to 160 ° C with the same pressure, the epoxy is completely cured and the molding process is completed.
  • the mold is excellent in the molding quality of the product even when molding at a constant temperature and pressure, it is designed to facilitate the extraction of the product from the mold even without a separate take-out device. It is composed of a upper plate and a lower plate and a middle part for supporting the upper plate and the lower plate, and a space in which the mixture is layered is formed between the upper plate and the lower plate, and grooves (for example, quadrilateral grooves) are formed on both sides of the middle part. At this time, the groove is a space in which the residues from the space between the upper plate and the lower plate can be moved by compression during the compression molding process. In the process, the moldings can be easily taken out without the upper and lower plates bonding.
  • the mixture is charged and spread evenly. Thereafter, the resin film is placed on the mixture, the top plate and the middle plate are assembled, and then compression molded in a hot press.
  • edges are uniformly distributed on the cross section and the surface, and it is possible to manufacture a highly conductive bipolar plate without compression or breakage and quality problems during compression extraction.
  • the bipolar plate manufactured using the mold may have a large area.
  • the area may be more than 600 cnf.
  • the bipolar plate may have an area of 600 to 3,500 cm 2 , and more preferably 600 to 2,500 cm 2 .
  • the present invention relates to the bipolar plate for redox
  • a method of manufacturing a redox flow battery including a manufacturing method.
  • the epoxy and the hardener were mixed at a ratio of 7: 3, and then uniformly stirred to prepare a thermosetting epoxy. Thereafter, using a general stirrer, the spherical inductive filler and the thermosetting epoxy were mixed and stirred at a ratio of 9: 1. After the mixture was prepared, the mixture was sieved to a diameter of 1 mm 3.
  • the first compression molding was carried out for 1 hour at a pressure of citf and a molding temperature of 60 ° C., and the pressure was released about 5 minutes to release the gas in the mold. Also, a pressure of 136 kg / cn was performed.
  • the bipolar plate was prepared by raising the temperature of the mold to 130 and maintaining the second compression molding for 1 hour while maintaining it.
  • a bipolar plate was manufactured from the same materials and processes as in Example 1.
  • Example 2 It was found that the electrical resistance of the bipolar plate was about 27 to 33 ⁇ ⁇ ⁇ (average 31 ⁇ ⁇ ⁇ ), which was superior to that of Example 1.
  • the bipolar plate prepared according to Example 2 was measured more than Example 1. It can be seen that the characteristics are more uniform than the specific resistivity distribution.
  • Test Example 2 Measurement of the bending strength and gas permeability of bipolar folate
  • Figure 9 shows the result of measuring the gas permeability.
  • the bipolar plate including the spherical axle of Example 1 exhibited a flexural strength of about 23 to 33 MPa (average 26 MPa), and the bipolar plate containing the acicular graphite of Example 2 was bent. The strength is better than the average 33Mpa, showing better characteristics.
  • the bipolar plate containing the spherical graphite of Example 1 maintains the gas permeability of 0 regardless of the measurement pressure. It can also be seen that the gas permeability remains 0 irrespective of the measurement pressure.
  • the graph of Example 1 is covered by the graph of Example 2.
  • the electrical resistance and the compressive strength of the plate were measured by the same method as in Example 1, and the electrical resistance was lower by an average of about 31 ⁇ ⁇ . ⁇ , and the flexural strength was about 33Mpa.
  • the electrical resistance of the self-made body is high, the electrical resistance of the molded product is better than that of the spherical structure, which has about three times the specific surface area compared to the spherical structure.
  • the compressive strength is slightly increased in the needle shape than the spherical shape.
  • the results of the present invention obtained by the two kinds of graphite materials described above are very close to the commercialization level.
  • the manufacturing method of the plate can dramatically lower the production cost to about one tenth of the cost compared to the process of impregnating a thermosetting resin binder on a paste that has been cut into a fixed thickness of an ingot or carbon chunk (ingot) in the prior art.
  • the bipolar plate is manufactured through a two-stage compression molding process, making it easy to manufacture large-area bipolar plates of over 700 crf. The use of a separate special thermal stirrer required for the complexation is not required, thereby reducing the manufacturing cost of the bipolar plate.
  • the manufacturing method of the bipolar plate for redox flow battery according to the embodiment of the present invention can easily increase the amount of the conductive filler up to 90wt% level of the entire bipolar plate without expensive additives for improving the conductivity, such as CNT. This makes it easy to increase the electrical and mechanical strength of bipolar plates.
  • the method of manufacturing a bipolar plate for a redox flow battery is to deposit a complex containing a epoxy, a hardener, and a conductive filler after the resin film is completely placed under the mold, and the resin is placed on the mixture again.
  • Bipolar folate can be rolled up to produce a bipolar plate at low cost without damage to the product without a separate drawer.
  • the present invention uses graphite or carbon ingots in the prior art.
  • bipolar plates are produced through a two-stage compression molding process using epoxy. It is easy to manufacture large-area bipolar plates of about 700 crf or more, and it is possible to reduce the cost of manufacturing bipolar plates by eliminating the need for a separate special thermal stirrer for complexing graphite and resin.
  • the present invention can easily increase the electrical conductivity and mechanical strength of the bipolar plate because it can easily increase the amount of the filler up to 90wt% of the entire bipolar plate without expensive additives for improving the conductivity, such as CNT. .
  • the present invention manufactures a bipolar plate by placing a resin film on a mold and then filling a compound containing a epoxy, a hardener, and a conductive filler, so that the bipolar plate can be manufactured at low cost without damage to the product without a separate takeout device. have.

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

본 발명은 레독스 플로우 전지용 바이폴라 플레이트의 제조방법에 관한 것이다. 이를 위해，본 발명은 (a)에폭시，경화제 및 도전성 필러를 혼합하여 흔합물을 제조하는 단계; 및 (b)상기 혼합물을 압축성형하여 제조된 도전성 필러 복합체를 포함하는 바이폴라 플레이트를 제조하는단계;를포함한다.

Description

명세서
발명의명칭:레독스플로우전지용바이폴라플레이트제조방법
. 기술분야
[1] 본발명은레독스플로우전지용바이폴라플레이트의제조방법에관한
것으로，특히전기전도성을향상시키기위해도전성필러인흑연의함량을 증대시킬수있고,압축성형에의해흑연과복합화된수지가표면으로유동하여 저항이크게증가하는문제점을해결할수있으며，대면적바이폴라플레이트 압축성형시별도의취출기구및시스템이없어도제품의손상없이성형가능한 저가의고효율압축성형이가능한레독스플로우전지용바이폴라플레이트의 제조방법에관한것이다.
배경기술
[2] 레독스플로우이차전지는이온교환막 (격막)의양측에다공성전극 (양극및 음극)과바이폴라플레이트 (Bipolar plate),그리고프레임으로구성되어있으며， 바이폴라플레이트는스택의각셀을분리하는판으로서전지의내부저항을 최소화하기위해도전성이요구되고,인접하는샐로전해액이새지않고확실히 차단되는특성이요구된다.또한，바이폴라플레이트는전해액에의한압력과 온도변화에의한열수축등도발생할수있기때문에높은기계적
강도 (인장강도)및다소의변형에의한파손이발생하지않은연신특성도 요구된다.
[3] 종래의바이폴라플레이트는도전성필러 (카본소재)또는구조체 (카본괴)와 바인더수지 (열가소성또는열경화성)，그리고기능성첨가제로구성된다. 종래에는레독스플로우전지의분리판또는바이폴라플레이트 (이하， '바이폴라 플레이트'로통칭함)를제조함에있어，혹연괴를절단및황삭가공에의해 요구되는치수로절단후평면연마를실시하고，최소 3회이상다수의수지함침 공정을실시한후최종적으로요구되는제품규격으로정밀절삭가공및 표면연마가공공정을가진다.그러나，이러한종래의공정은제품제조비용이 매우고가이며，또한품질및치수의균일성이치공구마모에따라변화하는 특성이있다.
[4] 한편，이러한문제점을해결하기위해흑연분말과열가소성또는열경화성 바인더수지의분말을건싀흔합하여흑연복합체를제조하고혹연복합체를 프레스금형으로압축성형하거나사출성형하여복합바이폴라플레이트를 제조하고있다.
[5] 종래의기술은위의구성을가지고있으며,일반적으로는고가의절삭가공에 의한방법에의해제조된제품을사용하고있으며，제품코스트문제를해결하기 위해압축및사출공정에의한방식으로흑연과수지의복합체바이폴라 플레이트제조연구를시도하고있다.
대체용지 (규칙 제 26조) [6] 최근에공지된압축성형또는사출성형에의한복합바이폴라플레이트는 기존의절삭가공및수지함침에의한공정에비해코스트가상당히낮아졌지만 제품성형성의불균일로인해표면연마와같은후처리공정을추가적으로 수행하고있다.따라서,종래의기술은지속적인원가절감에한계가있으며， 특히유동성및분산성이요구되는압축및사출성형에적합한소재선정및 분산기술이요구된다. ᅳ ᅳ
[7] 그리고,상술한종래의기술은연료전지용으로바이폴라플레이트의크기가 lOOcrf로비교적 작은소형기술에기반하며,레독스플로우전지와같이약 700crf 이상의바이폴라플레이트에대해서는아직확인되지않고있다.
[8] 또한,대면적구조의바이폴라플레이트는성형성의불량를이상대적으로매우 높고，금형의성형온도와압력을균일하게유지하는데추가적인금형설계와 제작비용이 예상되며,압축성형시제품표면으로바인더고분자가유동하는 특성으로인해표면을재가공해야하는문제점과제품의부위별성형성불량이 발생하는문제점이 있다.
[9] 그리고，종래의기술은카본과바인더의복합수지복합체를제조하는공정이 매우길고,복잡하며,고온과압력을가해서제조하기 때문에카본과고분자의 고유물성이변화될가능성이 있고，균일한입자의크기로제어하는데높은 비용의공정기술이필요한문제점이 있다.
발명의상세한설명
기술적과제
[10] 따라서，본발명은상기와같은종래기술의문제점을해결하기위해혹연의 함량을증대시켜 전기전도도및기계적강도를향상시키고,압축성형시별도의 취출기구없이도제품의손상없이 저가로성형할수있는레독스플로우전지용 바이폴라플레이트의제조방법을제공하는것을목적으로한다.
과제해결수단
[ 1 1] 본발명의일측면에따르면，
[12] (a)에폭시，경화제및도전성필러를흔합하여혼합물을제조하는단계;및 (b) 상기혼합물을압축성형하여바이폴라플레이트를제조하는단계；를포함하는 레독스플로우전지용바이폴라폴레이트의제조방법이제공된다.
[13] 단계 (b)의압축성형이상기혼합물을몰드에층전시켜가열및가압함으로써 수행될수있다.
[ 14] 상기에폭시는 EEW(Epoxy Equivalent Weight)가 1 84내지 190g/eq이고，점도가 1 1 ,500내지 13,500cps이고,비중이 0.8내지 1.5일수있다.
[15ᅵ 상기도전성필러가흑연，금속및세라믹소재중에서선택된 1종이상일수 있다.
[16] 상기혹연이침상형혹연또는구형혹연일수있다.
[17] 상기혹연이침상형혹연일수있디-. [18] 상기도전성필러는입자저항률이 100내지 150mQ cm이고，평균입경이 5내지
30//m이고，비표면적이 0.3내지 3.0m7g이고,밀도가 1.5내지 3.0g/cm '일수있다.
[ 19] 상기혼합물이,에폭시 100중량부;경화제 25내지 67중량부;및도전성필러
125내지 1 ,510중량부；를포함할수있다.
[20] 단계 (b)의압축성형이상기혼합물을두개의수지필름사이에포함시켜
몰드에충전시킨후,가열및가압함으로써수행될수있다.
[21] 상기수지필름은폴리에스터 (PET)또는폴리이미드 (PI)를사용할수있고, 바람직하게는폴리에스터 (PET)를사용할수있디-.
[22] 단계 (b)이전에상기흔합물을체에통과시켜 입자를균일하게하는단계를 추가로포함할수있다.
[23] 단계 (b)의압축성형이상이한온도에서두단계로수행될수있다.
[24] 단계 (b)기 ·, (b- 1)상기흔합물을 80내지 200kgf/orf의압력, 50내지 70°C의
온도에서압축성형하는단계;및 (b-2)단계 (b- l )의 결과물을 80내지
200kgf/orf의압력， 100내지 160oC의온도에서압축성형하는단계；를포함할수 있다.
[25] 단계 (b-l)및단계 (b-2)의압축성형이 30분내지 2시간동안수행될수있다.
[26] 상기몰드를이용하여제조된바이폴라플레이트가대면적일수있다.
[27] 상기바이폴라플레이트는면적이 600 crf 이상일수있다.
[28] 상기바이폴라플레이트는면적이 600내지' 3,500 cnf 일수있다.
[29] 본발명의다른또하나의측면에따르면,상기 제조방법을포함하는레독스 플로우전지의 제조방법이제공된다.
발명의효과
[30] 상술한바와같이본발명은종래기술에서혹연또는카본덩어리 (잉곳)를
일정한두께로절단가공한플레이트에열경화성수지바인더를함침시키는 공정에비해생산원가를약 1/10수준으로획기적으로낮출수있고，에폭시를 사용하여 2단계의압축성형공정을통해바이폴라플레이트를제작하기때문에 약 700cnf 이상의대면적바이폴라플레이트의제작이용이하며，흑연과수지의 복합화에필요한별도의특수열교반기의사용이불필요하므로바이폴라 플레이트의제조비용을줄일수있다.
[31] 또한,본발명은 CNT등도전성향상을위한고가의 첨가제없이도흑연필러의 양을바이폴라플레이트전체의 90wt%수준까지용이하게증가시킬수있기 때문에바이폴라플레이트의 전기전도도및기계적강도를쉽게높일수있다.
[32] 그리고,본발명은몰드에수지필름을깓후에폭시,경화제및도전성필러를 포함하는흔합물을층전시켜바이폴라플레이트를제조하기 때문에별도의 취출장치없이도제품의손상없이바이폴라플레이트를저가로제작할수있다. 도면의간단한설명
[33] 도 은본발명에실시예에사용된도전성필러의형상을나타낸것이다. [34] 도 2는본발명에따른바이폴라플레이트용에폭시 ,경화제및도전성필러를 포함하는흔합물의분말상태를나타내는도면이디-.
[35] 도 3은본발명에따른바이폴라플레이트의 제조방법을설명하기위한
압축성형용몰드의개략도이다.
[36] 도 4는본발명에따른레독스플로우전지용바이폴라플레이트의제조방법에 의해제조된바이폴라플레이트시작품을나타내는도면이다.
[37] 도 5는본발명에따른레독스플로우전지용바이폴라플레이트의제조방법에 의해제조된바이폴라플레이트시작품의표면및단면싱 -태에대한 SEM분석 결과도이디-.
[38] 도 6은본발명에따른레독스플로우전지용바이폴라플레이트의제조방법에 의해제조된바이폴라플레이트시작품의단면상태에대한 EPMA분석 결과도이다.
[39] 도 7은본발명에따른레독스플로우전지용바이폴라플레이트의 제조방법에 의해제조된바이폴라플레이트의전기저항측정결과를나타내는그래프이다.
[4이 도 8은본발명에따른레독스플로우전지용'바이폴라플레이트의제조방법에 의해제조된바이플라플레이트의굴곡강도측정결과를나타내는그래프이다.
[41] 도 9는본발명에따른레독스플로우전지용바이폴라플레이트의제조방법에 의해제조된바이폴라플레이트의가스투과도측정 결과를나타내는
그래프이다.
발명의실시를위한최선의 형태
[42] 이하, ¾부된도면을참조하여본발명이속하는기술분야에서통상의지식을 가진자가본발명을용이하게실시할수있는바람직한실시예를상세히 설명한다.다만，본발명의바람직한실시예에대한동작원리를상세하게 설명함에 있어관련된공지 기능또는구성에대한구체적인설명이본발명의 요지를불필요하게흐릴수있다고판단되는경우에는그상세한설명을 생략한다.
[43] 또한，도면전체에걸쳐유사한기능및작용을하는부분에 대해서는동일한 도면부호를사용한다.
[44] 또한,이하에서사용될제 1 ,제 2등과같이서수를포함하는용어는다양한 구성요소들을설명하는데사용될수있지만，상기구성요소들은상기용어들에 의해한정되지는않는다.상기용어들은하나의구성요소를다른
구성요소로부터구별하는목적으로만사용된다.예를들어,본발명의권리 범위를벗어나지않으면서제 I구성요소는제 2구성요소로명명될수있고， 유사하게제 2구성요소도제 1구성요소로명명될수있다.
[45] 덧붙여，명세서 전체에서어떤부분이다른부분과 '연결'되어있다고할때 이는직접적으로연결되어있는경우뿐만아니라그증간에다른구성요소를 사이에두고간접적으로연결되어 있는경우도포함한다.또한,어떤구성요소를 '포함 '한다는것은특별히반대되는기재가없는한다른구성요소를제외하는 것이아니라다른구성요소를더포함할수있는것올의미한다.
[46]
[47] 이하，본발명의 레독스플로우전지용바이폴라플레이트의제조방법에대해 설명하도록한다.
[48] 본발명의레독스플로우전지용바이폴라플레이트의제조방법은원료로서 도전성필러,수지 (에폭시및경화제)및첨가제둥을준비한다.
[49] 이때,에폭시는 EEW(Epoxy Equivalent Weight)가 184내지 190g/eq이고，점도가 1 1,500내지 13,500cps이고，비중이 1.0내지 1.5일수있디-.
[50] 상기도전성필러는혹연，금속，세라믹소재등이가능하다.
[51] 상기도전성필러는입자저항율이 100내지 150mQ.cm이고，평균입경이 5내지 30 이고,비표면적이 0.3내지 3.0n /g이고,밀도가 1 .5내지 3.0g/cirf일수있고, 바람직하게는 [표 I ]과같은물성을갖는다.참고로,하기흑연 1. (구형흑연)및 혹연 2(침상형혹연)의형상을도 1에나타내었다.
[52]
[53] [표 1 ]
Figure imgf000006_0001
[54]
[55] 먼저,에폭시，경화제및도전성필러를혼합하여혼합물을제조한다 (단계 a).
[56] 상기흔합물은에폭시 100중량부,경화제 25내지 67증량부및도전성 필러
125내지 1 ,5】 0중량부를포함할수있다.
[57] 이때,상기경화제는바람직하게는 30내지 60중량부,더욱바람직하게는 35 내지 55중량부로포함될수있다.
[58] 상기도전성필러는바람직하게는 500내지 1400중량부,더욱바람직하게는
800내지 1200증량부로포함될수있다.
[59] 상기에폭시와경화제는혼합되어도상온에서액상으로존재하기 때문에
도전성필러인흑연과쉽게흔합될수있다.
[60] 상기흔합물의흑연이균일하게분포되도록상온에서혼합및교반할수있다.
[61 ] 이와같이에폭시，경화제및도전성필러의흔합비율구간내에서상온의
조건에서흔합및교반을실시하여도균일한분산이가능하며,압축성형공정에 의한유동성을층족시킬수있는범위이다. ' [62] 한편,에폭시,경화제및도전성필러를포함하는상기흔합물은도 2에도시된 분말상태와갈이상기혼합물분말의입자를균일하게하기위해일정크기의 직경 (예를들면, 1画)을갖는체에친다.
[63] 다음으로,상기흔합물을압축성형하여바이폴라플레이트를제조한다 (단계 b).
[64] 상기압축성형은상기흔합물을몰드에층전시켜가열및가압함으로써수행될 수있다.
[65] 이때，몰드에는별도의취출장치가없기때문에별도의취출기구가없더라도 제품에손상없이성형할수있도록충전전에몰드의하부에수지필름을깐후 상기혼합물을충전할수있다.상기수지필름은폴리에스터 (PET)또는 폴리이미드 (PI)를사용할수있고,바람직하게는폴리에스터 (PET)를사용할수 있다.또한，상기압축성형 전에상기흔합물상에수지필름을위치시킨후 압축성형을수행할수있다.
[66] 상기 압축성형은상이한온도에서두단계 (단계 b-1 및단계 b-2)로수행될수 있다.
[67] 먼저，첫번째압축성형은 80내지 200kgf/crf의압력및 50내지 70oC의
온도에서 30분내지 2시간동안수행될수있다 (단계 b-1).
[68] 바람직하게는 100내지 180kgf/crf의압력및 52내지 68°C의온도에서 40분 내지 1시간 30분동안수행될수있고，더욱바람직하게는 1 10내지 160kgf/crf의 압력및 55내지 65°C의온도에서 45분내지 1시간 15분동안수행될수있다.
[69] 다음으로,두번째압축성형은 80내지 200kgf/cnf의압력및 100내지 160°C의 온도에서 30분내지 2시간동안수행될수있다 (단계 b-2).
[70] 바람직하게는 100내지 180kgf/cn의압력및 1 10내지 150°C의온도에서 40분 내지 1시간 30분동안수행될수있고,더욱바람직하게는 1 10내지 1.60kgf/c'tn'의 압력및 120내지 140oC의온도에서 45분내지 1시간 15분동안수행될수있다.
[71 ] 여기에서상기흔합물에대해일정한압력하에서 50oC ~ 70 를유지하는
것 (단계 b-1 )은에폭시의물성 (용해도)에기인하여유동성 (흐름성)이가장좋은 상태가되어몰드내에서수지간의성형성을증가시키는조건이기 때문이며, 70°C이상에서는유동성이중지되어 경화반웅이 시작되고,동일한압력으로 100oC ~ 160°C의온도로증가시키면에폭시는완전히경화되어성형공정이 완결된다.
[72] 한편,몰드는일정한온도와압력에서성형할경우에도제품의성형품질이 우수하며，별도의취출장치가없어도몰드에서 제품의취출이용이하도록 설계되었다.다시 말해,몰드는도 3에도시된바와같미상판과하판및상기 상판과하판을지지할수있는중간부로구성되고，상판과하판사이에는상기 혼합물이층전되는공간이형성되며，중간부의양면에는홈 (예를들면， 4각홈)이 형성된다.이때,홈은압축성형공정시압축에의해상판과하판사이의 공간에서넘어오는잔류물이이동할수있는공간이고,이홈에의해압축성형 공정시상판과하판이접착되지않고성형물이쉽게취출될수있다.
[73] 그리고,상기와같은몰드가준비되면,하판과중간판을먼저조립한후
중간부와증간부사이에배치되는하판위에수지필름을깔고,그위에
혼합물을충전하여골고루펼친다.이후,상기흔합물위에수지필름을올리고， 상판과중간판을조립한후핫프레스에서압축성형할수있다.
[74] 이와같은조건에의해제작된시작품은도 4내지도 6에도시된바와같이
단면과표면에혹연이균일하게분산되었음을알수있고,압축성형후취출 과정에서파손및크랙등의품질의문제없이도전성이우수한바이폴라 플레이트를제작할수있게된다.
[75] 상기몰드를이용하여제조된바이폴라플레이트는대면적일수있으며,
면적이 600 cnf 이상일수있다.바람직하게는상기바이폴라플레이트는면적이 600내지 3,500 cm2일수있으며，더욱바람직하게는 600내지 2,500 cm2일수있다.
[76] 또힌、본발명은상술한레독스폴로우전지용바이폴라플레이트의
제조방법을포함하는레독스플로우전지의제조방법을제공한다.
발명의실시를위한형태
[77] 실시예 1
[78] 출발물질로에폭시 ,경화제및구형흑연 (표 1의흑연 1)을준비하고,상기
에폭시와경화제를 7:3의비율로흔합한후균일하게교반하여열경화성 에폭시를제조하였다.이후상온에서일반교반기를이용하여구형혹연필러와 상기열경화성에폭시를 9: 1의비율로흔합및교반하여혼합물을제조한후 상기혼합물을직경 1睡의체에쳤다.
[79] 이후，금형몰드하부에폴리에스터 (PET)필름을 1장깔고상기흔합물을금형 몰드의직사각형홀 (32cm X 23cm)에층전한후폴리에스터 (PET)필름으로상기 혼합물을덮고， 136kg/citf의압력과 60°C의성형온도에서 I시간동안제 1 압축성형하고，몰드내의가스를유출시키기위해 1분동안압력을풀어주는 공정을약 5회실시하였다.또한， 136kg/cn의압력을유지한상태에서몰드의 온도를 130 로올린후 1시간동안제 2압축성형을유지하여바이폴라 플레이트를제조하였다.
[8이
[81] 실시예 2
[82] 도전성필러인혹연을침상형 (표 1의혹연 2)으로변경한것을제외하고는
실시예 1과동일한소재와공정으로바이폴라플레이트를제조하였다.
[83]
[84] · [시험예]
[85]
[86] 시험예 1 :바이폴라폴레이트의 ？ᅥ기저함특성측정
[87] 도 7은본발명의실시예 1및 2에따라제조된바이폴라플레이트의전기저항 특성을측정한결과를나타낸것이다.
[88] 도 7을참조하면,상기실시예 1의구형흑연을적용하여제조된바이폴라
플레이트의전기저항특성을살펴보면，약 30내지 45ηιΩ·αιι (평균 37ηΊΩ·αη)의 • 수준임을알수있었다.또한，실시예 2의침상형흑연을적용하여 제조된
바이폴라플레이트의 전기저항은약 27내지 33ΓηΩ·αιι (평균 31πιΩ·αη)수준으로 실시예 1보다우수한특성을갖는다는것을알수있었다.또한，실시예 2에의해 제조된바이폴라플레이트는실시예 1보다측정된비저항산포에서보다 균일한특성을나타냄을알수있었다.
[89]
[90] 시험예 2:바이폴라폴레이트의금곡강도및가스투과도측정
[91] 도 8은본발명의실시예 1및 2에따라제조된바이폴라플레이트의
굴곡강도를측정하여나타낸결과이고,도 9는가스투과도를측정한결과를 나타낸것이다.
[92] 도 8을참조하면，실시예 1의구형혹연을포함하는바이폴라플레이트는굴곡 강도가대략 23내지 33Mpa (평균 26MPa)정도로나타났고，실시예 2의 침상형 흑연을포함하는바이폴라플레이트는굴곡강도가평균 33Mpa수준으로더 우수한특성을나타내는것으로나타났다.
[93] 또한,도 9를참조하면,실시예 1의구형흑연을포함하는바이폴라플레이트는 측정압력에관계없이가스투과도가 0을유지함을알수있다.실시예 2의 침상형혹연을포함하는바이폴라플레이트또한측정압력에관계없이 가스투과도가 0을유지함을알수있다.참고로도 9에서실시예 1의그래프는 실시예 2의그래프에가려져있다.
[94] 시험예 1및시험예 2를참조하면,실시예 2에따라제조된바이폴라
플레이트의 전기저항과압축강도를실시예 1과동일한방법으로측정한결과 전기저항은평균약 31 ηιΩ.αη로더욱낮고,굴곡강도도 33Mpa수준으로더 우수한특성을나타낸다.여기에서 침상형흑연소재가자체의 전기저항은 높지만성형된제품의전기저항이구형보다더우수한결과를얻는것은침상형 구조가구형구조에비해비표면적이약 3배정도많고，침상형구조가구형 구조에비해전자이동경로를확보하는데더유리하기 때문이며，이러한 이유로압축강도또한구형보다침상형에서다소증가하게된다.한편,상기와 같은 2종류의흑연물질에의해얻어진본발명의결과는상용화수준으로매우 근접한특성임을알수있다.
[95] 이와같이본발명의실시예에따른레독스플로우전지용바이폴라
플레이트의제조방법은종래기술에서혹연또는카본덩어리 (잉곳)를일정한 두께로절단가공한풀레이트에열경화성수지바인더를함침시키는공정에 비해생산원가를약 1/10수준으로획기적으로낮출수있고，에폭시를사용하여 2단계의압축성형공정을통해바이폴라플레이트를제작하기때문에약 700crf 이상의대면적바이폴라플레이트의제작이용이하며,흑연과에폭시의 복합화에필요한별도의특수열교반기의사용이불필요하므로바이폴라 플레이트의제조비용을줄일수있게된다.
[96] 또한,본발명의실시예에따른레독스플로우전지용바이폴라플레이트의 제조방법은 CNT등도전성향상을위한고가의첨가제없이도도전성필러의 양을바이폴라플레이트전체의 90wt%수준까지용이하게증가시킬수있기 때문에바이폴라플레이트의 전기전도도및기계적강도를용이하게높일수 있게된다.
[97] 그리고，본발명의실시예에따른레독스플로우전지용바이폴라플레이트의 제조방법은몰드하부에수지필름올깐후에폭시，경화제및도전성필러를 포함하는흔합물을층전시키고,상기흔합물위에다시수지필름을을려 바이폴라폴레이트를제조하기때문에별도의취출장치없이도제품의손상 없이바이폴라플레이트를저가로제작할수있다.
[98]
[99] 이상에서설명한바와같이，본발명의상세한설명에서는본발명의바람직한 실시예에관해서설명하였으나，이는본발명의가장양호한실시예를
예시적으로설명한것이지본발명을한정하는것은아니다.또한，본발명이 속하는기술분야의통상의지식을가진자라면누구나본발명의기술사상의 범주를벗어나지않는범위내에서다양한변형및모방이가능함은물론이다-. 따라서，본발명의권리범위는설명된실시예에국한되어 정해져서는안되며， 후술하는청구범위뿐만아니라이와균등한것들에의해정해져야한다.
산업상이용가능성
[ 100] 상술한바와같이본발명은종래기술에서흑연또는카본덩어리 (잉곳)를
일정한두께로절단가공한플레이트에열경화성수지바인더를함침시키는 공정에비해생산원가를약 1/10수준으로획기적으로낮출수있고，에폭시를 사용하여 2단계의압축성형공정을통해바이폴라플레이트를제작하기때문에 약 700crf 이상의대면적바이폴라플레이트의제작이용이하며，흑연과수지의 복합화에필요한별도의특수열교반기의사용이불필요하므로바이폴라 플레이트의제조비용을줄일수있다.
[101] 또한，본발명은 CNT등도전성향상을위한고가의 첨가제없이도혹연필러의 양을바이폴라플레이트전체의 90wt%수준까지용이하게증가시킬수있기 때문에바이폴라플레이트의전기전도도및기계적강도를쉽게높일수있다.
[ 102] 그리고，본발명은몰드에수지필름을깐후에폭시，경화제및도전성필러를 포함하는흔합물을충전시켜바이폴라플레이트를제조하기때문에별도의 취출장치없이도제품의손상없이바이폴라플레이트를저가로제작할수있다.

Claims

청구범위
[청구항 1] (a)에폭시，경화제및도전성필러를흔합하여혼합물을제조하는단계;
및
(b)상기흔합물을압축성형하여 제조된도전성필러복합체를포함하는 바이폴라플레이트를제조하는단계；를
포함하는레독스플로우전지용바이폴라플레이트의제조방법.
[청구항 2] 제 1항에있어서，
단계 (b)의압축성형이상기흔합물을몰드에층전시켜가열및 가압함으로써수행되는것을특징으로하는레독스플로우전지용 바이폴라플레이트의제조방법.
[청구항 3] .제1항에 있어서,
상기에폭시는 EEW(Epoxy Equivalent Weight)가 184내지 190g/eq이고, 점도가 1 1 ,500내지 13,500cps이고，비중이 1 .0내지 1.5인것을특징으로 하는레독스플로우전지용바이폴라플레이트의 제조방법.
[청구항 4] 제 1항에 있어서,
상기도전성필러가흑연,금속및세라믹소재중에서선택된 1종이상인 것을특징으로하는레독스플로우전지용바이폴라플레이트의 . 제조방법.
[청구항 5] 제 4항에 있어서，
상기흑연이침상형흑연또는구형흑연인것을특징으로하는레독스 플로우전지용바이폴라플레이트의제조방법.
[청구항 6] 제 5항에 있어서,
상기흑연이침상형흑연인것을특징으로하는레독스플로우전지용 바이폴라플레이트의제조방법 .
[청구항 7] 제 1항에 있어서,
상기도전성필러는입자저항률이 100내지 150m. cm이고，평균입경이 5 내지 30 이고，비표면적이 0.3내지 3.0in7g이고,밀도가 1.5내지
3.0g/cirf인것을특징으로하는레독스플로우전지용바이폴라
플레이트의 제조방법.
[청구항 8] 제 1항에 있어서,상기흔합물이，
에폭시 100중량부;
경화제 25내지 67중량부;및
도전성필러 125내지 1 ,510중량부；를포함하는것을특징으로하는 레독스플로우전지용바이폴라플레이트의 제조방법.
[청구항 9] 제 2항에 있어서,
단계 (b)의압축성형이상기흔합물을두개의수지필름사이에포함시켜 몰드에층전시킨후,가열및가압함으로써수행되는것을특징으로하는 레독스플로우전지용바이폴라플레이트의 제조방법.
[청구항 10] 제 9항에 있어서,
단계 (b)이전에상기혼합물을체에통과시켜 입자를균일하게하는 단계를추가로포함하는것을특징으로하는레독스폴로우전지용 바이폴라폴레이트의 제조방법ᅳ
[청구항ᅵ 1 ] 제 1항에 있어서,
단계 (b)의압축성형이상이한온도에서두단계로수행되는것을 특징으로하는레독스플로우전지용바이폴라플레이트의제조방법.
[청구항 12] 제 1 1항에 있어서，
단계 (b)가,
(b-1)상기혼합물을 80내지 200kgf/crf의압력, 50내지 70°C의은도에서 압축성형하는단계;및
(b-2)단계 (b- 1 )의결과물을 80내지 200kgf/cirf의압력， 100내지 I 60°C의 온도에서압축성형하는단계;를포함하는것을특징으로하는레독스 폴로우전지용바이폴라플레이트의제조방법.
[청구항 13] 제 12항에 있어서，
단계 (b- 1 )및단계 (b-2)의압축성형이 30분내지 2시간동안수행되는 것을특징으로하는레독스플로우전지용바이폴라플레이트의 제조방법.
[청구항 14] 제 2항에 있어서,
상기몰드를이용하여 제조된바이폴라플레이트가대면적인것을 특징으로레독스플로우전지용바이폴라플레이트의제조방법.
[청구항 15] 제 M항에 있어서，
상기바이폴라플레이트는면적이 600 crf이상인것을특징으로하는 레독스플로우전지용바이폴라플레이트의 제조방법.
[청구항 16] 제 15항에 있어서,
상기바이폴라플레이트는면적이 600내지 3,500 cnf인것을특징으로 하는레독스플로우전지용바이폴라폴레이트의제조방법'.
[청구항 Π] 게 1항의제조방법올포함하는레독스플로우전지의 제조방법.
PCT/KR2015/009088 2014-09-01 2015-08-28 레독스 플로우 전지용 바이폴라 플레이트 제조 방법 Ceased WO2016036072A1 (ko)

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