TWI766307B - Method of electrode fabrication for supper-thin flow-battery - Google Patents

Abstract

A method is provided to fabricate electrodes. The electrodes are used in supper-thin flow-batteries. A semi-finished cured film is prepared though steps of glue-mixing, impregnating, and baking. The semi-finished cured film is pressed with different materials to fabricate various types of polar plate according to applications. Thus, the present invention is characterized in that a composite material is processed with impregnation for fabricating thin electrodes containing supporting materials with thickness controllable. Therein, the fabricated obtains excellent hindrance to the permeation of vanadium ions; vertical-penetration volume resistance is controlled by adjusting the blending ratios of conductive carbonaceous matters; and the demand of conductivity is thus met. Besides, the semi-finished cured film therein is prepared according to conditions to obtain a bi-polar plate, a copper-contained current-collecting plate, or other electrode material like carbon felt, carbon paper, etc. to be combined into an integrated electrode mold. Consequently, different products are obtained with different materials, where the fabrication is simple without using a high-temperature carbonization device and a component cost of flow battery is effectively reduced.

Description

Electrode process for ultra-thin flow batteries

The present invention relates to an electrode manufacturing process for an ultra-thin flow battery, in particular to a thin electrode with a controllable thickness and a supporting material produced by using a composite material impregnation process, in particular, it can be prepared into bipolar plates, containing Copper collector end plates, or combined with other electrode materials to form an integrated electrode mold.

In recent years, with the gradual expansion of the fuel cell application market, the bipolar plate, a key component, has also received increasing attention. The bipolar plate is gradually transformed from the early high-density graphite plate to the composite carbon plate.

The carbon-carbon composite material is made by combining carbon fiber and resin substrate. The Porvair Company worked on the initial slurry casting process, which consisted of carbon fibers (approximately 400 x 10 [mu]m) suspended in a water/phenolic resin mix. The phenolic binder enables the component to be cross-linked and hardened after extruding the characteristic shape of the flow field in the mold, followed by resin carbonization and chemical vapor infiltration (CVI) at high temperature. The purpose of carbonization is to convert the insulating resin into electrical conductivity. of carbon. At the same time of carbonization, the resin substrate will lose a certain proportion of its weight to cause voids. In order to prevent gas leakage caused by pores, a chemical vapor infiltration process is required. This is a process of depositing carbon in a gas-phase chemical reaction at the pores of the material, making the sheet impermeable to reactants and greatly increasing the surface conductivity. The chemical vapor infiltration procedure is to pass the methane-containing gas into the module at 1500°C for thermal cracking reaction, resulting in the deposition of carbon particles on the periphery of the original carbon fiber. Elevating the chemical vapor infiltration process temperature can lead to the pyrolysis of the phenolic binder, resulting in a pure carbon-carbon composite, which improves the Surface conductivity, reducing bulk carbon-carbon composite volume resistivity, as shown in Figure 2. However, this conventional technology uses relatively expensive and complicated chemical vapor infiltration equipment, needs to be fed with argon gas, and the required temperature needs to reach a high temperature of 1350~1500 °C, which is undoubtedly an expensive process solution, and this process can only It is impossible to manufacture a variety of different components when the bipolar plate is obtained, and the manufacturing process is complicated and inflexible, and the production cost is also too high.

In addition, the Republic of China Patent Publication No. I585139 discloses a "resin composition and conductive resin film", which is granulated by a melt-kneader and cooled by a calendering machine or an extruder and a T-film die to obtain a membrane. However, this conventional technique is made with thermoplastic resin, which has poor heat resistance and rigidity, and can only produce one product.

In view of the above-mentioned manufacturing process, either only bipolar plates can be obtained, or only one product can be produced, which cannot solve the problems of lack of flexibility in the manufacturing process, high manufacturing cost and difficulty in mass production. Therefore, ordinary users cannot meet the needs of users in actual use.

The main purpose of the present invention is to overcome the above-mentioned problems encountered in the prior art and provide a semi-finished cured film prepared through the steps of glue mixing, impregnation and baking. Electrode manufacturing process for ultra-thin flow batteries that can produce various types of plates by pressing.

Another object of the present invention is to provide a thin electrode with a controllable thickness and a support material produced by the impregnation process of the composite material, which has an excellent function of blocking the penetration of vanadium ions and can adjust the mixing ratio of conductive carbon to control the longitudinal penetration. Through-volume resistance value, in order to meet the requirements of conductive characteristics of the electrode process for ultra-thin flow batteries.

Another object of the present invention is to provide a semi-finished cured film that can be prepared into bipolar plates, copper-containing current collector end plates, or combined with other electrode materials such as carbon felt, carbon paper, etc. to form an integrated electrode mold according to process conditions. As long as different materials are matched, different products can be obtained. The process is simple and does not require high temperature carbonization equipment, which can effectively reduce the component cost of flow batteries. The electrode process for ultra-thin flow batteries.

30kgf/cm²之壓合壓力，及料溫溫度需大於交聯硬化反應溫度且料溫至少持續110min進行壓合，以取得一成品極板，該成品極板為體積電阻率在10^-1ohm．m或低於10^-1ohm．m之超薄液流電池用之電極。 In order to achieve the above purpose, the present invention relates to an electrode manufacturing process for an ultra-thin flow battery, which at least comprises the following steps: a glue-adjusting step: adding a cross-linking hardener, conductive powder and thermosetting resin, and preparing a colloid according to the weight ratio material, and homogenized and stirred for more than 10min to form a colloidal solution; impregnation step: impregnate a support material in the colloidal solution to control the resin content (RC); baking step: bake and dry the impregnated colloidal solution to The semi-finished cured film is formed; and the lamination step: the semi-finished cured film is laminated according to the required thickness, and then pressed on the gauge.

The pressing pressure of 30kgf/cm ² and the material temperature should be higher than the cross-linking hardening reaction temperature and the material temperature should be pressed for at least 110 minutes to obtain a finished electrode plate with a volume resistivity of 10 ^-1 ohm. . m or less than 10 ^-1 ohm. Electrodes for ultra-thin flow batteries of m.

In the above embodiments of the present invention, the cross-linking hardener is amine, amide, nitrogen-containing heterocyclic organic compound, phenolic, phosphorus-containing group type, acid anhydride type, high nitrogen type composition or a group of the foregoing. 1 or more kinds of composition.

In the above embodiments of the present invention, the amines are dicyandiamide (Dicy), the phenolic compounds are phenol novolac (PN), and the phosphorus-containing group types are 10-oxidation-9, 10-di Oxide-9-epoxy-10-phosphine (9,10-Dihydro-9-oxa-10phosphaphenanthrene10-oxide, DOPO), the anhydride type is styrene-maleic anhydride (SMA), and The high nitrogen type is amino triazine novolac (ATN).

In the above-mentioned embodiment of the present invention, the conductive powder is 95% (inclusive) or more fixed carbon, conductive high-carbon low-ash (1% (inclusive) or below) powder with a particle size (inclusive) or below of 100 mesh (mesh) body composition.

In the above-mentioned embodiment of the present invention, a small amount of carbon nanotubes can be added to the conductive powder to improve the volume resistivity. The carbon nanotubes are single-layer or multi-layer coaxial tubular shapes with a diameter of 0.5-150 nm and a length of 0.1- 250μm carbon fiber (also known as carbon filament, carbon tube, graphite fiber or carbon nanofiber).

In the above embodiments of the present invention, the thermosetting resin is a halogen resin or a non-halogen resin.

In the above-mentioned embodiments of the present invention, the halogen resin is a brominated epoxy resin with a bromine content of 20-50% produced by the reaction of the base epoxy resin with Tetrabromobisphenol A (TBBA).

In the above embodiments of the present invention, the base epoxy resin may be bisphenol A epoxy resin or bisphenol F epoxy resin.

In the above embodiments of the present invention, the non-halogen resin is a basic epoxy resin or a phosphorus-containing epoxy resin, and the phosphorus-containing epoxy resin can be obtained by reacting any basic epoxy resin with an organic cyclic phosphide (HCA). The side chain phosphorus epoxy resin.

In the above embodiments of the present invention, the basic epoxy resin can be bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, and naphthol novolac epoxy resin. Epoxy resin, or bisphenol A novolac type epoxy resin.

其中n為1~30，R₁為H或C₁~C₆之基團，G為下式(2)所示之基團，X為G或下式(3)所示之基團，但至少一X為下式(3)所示之基團，其中DOPO為9,10-二氫-9-噁基-10-磷菲基-10-氧化物(9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide)，且磷氮環氧樹脂之分子量為400~3000：

其中R₂與R₃為H或C₁~C₆之基團。 In the above embodiments of the present invention, the non-halogen resin can be a phosphorus-nitrogen epoxy resin, and the phosphorus-nitrogen epoxy resin is a compound represented by the following formula (1):

wherein n is 1~30, R ₁ is H or a group of C ₁ -C ₆ , G is a group represented by the following formula (2), X is a group represented by G or the following formula (3), but At least one X is a group represented by the following formula (3), wherein DOPO is 9,10-dihydro-9-oxa-10-phosphophenanthrenyl-10-oxide (9,10-dihydro-9-oxa -10-phosphahenanthrene-10-oxide), and the molecular weight of phosphorus nitrogen epoxy resin is 400~3000:

Wherein R ₂ and R ₃ are H or C ₁ -C ₆ groups.

In the above embodiment of the present invention, the support material can be selected from a conductive carbon fiber woven cloth with at least 12,000 filaments in a bundle of carbon fibers, or a glass fiber woven cloth with a cloth basis weight of less than 120 g/m ² .

In the above embodiments of the present invention, the support material can be selected from fine-mesh soft iron mesh or graphite woven cloth.

In the above embodiments of the present invention, the semi-finished cured film can be combined with carbon felt, carbon paper, the finished electrode plate or a combination thereof to form an integrated electrode mold.

In the above embodiments of the present invention, the semi-finished cured film can be prepared into bipolar plates, copper-containing current collector end plates or combined with carbon felt or carbon paper to form an integrated electrode mold according to process conditions.

s11~s14: electrode manufacturing steps

1: Cross-linking hardener

2: Conductive powder

3: Thermosetting resin

4: colloidal solution

5: Support material

6: Aluminum foil or copper foil or electrode material containing release agent

Fig. 1 is a schematic diagram of the preparation process of the plastic electrode plate of the present invention.

Figure 2 is a schematic diagram of a conventional carbon-carbon composite material manufacturing process.

Please refer to "FIG. 1", which is a schematic diagram of the preparation process of the plastic electrode plate of the present invention. As shown in the figure: the present invention is an electrode manufacturing process for an ultra-thin flow battery, which at least comprises the following steps:

Glue mixing step s11 : adding cross-linking hardener 1 , conductive powder 2 and thermosetting resin 3 , preparing a colloidal material according to weight ratio, and stirring uniformly for more than 10 minutes to form a colloidal solution 4 .

Impregnation step s12 : impregnating a support material 5 in the colloid solution 4 to control the resin content (RC).

Baking step s13 : baking and drying the impregnated colloid solution to form a semi-finished cured film.

30kgf/cm²之壓合壓力，及料溫溫度需大於交聯硬化反應溫度且料溫至少持續110min進行壓合，以取得一成品極板，該成品極板為體積電阻率在10^-1ohm．m或低於10^-1ohm．m之超薄液流電池用之電極。如是，藉由上述揭露之流程構成一全新之超薄液流電池用電極製程。 Lamination step s14: Laminate the semi-finished cured film according to the required thickness, and press the semi-finished film on the gauge.

The pressing pressure of 30kgf/cm ² and the material temperature should be higher than the cross-linking hardening reaction temperature and the material temperature should be pressed for at least 110 minutes to obtain a finished electrode plate with a volume resistivity of 10 ^-1 ohm. . m or less than 10 ^-1 ohm. Electrodes for ultra-thin flow batteries of m. In this way, a brand-new electrode fabrication process for ultra-thin flow batteries is formed by the above disclosed process.

The above-mentioned combined hardeners are composed of amines, amides, nitrogen-containing heterocyclic organic compounds, phenolic, phosphorus-containing group-type, acid anhydride-type, high-nitrogen-type compositions or one or more of the aforementioned groups; and The amine is dicyandiamide (Dicy), the phenolic is phenol novolac (PN), The phosphorus-containing group type is 10-oxidation-9, 10-dioxide-9-epoxy-10-phosphaphenanthrene (9,10-Dihydro-9-oxa-10phosphaphenanthrene10-oxide, DOPO), and the acid anhydride type is benzene Ethylene maleic anhydride copolymer (styrene-maleic anhydride, SMA), and the high nitrogen type is amino triazine novolac (ATN).

The above-mentioned conductive powder is above 95% (inclusive) fixed carbon, 100 mesh (mesh) particle size (inclusive) or less conductive high carbon low ash content (1% (inclusive) or less) powder composition, and further A small amount of carbon nanotubes can be added to improve the volume resistivity. The carbon nanotubes refer to single-layer or multi-layer coaxial tubular carbon fibers with a diameter of 0.5~150nm and a length of 0.1~250μm, also known as carbon filaments and carbon tubes. , graphite fiber or carbon nanofiber, etc.

其中n為1~30，R1為H或C₁~C₆之基團，G為下式(2)所示之基團，X為G或下式(3)所示之基團，但至少一X為下式(3)所示之基團，其中DOPO為9,10-二氫-9-噁基-10-磷菲基-10-氧化物(9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide)，且磷氮環氧樹脂之分子量為400~3000：

其中R₂與R₃為H或C₁~C₆之基團。典型的環氧熱固型樹脂的結構式如下：

The above-mentioned thermosetting resins are halogen resins or non-halogen resins. Wherein, the halogen resin is a base epoxy resin reacted with Tetrabromobisphenol A (TBBA) to produce a brominated epoxy resin with a bromine content of 20-50%, and the base epoxy resin can be a bisphenol A type epoxy resin Resin, or bisphenol F-type epoxy resin; the non-halogen resin is a base epoxy resin or a phosphorus-containing epoxy resin, and the phosphorus-containing epoxy resin can be carried out using any base epoxy resin and organic cyclic phosphide (HCA) The side chain phosphorus-containing epoxy resin obtained by the reaction, and the basic epoxy resin can be bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin , Naphthol novolac epoxy resin, or bisphenol A novolac epoxy resin, etc., which can be reacted with organic cyclic phosphide (HCA) to obtain a side chain phosphorus-containing epoxy resin. Further, the non-halogen resin can be a phosphorus-nitrogen epoxy resin, and the phosphorus-nitrogen epoxy resin is a compound represented by the following formula (1):

wherein n is 1~30, R1 is H or a group of C ₁ -C ₆ , G is a group represented by the following formula (2), X is a group represented by G or the following formula (3), but at least -X is a group represented by the following formula (3), wherein DOPO is 9,10-dihydro-9-oxa-10-phosphophenanthrenyl-10-oxide (9,10-dihydro-9-oxa- 10-phosphahenanthrene-10-oxide), and the molecular weight of phosphorus nitrogen epoxy resin is 400~3000:

Wherein R ₂ and R ₃ are H or C ₁ -C ₆ groups. The structural formula of a typical epoxy thermosetting resin is as follows:

Epoxy thermosetting resins have many properties due to structural factors:

1. Strong adhesion: After the epoxy thermosetting resin reacts with amines, hydroxyl groups, ether bonds and extremely active epoxy groups will be generated in the structure. These structures can make the molecules of the epoxy thermosetting resin and the adjacent ones. The interface produces chemical bonds, especially the epoxy group can produce cross-linking polymerization under the action of the hardener to form a three-way network structure macromolecule, so that the molecule itself maintains a certain cohesion.

2. Good mechanical strength: The hardened epoxy thermosetting resin has strong cohesion, which makes the molecular structure very closely arranged, so its mechanical strength is relatively higher than other resins.

3. Good stability and processing performance: Epoxy thermosetting resin does not produce volatile substances when hardened and has high chemical stability, which can be suitable for many different processing conditions. And after hardening, the main chain of epoxy thermosetting resin is formed by three-way cross-linking of ether bond and benzene ring, so it is resistant to acid and alkali, and its performance is better than that of phenolic resin and polyester resin.

4. Good heat resistance: The cured product of epoxy thermosetting resin can generally be heat resistant to about 100℃, and the resin of special heat resistance grade can be heat resistant to above 200℃.

5. Good electrical insulation: The hardened epoxy thermosetting resin has low water absorption and no longer has active groups and free ions, so it has excellent electrical insulation.

6. Low hardening shrinkage: The hardening process of epoxy thermosetting resins mainly relies on the ring-opening addition polymerization of epoxy groups, so low molecular weight products will not be produced during the hardening process, and due to the intermolecular hydrogen bonds. Therefore, the curing shrinkage of epoxy thermosetting resin is the lowest among all thermosetting resin types. Common resin types include phenolic resin, silicone resin, polyester resin and epoxy resin.

The hardeners of epoxy thermosetting resins are classified as follows according to the reaction mechanism and hardening temperature:

1. According to the classification of response agencies

(1) Catalysts, such as tertiary amines, boron trifluoride-amine complexes, etc.

(2) Those that react with epoxy thermosetting resin functional groups, such as amines, acid anhydrides, cyanate esters, etc.

2. According to the hardening reaction temperature classification: Generally speaking, using a hardener with a high hardening temperature can obtain a more heat-resistant hardened product.

(1) Hardening at room temperature, for example: polyamide resin, diethylene triamine, etc.

(2) Medium temperature hardening, for example: diethyl amino propyl amine (diethyl amino propyl amine) and the like.

(3) High temperature hardening, such as dicyandiamide, cyanate ester, etc.

The thermosetting resin of the present invention is an epoxy thermosetting resin. When it is uniformly mixed with a cross-linking hardener in a certain proportion to produce a cross-linking reaction and hardening, it will form a three-dimensional network structure, so it has special physical properties, Chemical properties, mechanical properties, heat resistance, insulation, and bonding, anti-corrosion, forming and other functions, so epoxy resin materials are not only used in the field of science and technology, such as: coating, bonding, insulation, civil construction materials and die casting Various electronic devices, integrated circuit packaging materials and circuit boards are also in the field of advanced technology, such as packaging and composite materials for electronics and aerospace.

The above-mentioned supporting material can be selected from fine mesh soft iron mesh, fine mesh soft carbon mesh, conductive carbon fiber woven cloth or glass fiber woven cloth. Among them, the conductive carbon fiber woven cloth refers to carbon fiber cloth>12K, that is, there are at least 12,000 monofilaments in a bundle of carbon fibers, which can ensure the excellent electrical conductivity, and the glass fiber woven cloth refers to the cloth basis weight of less than 120g/ m ² .

The semi-finished cured film mentioned above can be combined with carbon felt, carbon paper, the finished electrode plate or a combination thereof to form an integrated electrode mold, and the semi-finished cured film can be prepared into bipolar plates and copper-containing current collector end plates according to process conditions .

When using, add cross-linking hardener, conductive high-carbon low-ash powder composition and thermosetting resin, mix the aforementioned materials into a colloidal material according to the weight ratio, and homogenously stir for more than 10 minutes to form a colloidal solution.

The colloidal solution is introduced into an impregnation tank, and the conductive carbon cloth or glass cloth is introduced into the impregnation tank as a support material, so that the colloidal solution is attached to the support material.

The support material and the colloid solution attached to it are baked and dried to form a semi-finished cured film.

10^-1ohm．m即完成一超薄液流電池用的電極。 The heat-resistant aluminum foil or copper foil containing release agent can be selected to be laminated with the semi-finished cured film according to the required thickness. The pressure of the gauge pressure is >30kgf/ ^cm2 , and the material temperature should be higher than the cross-linking hardening reaction temperature and the material temperature. Lamination is carried out in an environment that lasts for at least 110 minutes. After pressing, the finished electrode plate is obtained. After volume resistivity measurement, as long as

^10-1 ohm. m is to complete an electrode for an ultra-thin flow battery.

When specifically prepared, the above-mentioned semi-finished cured film can be used to produce various types of polar plates, including:

Application of the first embodiment: The semi-finished cured film and carbon felt are pressed together to form an integrated thin electrode plate containing carbon felt.

Application of the second embodiment: The semi-finished cured film and carbon paper are pressed together to form a carbon-paper integrated thin polar plate.

Application of the third embodiment: The finished electrode plate containing copper foil on one side, the semi-finished cured film and the carbon felt are pressed together to form an integrated thin electrode plate containing carbon felt (end plate application).

The application of the fourth embodiment: The finished electrode plate containing copper foil on one side, the semi-finished cured film and the carbon paper are pressed together to form an integrated thin electrode plate containing carbon paper (end plate application).

In this way, the present invention uses the composite material impregnation process to produce thin electrodes with controllable thickness and supporting materials, and prepares excellent functions of blocking vanadium ion penetration and can adjust the mixing ratio of conductive carbonaceous materials to control the longitudinal penetration volume resistance value, so as to achieve Meet the electrical conductivity requirements. In addition, the semi-finished cured film can be prepared into bipolar plates, copper-containing current collector end plates, or combined with other electrode materials such as carbon felt, carbon paper, etc. to form an integrated mold according to the process conditions. For different products, the process is simple and does not require high-temperature carbonization equipment, which can effectively reduce the component cost of flow batteries.

To sum up, the present invention is an electrode manufacturing process for ultra-thin flow batteries, which can effectively improve various shortcomings of conventional methods. The composite material impregnation process is used to produce thin electrodes with controllable thickness and supporting materials. It has excellent function of blocking vanadium ion penetration and can adjust the proportion of conductive carbonaceous material to control the volume resistance value of vertical penetration to meet the requirements of conductive characteristics, and the semi-finished cured film can be prepared into bipolar plates according to the process conditions , copper-containing collector end plates, or combined with other electrode materials such as carbon felt, carbon paper, etc. to form an integrated electrode mold, thereby making the invention more advanced, more practical, and more in line with the needs of users. If the requirements for an invention patent application are met, a patent application may be filed in accordance with the law.

However, the above are only preferred embodiments of the present invention, and should not limit the scope of implementation of the present invention; therefore, any simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the contents of the description of the invention , shall still fall within the scope covered by the patent of the present invention.

s11~s14: electrode manufacturing steps

1: Cross-linking hardener

2: Conductive powder

3: Thermosetting resin

4: colloidal solution

5: Support material

6: Aluminum foil or copper foil or electrode material containing release agent

Claims (14)

An electrode manufacturing process for an ultra-thin flow battery, which at least comprises the following steps: a glue-adjusting step: adding a cross-linking hardener, a conductive powder and a thermosetting resin, preparing a colloidal material according to the weight ratio, and stirring uniformly for more than 10 minutes to form a A colloidal solution, wherein the conductive powder is a combination of 95% (inclusive) or more of fixed carbon and 100 mesh (mesh) particle size (inclusive) or less of conductive high-carbon and low ash content (1% (inclusive) or less) powder combination carbon nanotubes, which are single-layer or multi-layer coaxial tubular carbon fibers with diameters ranging from 0.5 to 150 nm and lengths of 0.1 to 250 μm (also known as carbon filaments, carbon tubes, and graphite fibers). or carbon nanofibers); impregnation step: impregnating a support material in the colloidal solution for Resin Content (RC) control; baking step: baking and drying the impregnated colloidal solution to form a semi-finished cured film; and Lamination step: Laminate the semi-finished cured film according to the required thickness, and press it on the gauge.

The pressing pressure of 30kgf/cm ² and the material temperature should be higher than the cross-linking hardening reaction temperature and the material temperature should be pressed for at least 110 minutes to obtain a finished electrode plate with a volume resistivity of 10 ^-1 ohm. . m or less than 10 ^-1 ohm. Electrodes for ultra-thin flow batteries of m. According to the electrode manufacturing process for ultra-thin liquid flow battery described in the first item of the claimed scope, the cross-linking hardener is amine, amide, nitrogen-containing heterocyclic organic compound, phenolic, phosphorus-containing group type, acid anhydride type, high nitrogen type composition, or one or more of the above-mentioned groups. According to the electrode manufacturing process for ultra-thin flow battery described in item 2 of the scope of the patent application, the amine is dicyandiamide (Dicy), the phenolic is phenol novolac (PN), and the phosphorus-containing The group type is 10-oxidation-9, 10-dioxide-9-epoxy-10-phosphaphenanthrene (9,10-Dihydro-9-oxa-10phosphaphenanthrene10-oxide, DOPO), the anhydride type is styrene maleate Acid anhydride copolymer (styrene-maleic anhydride, SMA), and the high nitrogen type is amino triazine Phenolic resin (amino triazine novolac, ATN). According to the electrode manufacturing process for the ultra-thin flow battery according to the first item of the claimed scope, the thermosetting resin is a halogen resin or a non-halogen resin. According to the electrode manufacturing process for ultra-thin flow battery described in item 4 of the scope of the patent application, wherein the halogen resin is a base epoxy resin reacted with Tetrabromobisphenol A (TBBA) to produce a bromine content of 20-50%. Brominated epoxy resin. According to the electrode manufacturing process for ultra-thin liquid flow battery described in item 5 of the claimed scope, the base epoxy resin is bisphenol A type epoxy resin or bisphenol F type epoxy resin. According to the electrode manufacturing process for ultra-thin flow battery as described in item 4 of the scope of the patent application, the non-halogen resin is a basic epoxy resin or a phosphorus-containing epoxy resin, and the phosphorus-containing epoxy resin is made of the basic epoxy resin and the phosphorus-containing epoxy resin. The side chain phosphorus-containing epoxy resin obtained by the reaction of organic cyclic phosphide (HCA). According to the electrode manufacturing process for ultra-thin liquid flow battery described in item 7 of the patent application scope, the basic epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Cresol novolac epoxy resin, naphthol novolac epoxy resin, or bisphenol A novolac epoxy resin. According to the electrode manufacturing process for ultra-thin flow battery described in item 4 of the claimed scope, the non-halogen resin is a phosphorus-nitrogen epoxy resin, and the phosphorus-nitrogen epoxy resin is a compound represented by the following formula (1):

wherein n is 1~30, R ₁ is H or a group of C ₁ -C ₆ , G is a group represented by the following formula (2), X is a group represented by G or the following formula (3), but At least one X is a group represented by the following formula (3), wherein DOPO is 9,10-dihydro-9-oxa-10-phosphophenanthrenyl-10-oxide (9,10-dihydro-9-oxa -10-phosphahenanthrene-10-oxide), and the molecular weight of phosphorus nitrogen epoxy resin is 400~3000:

Wherein R ₂ and R ₃ are H or C ₁ -C ₆ groups. According to the electrode manufacturing process for ultra-thin flow battery described in item 1 of the scope of the patent application, the support material can be selected from a conductive carbon fiber woven cloth with at least 12,000 monofilaments in a bundle of carbon fibers, or a cloth with a low base weight Glass fiber woven cloth at 120g/ ^m2 . According to the electrode manufacturing process for ultra-thin liquid flow battery as described in item 1 of the claimed scope, the support material can be selected from fine-mesh soft iron mesh or graphite woven cloth. According to the electrode manufacturing process for ultra-thin flow battery described in item 1 of the scope of the patent application, the finished electrode plate can be a electrode plate without copper foil or a electrode plate containing copper foil on one side. According to the electrode manufacturing process for ultra-thin flow battery described in item 1 of the scope of the patent application, the semi-finished cured film can be combined with carbon felt, carbon paper, the finished electrode plate or a combination thereof to form an integrated mold. According to the manufacturing process of electrodes for ultra-thin flow batteries as described in item 1 or 13 of the scope of the patent application, the semi-finished cured film can be prepared into bipolar plates, copper-containing current collector end plates, or carbon felt or Carbon paper is combined into an integrated electrode mold.

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