CN102738474B - Composite porous electrode, single cell and cell stack containing same and preparation method thereof - Google Patents
Composite porous electrode, single cell and cell stack containing same and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a composite porous electrode, a single cell and cell stack containing the same and a preparation method thereof. The composite porous electrode comprises a porous electrode body and an intensified part distributed in the porous electrode body, wherein the bending resistance of the intensified part is superior to that of the porous electrode body, and the intensified part is penetrated through the porous electrode body along the thickness direction of the porous electrode body. After assembling the porous electrode body and the intensified part having better bending resistance than the porous electrode body to form the composite porous electrode, the composite porous electrode has conductivity and a porous structure, and simultaneously, the rigidity and modulus thereof are also increased. In case of the combination with a collection plate or pole plate, a favorable interfacial combination with the collection plate or pole plate can be achieved by controlling the composite porous electrode to produce a small compression amount, so that the contact resistance in between can be reduced, thereby not affecting the penetration and diffusion of the electrolyte in the composite porous electrode and the smooth implementation of the redox reaction, and ensuring lower contact resistance between the composite porous electrode and the collection plate or pole plate.
Description
Technical Field
The invention relates to the field of flow batteries, in particular to a composite porous electrode, a single cell and a cell stack containing the composite porous electrode and a preparation method of the composite porous electrode.
Background
Vanadium ion V is respectively used for all-vanadium redox flow batteries2+/V3+And V4+/V5+As a positive and negative electrode redox couple of the battery, positive and negative electrolytes are respectively stored in two liquid storage tanks, and an acid-proof liquid pump drives the active electrolyte to a reaction site (battery stack) and then returns to the liquid storage tanks to form a circulating liquid flow loop so as to realize the charging and discharging process. In an all-vanadium redox flow battery energy storage system, the charge and discharge performance, particularly the charge and discharge power and efficiency, of the whole system is determined by the performance of a battery stack. The cell stack is formed by sequentially stacking and pressing a plurality of single cells in series. The composition of a conventional flow cell is shown in fig. 1. The liquid flow frame is 1 ', the current collecting plate is 2 ', the porous electrode is 3 ', the diaphragm is 4 ', each component forms a single cell, and the cell stack 5 ' is formed by stacking N single cells.
The all-vanadium redox flow battery stores charges and supplies power to the outside through electrochemical redox reaction of electrolyte, wherein a porous electrode with a large specific surface area is a place for redox reaction of the electrolyte and is an area for generating electrons and protons, so that the performance of the porous electrode has great influence on the charge and discharge efficiency of the vanadium redox flow battery. When the porous electrode and the current collector are combined, the porous electrode is a sponge-like porous carbon material, so that the porosity is high, the hardness is low, the elasticity is certain, and a large contact resistance can be generated between the porous electrode and the current collector. Therefore, a certain pressure is generally required to be applied to make the porous electrode and the current collecting plate tightly attached and well contacted, but when the pressure is applied, the porous electrode is compressed in the force-receiving direction, the pore diameter of the porous electrode is reduced after the compression, the porosity is reduced, and the smooth progress of the permeation diffusion and the oxidation-reduction reaction of the electrolyte is influenced, so a balance value is required to be found between the compression amount of the porous electrode and the contact resistance between the porous electrode and the current collecting plate, namely, the contact resistance between the porous electrode and the current collecting plate is reduced as far as possible under the conditions that the pore diameter and the porosity of the porous electrode are not excessively reduced, and the permeation and the diffusion of the electrolyte are not influenced. However, the porous electrode is generally low in hardness and fluffy, and even if the compression amount is large in practical use, the contact resistance between the porous electrode and the current collecting plate is still large, which is a large loss on the charge and discharge efficiency of the vanadium battery.
Disclosure of Invention
The invention provides a composite porous electrode, a single cell and a cell stack containing the composite porous electrode and a preparation method of the composite porous electrode, which are used for solving the problem that the porosity and hardness of the porous electrode in the prior art are difficult to balance.
According to an aspect of the present invention, there is provided a composite porous electrode including a porous electrode body and reinforcing portions distributed in the porous electrode body and having superior bending resistance to the porous electrode body, the reinforcing portions penetrating the porous electrode body in a thickness direction of the porous electrode body.
Further, the porous electrode body and the reinforcing portion are integrally formed, and the reinforcing portion is formed by forming a resin layer on the inner wall of the pores in a partial region of the porous electrode body.
Further, the porous electrode body is provided with scattered installation through holes, the reinforcing part is in interference fit with the installation through holes, and the reinforcing part is made by forming a resin layer on the inner walls of pores of the porous material; or the reinforcing part is made of one of the group consisting of foamed polyurethane, foamed polyvinyl chloride and foamed polyethylene.
Further, when the reinforcement part is formed by forming a resin layer in the inner walls of pores of the porous electrode body or by forming a resin layer on the inner walls of pores in a partial region of the porous material, the total weight of the resin layer is 1 to 99% of the total weight of the reinforcement part.
Further, the resin layer is formed by a thermoplastic resin composition or a thermosetting resin composition, wherein the thermoplastic resin composition comprises a thermoplastic resin and an auxiliary material with the weight content of 0-25% of the thermoplastic resin composition; or the thermosetting resin composition comprises thermosetting resin and auxiliary materials with the weight content of 0-25% of the thermosetting resin composition.
Furthermore, the auxiliary materials are reinforcing components and/or functional components, the reinforcing components are inorganic silicate particles, short fibers or montmorillonite, and the functional components are carbon black and carbon nano tubes.
Further, the total volume of the reinforced parts is less than half of the total volume of the composite porous electrode.
According to another aspect of the present invention, there is also provided a method of manufacturing the above-described composite porous electrode, when the composite porous electrode includes the porous electrode body and the reinforcing portion which are integrally formed, the method including the steps of: a1, dividing a plurality of areas to be formed with strengthening parts in the porous electrode body as strengthening part matrixes; and A2, impregnating a resin material into the internal pores of the reinforcement part matrix, and adhering a resin layer on the inner walls of the pores of the reinforcement part matrix to form a reinforcement part, thereby obtaining the composite porous electrode; or when the composite porous electrode comprises the porous electrode body and the strengthening part which are separately arranged, the preparation method comprises the following steps: b1, dividing a plurality of areas to be formed with the strengthening parts in the porous electrode body, and forming mounting through holes for mounting the strengthening parts in the areas; b2, impregnating a resin material into the internal pores of the matrix of the reinforcing part, adhering a resin layer on the inner walls of the pores of the matrix, and manufacturing the matrix adhered with the resin layer on the inner walls of the pores into the reinforcing part with the volume same as the internal volume of the mounting through hole; b3, embedding the reinforcing part into the mounting through hole, and attaching the reinforcing part to the inner wall of the mounting through hole to obtain the composite porous electrode; or when the composite porous electrode comprises the porous electrode body and the reinforcing part which are separately arranged, the preparation method comprises the following steps: c1, dividing a plurality of areas of the reinforcing part to be formed in the porous electrode body and forming mounting through holes for mounting the reinforcing part in the areas; c2, manufacturing one of the group consisting of porous polyurethane resin, porous PVC resin and porous PE resin into a reinforced part with the volume same as the internal volume of the installation through hole; and C3, embedding the reinforcing part into the mounting through hole, and adhering the reinforcing part to the inner wall of the mounting through hole to obtain the composite porous electrode.
Further, the resin material is a thermoplastic resin composition or a thermosetting resin composition, and the thermoplastic resin composition comprises a thermoplastic resin polymer and an auxiliary material with the weight content of 0-25% of the thermoplastic resin composition; or the thermosetting resin composition comprises a thermosetting resin polymer and an auxiliary material with the weight content of 0-25% of the thermosetting resin composition; the preparation method comprises the following steps of A2 or B2: s11, heating the resin material to form a resin material melt; s12, soaking the resin material melt into the pores of the strengthening part matrix; and S13, solidifying the resin material melt to form the reinforced part with the resin layer on the inner wall of the pore of the reinforced part matrix.
Further, the resin material is a thermoplastic resin composition, and the thermoplastic resin composition comprises a thermoplastic resin polymer and an auxiliary material with the weight content of 0-25% of the composition; the preparation method comprises the following steps of A2 or B2: s21, dissolving the resin material in a solvent to form a resin material solution with the mass concentration of the resin material being 0.5-20%; s22, impregnating the resin material solution into the pores of the reinforcing part base body; and S23, volatilizing the solvent in the reinforced part matrix, and adhering the resin material on the inner wall of the pore of the reinforced part matrix to form the reinforced part with the resin layer.
Further, the resin material is a monomer or prepolymer composition, and comprises: one of a thermoplastic resin monomer, a thermoplastic resin prepolymer, a thermosetting resin monomer or a thermosetting resin prepolymer, and an auxiliary material with the weight content of 0-25% of the monomer or prepolymer composition; the preparation method comprises the following steps of A2 or B2: s31, heating the monomer or prepolymer composition to form a monomer or prepolymer composition melt; s32, soaking the monomer or prepolymer composition into the pores of the strengthening part substrate; s33, carrying out polymerization reaction between monomers in the pores of the reinforced part matrix or between monomers of the prepolymer composition melt or between prepolymers to form a polymer; and S34, solidifying the polymer to form the reinforced part with the resin layer on the inner wall of the pore of the reinforced part matrix.
Further, when the monomer or prepolymer composition contains a thermoplastic resin monomer or prepolymer, step S31 further includes a step of adding an initiator in an amount of 0.1% to 1% to the resin monomer or prepolymer composition; when the monomer or prepolymer composition contains a thermosetting resin monomer or prepolymer, step S31 further includes the step of adding 0.1% to 1% of a catalyst and/or a curing agent to the resin monomer or prepolymer composition.
Further, the resin material is a monomer or prepolymer composition, and the monomer or prepolymer composition comprises: a thermoplastic resin monomer or a thermoplastic resin prepolymer or a thermosetting resin monomer or a thermosetting resin prepolymer and an auxiliary material with the weight content of 0-25% of the monomer or prepolymer composition; the preparation method comprises the following steps of A2 or B2: s41, dissolving the monomer or prepolymer composition in a solvent to form a monomer or prepolymer composition solution with the mass concentration of 0.5-20%; s42, dipping the monomer or prepolymer composition solution into the pores of the strengthening part matrix; s43, carrying out polymerization reaction between monomers in the pores of the reinforced part matrix or between monomers of the prepolymer composition solution or between the prepolymers to form a polymer; and S44, volatilizing the solvent, the unreacted monomer and the unreacted prepolymer in the reinforcement matrix, and curing the polymer on the inner walls of the pores of the reinforcement matrix to form the reinforcement having the resin layer.
Further, when the monomer or prepolymer composition contains a thermoplastic resin monomer or prepolymer, step S41 further includes dissolving an initiator and the monomer or prepolymer composition together in a solvent to form a monomer or prepolymer composition solution; when the monomer or prepolymer composition contains a thermosetting resin monomer or prepolymer, step S41 further includes dissolving the catalyst and/or the curing agent and the monomer or prepolymer composition together in a solvent to form a monomer or prepolymer composition solution.
Furthermore, the auxiliary materials are reinforcing components and/or functional components, the reinforcing components are inorganic silicate particles, short fibers or montmorillonite, and the functional components are carbon black and carbon nano tubes.
According to yet another aspect of the invention there is provided a liquid flow cell comprising a porous electrode and a current collector plate, the porous electrode being the composite porous electrode described above.
According to yet another aspect of the invention, a flow battery stack is also provided, comprising at least one flow cell, wherein the flow cell comprises the composite porous electrode.
When the compound porous electrode is formed by assembling the porous strengthening part with bending resistance superior to that of the porous electrode body and the porous electrode body, the compound porous electrode has conductivity and a porous structure, meanwhile, the strengthening part plays a skeleton supporting role for the compound porous electrode, the hardness and modulus of the porous electrode body are improved, and when the compound porous electrode is combined with the current collecting plate or the polar plate, the compound porous electrode can be well combined with the current collecting plate or the polar plate under the condition that the current collecting plate or the polar plate can generate a small compression amount under control, so that the contact resistance between the current collecting plate and the polar plate is reduced, the smooth proceeding of the permeation diffusion and the oxidation reduction reaction of the electrolyte in the compound porous electrode is not influenced, and the effect of the lower contact resistance between the compound porous electrode and the current collecting plate or the polar plate can be ensured.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, illustrate preferred embodiments of the invention and together with the description serve to explain the principle of the invention. In the figure:
FIG. 1 shows a schematic of a cell and cell stack assembly as commonly used in the prior art;
FIG. 2 shows a schematic view of a prior art porous electrode and collector plate assembly;
FIG. 3 illustrates a cross-sectional view of a composite porous electrode according to an embodiment of the invention; and
fig. 4 shows a schematic view of the assembly of a composite porous electrode with a current collector plate according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail below with reference to the drawings in the embodiments of the present invention, but the following embodiments and drawings are only used for understanding the present invention, and do not limit the present invention, and the present invention can be implemented in various ways as defined and covered by the claims.
In an exemplary embodiment of the present invention, a composite porous electrode is provided, as shown in fig. 3, the composite porous electrode 3 includes a porous electrode body 31 and reinforcing portions 33 distributed in the porous electrode body 31 and having superior bending resistance to the porous electrode body 31, the reinforcing portions 33 penetrating the porous electrode body 31 in a thickness direction of the porous electrode body 31.
When the porous strengthening part 33 with bending resistance superior to that of the porous electrode body 31 and the porous electrode body 31 are assembled to form the composite porous electrode 3, the composite porous electrode 3 has conductivity and a porous structure, and the strengthening part 33 plays a skeleton supporting role for the composite porous electrode 3, so that the hardness and modulus of the porous electrode body 31 are improved, and when the composite porous electrode 3 is combined with the current collecting plate 2 or the polar plate, the composite porous electrode can be controlled to generate a smaller compression amount, as shown in fig. 4, the composite porous electrode can be well combined with the current collecting plate 2 or the polar plate, so that the contact resistance between the two is reduced, and the effects of not affecting the smooth permeation diffusion and oxidation reduction reaction of electrolyte in the composite porous electrode 3 and ensuring that the composite porous electrode 3 and the current collecting plate 2 or the polar plate have lower contact resistance are achieved.
In a preferred embodiment of the present invention, the porous electrode body 31 and the reinforcing portion 33 are integrally formed, and the reinforcing portion 33 is formed by forming a resin layer on the inner wall of the pores in a partial region of the porous electrode body 31. Some areas are defined on the porous electrode body 31 as formation areas of the reinforcing portion 33, and a resin layer is formed on the inner walls of the pores in the areas, thereby obtaining the reinforcing portion 33 having a bending strength greater than that of the porous electrode body 31. When the electrolyte flows through the inside of the integrally formed composite porous electrode 3, the contact resistance with the collector plate 2 is reduced, and the resistance received by the inside of the composite porous electrode 3 is also small.
In a preferred embodiment of the present invention, the porous electrode body 31 is provided with scattered mounting through-holes, the reinforcing portion 33 is interference-fitted with the mounting through-holes, and the reinforcing portion 33 is made by forming a resin layer on the inner walls of pores of the porous material; or the reinforcing part 33 is made of one of the group consisting of foamed polyurethane, foamed polyvinyl chloride, and foamed polyethylene. The porous electrode body 31 and the reinforcing part 33 are separately provided, and the reinforcing part 33 is provided in the mounting through hole of the porous electrode body 31 to be in interference fit with each other, so that the compression amount of the composite porous electrode 3 and the contact resistance with the current collecting plate 2 during assembly can be reduced, furthermore, this combination of the composite porous electrode 3 allows the reinforcing portion 33 to be fabricated separately, and the porous material for making the reinforcement part 33 has various choices, and may be one of the same material as the porous electrode body 31, and may also be one of the group consisting of conventional materials in the prior art such as foamed polyurethane, foamed polyvinyl chloride, foamed polyethylene, as long as the porous material satisfying the bending resistance of the reinforcement part 33 superior to that of the porous electrode body 31 can be used in the present invention, of course, the reinforcing portion 33, which is a part of the composite porous electrode 3, must also have electrolyte corrosion resistance.
Preferably, when the reinforcement part 33 is made by forming a resin layer on the inner walls of the pores in a partial region of the porous electrode body 31, or when the reinforcement part is made by forming a resin layer in the inner walls of the pores of the porous material, the total weight of the resin layer is 1 to 99% of the total weight of the reinforcement part 33. When the reinforcing part 33 is made of the same material as the porous electrode body 31, the weight of the resin layer as a part of the reinforcing part 33 is controlled to be within 1 to 99% of the total weight of the reinforcing part 33, so that the composite porous electrode 3 can be supported, and the electrolyte can flow through the reinforcing part 33 while maintaining the porous property.
In the composite porous electrode, the resin layer is formed by a thermoplastic resin composition or a thermosetting resin composition, and the thermoplastic resin composition comprises a thermoplastic resin and an auxiliary material with the weight content of 0-25% of the thermoplastic resin composition; or the thermosetting resin composition comprises thermosetting resin and auxiliary materials with the weight content of 0-25% of the thermosetting resin composition.
The group of thermoplastic resins useful in the present invention include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyetheretherketone; thermosetting resins useful in the present invention include, but are not limited to, epoxy resins, polyurethanes, phenolic resins, urea-formaldehyde resins, polyimides; in order to further enhance the supporting effect of the resin layer or reduce the influence of the resin layer on the performance of the composite porous electrode 3, an auxiliary material may be mixed into the thermoplastic resin or the thermosetting resin, and the weight of the auxiliary material is generally controlled to be less than 25% of the total weight of the composition, so as to avoid affecting the curing of the resin.
Preferably, the auxiliary material in the above embodiment is a reinforcing component and/or a functional component, the reinforcing component is inorganic silicate particles, short fibers or montmorillonite, and the functional component is carbon black or carbon nanotubes. The reinforcing component serves to further enhance the bending resistance of the reinforcing portion 33, and the functional component serves to compensate for the defect of the decrease in the electrical conductivity of the composite porous electrode 3 caused by the non-conductive substance such as resin.
The reinforcing portion 33 of the present invention is provided mainly for enhancing the bending resistance of the composite porous electrode 3, but the reinforcing portion 33 improves the bending resistance and has a certain adverse effect on the porosity inside the composite porous electrode 3, and therefore, in order to balance the porosity and the bending resistance and to obtain a good charge/discharge efficiency, the total volume of the reinforcing portion 33 is less than half of the total volume of the composite porous electrode 3.
In another exemplary embodiment of the present invention, there is also provided a method of manufacturing the composite porous electrode of the present invention, when the composite porous electrode includes the porous electrode body 31 and the reinforcement portion 33 which are integrally formed, the method including the steps of: a1, dividing the region in the porous electrode body 31 where the reinforcement 33 is to be formed as a reinforcement base; and a2, impregnating a resin material into the internal pores of the reinforcement base, and adhering a resin layer to the inner walls of the pores of the reinforcement base to form the reinforcement 33, thereby obtaining a composite porous electrode 3; or when the composite porous electrode 3 includes the porous electrode body 31 and the reinforcing part 33 which are separately provided, the preparation method includes the steps of: b1, dividing a plurality of regions where the reinforcing parts 33 are to be formed in the porous electrode body 31, and forming mounting through holes for mounting the reinforcing parts 33 in the regions; b2, impregnating a resin material into the internal pores of the matrix of the reinforcing part 33, adhering a resin layer to the inner walls of the pores of the matrix, and forming the matrix with the resin layer adhered to the inner walls of the pores into the reinforcing part 33 having the same volume as the internal volume of the mounting through hole; b3, embedding the reinforcing part 33 into the installation through hole, and adhering the reinforcing part 33 to the inner wall of the installation through hole to obtain the composite porous electrode 3; or when the composite porous electrode 3 includes the porous electrode body 31 and the reinforcing part 33 which are separately provided, the preparation method includes: c1, dividing a plurality of areas where the reinforcing parts 33 are to be formed in the porous electrode body 31, and forming mounting through holes for mounting the reinforcing parts 33 in the areas; c2, manufacturing one of the group consisting of porous polyurethane resin, porous PVC resin and porous PE resin into a reinforced part 33 having the same volume as the internal volume of the mounting through hole; and C3, fitting the reinforcing part 33 into the mounting through-hole, and bonding the reinforcing part 33 to the inner wall of the mounting through-hole to obtain the composite porous electrode 3.
By forming a plurality of scattered regions on the porous electrode body 31 as regions where reinforcing part bases of the reinforcing parts are located and installing the reinforcing parts 33 in the regions, the entire porous electrode body 31 can be supported regardless of whether the reinforcing parts 33 are provided integrally with the porous electrode body 31 or separately.
When both are integrally provided, a method of impregnating the resin material into the internal pores of the porous electrode body 31 by an impregnation method is easily realized, such as placing the porous electrode body 3 vertically and horizontally in the thickness direction, placing the resin material at the upper end of the reinforcement base and gradually impregnating it into the pores inside the reinforcement base by the gravity of the resin material; in order to accelerate the impregnation speed, the two ends of the reinforced part matrix are connected with pipelines with the same shape, resin materials are introduced from one end of the pipeline and pressurized, the other end of the pipeline is vacuumized, the pipelines on the two sides form a large pressure difference, so that the resin materials are impregnated into the reinforced part matrix, the resin materials can be adhered to the inner wall of the pores of the reinforced part matrix to form the reinforced part 33 to play a role in supporting the porous electrode body 31, and the obtained composite porous electrode 3 has good bending resistance and porosity.
When the reinforcing part and the porous electrode body 31 are separately arranged, the reinforcing part 33 can be manufactured independently, and in order to meet the requirement that the bending resistance of the reinforcing part 33 is better than that of the porous electrode body 31, the reinforcing part 33 can be prepared by a plurality of optional preparation methods, and when the material of the reinforcing part base body is the same as that of the porous electrode body 31, resin can be impregnated in the base body of the reinforcing part 33, so that the reinforcing part 33 with the resin layer is formed; when the reinforcing part 33 is made of one of the group consisting of porous urethane resin, porous PVC resin, and porous PE resin, the matrix of the reinforcing part 33 may be further impregnated with resin or may be directly used as the material of the reinforcing part 33, that is, any one of the group consisting of porous urethane resin, porous PVC resin, and porous PE resin may be directly cut or etched to form the reinforcing part 33 having the same volume as the internal volume of the installation through-hole. The material used for the reinforcing portion substrate of the present invention is variously selected, and is not limited to the porous urethane resin, the porous PVC resin, and the porous PE resin, and any satisfactory porous material may be used in the present invention, and it is needless to say that the reinforcing portion as a part of the composite porous electrode 3 must have the electrolyte corrosion resistance at the same time.
The present invention also provides a preferable production method of the above-described reinforcing part 33, depending on the resin material used.
In a preferred embodiment of the present invention, the resin material is a thermoplastic resin composition or a thermosetting resin composition, and the thermoplastic resin composition includes a thermoplastic resin polymer and 0 to 25 wt% of an auxiliary material of the thermoplastic resin composition; or the thermosetting resin composition comprises a thermosetting resin polymer and an auxiliary material with the weight content of 0-25% of the thermosetting resin composition; the preparation method comprises the following steps of A2 or B2: s11, heating the resin material to form a resin material melt; s12, soaking the resin material melt into the pores of the strengthening part matrix; and S13, solidifying the resin material melt to form the reinforced part 33 with the resin layer on the inner wall of the pore of the reinforced part matrix. The reinforcing portion 33 can be formed by impregnating a melt of a composition having a thermosetting resin polymer or a thermoplastic resin polymer into the pores of the reinforcing portion substrate, and curing the composition on the inner walls of the pores of the reinforcing portion substrate by adjusting conditions such as an appropriate temperature according to the properties of the resin used.
In another preferred embodiment of the present invention, the resin material is a thermoplastic resin composition, and the thermoplastic resin composition comprises a thermoplastic resin polymer and 0-25 wt% of an auxiliary material; the preparation method comprises the following steps of A2 or B2: s21, dissolving the resin material in a solvent to form a resin material solution with the mass concentration of the resin material being 0.5-20%; s22, impregnating the resin material solution into the pores of the reinforcing part base body; and S23, volatilizing the solvent in the reinforcement part matrix, and adhering the resin material to the inner walls of the pores of the reinforcement part matrix to form the reinforcement part 33 having the resin layer. The impregnation method, in which the composition having the thermoplastic resin polymer is dissolved in a good solvent for the thermoplastic resin and impregnated into the reinforcement matrix in a state of being dispersed in the solvent, is more advantageous for the dispersion of the thermoplastic resin polymer in the pores of the reinforcement matrix, and when the solvent is volatilized and under appropriate conditions, the composition is cured on the inner walls of the pores of the reinforcement matrix to form the reinforcement 33 having the resin layer. The mass concentration of the resin material in the formed resin material solution is controlled to be 0.5-20%, so that the resin material solution can be quickly impregnated into the pores, and the effect of forming a resin layer on the inner walls of the pores can be realized. When the resin material comprises a thermoplastic resin polymer, solvents for dissolving it include, but are not limited to, toluene, xylene, and tetrahydrofuran.
In another preferred embodiment of the present invention, the resin material is a monomer or prepolymer composition, and the monomer or prepolymer composition comprises: one of a thermoplastic resin monomer, a thermoplastic resin prepolymer, a thermosetting resin monomer and a thermosetting resin prepolymer, and an auxiliary material with the weight content of 0-25% of the monomer or prepolymer composition; the preparation method comprises the following steps of A2 or B2: s31, heating the monomer or prepolymer composition to form a monomer or prepolymer composition melt; s32, soaking the monomer or prepolymer composition into the pores of the strengthening part substrate; s33, carrying out polymerization reaction between monomers in the pores of the reinforced part matrix or between monomers of the prepolymer composition melt or between prepolymers to form a polymer; and S34, solidifying the polymer to form the reinforced part 33 with the resin layer on the inner wall of the pore of the reinforced part matrix.
When a monomer or a prepolymer of a thermoplastic resin or a thermosetting resin is selected as a part of the composition, the monomer or the prepolymer has a smaller molecular weight than that of the polymer, and is easily dispersed and quickly impregnated into the pores of the reinforcement matrix in the reinforcement matrix, and after the impregnation is completed, the monomer or the prepolymer is polymerized under appropriate conditions to form the polymer, and the reinforcement 33 having a resin layer is formed after curing.
In another preferred embodiment of the present invention, the resin material is a monomer or prepolymer composition, and the monomer or prepolymer composition comprises: a thermoplastic resin monomer or a thermoplastic resin prepolymer or a thermosetting resin monomer or a thermosetting resin prepolymer and an auxiliary material with the weight content of 0-25% of the monomer or prepolymer composition; the preparation method comprises the following steps of A2 or B2: s41, dissolving the monomer or prepolymer composition in a solvent to form a monomer or prepolymer composition solution with the mass concentration of 0.5-20%; s42, dipping the monomer or prepolymer composition solution into the pores of the strengthening part matrix; s43, carrying out polymerization reaction between monomers in the pores of the reinforced part matrix or between monomers of the prepolymer composition solution or between the prepolymers to form a polymer; and S44, volatilizing the solvent, the unreacted monomer and the unreacted prepolymer in the reinforcement matrix, and solidifying the polymer to form the reinforcement 33 having the resin layer on the inner walls of the pores of the reinforcement matrix.
The thermoplastic monomer or prepolymer is dissolved in the solvent so that the monomer or prepolymer exists in the solvent in a dispersed form, when the monomer or prepolymer is dipped into the reinforcement part matrix, the monomer or prepolymer diffuses in the pores of the reinforcement part matrix at a high speed and polymerizes to form a polymer under a proper condition, and after the solvent is volatilized, the monomer or prepolymer is solidified on the inner walls of the pores of the reinforcement part matrix to form the reinforcement part 33 with the resin layer. When the monomer or prepolymer composition solution is dipped into the porous electrode body 31, the aim of rapid dipping is fulfilled, and the concentration of the monomer or prepolymer therein is enough to polymerize to form a polymer, so that the mass concentration of the monomer or prepolymer composition in the monomer or prepolymer composition solution is 0.5-20%. After the polymer is formed, in order to promote the polymer to be cured and to prevent the unreacted monomer and the unreacted prepolymer from remaining in the porous electrode body 31 to cause excessive blockage of the pores of the formed composite porous electrode 3, and to prevent the solvent from remaining in the porous electrode body 31 and then being mixed into the electrolyte during the operation of the porous electrode to affect the performance of the battery, it is generally necessary to remove them, and the solvent, the unreacted monomer and the unreacted prepolymer may be volatilized by heating and ventilation means.
Meanwhile, in order to increase the impregnation speed of the resin material and improve the preparation efficiency of the composite porous electrode 3 in the above embodiment, the fluidity may be improved by increasing the solution pressure or the melt pressure or by decreasing the concentration of the solution or the viscosity of the melt at the end where the resin material or the composition is impregnated. Reducing the concentration of the solution or the viscosity of the melt may be accomplished by increasing the temperature, reducing the concentration of the solution, or adding a diluent to the melt, and diluents that may be used in the present invention include, but are not limited to, agents such as toluene, ethanol, acetone, butanol, dibutyl ester, and the like.
In the above preferred embodiment, the auxiliary material is a reinforcing component and/or a functional component, the reinforcing component is inorganic silicate particles, short fibers or montmorillonite, and the functional component is carbon black or carbon nanotubes. The reinforcing component serves to further enhance the bending resistance of the reinforcing portion 33, and the functional component serves to compensate for the defect of the decrease in the electrical conductivity of the composite porous electrode 3 caused by the non-conductive substance such as resin.
In order to further accelerate the preparation speed of the composite porous electrode, when the monomer or prepolymer composition contains a thermoplastic resin monomer or prepolymer, the step S31 further comprises the step of adding 0.1-1% of initiator into the resin monomer or prepolymer composition; when the monomer or prepolymer composition contains a thermosetting resin monomer or prepolymer, step S31 further includes the step of adding 0.1% to 1% of a catalyst and/or a curing agent to the resin monomer or prepolymer composition.
Similarly, in order to further increase the preparation speed of the composite porous electrode, when the monomer or prepolymer composition contains a thermoplastic resin monomer or prepolymer, step S41 further includes dissolving the initiator and the monomer or prepolymer composition together in a solvent to form a monomer or prepolymer composition solution; when the monomer or prepolymer composition contains a thermosetting resin monomer or prepolymer, step S41 further includes dissolving the catalyst and/or the curing agent and the monomer or prepolymer composition together in a solvent to form a monomer or prepolymer composition solution.
When the composition contains a thermoplastic resin monomer or prepolymer, initiators that may be used in the present invention include, but are not limited to, azo initiators, peroxide initiators, and ultraviolet light; when the composition contains thermosetting resin monomers or prepolymers, the catalysts which can be used in the invention are various catalysts such as acids, alkalis, amphiphats and the like which can initiate the polymerization reaction of the used resin; the curing agent usable in the present invention is any of various curing agents capable of initiating a curing reaction of the resin used, such as a normal temperature, a medium temperature or a high temperature.
In another exemplary embodiment of the present invention, there is also provided a liquid flow cell comprising a porous electrode and a current collecting plate 2, wherein the porous electrode is the composite porous electrode 3. On the basis that the electrolyte permeation diffusion and the oxidation-reduction reaction of the composite porous electrode are improved, the charge and discharge efficiency of a single cell is improved.
In yet another exemplary embodiment of the present invention, there is also provided a flow battery stack including at least one flow cell including the composite porous electrode 3 described above. On the basis that the electrolyte permeation diffusion and the oxidation-reduction reaction of the composite porous electrode are improved, the charge-discharge efficiency of the battery stack is also improved.
The following will further explain the advantageous effects of the present invention in combination with examples and comparative examples.
Example 1
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 36mm by 8 mm. Polystyrene is selected as impregnating resin, and dimethylformamide is selected as a solvent.
Preparation process
Preparing a strengthening part matrix: dividing two groups of parallel cylindrical areas on the graphite felt, wherein each group of areas is provided with three cylindrical areas, adjacent cylindrical areas between the groups are correspondingly arranged, the total volume of all the cylindrical areas is 20% of the total volume of the composite porous electrode, the graphite felt in the area is cut out to be used as a reinforcing part matrix, and the rest graphite felt with cylindrical through holes is used as a porous electrode body;
preparing a reinforcing part: dissolving polystyrene resin in dimethylformamide to form a solution with the mass concentration of 18%, then immersing the strengthening part matrix into the solution, slowly heating the solution to 155 ℃, and keeping the temperature for 6 hours to gradually and completely volatilize the dimethylformamide after the solution is uniformly immersed into the strengthening part matrix; slowly cooling to 25 deg.C to precipitate and solidify polystyrene to obtain resin layer containing polystyrene resin, wherein the resin layer and the reinforcing part matrix form a reinforcing part, and the total weight of the resin layer is 10% of the total weight of the obtained reinforcing part;
preparing a composite porous electrode: the reinforcing part is installed in the cylindrical through hole of the porous electrode body to obtain the composite porous electrode.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 1.
Example 2
Raw materials: the graphite felt is selected as a porous electrode body material, the porosity is 85%, and the external dimension is 36mm by 8 mm. High-density polyethylene is selected as impregnating resin.
Preparation process
Preparing a strengthening part matrix: dividing two groups of parallel areas on the graphite felt, wherein each group of areas is provided with three cylindrical areas which are isolated from each other, adjacent cylindrical areas between the groups are correspondingly arranged, and the total volume of all the cylindrical areas is 15 percent of the total volume of the composite porous electrode;
preparing a reinforcing part: melting high-density polyethylene into a melt at 180 ℃; and then placing the melt at the upper end of the strengthening part matrix, so that the melt is immersed into the strengthening part matrix, after the melt is uniformly immersed into the strengthening part matrix, slowly cooling to 25 ℃ to precipitate and solidify the polyethylene resin, so as to form a resin layer containing the high-density polyethylene resin, and forming a strengthening part by the resin layer and the strengthening part matrix to obtain the composite porous electrode, wherein the total weight of the resin layer is 95% of the total weight of the obtained strengthening part.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 2.
Example 3
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 36mm by 8 mm. Styrene is selected as an impregnation material, a solvent is toluene, and an initiator is azobisisobutyronitrile.
Preparation process
Preparing a strengthening part matrix: dividing three groups of parallel areas on the graphite felt, wherein each group of areas is provided with three cuboid areas which are isolated from each other, adjacent cuboid areas between the groups are arranged in a staggered mode, and the total volume of all the cuboid areas is 48% of the total volume of the composite porous electrode;
preparing a composite porous electrode: mixing azobisisobutyronitrile and a styrene monomer to form a composition containing 0.8wt% azobisisobutyronitrile, and dissolving the composition in toluene to form a solution having a mass concentration of 2 wt%; placing the graphite felt in a flat bottom reactor equipped with a degassing and heating device, the reactor having a size of 40mm x 35mm, and then adding the above solution to the reactor to immerse the solution in the matrix of the reinforcement part by: connecting pipelines with the same shape as the reinforced part matrix at two ends of the reinforced part matrix, introducing the added solution from one end of the pipeline and pressurizing, vacuumizing the other end of the pipeline, and forming a large pressure difference between the pipelines at two sides to ensure that the solution is impregnated into the reinforced part matrix; then raising the temperature of the reactor to 110-115 ℃, keeping the temperature for 4.5 hours to polymerize a small amount of styrene to form polystyrene, then continuing raising the temperature to 150-160 ℃, keeping the temperature for 3 hours to polymerize most of styrene to form polystyrene, and finishing the polymerization reaction, wherein the conversion rate of the monomer can reach 95%; and starting an air exhaust device to exhaust unpolymerized styrene monomers and micromolecular substances, cooling to room temperature to form a resin layer containing polystyrene resin, and forming a reinforced part by the resin layer and a reinforced part matrix to obtain the composite porous electrode, wherein the total weight of the resin layer is 2.5% of the total weight of the reinforced part.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 3.
Example 4
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 36mm by 8 mm. Styrene is selected as an impregnant, and azodiisobutyronitrile is selected as an initiator.
Preparation process
Preparing a strengthening part matrix: dividing three groups of parallel areas on the graphite felt, wherein each group of areas is provided with three cuboid areas which are isolated from each other, adjacent cuboid areas between the groups are arranged in a staggered mode, the total volume of all the cuboid areas is 40% of the total volume of the composite porous electrode, the graphite felt in the areas is cut out to serve as a reinforcing part base body, and the rest of the graphite felt with cuboid through holes serves as a porous electrode body;
preparing a reinforcing part: placing graphite felt in a closed flat-bottom reactor equipped with a degassing and heating device, the reactor size being 40mm x 35mm, then adding a styrene monomer containing 1wt% azobisisobutyronitrile to the reactor, immersing the reinforcing matrix in styrene, and introducing N into the reactor2Protecting, then raising the temperature of the reactor to 115-120 ℃, and keeping the temperature for 4.7 hours, so that the styrene monomer is pre-polymerized, and the conversion rate of the monomer in the process can reach 48%. Then, continuously raising the temperature to 175-180 ℃, keeping the temperature for 3.5 hours, carrying out post polymerization on the polystyrene prepolymer, and finishing the polymerization reaction, wherein the conversion rate of the monomer can reach 95%; open convulsions rowThe gas device discharges unpolymerized styrene monomer and micromolecule substances, and the resin layer containing polystyrene resin is formed after cooling to room temperature, the reinforcing part is composed of the resin layer and the reinforcing part matrix, and the total weight of the resin layer is 95 percent of the total weight of the reinforcing part;
preparing a composite porous electrode: the reinforcing part is installed in a cuboid through hole of the porous electrode body to obtain the composite porous electrode.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 4.
Example 5
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 36mm by 8 mm. Polyurethane monomer toluene diisocyanate and polyester polyol are selected as impregnants, a catalyst is triethylene diamine, a chain extender is ethylene diamine, and a cross-linking agent is glycerol.
Preparation process
Preparing a strengthening part matrix: dividing three groups of parallel cylindrical regions on the graphite felt, wherein each group of regions comprises three cylindrical regions, the adjacent cylindrical regions between the groups are correspondingly arranged, the total volume of all the cylindrical regions is 30% of the total volume of the composite porous electrode, cutting the graphite felt in the region to be used as a reinforcing part matrix, and using the remaining graphite felt with cylindrical through holes as a porous electrode body;
preparing a reinforcing part: dissolving a polyurethane monomer toluene diisocyanate, polyester polyol, a catalyst triethylene diamine, a chain extender ethylene diamine and a cross-linking agent glycerol in a solvent toluene according to a mass ratio of 50:100:0.5:2.5:0.7 to form a solution. The solvent content in the solution was 90%. Then immersing the reinforced part matrix into the solution, raising the temperature to 95 ℃ after the solution is uniformly immersed into the reinforced part matrix, keeping the temperature for 20 hours, then raising the temperature to 115 ℃ to completely volatilize the solvent toluene, then lowering the temperature to 30 ℃, solidifying and separating out the polyurethane resin obtained by polymerization, thus forming a resin layer containing the polyurethane resin, wherein the reinforced part is composed of the resin layer and the reinforced part matrix, and the weight of the resin layer is 45 percent of the total weight of the reinforced part;
preparing a composite porous electrode: the reinforcing part is installed in the cylindrical through hole of the porous electrode body to obtain the composite porous electrode.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 5.
Example 6
Raw materials: the graphite felt is selected as a porous electrode body material, the porosity is 85%, and the external dimension is 30mm by 6 mm. E-44 type bisphenol A epoxy resin is selected as impregnating resin, and the curing agent is diethylenetriamine.
Preparation process
Preparing a strengthening part matrix: dividing three groups of parallel cylindrical regions on the graphite felt, wherein each group of regions comprises three cylindrical regions, adjacent cylindrical regions between the groups are correspondingly arranged, and the total volume of all the cylindrical regions is 30 percent of that of the composite porous electrode;
preparing a composite porous electrode: firstly, uniformly mixing E-44 type epoxy resin and diethylenetriamine according to the proportion of 100:9, then soaking the melt into a strengthening part matrix by the same method as the embodiment 3, solidifying for 7 days at room temperature, then heating to 80-100 ℃, solidifying for 2 hours, and slowly cooling to room temperature, wherein the resin layer and the strengthening part matrix form a strengthening part, and the total weight of the resin layer is 96.5% of the weight of a strengthening area, thus obtaining the composite porous electrode.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 6.
Example 7
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 30mm 6 mm. The impregnating resin is a composition consisting of nylon 6 and carbon black, and the weight content of the carbon black is 18 wt%.
Preparation process
Preparing a strengthening part matrix: dividing three groups of parallel cylindrical regions on the graphite felt, wherein each group of regions comprises three cylindrical regions, adjacent cylindrical regions between the groups are correspondingly arranged, and the total volume of all the cylindrical regions is 30 percent of that of the composite porous electrode;
preparing a composite porous electrode: the composition was heated to 250 ℃ to melt it into a melt, and then the melt was fully immersed in the matrix of the reinforcement part by the same method as in example 3, followed by slow cooling to 30 ℃ to solidify it to form a resin layer containing a composition of nylon 6 and carbon black, and the reinforcement part was composed of the resin layer and the matrix of the resin layer to obtain a composite porous electrode, the total weight of the resin layer being 98.5% of the total weight of the reinforcement part.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 7.
Example 8
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 30mm 6 mm. The impregnating resin is a composition consisting of low-density polyethylene and montmorillonite, and the weight content of the montmorillonite is 3%.
Preparation process
Preparing a strengthening part matrix: dividing three groups of parallel cylindrical regions on the graphite felt, wherein each group of regions comprises three cylindrical regions, the adjacent cylindrical regions between the groups are correspondingly arranged, the total volume of all the cylindrical regions is 30% of the total volume of the composite porous electrode, cutting the graphite felt in the region to be used as a reinforcing part matrix, and using the remaining graphite felt with cylindrical through holes as a porous electrode body;
preparing a reinforcing part: firstly, the low-density polyethylene/montmorillonite composition is prepared by the following steps of (by weight ratio) 93: 7 is dissolved in benzene at 78 ℃ to form a solution with the concentration of 6 percent; then the strengthening part is immersed into the solution, the solution is evenly immersed into the graphite felt, the solution is slowly heated to 95 ℃ to gradually and completely volatilize the solvent, and then the solution is slowly cooled to 30 ℃ to precipitate and solidify the low-density polyethylene/montmorillonite composition, so that a resin layer containing the low-density polyethylene/montmorillonite composition is formed, the strengthening part is composed of the resin layer and a strengthening part matrix, and the total weight of the resin layer is 4% of the total weight of the strengthening part.
Preparing a composite porous electrode: the reinforcing part is installed in the cylindrical through hole of the porous electrode body to obtain the composite porous electrode.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 8.
Example 9
Raw materials: the graphite felt is selected as the material of the porous electrode body, the porosity is 85%, and the external dimension is 30mm 6 mm.
Preparing a composite porous electrode: three groups of parallel cylindrical regions are divided on the graphite felt, each group of regions is provided with three cylindrical regions, adjacent cylindrical regions between the groups are correspondingly arranged, the total volume of all the cylindrical regions is 30% of the total volume of the composite porous electrode, the graphite felt in the region is cut to form an installation through hole for manufacturing the reinforcing part, and the foamed polyurethane is used as a raw material to prepare the reinforcing part with the same volume as that of the installation through hole in a cutting mode. The reinforcing portion is fitted into the mounting through-hole to obtain a composite porous electrode.
The current collecting plate, the liquid flow frame, the separator and the composite porous electrode were assembled to obtain a single cell of example 9.
Comparative example 1
The graphite felt is selected as a porous electrode, the porosity is 85%, and the external dimension is 30mm by 6 mm. And the porous electrode, a current collecting plate, a liquid flow frame and a diaphragm are assembled into a single cell of comparative example 1.
The electrodes and cells of examples 1-9 and comparative example 1 were tested and the results are shown in table 1.
TABLE 1
| Porosity (%) | Contact resistance (m omega) | Charge and discharge efficiency (%) | |
| Example 1 | 81 | 6.23 | 91.2 |
| Example 2 | 68 | 5.74 | 90.2 |
| Example 3 | 72 | 6.14 | 90.5 |
| Example 4 | 60 | 5.68 | 92.0 |
| Example 5 | 70 | 6.08 | 90.8 |
| Example 6 | 60 | 5.96 | 90.3 |
| Example 7 | 61 | 5.48 | 92.6 |
| Example 8 | 76 | 6.06 | 90.7 |
| Example 9 | 83 | 6.20 | 90.9 |
| Comparative example 1 | 85 | 6.57 | 89.2 |
As can be seen from the data in table 1, the porosity of the composite porous electrodes obtained in examples 1 to 9 is lower than that of the porous electrode in comparative example 1, but the contact resistance between the composite porous electrode and the electrode plate is greatly improved due to the existence of the strengthening part, and particularly, the improvement is more obvious in example 7; thereby improving the charge and discharge efficiency of the single cell as compared with comparative example 1.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A composite porous electrode, characterized in that the composite porous electrode (3) comprises a porous electrode body (31) and reinforcing portions (33) distributed in the porous electrode body (31) and having superior bending resistance to the porous electrode body (31), the reinforcing portions (33) penetrating the porous electrode body (31) in a thickness direction of the porous electrode body (31), wherein,
the porous electrode body (31) is provided with scattered installation through holes, the reinforcing part (33) is in interference fit with the installation through holes, and the reinforcing part (33) is made by forming a resin layer on the inner walls of pores of the porous material; or the reinforcing part (33) is made of one of the group consisting of foamed polyurethane, foamed polyvinyl chloride and foamed polyethylene.
2. The composite porous electrode according to claim 1, wherein when the reinforcement portion (33) is made by forming a resin layer in the inner walls of pores of the porous material, the total weight of the resin layer is 1 to 99% of the total weight of the reinforcement portion (33).
3. The composite porous electrode according to claim 1, wherein the resin layer is formed of a thermoplastic resin composition or a thermosetting resin composition,
the thermoplastic resin composition comprises thermoplastic resin and an auxiliary material with the weight content of 0-25% of the thermoplastic resin composition; or
The thermosetting resin composition comprises thermosetting resin and auxiliary materials with the weight content of 0-25% of the thermosetting resin composition.
4. The composite porous electrode according to claim 3, wherein the auxiliary material is a reinforcing component and/or a functional component, the reinforcing component is inorganic silicate particles, short fibers or montmorillonite, and the functional component is carbon black or carbon nanotubes.
5. Composite porous electrode according to claim 1, characterized in that the total volume of said reinforcement (33) is less than half the total volume of said composite porous electrode (3).
6. A method of making a composite porous electrode according to claim 1,
the preparation method comprises the following steps:
b1, dividing a plurality of regions in the porous electrode body (31) where the reinforcing parts (33) are to be formed, and forming mounting through holes in the regions where the reinforcing parts (33) are to be mounted;
b2, impregnating a resin material into the inner pores of the matrix of the reinforcing part (33), adhering a resin layer on the inner walls of the pores of the matrix, and manufacturing the matrix with the resin layer adhered on the inner walls of the pores into the reinforcing part (33) with the volume same as the inner volume of the mounting through hole; and
b3, embedding the reinforcing part (33) into the installation through hole, and adhering the reinforcing part (33) to the inner wall of the installation through hole to obtain the composite porous electrode (3);
or,
the preparation method comprises the following steps:
c1, dividing a plurality of areas where the reinforcing parts (33) are to be formed in the porous electrode body (31), and forming mounting through holes for mounting the reinforcing parts (33) in the areas;
c2, manufacturing one of the group consisting of porous polyurethane resin, porous PVC resin and porous PE resin into the reinforcing part (33) with the volume same as the internal volume of the installation through hole; and
and C3, embedding the reinforcing part (33) into the mounting through hole, and adhering the reinforcing part (33) to the inner wall of the mounting through hole to obtain the composite porous electrode (3).
7. The production method according to claim 6,
the resin material is a thermoplastic resin composition or a thermosetting resin composition,
the thermoplastic resin composition comprises a thermoplastic resin polymer and an auxiliary material with the weight content of 0-25% of the thermoplastic resin composition; or
The thermosetting resin composition comprises a thermosetting resin polymer and an auxiliary material with the weight content of 0-25% of the thermosetting resin composition;
the step B2 of the preparation method further comprises the following steps:
s11, heating the resin material to form a resin material melt;
s12, enabling the resin material to be immersed into the pores of the strengthening part matrix in a melting mode; and
s13, solidifying the resin material melt on the pore inner wall of the strengthening part substrate to form the strengthening part (33) with the resin layer.
8. The preparation method according to claim 6, wherein the resin material is a thermoplastic resin composition comprising a thermoplastic resin polymer and 0-25 wt% of an auxiliary material;
the step B2 of the preparation method further comprises the following steps:
s21, dissolving the resin material in a solvent to form a resin material solution with the mass concentration of 0.5-20%;
s22, impregnating the resin material solution into the pores of the reinforcement base body; and
and S23, volatilizing the solvent in the strengthening part matrix, and adhering the resin material on the inner wall of the pore of the strengthening part matrix to form the strengthening part (33) with the resin layer.
9. The method of claim 6, wherein the resin material is a monomer or prepolymer composition comprising: one of a thermoplastic resin monomer, a thermoplastic resin prepolymer, a thermosetting resin monomer or a thermosetting resin prepolymer, and an auxiliary material with the weight content of 0-25% of the monomer or prepolymer composition;
the step B2 of the preparation method further comprises the following steps:
s31, heating the monomer or prepolymer composition to form a monomer or prepolymer composition melt;
s32, immersing the monomer or prepolymer composition melt into the pores of the strengthening part substrate;
s33, enabling the monomers or the prepolymers of the monomer or prepolymer composition melt in the pores of the reinforced part matrix to have polymerization reaction to form polymers; and
s34, solidifying the polymer to form the reinforced part (33) with the resin layer on the inner wall of the pore of the reinforced part matrix.
10. The production method according to claim 9,
when the monomer or prepolymer composition contains a thermoplastic resin monomer or prepolymer, the step S31 further includes a step of adding an initiator to the resin monomer or prepolymer composition in an amount of 0.1% to 1%;
when the monomer or prepolymer composition contains a thermosetting resin monomer or prepolymer, the step S31 further includes the step of adding 0.1% -1% of catalyst and/or curing agent to the resin monomer or prepolymer composition.
11. The method of claim 6, wherein the resin material is a monomer or prepolymer composition comprising: a thermoplastic resin monomer or a thermoplastic resin prepolymer or a thermosetting resin monomer or a thermosetting resin prepolymer and an auxiliary material with the weight content of 0-25% of the monomer or prepolymer composition;
the step B2 of the preparation method further comprises the following steps:
s41, dissolving the monomer or prepolymer composition in a solvent to form a monomer or prepolymer composition solution with the mass concentration of 0.5-20%;
s42, soaking the monomer or prepolymer composition solution into the pores of the reinforcement part base body;
s43, enabling the monomers or the prepolymers of the monomer or prepolymer composition solution in the pores of the reinforced part matrix to generate polymerization reaction to form polymers; and
s44, volatilizing the solvent, the unreacted monomer and the unreacted prepolymer in the reinforced part matrix, and solidifying the polymer on the inner wall of the pore of the reinforced part matrix to form the reinforced part (33) with the resin layer.
12. The production method according to claim 11,
when the monomer or prepolymer composition contains a thermoplastic resin monomer or prepolymer, the step S41 further includes dissolving an initiator and the monomer or prepolymer composition together in a solvent to form a monomer or prepolymer composition solution;
when the monomer or prepolymer composition contains a thermosetting resin monomer or prepolymer, the step S41 further includes dissolving a catalyst and/or a curing agent together with the monomer or prepolymer composition in a solvent to form a monomer or prepolymer composition solution.
13. The preparation method according to any one of claims 7 to 12, wherein the auxiliary material is a reinforcing component and/or a functional component, the reinforcing component is inorganic silicate particles, short fibers or montmorillonite, and the functional component is carbon black or carbon nanotubes.
14. Liquid flow cell comprising a porous electrode and a current collector plate (2), characterized in that said porous electrode is a composite porous electrode (3) according to any one of claims 1 to 5.
15. A flow cell stack comprising at least one flow cell, characterized in that the flow cell comprises a composite porous electrode (3) according to any one of claims 1 to 5.
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| EP3275032A1 (en) * | 2015-03-24 | 2018-01-31 | 3M Innovative Properties Company | Porous electrodes and electrochemical cells and liquid flow batteries therefrom |
| CN110071303A (en) * | 2018-01-23 | 2019-07-30 | 北京普能世纪科技有限公司 | A kind of carbon felt and the flow cell pile with the carbon felt |
| CN112086653B (en) * | 2019-06-14 | 2022-04-22 | 江苏泛宇能源有限公司 | Graphite felt structure for flow battery and flow battery using same |
| CN110556550A (en) * | 2019-08-01 | 2019-12-10 | 武汉中极氢能产业创新中心有限公司 | Flow field plate and air-cooled electric pile |
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|---|---|---|---|---|
| CN1378708A (en) * | 1999-10-08 | 2002-11-06 | 瑞威欧公司 | Electrochemical electrode for fuel cell |
| CN1719619A (en) * | 2004-07-08 | 2006-01-11 | 住友化学株式会社 | Porous electrode,apparatus containing same and mfg. method thereof |
| JP2006322068A (en) * | 2005-04-21 | 2006-11-30 | Nagamine Seisakusho:Kk | Porous member, and method for producing the same |
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| JP2011210450A (en) * | 2010-03-29 | 2011-10-20 | Panasonic Corp | Cell electrode plate and cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378708A (en) * | 1999-10-08 | 2002-11-06 | 瑞威欧公司 | Electrochemical electrode for fuel cell |
| CN1719619A (en) * | 2004-07-08 | 2006-01-11 | 住友化学株式会社 | Porous electrode,apparatus containing same and mfg. method thereof |
| JP2006322068A (en) * | 2005-04-21 | 2006-11-30 | Nagamine Seisakusho:Kk | Porous member, and method for producing the same |
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