CN112436172A - Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery - Google Patents
Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery Download PDFInfo
- Publication number
- CN112436172A CN112436172A CN201910792903.0A CN201910792903A CN112436172A CN 112436172 A CN112436172 A CN 112436172A CN 201910792903 A CN201910792903 A CN 201910792903A CN 112436172 A CN112436172 A CN 112436172A
- Authority
- CN
- China
- Prior art keywords
- bipolar plate
- plate
- porous electrode
- composite electrode
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to a liquid flow energy storage battery with a porous electrode and a bipolar plate which are integrally cured. The battery comprises 2 porous electrodes 1, 2 bipolar plates 2, an ion exchange membrane 3 and 2 flow frames 4, wherein the porous electrodes 1 and the bipolar plates 2 are sintered and cured into composite electrode plates 5 at high temperature through conductive adhesives, the 2 flow frames 4 are sleeved on the 2 composite electrode plates 5 and are mutually attached to form a closed space, the closed space between the flow frames 4 and the 2 composite electrode plates 5 provides a flow channel and a place for electrolyte solution, and the ion exchange membrane 3 is arranged between the 2 composite electrode plates 5. The ohmic resistance test result shows that the integrated electrode bipolar plate of the invention can improve the voltage efficiency and energy efficiency of battery charging and discharging.
Description
Technical Field
The invention relates to the technical field of battery processing and manufacturing and structural design, in particular to a liquid flow energy storage battery with a porous electrode and a bipolar plate integrated in curing.
Background
The liquid flow energy storage battery has the advantages of long cycle life, high safety, independent design of power and capacity, strong overcharge and overdischarge capabilities and the like. The energy storage device is mainly applied to the fields of peak shaving energy storage, backup emergency power supply and the like of renewable energy power stations such as wind power stations, solar photovoltaic power stations and the like, and can play roles in stabilizing renewable energy power generation, improving energy conversion efficiency and the like.
The single cell of the liquid flow energy storage battery generally consists of two porous electrodes (porous carbon or porous graphite), two bipolar plates, an ion exchange membrane and two electrolyte flow frames. The cell is usually assembled by means of a filter press from the above components, and the porous electrode is compressed by the pressing force provided by the two end pressing plates and the bolts to ensure that the contact resistance between the porous electrode and the bipolar plate is at a proper value and the sealing requirement of the cell needs to be maintained, so that the pressing force is usually large.
This places special demands on the physical properties of the porous electrodes and bipolar plates:
first, the porous electrode should have a certain thickness to accommodate the pressing force of the battery, and if the porous electrode is too thin, the active specific surface area of the electrode and the flow cross-sectional area of the electrolyte after compression are correspondingly reduced, which is disadvantageous to electrochemical reaction and may cause an increase in mass transfer resistance of the electrolyte to increase concentration polarization; however, too thick a porous electrode will result in an increase in cell compressive force.
Secondly, the bipolar plate should have high electrical conductivity, strong mechanical strength and good corrosion resistance. Graphite-based bipolar plates, such as graphite plates, carbon-plastic composite plates, and the like, are currently the most widely used. However, the graphite material is very brittle, must be handled with great care during assembly due to the high compressive forces of the battery, and must be sufficiently thick, which greatly increases its production costs.
Currently, in the existing research literature, Lee et al have made some research works on the integration of composite bipolar plates for flow batteries and bipolar plates and porous electrodes, and they developed a series of novel composite bipolar plates including graphite-coated carbon/epoxy resin composite bipolar plates, carbon fiber/polyethylene composite bipolar plates, nanoparticle-embedded carbon fiber/fluorine-containing elastomer composite bipolar plates, and the like. And the porous electrodes such as carbon fiber felt, carbon cloth and the like are integrated with the composite bipolar plate by a hot pressing method to obtain the integrated electrode composite bipolar plate. The technology for preparing the composite bipolar plate is characterized in that organic polymer materials such as epoxy resin, polyethylene and the like are filled into a porous carbon or porous graphite material substrate, and then the polymer materials are melted and attached to the porous carbon material through hot pressing (the hot pressing temperature is generally not more than 200 ℃), so that the polymer materials do not have conductivity, and conductive materials such as carbon fibers, conductive nanoparticles and the like are often required to be doped. In addition, the method for manufacturing the integrated electrode composite bipolar plate is also a hot pressing method, and the porous electrode and the composite bipolar plate are physically bonded by using the viscosity of the melted polymer material. From the technical effect, the integrated composite electrode bipolar plate prepared by the method has large ohmic resistance, and the voltage efficiency and the energy efficiency of the battery are not high. And due to the limitation of the manufacturing process conditions, when the area size of the electrode is increased, the requirements on equipment are high, the manufacturing cost is high, and the large-scale production is not facilitated.
Disclosure of Invention
The invention aims to provide a liquid flow energy storage battery with a porous electrode and a bipolar plate which are integrally cured, aiming at the defects of the prior art.
The porous electrode and the bipolar plate are bonded by the conductive adhesive and then are solidified into a whole through high-temperature sintering, and the integrated electrode and bipolar plate integrated body has excellent conductive performance, chemical corrosion resistance and electrochemical corrosion resistance.
The ohmic resistance test result shows that the conductivity of the integrated electrode bipolar plate is slightly reduced before integration, but the specific surface area and the flow cross-sectional area of the porous electrode are not reduced by compression because the compression of the electrode is not required to be considered when the battery is assembled, the ohmic impedance and the concentration polarization impedance are reduced when the corresponding battery runs compared with the electrode compression, and finally the voltage efficiency and the energy efficiency of battery charging and discharging are improved, and the conclusion is proved by a single battery charging and discharging performance test experiment.
The first aspect is a product technical scheme:
a liquid flow energy storage battery with a porous electrode and a bipolar plate which are solidified into a whole,
the battery comprises 2 porous electrodes 1, 2 bipolar plates 2, an ion exchange membrane 3 and 2 flow frames 4, wherein the porous electrodes 1 and the bipolar plates 2 are sintered and solidified into composite electrode plates 5 at high temperature through conductive adhesives, the 2 flow frames 4 are sleeved on the 2 composite electrode plates 5 and mutually jointed to form a closed space, the closed space between the flow frames 4 and the 2 composite electrode plates 5 provides a flow passage and a place for electrolyte solution, the ion exchange membrane 3 is arranged between the 2 composite electrode plates 5,
the thickness of the conductive adhesive coating sintered and cured between the composite electrode plates 5 is 1-100 mu m.
Further, the bipolar plate 2 is one of a graphite plate, a carbon fiber plate, a graphite fiber plate and a carbon plastic plate;
further, the porous electrode 1 is a porous carbon material or a porous graphite material, including but not limited to a pitch-based graphite felt, a polyacrylonitrile-based graphite felt, a viscose-based graphite felt, a carbon fiber felt, a carbon cloth, a carbon paper, and the like; further preferably, the porosity of the porous electrode 1 is 0.40-0.95, and the thickness is 2-10 mm;
further, the ion exchange membrane 3 is any one of a cation exchange membrane and an anion exchange membrane, and is more preferably a perfluorosulfonic acid type cation exchange membrane, a polysulfone type anion exchange membrane, or a polybenzimidazole type anion exchange membrane.
The second aspect is a technical scheme of the preparation method:
the preparation method of the composite electrode plate 5 comprises the following steps:
(1) coating a conductive adhesive on the surface of the bipolar plate 2, wherein the thickness of the conductive adhesive coating is 1-100 mu m;
(2) and (3) bonding and pressing the porous electrode 1 to be bonded and the bipolar plate 2 together, and then placing the bonded porous electrode and the bipolar plate in a vacuum furnace for sintering for 1-5 hours at the temperature of 500-1000 ℃ to prepare the integrated composite electrode plate 5.
Further, the coating method of the conductive adhesive is any one of blade coating, brushing, spin coating, spray coating and dipping.
The third aspect is the technical scheme of the conductive adhesive:
the conductive adhesive comprises a high polymer material, a conductive agent and a sintering aid,
according to the mass ratio of the components,
the proportion of the high polymer material, the conductive agent and the sintering aid is (10-1): (10-1): 1;
wherein the high polymer material is at least one of epoxy resin, phenolic resin, polyethylene, polypropylene and polysulfone,
the conductive agent is at least one of carbon powder, carbon black, carbon nano fiber, graphite powder, silver powder, nickel powder and zinc powder,
the sintering aid is selected from TiC, WC and B4C、SiC、SiO2、Al2O3And Al4C3At least one of (1).
Further, the polymer material is in a powdery shape, and the purity is 95% -99.8%;
furthermore, the conductive agent material is in a powdery or fibrous shape, the particle size is between 10nm and 10 mu m, and the purity is 99.5 to 99.95 percent;
furthermore, the sintering aid material is powdery, has a morphology of 10 nm-10 μm and a purity of 95-99.5%.
The key point of the invention is to provide a composite electrode plate formed by integrally curing a porous electrode and a bipolar plate, wherein the high polymer materials of the conductive adhesive, such as epoxy resin, phenolic resin and the like, can be carbonized along with the rise of temperature in the sintering process, and the carbonization process is accompanied with chemical reaction and the generation of new substances, such as CO and H2O and H2. The formation of these gaseous species causes the bonding layer to be microporous, but at the same time these gaseous species will react with a sintering aid such as B4C and SiO2The reaction forms ceramic or glass phase crystals which have fluidity at high temperature and enter micropores formed after the carbonization of the high polymer material, thereby enhancing the bonding strength of the adhesive.
Further analysis shows that the invention utilizes the high-temperature sintering characteristic of the conductive adhesive to bond and solidify the porous electrode and the bipolar plate together, thereby not only achieving the required bonding strength between the porous electrode and the bipolar plate in actual use, but also improving the service life of the bipolar plate of the integrated electrode; and the problem of contact resistance between the porous electrode and the bipolar plate is solved by adding the conductive agent. Therefore, the porous electrode and the bipolar plate are tightly solidified together under the uncompressed condition, the specific surface area and the flow cross section area of the porous electrode can be kept unchanged, and the contact resistance between the porous electrode and the bipolar plate can be kept at a lower level, so that the ohmic resistance and the concentration polarization resistance of the battery in the charging and discharging processes are reduced, and the voltage efficiency and the energy efficiency of the battery are higher. As shown in fig. 6, which is a cross-sectional sem image of the sintered bipolar plate with integrated electrode in example 1, it can be clearly seen from fig. 6 that the graphite plate is arranged below the bipolar plate with integrated electrode, the graphite felt is arranged above the bipolar plate with integrated electrode, the sintered adhesive layer forms ceramic/glass phase crystals at the middle distinct boundary, and the conductive adhesive is solidified with the graphite plate and the graphite felt into a whole after being sintered.
The porous electrode and the bipolar plate are solidified into a whole, and the compression of the porous electrode and the pressure-resistant problem of the bipolar plate brought by the compression of the porous electrode in the traditional filter-pressing type assembly are not needed to be considered, so that the porous electrode is not compressed, the active specific surface area of the porous electrode is not reduced, the porous electrode can be thin enough to meet the flow of fluid, and the pressing force of the battery only needs to meet the sealing requirement.
In addition, after the porous electrode and the bipolar plate are integrated, the battery assembly is convenient, and the pressing force of the battery assembly is correspondingly reduced because the electrode does not need to be compressed, and the requirements on various physical properties of the bipolar plate are correspondingly reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a preparation method for solidifying an electrode and a bipolar plate for a flow battery into a whole, which utilizes a conductive adhesive and is sintered at high temperature, so that the components of the conductive adhesive are subjected to chemical change in the sintering process to form stronger binding force to solidify a porous electrode and the bipolar plate into a whole, and the porous electrode does not need to be compressed when an integrated composite electrode plate is assembled into the battery, so that the specific surface area and the flow cross section area of the porous electrode cannot be reduced due to compression, and the charging and discharging voltage efficiency and the energy efficiency of the battery are improved compared with those before the integration;
(2) in addition, because the porous electrode does not need to be compressed when the battery is assembled, the pressing force of the battery is reduced, and the performance requirements of the battery on all components (including a bipolar plate, a diaphragm, an end pressing plate, a sealing element, a fastening bolt and the like) of the battery are reduced.
(3) The conductive adhesive for preparing the integrated composite electrode plate has the advantages of easily available raw materials, low cost, simple process, difficult oxidation after high-temperature sintering, good curing performance, excellent conductive performance, strong acid corrosion resistance and electrochemical corrosion resistance.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is an exploded schematic view of a flow battery structure.
FIG. 2 is a schematic diagram of a 5 ohm resistance test of the cured integrated composite electrode plate.
FIG. 3 shows the results of 5 ohm resistance testing of the cured integrated composite electrode plate made with different conductive adhesives and preparation processes.
FIG. 4 shows different conductive adhesives and curing integrated composite electrode plate 5 pairs VO prepared by preparation process2 ++H2SO4And (5) the result of the solution soaking durability test.
Figure 5 is a graph comparing cell performance results before and after integration of comparative example 1 electrode and bipolar plate,
wherein, (a) the battery charge-discharge curve (current density 50 mA/cm)2) (b) voltage efficiency, (c) energy efficiency, (d) discharge capacity
Fig. 6 is a cross-sectional electron micrograph of the sintered integrated composite electrode plate 5 in example 1.
Fig. 7 example 8 energy storage battery example battery cycling performance.
Detailed Description
The present invention will now be described in more detail with reference to the accompanying drawings, in which preferred embodiments of the invention are shown, it being understood that one skilled in the art may modify the invention herein described while still achieving the beneficial results of the present invention. Accordingly, the following description should be construed as broadly as possible to those skilled in the art and not as limiting the invention.
Example 1:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
mixing epoxy resin powder, graphite powder and B4C is uniformly mixed according to the mass ratio of 1:1:1, wherein the purity of graphite powder is 99.95 percent (5000 meshes), B4The purity of C is 98% (1-10 μm) to obtain a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is analytically pure with the purity of more than 99.7 percent, and thus obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a graphite plate (with the diameter of 5cm and the thickness of 2 mm), a polyacrylonitrile-based graphite felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the graphite plate, and then the graphite plate is sintered for 1 hour in a vacuum furnace at the temperature of 600 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
The resistance test is performed on the composite electrode plate 5, and the specific test method is shown in fig. 2: the integrated bipolar plate 5 is arranged between two gold-plated copper blocks 6 with the diameter of 5cm, the two copper blocks are arranged on a universal tester 7 and connected with a micro-resistance tester 8 through a lead, the pressure between the copper blocks and the composite electrode plate 5 is adjusted through the universal tester 7, and the resistance values under different pressures are measured.
After the resistance measurement is finished, the composite electrode plate 5 is soaked in VO2 ++H2SO4In the solution, the bonding effect was observed and the duration of time (in days) from the beginning of the soaking until the separation of the electrode and bipolar plate occurred was recorded.
The results of the ohmic resistance test and the soaking durability test are shown in fig. 3 and 4, respectively.
Example 2:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
phenolic resin powder, graphite powder and B4C is uniformly mixed according to the mass ratio of 1:1:1, wherein the graphite powder and the B are mixed4The purity and particle size of C were the same as in example 1 to give a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is the same as the ethylene glycol in the embodiment 1, and obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a graphite plate (with the diameter of 5cm and the thickness of 2 mm), a polyacrylonitrile-based graphite felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the graphite plate, and then the graphite plate is sintered for 1 hour in a vacuum furnace at the temperature of 800 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
Ohmic resistance and soaking durability tests are respectively carried out on the integrated composite electrode plate 5, and the specific test method is the same as that of the embodiment 1.
The results of the experiment are shown in fig. 3 and 4.
Example 3:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
phenolic resin powder, graphite powder and B4C is uniformly mixed according to the mass ratio of 1:1:1, wherein the graphite powder and the B are mixed4The purity and particle size of C were the same as in example 1 to give a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is the same as the ethylene glycol in the embodiment 1, and obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a graphite plate (with the diameter of 5cm and the thickness of 2 mm), a polyacrylonitrile-based graphite felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the graphite plate, and then the graphite plate is sintered for 1 hour in a vacuum furnace at the temperature of 1000 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
Ohmic resistance and soaking durability tests are respectively carried out on the integrated composite electrode plate 5, and the specific test method is the same as that of the embodiment 1.
The results of the experiment are shown in fig. 3 and 4.
Example 4:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
phenolic resin powder, graphite powder and B4C is uniformly mixed according to the mass ratio of 1:0.5:0.5, wherein the graphite powder and the B are mixed4The purity and particle size of C were the same as in example 1 to give a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is the same as the ethylene glycol in the embodiment 1, and obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a graphite plate (with the diameter of 5cm and the thickness of 2 mm), a polyacrylonitrile-based graphite felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the graphite plate, and then the graphite plate is sintered for 1 hour in a vacuum furnace at the temperature of 800 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
Ohmic resistance and soaking durability tests are respectively carried out on the integrated composite electrode plate 5, and the specific test method is the same as that of the embodiment 1.
The results of the experiment are shown in fig. 3 and 4.
Example 5:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
mixing epoxy resin powder, graphite powder and B4C, according to the weight ratio of 1: uniformly mixing the graphite powder and the B powder in a mass ratio of 1:14The purity and particle size of C were the same as in example 1 to give a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is the same as the ethylene glycol in the embodiment 1, and obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a graphite plate (with the diameter of 5cm and the thickness of 2 mm), a polyacrylonitrile-based graphite felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the graphite plate, and then the graphite plate is sintered for 1 hour in a vacuum furnace at the temperature of 800 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
Ohmic resistance and soaking durability tests are respectively carried out on the integrated composite electrode plate 5, and the specific test method is the same as that of the embodiment 1.
The results of the experiment are shown in fig. 3 and 4.
Example 6:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
phenolic resin powder, graphite powder and B4C, according to the weight ratio of 1: uniformly mixing the graphite powder and the B powder in a mass ratio of 1:14The purity and particle size of C were the same as in example 1 to give a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is the same as the ethylene glycol in the embodiment 1, and obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a carbon plastic plate (with the diameter of 5cm and the thickness of 2 mm), a carbon fiber felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the carbon plastic plate, and then the carbon fiber felt is sintered for 1 hour in a vacuum furnace at the temperature of 800 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
Ohmic resistance and soaking durability tests are respectively carried out on the integrated composite electrode plate 5, and the specific test method is the same as that of the embodiment 1.
The results of the experiment are shown in fig. 3 and 4.
Example 7:
the embodiment provides a preparation method of a conductive adhesive, which comprises the following steps:
mixing epoxy resin powder, graphite powder and B4C, according to the weight ratio of 1: uniformly mixing the graphite powder and the B powder in a mass ratio of 1:14The purity and particle size of C were the same as in example 1 to give a mixture. And (3) putting 1g of the mixture into 2ml of ethylene glycol, stirring and dissolving, wherein the ethylene glycol is the same as the ethylene glycol in the embodiment 1, and obtaining the conductive adhesive.
The application comprises the following steps:
the conductive adhesive is uniformly coated on a carbon plastic plate (with the diameter of 5cm and the thickness of 2 mm), a carbon fiber felt (with the diameter of 5 cm) with the thickness of 4mm is bonded and pressed together with the carbon plastic plate, and then the carbon fiber felt is sintered for 1 hour in a vacuum furnace at the temperature of 800 ℃ to prepare the composite electrode plate 5 which is solidified into a whole.
Ohmic resistance and soaking durability tests are respectively carried out on the integrated composite electrode plate 5, and the specific test method is the same as that of the embodiment 1.
The results of the experiment are shown in fig. 3 and 4.
Comparative example 1:
a contact resistance test was performed by placing a graphite plate (diameter 5cm, thickness 2 mm) and a polyacrylonitrile-based graphite felt (diameter 5 cm) 4mm thick, with the graphite felt on top and the graphite plate on bottom, between two 5cm diameter gold-plated copper blocks as described in example 1. The resistance between the graphite plate and the porous electrode was measured at different pressures.
The results of the experiment are shown in FIG. 3.
Comparative example 1:
the present invention is described by comparative example 1 that, in comparison with the composite electrode plate 5 of example 5 of the present invention, the porous electrode plate that is not compressed with a binder, and the porous electrode plate that is not compressed with a binder, the battery performance of the composite electrode plate 5 of example 5 of the present invention is superior to the above-described two under the same conditions.
The comparative tests are as follows:
the polyacrylonitrile-based graphite felt is respectively embedded into 2 flow frames 4, an ion exchange membrane 3 is arranged between 2 multi-graphite plates, the conductive adhesive described in the embodiment 5 is uniformly coated on the 2 graphite plates (5 cm multiplied by 2 mm), the polyacrylonitrile-based graphite felt (3.3 cm multiplied by 3.3 cm) with the thickness of 4mm is bonded and pressed together, and then the polyacrylonitrile-based graphite felt is arranged in a vacuum furnace at 800 ℃ for sintering for 1 hour to prepare the composite electrode plate 5 which is solidified into a whole.
The integrated composite electrode plate 5 is applied to an all-vanadium redox flow battery, the electrolyte is a mixed solution of 1.5 mol/L vanadium ions and 3 mol/L sulfuric acid, the volumes of the electrolytes of the positive electrode and the negative electrode are both 50ml, the battery performance test is carried out on the assembled all-vanadium redox flow battery monocell, the upper limit of the charging voltage of the battery is set to be 1.75V, and the lower limit of the discharging voltage is set to be 0.8V (marked as A).
And (3) assembling the graphite plate and the graphite felt with the same specification without using a binder into a single cell for testing the battery performance, wherein the electrolyte and the battery voltage are set to be consistent with A (marked as B).
And (3) taking the graphite plate with the same specification and a graphite felt (3.3 cm multiplied by 3.3 cm) with the thickness of 5mm, assembling the graphite plate and the graphite felt into a single cell without using a binder, and testing the performance of the cell, wherein the electrolyte and the voltage of the cell are set to be consistent with those of A (marked as C).
In all three cases, the thickness of the electrode frame is 4 mm.
As shown in fig. 5, it can be found that: in the absence of binder, in the case of a porous electrode without compression (symbol B), the contact resistance with the bipolar plate is large, resulting in a cell having a starting voltage of about 60mV higher when charged than a cell using a bipolar plate with an integrated electrode (symbol a), and a starting voltage of about 70mV lower when discharged, with severe polarization (fig. 5 a). Meanwhile, in the case where the porous electrode compression ratio is 20% without using the binder (symbol C), the initial voltage at the time of charging is still 40mV higher than that of the cell a using the integrated electrode bipolar plate, and the initial voltage at the time of discharging is still 40mV lower than that, and the polarization is still relatively severe (fig. 5 a).
Cell a using the integrated electrode bipolar plate has higher voltage and energy efficiency than cell B and cell C when not in use (fig. 5B, 5C) when charged and discharged at different current densities. From the cell capacity curve (FIG. 5 d), the discharge capacities of cell B and cell C were lower at different current densities than cell A using the integrated electrode bipolar plate, and cell A was at a higher current density (150 mA/cm)2) The cell can still be normally charged and discharged, and the discharge capacity of the cell B and the cell C without using the binder is almost zero at this current density.
As can be seen from comparison of the mark a (sample of example 1) in the comparative example 2 with the marks B and C, respectively, the porous electrode 1 and the bipolar plate 2 are sintered and cured at high temperature by the conductive adhesive to have a larger discharge capacity of the composite electrode plate 5; furthermore, the mark A effectively avoids the polarization phenomenon and is used for measuring the current density (150 mA/cm)2) The cell can still be charged and discharged normally, and the discharge capacity of the labels B and C at the current density is almost zero.
Example 8: porous electrode and bipolar plate curing integrated liquid flow energy storage battery example
The flow energy storage battery integrally cured by the composite electrode plate 5 of example 1 is shown in an exploded structural view of the flow energy storage battery of fig. 1,
a liquid flow energy storage battery with a porous electrode and a bipolar plate cured integrally comprises 2 composite electrode plates 5 prepared in the embodiment 1, an ion exchange membrane 3 and 2 flow frames 4,
2 flow frames 4 are sleeved on the 2 composite electrode plates 5 and are mutually jointed to form a closed space, the closed space between the flow frames 4 and the 2 composite electrode plates 5 provides a flow channel and a place for electrolyte solution, an ion exchange membrane 3 is arranged between the 2 composite electrode plates 5,
wherein the thickness of the conductive adhesive coating between the composite electrode plates 5 is 70-80 μm.
The electrolyte and the charge/discharge voltage of the battery were set at 50mA/cm for the battery in the same manner as in comparative example 12And carrying out charge-discharge cycle performance test under the current density. As shown in fig. 7, the current efficiency, voltage efficiency and energy efficiency of the battery are very stable after 100 charge and discharge cycles, and the efficiency of each battery is similar to that of the battery marked as a in comparative example 1 (compare with curve a in fig. 5 b), which is superior to the performance of the battery without the composite bipolar plate.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be understood that any modification, equivalent replacement, improvement or the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A liquid flow energy storage battery with a porous electrode and a bipolar plate solidified into a whole is characterized by comprising 2 porous electrodes (1), 2 bipolar plates (2), an ion exchange membrane (3) and 2 flow frames (4),
the porous electrode (1) and the bipolar plate (2) are solidified into a composite electrode plate (5) through a coating formed by high-temperature sintering of a conductive adhesive, wherein the thickness of the coating sintered by the conductive adhesive of the composite electrode plate (5) is 1-100 mu m,
the two flow frames (4) are respectively sleeved on the corresponding composite electrode plates (5) and are mutually attached to form a closed space, the closed space between the flow frames (4) and the two composite electrode plates (5) is a flow channel and a place of electrolyte solution, and the ion exchange membrane (3) is arranged between the two composite electrode plates (5).
2. The integrated liquid flow energy storage battery with the solidified porous electrode and the bipolar plate as claimed in claim 1, wherein the porous electrode (1) comprises but is not limited to pitch-based graphite felt, polyacrylonitrile-based graphite felt, viscose-based graphite felt, carbon fiber felt, carbon cloth, and carbon paper.
3. The flow energy storage battery with the integrated solidified porous electrode and bipolar plate as claimed in claim 2, wherein the porosity of the porous electrode (1) is 0.40-0.95, and the thickness is 2-10 mm.
4. A porous electrode and bipolar plate consolidated flow energy storage battery according to claim 1, characterized in that said ion exchange membrane (3) comprises but is not limited to cation exchange membrane of perfluorosulfonic acid type, anion exchange membrane of polysulfone type, anion exchange membrane of polybenzimidazole type.
5. A preparation method of a composite electrode plate (5) is characterized by comprising the following steps:
coating a conductive adhesive on the surface of the bipolar plate (2), wherein the thickness of the conductive adhesive coating is 1-100 mu m;
and (3) bonding and pressing the porous electrode (1) to be bonded and the bipolar plate (2) together, and then placing the porous electrode and the bipolar plate in a vacuum furnace to sinter for 1-5 hours at the temperature of 500-1000 ℃ to prepare the integrated composite electrode plate (5).
6. The method for manufacturing the composite electrode plate according to claim 5, wherein the coating method of the conductive adhesive is any one of blade coating, brushing, spin coating, spray coating and dipping.
7. The conductive adhesive is characterized by comprising a high polymer material, a conductive agent and a sintering aid,
according to the mass ratio of the components,
the proportion of the high polymer material, the conductive agent and the sintering aid is (10-1): (10-1): 1;
wherein the high polymer material is at least one of epoxy resin, phenolic resin, polyethylene, polypropylene and polysulfone,
the conductive agent is at least one of carbon powder, carbon black, carbon nano fiber, graphite powder, silver powder, nickel powder and zinc powder,
the sintering aid is selected from TiC, WC and B4C、SiC、SiO2、Al2O3And Al4C3At least one of (1).
8. The conductive adhesive according to claim 7, wherein the polymer material is in a powder form with a purity of 95% to 99.8%,
the conductive agent material is in a powdery or fibrous shape, the particle size is between 10nm and 10 mu m, the purity is between 99.5 and 99.95 percent,
the sintering aid material is powdery in shape, has the particle size of 10 nm-10 mu m and the purity of 95-99.5 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910792903.0A CN112436172A (en) | 2019-08-26 | 2019-08-26 | Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910792903.0A CN112436172A (en) | 2019-08-26 | 2019-08-26 | Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112436172A true CN112436172A (en) | 2021-03-02 |
Family
ID=74690521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910792903.0A Pending CN112436172A (en) | 2019-08-26 | 2019-08-26 | Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112436172A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117423881A (en) * | 2023-12-14 | 2024-01-19 | 江苏米格新材料股份有限公司 | Method for improving effective contact surface of flow battery electrode and bipolar plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009376A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Integrated pole dual-pole board for oxidation deoxidization liquid energy-storing battery and its preparation |
| CN101719556A (en) * | 2009-11-24 | 2010-06-02 | 攀枝花新钢钒股份有限公司 | Pile structure of redox flow battery |
| KR20180024252A (en) * | 2016-08-29 | 2018-03-08 | 한국에너지기술연구원 | Redox flow battery |
| US20190165385A1 (en) * | 2016-08-05 | 2019-05-30 | H2, Inc. | Unit cell for redox flow battery, for reducing pressure drop caused by electrolyte flow in stack |
-
2019
- 2019-08-26 CN CN201910792903.0A patent/CN112436172A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101009376A (en) * | 2006-01-25 | 2007-08-01 | 中国科学院大连化学物理研究所 | Integrated pole dual-pole board for oxidation deoxidization liquid energy-storing battery and its preparation |
| CN101719556A (en) * | 2009-11-24 | 2010-06-02 | 攀枝花新钢钒股份有限公司 | Pile structure of redox flow battery |
| US20190165385A1 (en) * | 2016-08-05 | 2019-05-30 | H2, Inc. | Unit cell for redox flow battery, for reducing pressure drop caused by electrolyte flow in stack |
| KR20180024252A (en) * | 2016-08-29 | 2018-03-08 | 한국에너지기술연구원 | Redox flow battery |
Non-Patent Citations (1)
| Title |
|---|
| MINGCHAO WANG等: "A user-friendly heat-resistant modified polymer-based adhesive for joining and repair of carbon/carbon composites", 《MATERIALS AND DESIGN》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117423881A (en) * | 2023-12-14 | 2024-01-19 | 江苏米格新材料股份有限公司 | Method for improving effective contact surface of flow battery electrode and bipolar plate |
| CN117423881B (en) * | 2023-12-14 | 2024-04-02 | 江苏米格新材料股份有限公司 | Method for improving effective contact surface of flow battery electrode and bipolar plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5081214B2 (en) | Organic electrolyte capacitor | |
| CN110970668B (en) | All-solid-state battery composite structure, preparation method and application thereof | |
| JP5623036B2 (en) | Molding material for fuel cell separator | |
| US20110143253A1 (en) | Catalyst and method for producing the same, membrane electrode assembly and method for producing the same, fuel cell member and method for producing the same, fuel cell, and electricity storage device | |
| CN112310413A (en) | Gas diffusion layer, preparation method and application thereof | |
| WO2016090867A1 (en) | Sulfonated polymer applied to lithium battery electrode as binder | |
| CN101877408A (en) | Current collector of liquid flow battery and liquid flow battery | |
| CN108346523A (en) | A kind of preparation method containing lithium an- ode of mixed type energy storage device | |
| CN105609703B (en) | Integrated electrode and manufacture method | |
| CN101409336A (en) | Composite electrode and preparation method thereof | |
| CN109216654A (en) | A kind of lithium ion battery of multilayer cathode pole piece and its preparation method and application | |
| CN110600704A (en) | Silicon/graphite composite material and preparation method and application thereof | |
| US4731310A (en) | Cathodic electrode | |
| CN108878893A (en) | A kind of fast charge negative electrode of lithium ion battery modified collector and preparation method thereof | |
| CN109167104A (en) | A kind of room temperature sodium-sulphur battery and preparation method thereof | |
| CN112436172A (en) | Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery | |
| CN210052799U (en) | Porous electrode and bipolar plate solidification integrated liquid flow energy storage battery | |
| CN108550905B (en) | Nano composite vanadium electrolyte, preparation method thereof and static vanadium battery comprising nano composite vanadium electrolyte | |
| CN116632268A (en) | Flow battery integrated electrode and flow battery | |
| CN110224143A (en) | Lead-acid battery collector, preparation method, pole plate and lead-acid battery | |
| CN102386440A (en) | High-power high-safety lithium ion secondary battery and preparation method thereof | |
| CN116145154A (en) | Phosphate sodium ion battery positive electrode material and preparation method thereof | |
| CN113299919B (en) | Positive pole piece and lithium ion battery comprising same | |
| CN109560272A (en) | A kind of novel dual metal oxide composite carbon nanometer tube material, preparation method and application | |
| JPH0690933B2 (en) | Stacked electrolytic cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210302 |