CN101752565A - Battery electrode and preparation method thereof and the vanadium flow battery that comprises this battery electrode - Google Patents
Battery electrode and preparation method thereof and the vanadium flow battery that comprises this battery electrode Download PDFInfo
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- CN101752565A CN101752565A CN200810186638A CN200810186638A CN101752565A CN 101752565 A CN101752565 A CN 101752565A CN 200810186638 A CN200810186638 A CN 200810186638A CN 200810186638 A CN200810186638 A CN 200810186638A CN 101752565 A CN101752565 A CN 101752565A
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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
- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The present invention relates to battery electrode, this electrode contains conductivity porous material substrate and polymer, to the described distribution of polymer of small part in the micropore of partially conductive porous material substrate, the polymer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata with this conductivity porous material substrate, lower floor and the intermediate layer that has every the liquid effect, wherein this polymer accounts for more than the 75 weight % of the total content of this polymer in the conductivity porous material substrate at the content in intermediate layer, and this polymer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymer in the conductivity porous material substrate.The present invention also provides the vanadium flow battery that comprises this battery electrode, and this vanadium flow battery is owing to eliminated contact resistance, thereby internal resistance is low and efficiency for charge-discharge is high.
Description
Technical field
The invention relates to the preparation method and the vanadium flow battery that comprises this battery electrode of a kind of battery electrode and this battery electrode.
Background technology
Vanadium flow battery is a kind of eco-friendly novel energy-storing system and energy conversion device efficiently, has that scale is big, the life-span is long, cost is low, efficient is high, nontoxic and eco-friendly characteristics.The large-scale electric energy that vanadium flow battery can be used as in wind energy and the solar power system stores and the use of effective conversion equipment; The peak load shifting and the balanced load that can also be used for electrical network play the effect that improves the quality of power supply and power station operation stability.
Vanadium flow battery is with vanadium (V) solion of the different valence state active material as cell reaction, and anode is V
4+/ V
5+Electricity is V to, negative pole
2+/ V
3+Electricity is right, and both positive and negative polarity electrolyte leaves in respectively in two storage tanks, by pump electrolyte is squeezed into battery during work.Separate inside battery conducting when discharging and recharging between the electrode both positive and negative polarity by cationic directional migration in the electrolyte with ionic membrane.The monocell of some is connected into battery pile, can exports the electric current and the voltage of rated power.
In practice,, improve the integrated degree of battery pile in order to reduce the volume of battery pile, usually use conductive bipolar plate, and place conductivity porous material substrate, for example graphite felt in the both sides of conductive bipolar plate, as reactive matrix, conductive bipolar plate has the double action every liquid and conduction.Conductive bipolar plate generally adopts high-density graphite plate or conductive plastic plate to make, and structure is comparatively complicated.
Because above-mentioned conductive bipolar plate is worked in the environment of highly acid and strong oxidizing property usually, therefore the corrosion resistance to the conductive bipolar plate material has proposed very high requirement.Simultaneously, in the battery assembling process, in order to guarantee the sealing of whole device, the battery pile both sides usually need to apply bigger pressure; But, because the fragility of graphite material own is big, if the discontinuity of graphite cake just very easily causes graphite cake to break.And the composite construction between conductive bipolar plate and the conductivity porous material substrate also can produce bigger contact resistance, and the problem that the conductivity porous material substrate comes off also very easily takes place in the use.In addition, higher as the cost of the high-density graphite plate of conductive bipolar plate, be unfavorable for reducing the cost of electrode.In sum, the existing combination electrode above shortcomings of being made up of conductivity porous material substrate and conductive bipolar plate have seriously limited popularizing of vanadium flow battery, and the battery electrode of development of new is imperative.
Summary of the invention
The objective of the invention is to overcome the conductivity porous material substrate of prior art and combination electrode that conductive bipolar plate is formed and have that graphite cake is easily broken, the conductivity porous material substrate easily comes off and the higher shortcoming of contact resistance of electrode, provides a kind of difficult fragmentation, conductivity porous material substrate can not come off and eliminate battery electrode of contact resistance and preparation method thereof; The present invention also further provides a kind of vanadium flow battery that comprises above-mentioned battery electrode.
According to battery electrode provided by the invention, wherein, this electrode contains conductivity porous material substrate and polymer, to the described distribution of polymer of small part in the micropore of partially conductive porous material substrate, the polymer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata with this conductivity porous material substrate, lower floor and the intermediate layer that has every the liquid effect, wherein, this polymer accounts for more than the 75 weight % of the total content of this polymer in the conductivity porous material substrate at the content in intermediate layer, and this polymer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymer in the conductivity porous material substrate.
The present invention also provides the preparation method of above-mentioned battery electrode, this method comprises to be made to the micropore of small part polymerisable monomer entering part conductivity porous material substrate, the polymerisable monomer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata successively with this conductivity porous material substrate, three layers of intermediate layer and lower floors, wherein, this polymerisable monomer accounts for more than the 75 weight % of the total content of this polymerisable monomer in the conductivity porous material substrate at the content in intermediate layer, and this polymerisable monomer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymerisable monomer in the conductivity porous material substrate; This method also comprises makes described polymerisable monomer polymerization.
The present invention also further provides a kind of vanadium flow battery, and this battery comprises battery electrode and electrolyte, and wherein, described battery electrode is an above-mentioned battery electrode provided by the invention.
Battery electrode provided by the invention, by polymer being embedded in the micropore in conductivity porous material substrate intermediate layer, it is airtight to make the micropore in conductivity porous material substrate intermediate layer be aggregated thing, thereby guarantee that this partially conductive porous material substrate has every the liquid effect, effectively play the effect that intercepts electrolyte; Simultaneously, because the conductivity porous material substrate still is structure as a whole, so the conductivity of conductivity porous material substrate still exists, thereby this conductivity porous material substrate can play the effect every liquid and conduction of conductive bipolar plate simultaneously.In addition, because polymer is filled in the micropore in conductivity porous material substrate intermediate layer, become as a whole with the conductivity porous material substrate, make the problem that battery electrode of the present invention has in use avoided the conductivity porous material substrate to come off and produce contact resistance.And, because the good toughness of polymer, elasticity is high and have excellent corrosion resisting performance, can be used as electrode every liquid and play the effect of sealing; And the specific area of conductivity porous material substrate is big, can be used as the carrier of cell reaction, and good chemical reactivity and response area is provided.Therefore, compact conformation, mechanical property excellence, favorable sealing property, non-contact resistance and the cost according to battery electrode of the present invention is low.This shows, can overcome the deficiency that the above-mentioned combination electrode of being made up of conductive bipolar plate and conductivity porous material substrate exists according to battery electrode of the present invention.
Description of drawings
Figure 1 shows that front view according to battery electrode of the present invention;
Figure 2 shows that vertical view according to battery electrode of the present invention;
Figure 3 shows that the method according to this invention prepares a kind of typical embodiment of battery electrode;
Figure 4 shows that the structural representation of the reactor of preparation battery electrode of the present invention;
Figure 5 shows that the schematic diagram of the method for the specific insulation of measuring battery electrode of the present invention;
Figure 6 shows that the schematic diagram of measuring battery electrode of the present invention every the method for fluidity.
Embodiment
According to battery electrode provided by the invention, wherein, this electrode contains conductivity porous material substrate and polymer, to the described distribution of polymer of small part in the micropore of partially conductive porous material substrate, the polymer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata with this conductivity porous material substrate, lower floor and the intermediate layer that has every the liquid effect, wherein, this polymer accounts for more than the 75 weight % of the total content of this polymer in the conductivity porous material substrate at the content in intermediate layer, and this polymer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymer in the conductivity porous material substrate.
The present invention introduces polymer in the part micropore of conductivity porous material substrate, described polymer is airtight with the micropore of this partially conductive porous material substrate, and the polymer that is distributed in the micropore of this partially conductive porous material substrate is divided into three layers of upper strata, intermediate layer and lower floors successively with this conductivity porous material substrate.Illustrated in figures 1 and 2 is front view and vertical view according to battery electrode of the present invention, wherein, the specific area of conductivity porous material substrate 11 is big, has very high chemical reactivity and response area, can be used as the matrix of the electrode reaction of battery, and play the effect of conduction; Polymer 12 has good chemical resistance and higher mechanical property, can be used as battery every liquid and seal, can also bear simultaneously pressure from the battery pile both sides; And polymer 12 is distributed in the middle part of conductivity porous material substrate 11, and is as a whole with 11 one-tenth of conductivity porous material substrate.Because according to there not being additional tack coat between the conductivity porous material substrate of battery electrode of the present invention and the polymer, therefore, battery electrode of the present invention can overcome existing combination electrode and have contact resistance and the caducous defective of graphite felt.
In the intermediate layer of conductivity porous material substrate of the present invention, at least partial polymer embeds the conductivity porous material substrate, and melting with the conductivity porous material substrate is the integral body of a densification, wherein, polymer plays the effect every liquid, and the conductivity porous material substrate then plays the effect of conduction.Therefore, the content of polymer in the intermediate layer should account for more than the 75 weight % of the total content of polymer in the conductivity porous material substrate, can be 75-100 weight %, is preferably 90-100 weight %; The content of polymer in the upper and lower then accounts for below the 25 weight % of the total content of polymer in the conductivity porous material substrate, can be 0-25 weight %, is preferably 0-10 weight %; And conductivity porous material substrate for the reactive matrix that is conventionally used as battery electrode, because the porosity of reactive matrix is big and density reactive matrix itself is less, therefore, the weight ratio of polymer and conductivity porous material can reach 1 usually in the intermediate layer: 0.12-0.18, the hole in the intermediate layer of conductivity porous material substrate almost all is aggregated thing and fills up in above-mentioned scope, this electrode is had every the liquid effect, to satisfy the actual requirement of using.The battery electrode for preparing in the embodiment of the invention all reach 100% every fluidity.
Polymer is divided into three layers of upper strata, intermediate layer and lower floors successively with the conductivity porous material substrate in the battery electrode of the present invention, and wherein, the intermediate layer has conduction and every the effect of liquid, the upper and lower then can be used as the matrix of cell reaction.The present invention is for the not special restriction of above-mentioned three layers thickness, as long as can satisfy the requirement of actual use.But in order to guarantee under the prerequisite of liquid, make electrode have bigger response area and higher reactivity, under the preferred situation, the thickness in described intermediate layer can account for the 20-60% of described conductivity porous material substrate gross thickness, and described upper and lower two-layer thickness ratio can be 1: 1-1.3.Among the present invention, except as otherwise noted, otherwise described thickness is meant from the beeline of upper strata to the lower floor direction of conductivity porous material substrate.For example, the thickness in described intermediate layer is meant the interface on intermediate layer and upper strata to the air line distance between the interface of intermediate layer and lower floor, and the both sides in intermediate layer to the upper surface of electrode or the air line distance of lower surface is respectively the thickness on upper strata and the thickness of lower floor.
Although in battery electrode of the present invention, described polymer can all be distributed in the partially conductive porous material substrate; But under the preferred condition, described battery electrode can also be distributed in the partially conductive porous material substrate for partial polymer at least, another part polymer then extend to protrude from this conductivity porous material substrate around.Described protrude from this conductivity porous material substrate around polymer can further improve battery electrode every fluidity and sealing and further raising mechanical strength of electrodes.The described width that protrudes from the polymer all around of this conductivity porous material substrate can decide according to the size of battery container and electrode.Generally speaking, the described width that protrudes from the polymer all around of this conductivity porous material substrate is the 10-13% of electrode width.The described amount that protrudes from the polymer all around of this conductivity porous material substrate can decide according to the porosity of battery container, conductivity porous material substrate and the size of electrode.Generally speaking, at the described width that protrudes from the polymer all around of this conductivity porous material substrate is the 10-13% of electrode width, and the porosity of described conductivity porous material substrate is under the situation of 50-95%, and the described amount that protrudes from the polymer all around of this conductivity porous material substrate can be the 15-25 weight % of described polymer total amount.The described thickness that protrudes from the polymer all around of this conductivity porous material substrate can be identical or different with the thickness in described conductivity porous material substrate intermediate layer, for example can be 0.8-1.2 times of intermediate layer thickness, but it is preferred identical with the thickness in described conductivity porous material substrate intermediate layer, so both can guarantee mechanical strength, and can guarantee again as the two-layer area that contacts with electrolyte about the conductivity porous material substrate of electrode as the conductivity porous material substrate intermediate layer of conductive bipolar plate.The battery electrode for preparing in the embodiment of the invention is that partial polymer is distributed in the micropore of partially conductive porous material, another part polymer then extend to protrude from the conductivity porous material substrate around, and described extend to protrude from the conductivity porous material substrate around the thickness of polymer and the consistency of thickness in described conductivity porous material substrate intermediate layer.
In battery electrode of the present invention, described polymer has the effect every liquid, sealing, also will bear the pressure from the battery pile both sides, thermal stability, higher chemical resistance also will have the good comprehensive mechanical performance simultaneously therefore to require polymer to have preferably.Therefore, satisfy above-mentioned requirements better in order to make described polymer, the glass transition temperature of described polymer is preferably 70-90 ℃; Described polymer is preferably the polymer with higher elasticity and toughness, it is the polymer that battery electrode of the present invention preferably has higher elongation at break, more specifically, the preferred elongation at break of polymer of the present invention is higher than 10% polymer, and further preferred elongation at break is the polymer of 20-100%.Described elongation at break is that polymeric material when fracture takes place at the increment of length direction and the percentage of material original length under the tensile stress effect.Concrete, polymer of the present invention can be the copolymer of polystyrene, Kynoar or styrene and vinylidene.Polystyrene has preferably that mechanical property also has chemical resistance preferably simultaneously, can acid and alkali resistance and the corrosion of salting liquid, and dissolution phenomena can not take place and electrode reaction is caused interference at electrolyte and electrode process; In addition, polystyrene with low cost, useful for the cost that reduces electrode.Therefore, under the preferred situation, the polymer in the battery electrode of the present invention is a polystyrene.
In the battery electrode of the present invention, described conductivity porous material substrate has conduction and as the effect of the matrix of electrode reaction.The present invention adopts this area material commonly used to get final product for conductivity porous material substrate and without particular limitation.In the specific embodiments of the invention with graphite felt as the conductivity porous material substrate.The porosity of described graphite felt can be 50-95%, and the porosity of the graphite felt of using in the embodiment of the invention is 85%.
The present invention also provides the preparation method of above-mentioned battery electrode, this method comprises to be made to the micropore of small part polymerisable monomer entering part conductivity porous material substrate, the polymerisable monomer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata successively with this conductivity porous material substrate, three layers of intermediate layer and lower floors, wherein, this polymerisable monomer accounts for more than the 75 weight % of the total content of this polymerisable monomer in the conductivity porous material substrate at the content in intermediate layer, and this polymerisable monomer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymerisable monomer in the conductivity porous material substrate; This method also comprises makes above-mentioned polymerisable monomer polymerization.
Making the method to the micropore of small part polymerisable monomer entering part conductivity porous material substrate can be that those skilled in the art are in conjunction with its obtainable various methods of grasping of ABC; a preferred embodiment of the invention; make the method to the micropore of small part polymerisable monomer entering part conductivity porous material substrate comprise that the side with the conductivity porous material substrate immerses in the protective agent; protective agent is entered in the micropore of a side of conductivity porous material substrate; in this conductivity porous material substrate, add polymerisable monomer then; make to the micropore of small part polymerisable monomer entering part conductivity porous material substrate; thereby the upper strata of gained conductivity porous material substrate; intermediate layer and lower floor are respectively for three layers and do not contain polymerisable monomer and protectant blanket layer; contain the layer of polymerisable monomer and contain protectant layer; described protective agent in the micropore of polymerisable monomer entering part conductivity porous material substrate and under the polymerizing condition for solid or described protective agent for do not dissolve mutually with described polymerisable monomer and density greater than the liquid of polymerisable monomer, described polymerisable monomer and protectant amount make the thickness of the layer that contains polymerisable monomer account for the 20-60% of the height overall thickness of conductivity porous material.The thickness of described polymerisable monomer solution is that the bottom surface with the lower floor of conductivity porous material substrate is that benchmark is determined.
Although according to the method for preparing battery electrode of the present invention, described protective agent and polymerisable monomer can only be in the lower floor and intermediate layer of conductivity porous material substrate.But for further improve battery electrode every fluidity, sealing and mechanical strength; under the preferred condition; described part protective agent and part polymerisable monomer can be in the lower floor and intermediate layer of conductivity porous material substrate, and another part protective agent and another part polymerisable monomer then can be in all around the lower floor and the intermediate layer of conductivity porous material respectively.
Figure 3 shows that the method according to this invention prepares a kind of typical embodiment of battery electrode.Wherein, 11 is the conductivity porous material substrate, and 12 is polymer, and 31 is polymerisable monomer, and 32 is protective agent, and 41 is the base of reactor.
To describe the preparation method of battery electrode of the present invention below in detail.
In the micropore that makes polymerisable monomer solution entering part conductivity porous material substrate; prepare comprise in the method for battery electrode of the present invention select for use fusing point at 50-70 ℃ inert substance as protective agent 32; it is liquid it to be become protective agent 32 heating, and with the step in the liquid protective agent 32 of conductivity porous material substrate 11 immersions.On the one hand protective agent can be used as the carrier that polymerisable monomer carries out the polymer that generates in the matrix of polymerization reaction and the polymerization reaction; described on the other hand protective agent can also play the effect of isolation, reaches only to immerse polymerisable monomer and carry out the purpose that polymerization generates polymer in the micropore at graphite felt middle part.
Described inert substance is meant to have certain chemistry and temperature stability, both be not dissolved in polymerisable monomer, do not participate in polymerization reaction yet, under the condition of heating, have good stability, the material of the phenomenon as degraded or release micromolecular compound so can not occur; Described in addition protective agent also should be easy to remove, and is convenient to remove after polymerization reaction is finished protective agent like this.Described protective agent can for do not dissolve mutually with polymerisable monomer and density greater than the inert fluid material of polymerisable monomer; Can also can to become flowability on the polymerization temperature liquid preferably in order to be heated to, and under room temperature (15-40 ℃) and polymerizing condition, all remain the inert substance of solid.All can be used as protective agent of the present invention as long as satisfy the material of above-mentioned requirements, under the preferred situation, protectant material of the present invention is paraffin or polyethylene glycol (PEG).
Paraffin is the mixture that carbon number is about the hydro carbons of 18-30, and the chemical property of paraffin is stable, and is easy to remove, and can satisfy the requirement of the present invention for the protective agent material.According to the difference of processing and refining degree, paraffin can be divided into paraffin wax fully refined, semi-refined paraffin wax and scale wax.For fear of the influence of impurity, of the present inventionly be preferably paraffin wax fully refined as protectant paraffin to battery electrode of the present invention.Described melting point of paraffin wax is 58-62 ℃; Preferred melting point of paraffin wax is 58-60 ℃.
Polyethylene glycol is to contain α, and the general name of the ethylene glycol polymer of ω-both-end hydroxyl is a kind of in the PTMEG.According to the difference of molecular weight, the outward appearance of polyethylene glycol can be no color or smell liquid or paraffin shape solid.Polyethylene glycol uses as protective agent among the present invention; therefore, polyethylene glycol preferably selects to be under the room temperature polyethylene glycol of paraffin shape solid, therefore; the fusion temperature of the preferred polyethylene glycol of the present invention is 64-70 ℃, and the fusion temperature of further preferred polyethylene glycol is 64-66 ℃.
Protectant amount can be determined according to the requirement of the electrode that will prepare among the present invention, comprises upper strata, intermediate layer and lower floor as long as can guarantee the electrode that makes, and guarantees that preferably the ratio of the upper and lower two-layer thickness of the electrode that makes is 1: 1-1.3.Further under the preferable case, protectant amount makes the thickness that immerses the electrode in the protective agent equal the upper thickness or the lower thickness of electrode.For example: needing the integral thickness of the electrode of preparation is 8 millimeters, and wherein, the thickness in intermediate layer is 4 millimeters, and the thickness of the upper and lower is respectively 2 millimeters, and then the lower surface with the conductivity porous material is a benchmark, and protectant height can be 2 millimeters, and the rest may be inferred.
Prepare and also comprise in the method for battery electrode of the present invention and place polymerisable monomer 31, make polymerisable monomer immerse step in the micropore at middle part of conductivity porous material substrate containing protectant conductivity porous material substrate.It is 1 that the amount of the polymerisable monomer in the micropore at the middle part of described immersion conductivity porous material substrate should make the weight ratio of polymer and conductivity porous material substrate: 0.12-0.18; The height of polymerisable monomer should guarantee that then the thickness ratio of three layers of the upper strata, intermediate layer of gained conductivity porous material substrate and lower floors is 1: 0.5-2.5: 1-1.3.For example; needing the integral thickness of the electrode of preparation is 8 millimeters; wherein; the thickness in intermediate layer is 4 millimeters; the thickness of the upper and lower is respectively 2 millimeters, and then the lower surface with the conductivity porous material is a benchmark, and protectant height can be 2 millimeters; the height of polymerisable monomer can be 4 millimeters, and the rest may be inferred.
Although as long as immerse the thickness that the thickness of the conductivity porous material substrate in the polymerisable monomer can guarantee the intermediate layer; but for further improve battery electrode of the present invention every fluidity, sealing and mechanical strength; the present invention preferably also is in the protective agent around the part (being lower floor or upper strata) that immerses protectant conductivity porous material substrate, and then only make intermediate layer and intermediate layer around be arranged in polymerisable monomer.When described protective agent is liquid, can be by control polymerisable monomer solution and protective agent does not dissolve each other and the density of polymerisable monomer solution realizes above-mentioned purpose less than protectant density; When described protective agent is the lower material of fusing points such as paraffin or polyethylene glycol, can makes the protective agent cooling become solid earlier, and then polymerisable monomer solution is joined this protective agent surface of solids realize.
The method for preparing battery electrode of the present invention also comprises the step that makes the polymerisable monomer polymerization generate polymer 12.Generate because polymer of the present invention is an original position, the polymer of generation need have the double action every liquid and sealing, and described polymer also will bear the pressure from the battery pile both sides.Therefore, generated in-situ polymer should fine and close, free of surface defects, has good thermal endurance, chemical resistance and good comprehensive mechanical performance.All can be used as polymerisable monomer of the present invention as long as satisfy the monomer of above-mentioned requirements.For further strengthen polymer every fluidity, sealing and mechanical strength, polymerisable monomer of the present invention is preferably the mixture of styrene, vinylidene or styrene and vinylidene.
In addition, in order further to improve mechanical performance, particularly elasticity and the toughness of polymer, make polymer can better bear pressure from the battery pile both sides, prolong the useful life of electrode, polymer of the present invention can also contain elastomer modifier.The present invention is also without particular limitation to the kind of elastomer modifier, adopt this area elastomer modifier commonly used to get final product, for example described elastomer modifier can be that butadiene-styrene rubber or the weight average molecular weight of 1000-500000 is the isoprene rubber of 1000-300000 for dibutyl phthalate, weight average molecular weight, is preferably dibutyl phthalate.Although the introducing of elastomer modifier can improve the elasticity and the toughness of polymer, the addition of elastomer modifier is bigger, the elastomer reunion easily takes place separate out, and worsens polymer properties on the contrary, and therefore, the content of elastomer modifier should be suitable.Total amount with polymer is a benchmark, and the content of elastomer modifier is 5-20 weight % among the present invention.Elastomer modifier of the present invention begins preceding adding in polymerization reaction, is about to elastomer modifier and adds in the polymerisable monomer, and make the polymerisable monomer that contains elastomer modifier immerse the conductivity porous material substrate.
The present invention is also without particular limitation to the condition of the polymerization reaction of polymerisable monomer, adopts method well known to those skilled in the art to get final product.Concrete, because no small-molecule substance generates in the Raolical polymerizable process, and reaction speed is fast, the reaction condition gentleness, and therefore the polymerization reaction of polymerisable monomer of the present invention can be Raolical polymerizable.For fear of the step that removes solvent, the polymerization methods of polymerisable monomer of the present invention can be polymerisation in bulk.
The mode that the Raolical polymerizable of polymerisable monomer of the present invention can adopt radical initiator to cause is carried out, and the present invention is also without particular limitation to the kind of initator.Adopting under protectant situation; the temperature of preferred described initator initiated polymerization is lower than protectant melting temperature, and for example: azodiisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, di-isopropyl peroxydicarbonate and di-cyclohexylperoxy di-carbonate all can be used as radical polymerization initiator of the present invention.The present invention adopts and determines that for method known in those skilled in the art the consumption of initator gets final product the consumption of initator and without particular limitation, is benchmark with the total amount of polymerisable monomer, and the consumption of described initator is 5-10 weight %.The condition of the polymerization reaction that radical initiator of the present invention causes can be carried out under for condition known in those skilled in the art, polymerization temperature is determined according to the decomposition temperature of selected initator, for example, with azodiisobutyronitrile as initator then polymerization temperature be generally 45-65 ℃, with dibenzoyl peroxide as initator then polymerization temperature be generally 70 ℃, with dilauroyl peroxide as initator then polymerization temperature be generally 60 ℃, with peroxide tert pivalate ester as catalyst then polymerization temperature be generally 55 ℃, with di-isopropyl peroxydicarbonate as initator then polymerization temperature be generally 45 ℃, with di-cyclohexylperoxy di-carbonate as initator then polymerization temperature be generally 45 ℃.But the temperature of polymerization reaction of the present invention is not limited in this.The present invention also has no particular limits polymerization reaction time, as long as polymerization time can guarantee that the glass transition temperature of the polymer that generates is at 70-90 ℃.
The polymerization reaction of polymerisable monomer of the present invention can also adopt the method for ultraviolet radiation to carry out.The present invention there is no special requirement for the equipment that produces ultraviolet light, adopts this area equipment commonly used to get final product, for example: high-pressure mercury lamp or be equipped with the quartz mercury lamp of filter.The present invention does not have special restriction to the condition that ultraviolet radiation carries out polymerization, adopts this area reaction condition commonly used, is that 70-90 ℃, elongation at break are 20-100% as long as guarantee the glass transition temperature of the polymer that generates.For example, with styrene as polymerisable monomer, with power be 500 watts high-pressure mercury lamp as ultraviolet source, light is apart from being 10cm, light application time is to obtain to satisfy the polymer of requirement of the present invention in 10 hours.Described light distance is the transmitting site of ultraviolet light and the air line distance between the irradiated material.Under further preferred condition, the method for ultraviolet radiation polymerization of the present invention can also be included in and add sensitising agent in the polymerisable monomer and promote polymerization.Described sensitising agent can adopt this area sensitising agent commonly used, for example: benzophenone or benzoin ether; Total amount with polymerisable monomer is a benchmark, and the consumption of described sensitising agent is 5-10 weight %.The reaction condition of the ultraviolet radiation polymerization under sensitising agent exists can carry out according to this area condition commonly used.For example, with styrene as polymerisable monomer, with high-pressure mercury lamp as ultraviolet source, the benzophenone that adds 5 weight % is as sensitising agent, with power be 500 watts high-pressure mercury lamp as ultraviolet source, light is apart from being 10cm, light application time is to obtain to satisfy the polymer of requirement of the present invention in 10 hours.
The present invention to the preparation battery electrode reactor there is no particular limitation, can be the various reactors of routine.For example, when adopting the radical initiator initiated polymerization, under preferred condition, reactor comprises the pump drainage device of air, and the material of reactor is preferably glass.Figure 4 shows that the object lesson that is suitable for a reaction vessel of the present invention.The inner space of reactor as shown in Figure 4 is made of the loam cake 42 of base 41 with bell shape; And the groove that also has indicated altitude on the base 41; On the loam cake 42 of described bell shape, be equipped with pump drainage gas port 43, can vacuumize operation with inert gas injecting to reactor by this pump drainage gas port; Dispose sealing ring 44 in the contact site of described bell shape loam cake and described base, guaranteed the sealing of whole system.
Because the upper strata of battery electrode of the present invention and the conductivity porous material substrate of lower floor are the matrixes that electrode carries out electrode reaction, therefore, prepare and also comprise in the step of battery electrode of the present invention and remove protective agent.When protective agent of the present invention is paraffin and polyethylene glycol; because above-mentioned two kinds of materials have good flowability when liquid being heated as; and fusing point all is not higher than or the not obvious glass transition temperature that is higher than polymer; therefore the present invention preferably removes protectant method and can the protective agent fusion be separated out for the heating of conductivity porous material substrate.In addition, because polyethylene glycol is water-soluble polymer, repeatedly soak and the method for washing also can be removed polyethylene glycol by hot water.
The present invention also further provides a kind of vanadium flow battery.Described vanadium flow battery comprises electrode and electrolyte, and described electrode is by electrode provided by the invention.Because being the battery electrode of the application of the invention, vanadium flow battery of the present invention improves battery performance, therefore, the present invention adopts method well known to those skilled in the art can prepare with the vanadium flow battery of battery electrode of the present invention as electrode for the composition of the preparation method of vanadium flow battery and electrolyte and without particular limitation.For example, described electrolyte can be 1-2.5mol/L for sulfuric acid, the vanadium ion concentration of 1-5mol/L, and the injection rate of electrolyte can be each 150-200mL of both positive and negative polarity.
According in the battery electrode of the present invention with polymer as every liquid and seal, bear pressure simultaneously from the battery pile both sides, with the conductivity porous material substrate as the matrix of electrode reaction and play the effect of conduction.Distribution of polymer in the described electrode is in the part micropore of conductivity porous material, melt as a whole with the conductivity porous material substrate, compact conformation, and do not have additional tack coat between the two, eliminated electrode contact resistance, avoided the problem that the conductivity porous material substrate comes off easily in the use; In addition, described polymer has good mechanical performance, thermal endurance and chemical resistance.Battery electrode of the present invention also has the simple and cheap characteristics of preparation method.
Further elaborate the present invention below in conjunction with embodiment.In following examples, partly be the intermediate layer with the conductivity porous material substrate corresponding to the polymer that protrudes from the conductivity porous material substrate, this thickness is the thickness in intermediate layer, and both sides are respectively the upper and lower.The total weight of weight by measuring conductivity porous material substrate self and the electrode that makes, the weight that the total weight of this electrode is deducted conductivity porous material substrate self obtains the total content of polymer in the electrode.The weight that the total content of polymer in this electrode is deducted the matrix polymer that protrudes from the conductivity porous material substrate promptly obtains the amount of the polymer in the conductivity porous material substrate.The ratio that the content of polymer in the intermediate layer accounts for the total content of this polymer in the conductivity porous material substrate records according to the method for following ethanol uptake.
Concrete method of testing is ethanol to be immersed on the upper strata of the battery electrode of preparation (only be the upper strata herein, do not comprise lower floor and intermediate layer) in, fully dipping is 10-15 minute, after making ethanol immerse in the micropore of porousness electric conducting material matrix fully, take out battery electrode and also wipe the ethanol of electrode surface with clean paper, take by weighing the weight of electrode, calculate and flood recruitment preceding and dipping rear electrode weight, calculate the actual volume of the hole on conductivity porous material substrate upper strata according to following formula:
V
1＝ΔW
1/ρ
1????????(1)
Wherein, V
1Be the actual volume of the hole on conductivity porous material substrate upper strata, mm
3
Δ W
1Behind upper strata with alcohol dipping conductivity porous material substrate, the recruitment of battery electrode weight, g;
ρ
1Be the density of ethanol, g/mm
3
Adopting uses the same method obtains the actual volume V of the hole of conductivity porous material substrate lower floor
3
THICKNESS CALCULATION according to the floor space of conductivity porous material substrate, porosity, upper strata goes out the theoretical displacement of the hole on conductivity porous material substrate upper strata, and concrete computing formula is as follows:
V
1’＝H
1×S×λ????????(2)
Wherein, V
1' be the theoretical displacement of the hole on conductivity porous material substrate upper strata, mm
3
H
1Be the thickness on conductivity porous material substrate upper strata, mm;
S is the area of the upper surface of conductivity porous material substrate, mm
2
λ is the porosity of conductivity porous material substrate.
Adopting uses the same method calculates the theoretical displacement V of the hole of conductivity porous material substrate lower floor
3'.
If the actual volume of upper strata and lower floor is all more than or equal to separately theoretical displacement, polymer is not all contained in the upper and lower that the conductivity porous material substrate is described, polymer in the conductivity porous material substrate all is arranged in the intermediate layer of conductivity porous material substrate, and promptly the content of polymer in the intermediate layer accounts for 100 weight % of the total content of this polymer in the conductivity porous material substrate.If V
1＜V
1' and/or V
3＜V
3', then illustrate in the part hole of the upper strata of conductivity porous material substrate and/or lower floor and filled partial polymer.Wherein, the weight of the polymer of upper strata and/or lower floor can be calculated according to following formula:
W
1＝(V
1’-V
1)×ρ
2????????(3)
W
3＝(V
3’-V
3)×ρ
2????????(4)
Wherein, W
1Be the weight of the polymer in the conductivity porous material substrate upper strata, g;
W
3Be the weight of the polymer in the conductivity porous material substrate lower floor, g;
ρ
2Be the averag density (can use the density of the polymer that protrudes from the conductivity porous material substrate herein) of polymer, g/mm
3
Under the uniform situation of the thickness of the polymer that protrudes from the conductivity porous material substrate, also can calculate the weight of the polymer in the conductivity porous material substrate according to the density of the weight of the polymer in the thickness in the floor space of the floor space of conductivity porous material substrate and inside reactor, intermediate layer, the battery electrode that makes and polymer, computing formula is as follows:
W
2＝W-(S’-S)×H
2×ρ
2????????(5)
Wherein, W
2Be the total weight of polymer in the conductivity porous material, g;
W is the total weight of the polymer in the battery electrode, g;
S ' is the floor space of inside reactor, mm
2
H
2Be the thickness in conductivity porous material intermediate layer, mm.
Among the present invention, adopt the polymer weight in the conductivity porous material substrate that this method obtains consistent, illustrate that it is rational that employing formula (5) calculates with polymer weight in the conductivity porous material substrate that obtains by preceding method.
Can calculate the weight of the polymer in the intermediate layer according to the total weight of polymer polymer in the weight of the upper strata of conductivity porous material substrate, lower floor and conductivity porous material substrate, the ratio of the total weight of polymer is polymer and accounts for the percentage of the total content of the polymer in the conductivity porous material substrate at the content in intermediate layer in this weight and the conductivity porous material substrate:
w＝(W
2-W
1-W
3)/W
2×100％
Wherein, w is the percentage that the weight of the polymer in the intermediate layer accounts for the total weight of the polymer in the conductivity porous material substrate, weight %.
Embodiment 1
Present embodiment is used to illustrate battery electrode of the present invention and preparation method thereof.
Be equipped with the pump drainage device of air and be of a size of that to add porosity in the flat reactor shown in Figure 4 of 34mm * 34mm * 40mm be 85% graphite felt, wherein, graphite felt is of a size of 30mm * 30mm * 8mm; Add refined paraffin wax then as protective agent in reactor, wherein, melting point of paraffin wax is 62 ℃, uses external heater to add heated paraffin, and it is liquid that its thawing is become, and soaked into graphite felt 3 minutes, and the degree of depth of the paraffin that control is melted is 2mm; Remove heater then, reduce temperature gradually, make paraffin solidify out into solid.Then, inject the mixture that contains 5 weight % azodiisobutyronitriles and 95 weight % styrene monomers in the reactor that contains protective agent and graphite felt, and soaked into graphite felt 6 minutes, the height that control contains the mixture of styrene monomer is 4mm; Then, use external heater that temperature of reactor is heated to 58 ℃, under this temperature, kept 10 hours, carry out Raolical polymerizable.After the question response device cools off fully, will contain graphite felt, polymer and protectant electrode and from reactor, take out, the electrode that obtains will be placed 65 ℃ baking oven, and protective agent is melted and separate out, obtain according to battery electrode of the present invention.Wherein, this battery electrode upper strata, the three layers of thickness separately in intermediate layer and lower floor are followed successively by 1.7 millimeters, 4.2 millimeters and 2.1 millimeters, and the weight of battery electrode is 5.2 times of graphite felt weight, also promptly in this battery electrode the content of polymer be 81 weight %, what protrude from polymer around the graphite felt matrix is 21 weight % of polymer total amount, 90 weight % of the polymer total amount in the graphite felt are arranged in the intermediate layer of graphite felt, and the weight ratio of polymer and graphite felt is 1: 0.18 in the intermediate layer.To the glass transition temperature of specific insulation, hot strength, elongation at break and polymer and the testing every fluidity of electrode of the electrode that makes, the result lists in table 1.
Embodiment 2
Present embodiment is used to illustrate battery electrode of the present invention and preparation method thereof.
Take out in outfit, to add porosity in the flat reactor shown in Figure 4 of 34mm * 34mm * 40mm be 85% graphite felt for exhaust apparatus and being of a size of, wherein, graphite felt is of a size of 30mm * 30mm * 8mm; Add polyethylene glycol then as protective agent in reactor, wherein, the fusing point of polyethylene glycol is 66 ℃, uses external heater heating polyethylene glycol, and it is liquid that its thawing is become, and soaked into graphite felt 3 minutes, and the degree of depth of the polyethylene glycol that control is melted is 2mm; Remove heater then, reduce temperature gradually, make polyethylene glycol solidify out into solid.Then, inject the mixture that contains 8 weight % di-isopropyl peroxydicarbonates and 92 weight % styrene monomers in the reactor that contains protective agent and graphite felt, and soaked into graphite felt 6 minutes, the height of control styrene monomer mixture is 4mm; Then, use external heater that temperature of reactor is heated to 45 ℃, under this temperature, kept 8 hours, carry out Raolical polymerizable.After the question response device cools off fully, will contain graphite felt, polymer and protectant electrode and from reactor, take out, the electrode that obtains will be placed 70 ℃ baking oven, and protective agent is melted and separate out, obtain according to battery electrode of the present invention.Wherein, this battery electrode comprises three layers of upper strata, intermediate layer and lower floors, three layers thickness is followed successively by 1.8 millimeters, 3.9 millimeters and 2.3 millimeters, and the weight of battery electrode is 5.1 times of graphite felt weight, also promptly in this battery electrode the content of polymer be 81 weight %, what protrude from polymer around the graphite felt matrix is 20 weight % of polymer total amount, 95 weight % of the polymer total amount in the graphite felt are arranged in the intermediate layer of graphite felt, and the weight ratio of polymer and graphite felt is 1: 0.16 in the intermediate layer.To the glass transition temperature of specific insulation, hot strength, elongation at break and polymer and the testing every fluidity of electrode of the electrode that makes, the result lists in table 1.
Embodiment 3
Present embodiment is used to illustrate battery electrode of the present invention and preparation method thereof.
Take out in outfit, to add porosity in the flat reactor shown in Figure 4 of 34mm * 34mm * 40mm be 85% graphite felt for exhaust apparatus and being of a size of, wherein, graphite felt is of a size of 30mm * 30mm * 8mm; Add polyethylene glycol then as protective agent in reactor, wherein, the fusing point of polyethylene glycol is 66 ℃, uses external heater heating polyethylene glycol, and it is liquid that its thawing is become, and soaked into graphite felt 3 minutes, and the degree of depth of the polyethylene glycol that control is melted is 2mm; Remove heater then, reduce temperature gradually, make polyethylene glycol solidify out into solid.Then, inject the mixture that contains 5 weight % di-cyclohexylperoxy di-carbonates, 30 weight % vinylidenes and 65 weight % styrene monomers in the reactor that contains protective agent and graphite felt, the height of control vinylidene and styrene monomer mixture is 4mm; Soak into after 6 minutes, use external heater that temperature of reactor is heated to 45 ℃, under this temperature, kept 8 hours, carry out Raolical polymerizable.After the question response device cools off fully, will contain graphite felt, polymer and protectant electrode and from reactor, take out, the electrode that obtains will be placed 70 ℃ baking oven, and protective agent is melted and separate out, obtain according to battery electrode of the present invention.Wherein, this battery electrode comprises three layers of upper strata, intermediate layer and lower floors, three layers thickness is followed successively by 1.8 millimeters, 4.2 millimeters and 2 millimeters, and the weight of battery electrode is 5.4 times of graphite felt weight, also promptly in this battery electrode the content of polymer be 81 weight %, what protrude from polymer around the graphite felt matrix is 22 weight % of polymer total amount, 100 weight % of the polymer total amount in the graphite felt are arranged in the intermediate layer of graphite felt, and the weight ratio of polymer and graphite felt is 1: 0.15 in the intermediate layer.To the glass transition temperature of specific insulation, hot strength, elongation at break and polymer and the testing every fluidity of electrode of the electrode that makes, the result lists in table 1.
Embodiment 4
Present embodiment is used to illustrate battery electrode of the present invention and preparation method thereof.
Take out in outfit, to add porosity in the flat reactor shown in Figure 4 of 34mm * 34mm * 40mm be 85% graphite felt for exhaust apparatus and being of a size of, wherein, graphite felt is of a size of 30mm * 30mm * 8mm; Add polyethylene glycol then as protective agent in reactor, wherein, the fusing point of polyethylene glycol is 66 ℃, use external heater heating polyethylene glycol, it is liquid that its thawing is become, and soaked into graphite felt 3 minutes, and the degree of depth of the polyethylene glycol that control is melted is 1.6mm; Remove heater then, reduce temperature gradually, make polyethylene glycol solidify out into solid.Then, in the reactor that contains protective agent and graphite felt, inject and contain the dibutyl phthalate modifier of 5 weight % azodiisobutyronitriles, 10 weight % and the mixture of 85 weight % styrene monomers, and fully soaking into graphite felt, the height of control styrene monomer mixture is 4.8mm; Soak into after 6 minutes, use external heater that temperature of reactor is heated to 62 ℃, under this temperature, kept 8 hours, carry out Raolical polymerizable.After the question response device cools off fully; to contain graphite felt, polymer and protectant electrode takes out from reactor; the electrode that obtains is washed with about 45 ℃ the hot-water soak of 500mL, carry out altogether five times, obtain according to battery electrode of the present invention to remove polyethylene glycol.Wherein, the thickness of the upper strata of battery electrode, intermediate layer and lower floor is followed successively by 1.6 millimeters, 4.8 millimeters and 1.6 millimeters; The weight of battery electrode is 6.1 times of graphite felt weight, also promptly in this battery electrode the content of polymer be 84 weight %, what protrude from polymer around the graphite felt matrix is 25 weight % of polymer total amount, 97 weight % of the polymer total amount in the graphite felt are arranged in the intermediate layer of graphite felt, and the weight ratio of polymer and graphite felt is 1: 0.16 in the intermediate layer.To the glass transition temperature of specific insulation, hot strength, elongation at break and polymer and the testing every fluidity of electrode of the electrode that makes, the result lists in table 1.
Embodiment 5
Present embodiment is used for explanation according to electrode of the present invention and preparation method thereof
The adding porosity is 85% graphite felt in being of a size of the flat reactor shown in Figure 4 of 34mm * 34mm * 40mm, and wherein, graphite felt is of a size of 30mm * 30mm * 8mm; Add paraffin wax fully refined then as protective agent in reactor, wherein, melting point of paraffin wax is 62 ℃, uses external heater to add heated paraffin, and it is liquid that its thawing is become, and soaked into graphite felt 3 minutes, and the degree of depth of the paraffin that control is melted is 3.2mm; Remove heater then, reduce temperature gradually, make paraffin solidify out into solid.Then, inject styrene monomer in the reactor that contains protective agent and graphite felt, the height of control styrene monomer mixture is 1.6mm; Soaking into after 6 minutes, pluck the loam cake of reactor, is that 500 watts high-pressure mercury lamp shines with power, and light is apart from being 10cm, and irradiation time is 10 hours.After reaction is finished, will contain graphite felt, polymer and protectant electrode and from reactor, take out, the electrode that obtains will be placed 65 ℃ baking oven, and protective agent is melted and separate out.Obtain according to battery electrode of the present invention.Wherein, the thickness of the upper strata of battery electrode, intermediate layer and lower floor is followed successively by 3.1 millimeters, 1.7 millimeters and 3.2 millimeters; The weight of battery electrode is 3.2 times of graphite felt weight, also promptly in this battery electrode the content of polymer be 69 weight %, what protrude from polymer around the graphite felt matrix is 15 weight % of polymer total amount, 92 weight % of the polymer total amount in the graphite felt are arranged in the intermediate layer of graphite felt, and the weight ratio of polymer and graphite felt is 1: 0.12 in the intermediate layer.To the glass transition temperature of specific insulation, hot strength, elongation at break and polymer and the testing every fluidity of electrode of the electrode that makes, the result lists in table 1.
Embodiment 6
Present embodiment is used for explanation according to electrode of the present invention and preparation method thereof
The adding porosity is 85% graphite felt in being of a size of the flat reactor shown in Figure 4 of 34mm * 34mm * 40mm, and wherein, graphite felt is of a size of 30mm * 30mm * 8mm; Add paraffin wax fully refined then as protective agent in reactor, wherein, melting point of paraffin wax is 62 ℃, uses external heater to add heated paraffin, and it is liquid that its thawing is become, and soaked into graphite felt 3 minutes, and the degree of depth of the paraffin that control is melted is 2mm; Remove heater then, reduce temperature gradually, make paraffin solidify out into solid.Then, inject the styrene monomer of the benzophenone that contains 5 weight % in the reactor that contains protective agent and graphite felt, the height of control styrene monomer mixture is 4mm; Soaking into after 6 minutes, pluck the loam cake of reactor, is that 500 watts high-pressure mercury lamp shines with power, and light is apart from being 10cm, and irradiation time is 8 hours.After reaction is finished, will contain graphite felt, polymer and protectant electrode and from reactor, take out, the electrode that obtains will be placed 65 ℃ baking oven, and protective agent is melted and separate out.Obtain according to battery electrode of the present invention.Wherein, the thickness of the upper strata of battery electrode, intermediate layer and lower floor is followed successively by 2 millimeters, 3.9 millimeters and 2.1 millimeters; The weight of battery electrode is 5.2 times of graphite felt weight, also promptly in this battery electrode the content of polymer be 81 weight %, 96 weight % of the polymer total amount in the graphite felt are arranged in the intermediate layer of graphite felt, and the weight ratio of polymer and graphite felt is 1: 0.12 in the intermediate layer.To the glass transition temperature of specific insulation, hot strength, elongation at break and polymer and the testing every fluidity of electrode of the electrode that makes, the result lists in table 1.
Performance test
Specific insulation: as shown in Figure 5, the battery electrode of making is compressed with two copper sheets, pass to the electric current of 10A, 20A or 30A respectively with constant-current source, and the voltage of measuring samples both sides, calculate the resistance of electrode respectively by Ohm's law, calculate the specific insulation of battery electrode respectively according to the relation between resistance and the specific insulation, the specific insulation that obtains under the different current strength is averaged and is the specific insulation of battery electrode.Among Fig. 5,11 is the conductivity porous material substrate, and 12 is polymer, and 51 is copper sheet, and 52 is binding post.
Every fluidity: as shown in Figure 6,, measure this and contain electrolyte and, use W with the starting weight of battery electrode of the present invention as the container of base with the base of battery electrode as the closed container of the sulfuric acid electrolyte that contains 3mol/L
0Expression; This container was placed 100 hours, measured the final weight of this container again, use W
100Expression; Be called every fluidity placing the final weight after 100 hours and the ratio percentage of starting weight.Among Fig. 6,11 is the conductivity porous material substrate, and 12 is polymer, and 61 is container, and 62 is electrolyte.Concrete computing formula every fluidity is as follows.
Every fluidity=W
100/ W
0* 100%
The specific insulation of the battery electrode that makes of test implementation example 1-6 and every fluidity according to the method described above.
The hot strength of polymer: the hot strength of measuring polymer according to GB 1040-79 specified test.
The elongation at break of polymer: the elongation at break of measuring polymer according to the GB10654-89 specified test.
The glass transition temperature of polymer: use Q100 differential scanning calorimeter (DSC) to measure the glass transition temperature of polymer; heating rate is 10 ℃/minute; Range of measuring temp is-20 ℃-200 ℃, and test is carried out under nitrogen protection, and nitrogen flow rate is 50mL/ minute.
Test hot strength, elongation at break and the glass transition temperature of the battery electrode polymer all around that makes by embodiment 1-6 according to the method described above.
Concrete test result is listed in table 1.
Table 1
| Numbering | Specific insulation (Ω cm) | Hot strength (MPa) | Elongation at break (%) | Every fluidity (%) | The glass transition temperature of polymer (℃) |
| Embodiment 1 | ??0.042 | ??19 | ??12 | ??100 | ??81 |
| Embodiment 2 | ??0.046 | ??21 | ??14 | ??100 | ??86 |
| Embodiment 3 | ??0.047 | ??20 | ??15 | ??100 | ??85 |
| Numbering | Specific insulation (Ω cm) | Hot strength (MPa) | Elongation at break (%) | Every fluidity (%) | The glass transition temperature of polymer (℃) |
| Embodiment 4 | ??0.043 | ??9 | ??70 | ??100 | ??70 |
| Embodiment 5 | ??0.045 | ??16 | ??11 | ??100 | ??90 |
| Embodiment 6 | ??0.048 | ??19 | ??14 | ??100 | ??82 |
As can be seen from Table 1, battery electrode according to the present invention have lower volume resistance and 100% every fluidity; Polymer has higher draw tensile strength and elongation at break, also has better heat-resisting simultaneously; Therefore battery electrode of the present invention satisfies the actual requirement of using.
The preparation of vanadium flow battery
(wherein, graphite cake is that 2mm, resistivity are 1.4 * 10 for the thickness available from German Xi Gemu company to the battery electrode of the graphite cake electrode preparation that battery electrode and the employing of the foregoing description 1-6 is purchased
-3The graphite cake of Ω cm, the graphite cake and the graphite felt extruding applying that are purchased are obtained battery electrode, wherein, the graphite felt source of using in graphite felt and the embodiment of the invention is identical) make vanadium liquid stream monocell respectively, wherein, the concentration of the total V density 1.5mol/L of electrolyte, sulfuric acid is that the injection rate of 3mol/L, electrolyte is each 200mL of both positive and negative polarity.
The battery performance test of vanadium flow battery
The above-mentioned vanadium flow battery that makes placed hold up a day BS9362 charge-discharge test cabinet, at 20mA/cm
2Current density under carry out charge or discharge, the charge-discharge performance of test battery.Wherein, the cut-ff voltage of the charging that the test efficiency for charge-discharge adopts is 1.7V, and the cut-ff voltage of discharge is 0.7V; Test charges and discharge the charge or discharge time that voltage platform adopts and was respectively 10 minutes, and when being respectively 5 minutes with the charge or discharge time, the voltage that obtains after being calculated voluntarily by instrument is as the voltage platform of charge or discharge.Test result is as shown in table 2.
Table 2
As can be seen from Table 2, vanadium flow battery provided by the invention promptly adopts the internal resistance of vanadium flow battery of battery electrode provided by the invention low, efficiency for charge-discharge is high.And vanadium flow battery of the present invention has been eliminated contact resistance owing to used battery electrode of the present invention, makes discharge voltage plateau rise, and discharge voltage is apparently higher than the battery that is purchased; Reduced the charging voltage platform simultaneously, charging voltage is starkly lower than and is purchased battery.Also promptly, the performance of vanadium flow battery provided by the invention obviously is better than the vanadium flow battery of prior art.
Claims (17)
1. battery electrode, it is characterized in that, this electrode contains conductivity porous material substrate and polymer, to the described distribution of polymer of small part in the micropore of partially conductive porous material substrate, the polymer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata with this conductivity porous material substrate, lower floor and the intermediate layer that has every the liquid effect, wherein, this polymer accounts for more than the 75 weight % of the total content of this polymer in the conductivity porous material substrate at the content in intermediate layer, and this polymer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymer in the conductivity porous material substrate.
2. battery electrode according to claim 1, wherein, in the described intermediate layer, the weight ratio of polymer and conductivity porous material substrate is 1: 0.12-0.18.
3. battery electrode according to claim 1 and 2, wherein, the thickness in described intermediate layer accounts for the 20-60% of described conductivity porous material substrate gross thickness.
4. battery electrode according to claim 3, wherein, described upper and lower two-layer thickness ratio is 1: 1-1.3.
5. battery electrode according to claim 1, wherein, at least the described polymer of another part extend to protrude from the conductivity porous material substrate around, described protrude from this conductivity porous material substrate around the amount of polymer be the 15-25 weight % of described polymer total amount.
6. according to claim 1,2 or 5 described battery electrodes, wherein, the glass transition temperature of described polymer is 70-90 ℃, and elongation at break is 20-100%.
7. battery electrode according to claim 6, wherein, described polymer is the copolymer of polystyrene, Kynoar or styrene and vinylidene.
8. according to claim 1,2 or 5 described battery electrodes, wherein, described conductivity porous material substrate is that porosity is the graphite felt of 50-95%.
9. the preparation method of the described battery electrode of claim 1, it is characterized in that, this method comprises to be made to the micropore of small part polymerisable monomer entering part conductivity porous material substrate, the polymerisable monomer that is distributed in the micropore of this partially conductive porous material substrate is divided into the upper strata successively with this conductivity porous material substrate, three layers of intermediate layer and lower floors, wherein, this polymerisable monomer accounts for more than the 75 weight % of the total content of this polymerisable monomer in the conductivity porous material substrate at the content in intermediate layer, and this polymerisable monomer is last, content in two-layer down accounts for below the 25 weight % of the total content of this polymerisable monomer in the conductivity porous material substrate; This method also comprises makes described polymerisable monomer polymerization.
10. preparation method according to claim 9; wherein; make the method to the micropore of small part polymerisable monomer entering part conductivity porous material substrate comprise that the side with the conductivity porous material substrate immerses in the protective agent; protective agent is entered in the micropore of a side of conductivity porous material substrate; in this conductivity porous material substrate, add polymerisable monomer then; make to the micropore of small part polymerisable monomer entering part conductivity porous material substrate; thereby the upper strata of gained conductivity porous material substrate; intermediate layer and lower floor are respectively for three layers and do not contain polymerisable monomer and protectant blanket layer; contain the layer of polymerisable monomer and contain protectant layer; described protective agent in the micropore of polymerisable monomer entering part conductivity porous material substrate and under the polymerizing condition for solid or described protective agent for do not dissolve mutually with described polymerisable monomer and density greater than the liquid of polymerisable monomer, described polymerisable monomer and protectant amount make the thickness of the layer that contains polymerisable monomer account for the 20-60% of the gross thickness of conductivity porous material.
11. preparation method according to claim 10, wherein, the consumption of described protective agent and polymerisable monomer make the lower floor of conductivity porous material substrate and intermediate layer around also be in protective agent and the polymerisable monomer respectively.
12. according to any described preparation method among the claim 9-11, wherein, the inlet of described polymerisable monomer makes in the intermediate layer, the weight ratio of polymer and conductivity porous material substrate is 1: 0.12-0.18.
13. according to any described preparation method among the claim 9-11, wherein, it is 1 that described protectant amount makes the upper and lower two-layer thickness ratio of gained conductivity porous material substrate: 1-1.3.
14. according to any described preparation method among the claim 9-11; wherein; this method also comprises removes described protective agent; described protective agent is paraffin and/or polyethylene glycol; make protective agent enter the conductivity porous material substrate a side micropore method for protective agent is heated to liquid; side with the matrix of conductivity porous material immerses in the protective agent then, removes protectant method and comprises the heating of conductivity porous material substrate, and the protective agent fusion is separated out.
15. according to any described preparation method among the claim 9-11, wherein, described conductivity porous material substrate is that porosity is the graphite felt of 50-95%.
16. preparation method according to claim 9, wherein, described polymerisable monomer is the mixture of styrene, vinylidene or styrene and vinylidene, the condition of polymerization reaction comprises that the temperature of polymerization is 45-62 ℃, polymerization reaction the time chien shih resulting polymers glass transition temperature be 70-90 ℃.
17. a vanadium flow battery, this battery comprises battery electrode and electrolyte, it is characterized in that, described battery electrode is any described battery electrode among the claim 1-8.
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| CN1307733C (en) * | 2003-07-04 | 2007-03-28 | 中南大学 | Preparation method of electrode for all-vanadium ion flow battery |
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| CN102738479A (en) * | 2011-04-15 | 2012-10-17 | 云廷志 | Integrated composite plate electrode |
| CN102738475A (en) * | 2011-04-15 | 2012-10-17 | 云廷志 | Manufacturing method of integrated combined electrode |
| CN102361091A (en) * | 2011-10-25 | 2012-02-22 | 中国东方电气集团有限公司 | Integrated electrode collector plate, manufacturing method thereof and flow battery comprising same |
| CN113574706A (en) * | 2019-04-24 | 2021-10-29 | 住友电气工业株式会社 | Bipolar plate, battery cell, battery pack and redox flow battery |
| CN113574706B (en) * | 2019-04-24 | 2024-03-29 | 住友电气工业株式会社 | Bipolar plate, battery cell, battery pack and redox flow battery |
| CN113410486A (en) * | 2021-06-03 | 2021-09-17 | 大连海事大学 | Flow battery bipolar plate material and preparation method thereof |
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| CN101752565B (en) | 2012-08-22 |
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