CN107516743A - A kind of preparation method of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping - Google Patents

A kind of preparation method of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping Download PDF

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CN107516743A
CN107516743A CN201710606468.9A CN201710606468A CN107516743A CN 107516743 A CN107516743 A CN 107516743A CN 201710606468 A CN201710606468 A CN 201710606468A CN 107516743 A CN107516743 A CN 107516743A
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transition metal
shell structure
exchange membrane
ions
core shell
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CN107516743B (en
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秦海英
林龙霞
褚雯
何燕
王娟
季振国
倪华良
迟洪忠
刘嘉斌
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GUANGDONG GUANHAO HIGH-TECH CO LTD
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Hangzhou Electronic Science and Technology University
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    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • H01M8/1074—Sol-gel processes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a kind of preparation method of core shell structure binary transition metal doping alkaline anion-exchange membrane.In its preparation method, present invention utilizes different transition metal ions, dispersiveness is different in organic matter, tiny nucleus is formed in organic matter using the high transition metal divalence Cu ions of decentralization, attract the transition metal ions of another doping to be grown by out-phase forming core, form the alkaline anion-exchange membrane of the core shell structure binary transition metal ion doping of the present invention.The present invention utilizes the binary transition metal ion being uniformly distributed in the matrix of alkaline anion-exchange membrane made from the method in core shell structure, and its center is divalence Cu ions, and shell is divalence Co or the Ni ion with catalysis characteristics.Core shell structure improves the catalysis characteristics of film, effectively reduces the fuel permeability of fuel cell, improves the ion on-state rate of film；The fuel cell being assembled into by anion-exchange membrane produced by the present invention shows excellent power generation performance.

Description

A kind of alkaline anion-exchange membrane of core shell structure binary transition metal ion doping Preparation method
Technical field
The present invention relates to fuel cell field, more particularly to polymer dielectric film fuel cell and preparation method thereof.
Background technology
Polymer dielectric film fuel cell is a kind of the chemical energy being stored in hydrogen and oxygen directly to be converted into electricity Can energy conversion apparatus, there is energy conversion efficiency height, can quickly start at room temperature and environment-friendly, is considered as Had broad application prospects in terms of transport facility power supply, become the study hotspot of nearest power technique fields.
Polymer dielectric film fuel cell can be divided into the acid using PEM generally according to the difference of conduction ion Property polymer dielectric film fuel cell（PEMFC）With the alkaline polymer electrolyte membrane fuel using alkaline anion-exchange membrane Battery（AEMFC）.At present, as PEMFC technology scaleizations and commercialization process deepen continuously, PEMFC technical application masters It is faced with following four problem：（1）Thin polymer film using costliness is used as amberplex；（2）Urged using rare platinum Agent；（3）Need good dynamic water management；（4）Production, storage and the transport of fuel hydrogen.
Direct akaline liquid fuel cell（DALFC）It is that one kind is directly used as fuel by the use of akaline liquid instead of gaseous hydrogen AEMFC, studying relatively broad liquid fuel at present has basic methanol solution, hydrazine solution and sodium borohydride solution.With routine PEMFC is compared, and akaline liquid fuel is used so that DALFC has following both sides outstanding advantage：（1）Liquid fires Material has higher energy density, is easy to store and transports, and is advantageous to improve the integrated level of battery；（2）Alkaline working environment can To accelerate the catalytic kineticses of hydrogen reduction, it is expected to that battery cost is greatly reduced using non-platinum catalyst.Therefore, DALFC research To realize the inexpensive and integrated offer thinking of polymer-membrane fuel battery.But DALFC development is equally faced with following bottle Neck, first, compared with PEM, the ionic conductivity of anion-exchange membrane used in DALFC (AEM) is low, at present research It is far below 50 mscm more-1；Second, the infiltration of liquid fuel reduces the utilization rate of fuel when DALFC works, and produced in negative electrode Raw mixed potential reduces battery operating voltage, or even Poisoning cathode catalyst, the serious output performance for damaging battery.
At present, the research for having various alkaline anion-exchange membranes reports that Zhang etc. triggers radical polymerization system by heating For quaternized polystyrene type ptfe composite enhancing film, the ionic conductivity of the film at room temperature reaches more a height of 49 mS·cm-1, for alkaline hydrazine fuel cell, 70oC obtains 110 mWcm-2Maximum power density.Li etc. is cast by solution Method is made by nanometer ZrO2Mix quaternized poly (arylene ether) ether sulfone and prepare composite membrane, 80oIonic conductivity brings up to 41.4 under C mS·cm-1.Above result of study significantly improves ionic conductivity by AEM structure regulating.Amberplex is most important Characteristic is ionic conductivity, but the infiltration that single raising AEM ionic conductivity is still difficult to solve liquid fuel in DALFC is asked Topic, and as the raising of ionic conductivity can be further exacerbated by the infiltration of liquid fuel.Therefore, research is a kind of has well The simply inexpensive alkali anion of ionic conductivity and fuel power generation function performance, fuel-resistant permeance property and preparation technology is handed over Changing development of the film to polymer dielectric film fuel cell has good meaning.
The content of the invention
For the technical problem of existing alkaline ion exchange membrane, the present inventor has in view of transition metal ions Catalysis characteristics, core shell structure is formed using binary transition metal, there is catalytic activity transition metal to be distributed in film for increase Uniformity and specific surface area, improve its catalysis characteristics, advantageously account for the liquid fuel being permeated in amberplex, drop The permeability of liquid fuel in low fuel battery, while the ionic conductivity for improving amberplex is ensured, so as to improve battery Power generation performance.Thus, object of the present invention is to provide it is a kind of and meanwhile have good ionic conductivity, fuel cell hair The preparation method of electrical property and the alkaline anion-exchange membrane of fuel-resistant permeability.
To realize the purpose of the present invention, the technical solution adopted by the present invention is, a kind of core shell structure binary transition metal from The preparation method of the alkaline anion-exchange membrane of son doping, comprises the following steps：
1）First, divalence Cu salt is dissolved in deionized water, be stirred at room temperature, obtain Cu salting liquids；
2）Pva powder is dissolved in step 1）In obtained Cu salting liquids, heat and stir, obtain the first colloidal sol；
3）It is step 1 by mole）10%~20% ammoniacal liquor of middle Cu ions mole adds step 2）The first of middle acquisition is molten Glue, be sufficiently stirred, and it is static ageing 1~4 hour；
4）Divalence Co inorganic salts or divalence Ni inorganic salts are dissolved in deionized water, obtain Co salt or Ni salting liquids；
5）By step 4）Solution add step 3）The first colloidal sol after ageing, is sufficiently stirred, and obtains the second colloidal sol；
6）Alkalescence anion-exchange resin is ground into fine powder and crosses screen cloth, is added to stirring to obtain suspension in deionized water, Suspension is added in the second colloidal sol, both carry out cross-linking reaction, form the first gel；And the first gel is stood 10~20 Minute, then by the bubble removal on surface；
7）By the first gel film forming for removing blibbing on substrate, dry；
8）Caustic dip pretreatment is carried out to the film after drying.
Further, divalence Co salt, preferably cobaltous dichloride or CoSO4, the divalence Cu salt is preferably dichloride copper.
Further, according to the content of transition metal ions, step 1 is determined）Add divalence Cu salt and step 4）Addition two The addition of valency Co inorganic salts or divalence Ni inorganic salts, the content of the transition metal ions are：0.1%~1%, the transition The content of metal ion refers to the mass percent of transition metal ions and polyvinyl alcohol, and the transition metal ions includes step 1）The Cu ions and step 4 of addition）Co the or Ni ions of addition；And step 1）In divalence Cu ions and step 4）Middle Co or The mass ratio of Ni ions is 3:1~1:3.
Further, step 2）Described in heating and temperature control at 80~95 degrees Celsius, stir 2.5~3 hours.
Further, the step 6）Add alkalescence anion-exchange resin and the step 2）Add pva powder Mass ratio be 1：2.
Further, the caustic dip, which pre-processes, is：The film dried is immersed in 1M KOH solutions 12~24 hours, taken out Rinsed repeatedly with deionized water.
In above-mentioned preparation method, the present inventor through studying discovery repeatedly, and Cu ions are in organic matter with respect to other Transition metal ions there is dispersiveness well, highly uniform can be dispersed in organic matter；In the present invention, Cu ions There is high degree of dispersion in polyvinyl alcohol, due to the alkalescent of ammoniacal liquor after ammoniacal liquor is added, its hydroxyl ionized is with uniformly dividing The Cu ions bindings being dispersed in polyvinyl alcohol, form tiny nucleus in polyvinyl alcohol molecule；Add again afterwards Co or Ni from Sub- solution, because Co, Ni, Cu belong to transition metal, chemical property is similar.Therefore Co the and Ni ions subsequently added preferentially exist Out-phase forming core growth is carried out on the Cu ion nucleating surfaces formed, forms the shell of the core shell structure, avoid Co or Ni ions itself form thick aggregate, reach the work of the specific surface area for the transition metal ions for improving the catalysis characteristics having With realizing the more effective fuel permeability for reducing fuel in amberplex, improve the ionic conductivity, most of amberplex The goal of the invention of the power generation performance of fuel cell is improved eventually.In addition, the preparation method technique of the present invention is simple, it is applicable extensive Industrial production.
The alkaline anion-exchange membrane of core shell structure binary transition metal ion doping made from preparation method of the present invention, should Alkaline anion-exchange membrane is using polyvinyl alcohol as matrix, using alkalescence anion-exchange resin as chemical active radical, in film matrix In be uniformly distributed binary transition metal ion in core shell structure, core is divalence Cu ions, and shell is the divalence with catalysis characteristics Co or Ni ions, the wherein diameter of Cu cores are 50-200 in the thickness of 200~300nm, divalence Co or Ni the ion shell formed nm。
Using alkaline anion-exchange membrane made from preparation method provided by the invention, using polyvinyl alcohol as film matrix, Because polyvinyl alcohol has, good film forming, mechanical property and chemical stability are excellent, and have good alcohol-rejecting ability. The doping of binary transition metal ion has been carried out in film, and by the doping of two kinds of binary transition metal ions, has formed binary The heterogeneous core shell structure of transition metal ions.Make use of in preparation process different transition metal ions in organic matter dispersiveness not Together, tiny nucleus is formed in organic matter using the high transition metal divalence Cu ions of decentralization, attracts another doping transition gold Belong to divalence Co or Ni ion of the ion for example with catalysis characteristics to grow by out-phase forming core, formed using divalence Cu ions as core, Another transition metal ions with catalysis characteristics is the core shell structure of shell.Due to high degree of dispersion of the Cu ions in organic matter, Its forming core is evenly distributed in organic matter, therefore the core shell structure of two eventually formed kind transition metal ions is in organic matter Equally it is evenly distributed, so as to obtain the alkaline anion-exchange membrane of core shell structure binary transition metal uniform ion distribution；And keep away When having exempted from the single doped transition metal ionses with catalysis characteristics into film, decentralization is bad, gold is formed during doping The problem of metal particles cluster, uneven filming performance ultimately resulted in；These equally distributed microfacies core shell structures, can be effective The ionic conductivity of amberplex is improved, the resistivity of fuel cell is reduced, finally improves the generating of fuel cell Energy.In an embodiment of the present invention, at 60 °C, the generating peak power output density of obtained amberplex in embodiment For 303 mW cm-2, its power generation performance is substantially better than the amberplex and in the market of single transition metal ion doping PEM N117.In addition, because the shell of core shell structure is the transition metal ions with catalysis characteristics, and the ratio table of shell Area is realized by core shell structure to be increased so that the fuel being permeated from galvanic anode, can be in amberplex in time Catalytic reaction, so as to more effectively reduce fuel permeability of the fuel in amberplex.
Brief description of the drawings
Fig. 1 is the glimmering of the alkaline anion-exchange membrane that two kinds of binary transition metal ion dopings of Cu and Co are made in embodiment 1 Light two-dimensional imaging figure.
Fig. 2 is the fluorescence two-dimensional imaging figure of the alkaline anion-exchange membrane of the Co ion dopings of comparative example 1.
Fig. 3 is the fluorescence two-dimensional imaging figure of the alkaline anion-exchange membrane of the Cu ion dopings of comparative example 2.
Fig. 4 is that power generation performance of the monocell assembled using the exchange membrane of embodiment 1 and comparative example 1 under 30 degrees Celsius is bent Line chart.
Fig. 5 is bent for the power generation performance using the monocell of the exchange membrane of embodiment 1 and comparative example 1 assembling at 60 c Line chart.
Fig. 6 is to be exchanged using the alkali anion of two kinds of binary transition metal ion dopings of Cu made from embodiment 2 and Co The power generation performance curve figure of the monocell of film assembling.
Embodiment
More specific detail is carried out to the present invention with reference to specific embodiment.
Embodiment 1：
The process for preparing the alkaline anion-exchange membrane of the core shell structure binary transition metal ion doping of the present embodiment is：
1）0.027g bis- is hydrated dichloride copper（The content of transition metal copper ion is 0.2 wt.%, i.e. transition metal copper ion Mass percent with polyvinyl alcohol is 0.2%,）It is added in 30 mL deionized waters, acquisition in 5 minutes is stirred at room temperature and contains binary copper The copper salt solution of ion；
2）By 5g polyvinyl alcohol（PVA）Powder is dissolved in the binary cobalt copper ion aqueous solution, is heated to 80 ~ 95 degrees Celsius, stirring 2.5 Obtain within~3 hours the first copper ion doped colloidal sol of binary；
3）It is step 1 by mole）10%~20% ammoniacal liquor of middle Cu ions mole adds step 2）The first of middle acquisition is molten Glue, be sufficiently stirred, and it is static ageing 1~4 hour；
4）0.04 g six is hydrated cobaltous dichloride（The content of transition metal cobalt ions is 0.2 wt.%, i.e. transition metal cobalt ions Mass percent with polyvinyl alcohol is that the mass ratio of 0.2%, Co ions and Cu ions is 1:1）It is added in deionized water, shape Into cobalt salt solution；
5）By step 4）Cobalt salt solution add step 3）Colloidal sol after ageing, is sufficiently stirred, and obtains the second colloidal sol；
6）2.5g alkalescence anion-exchange resins are taken to be ground into fine powder, the stainless steel mesh for crossing 120 mesh obtains uniform basic resin Powder, it is added to stirring to obtain suspension in deionized water；Suspension is added in the second colloidal sol, both be crosslinked instead Should, form gel；And gel is stood 10~20 minutes, then by the bubble removal on surface；
7）The gel for having removed blibbing is scraped on glass plate with blade applicator, sets film forming thickness as 1000 microns, it is natural Dry；
8）Film after drying is immersed in 1M KOH solutions 12~24 hours, then takes out and is rinsed repeatedly with deionized water, is made Obtain the alkaline anion-exchange membrane of the core shell structure binary transition metal ion doping of the present embodiment.
Embodiment 2
Prepare the process and embodiment 1 of the core shell structure binary transition metal ion doping alkaline anion-exchange membrane of the present embodiment Difference be：The transition metal salt cobaltous dichloride of use is different with the addition of dichloride copper, the present embodiment step 1）In two The addition quality of hydration dichloride copper is 0.0405g, step 4）In six hydration cobaltous dichlorides addition quality be 0.02 g, i.e. Co The mass ratio of ion and Cu ions is 1:3.
Embodiment 3
Prepare the process and embodiment 1 of the core shell structure binary transition metal ion doping alkaline anion-exchange membrane of the present embodiment Difference be：The transition metal salt cobaltous dichloride of use is different with the addition of dichloride copper, the present embodiment step 1）In six The quality of hydration cobaltous dichloride is 0.12 g, and the quality of two hydration dichloride copper is 0.027g, i.e. the matter of Co ions and Cu ions Amount is than being 3:1.
In the preparation process of inventor, the ratio that transition metal cobalt salt and mantoquita are added in above-described embodiment is adjusted, or Person replaces with transition metal cobalt salt the divalent nickel salt of transition metal, when the mass ratio of Co ions or Ni ions and Cu ions is 1: 3~3:Between 1, the performance of the alkaline anion-exchange membrane of obtained core shell structure binary transition metal ion doping and each implementation Example is quite.
Comparative example 1
The process for preparing the ZnO thin film alkaline anion-exchange membrane of this comparative example is：
1）0.08 g six is hydrated cobaltous dichloride（The content of transition metal ions is 0.4%, i.e. transition metal ions and polyethylene The mass percent of alcohol is 0.4%）It is added in 30 mL deionized waters, is stirred at room temperature 5 minutes and obtains the water containing divalent cobalt ion Solution；
2）5g PVA powder is dissolved in the divalent cobalt ion aqueous solution, is heated to 80 ~ 95 degrees Celsius, stirs 2.5 ~ 3 hours and obtains The PVA gels of divalent cobalt ion doping；
3）2.5g alkalescence anion-exchange resins are taken to be ground into fine powder, the stainless steel mesh for crossing 120 mesh obtains uniform basic resin Powder, it is added in deionized water and forms solution, then solution is added to and has been cooled to 50 degrees Celsius of divalent cobalt ion and mixes Miscellaneous PVA gels, both carry out cross-linking reaction, form the PVA-AER gels of transitional metal ion Co doping；
4）The gel is scraped on glass plate with blade applicator, sets film forming thickness as 1000 microns, naturally dry；
5）Film after drying is immersed in 1M KOH solutions 12 ~ 24 hours, then takes out and is rinsed repeatedly with deionized water.
Comparative example 2
The process for preparing the copper ion doped alkaline anion-exchange membrane of this comparative example is：
1）0.053 g bis- is hydrated dichloride copper（The content of transition metal ions is 0.4%, i.e. transition metal ions and polyethylene The mass percent of alcohol is 0.4%）It is added in 30 mL deionized waters, is stirred at room temperature 5 minutes and obtains the water containing bivalent cupric ion Solution；
2）5g PVA powder is dissolved in the bivalent cupric ion aqueous solution, is heated to 80 ~ 95 degrees Celsius, stirs 2.5 ~ 3 hours and obtains The PVA gels of bivalent cupric ion doping；
3）2.5g alkalescence anion-exchange resins are taken to be ground into fine powder, the stainless steel mesh for crossing 120 mesh obtains uniform basic resin Powder, it is added in deionized water and forms solution, then solution is added to and has been cooled to 50 degrees Celsius of bivalent cupric ion and mixes Miscellaneous PVA gels, both carry out cross-linking reaction, form the PVA-AER gels of transition metal ions Cu doping；
4）The gel is scraped on glass plate with blade applicator, sets film forming thickness as 1000 microns, naturally dry；
5）Film after drying is immersed in 1M KOH solutions 12 ~ 24 hours, then takes out and is rinsed repeatedly with deionized water.
More than, the alkalescence anion-exchange resin used in each embodiment and comparative example is given birth to for Alfa Aesar companies of the U.S. The IRA-402 of the Amberlite series of production（OH）Basic resin（AER resins）.
Performance test：
Because Cu ions do not have catalysis characteristics in alkaline anion-exchange membrane, therefore, except XRF two-dimensional imaging is surveyed Examination, the performance test subsequently influenceed by the catalysis characteristics of obtained alkaline anion-exchange membrane, to Cu ions made from comparative example 2 The anionic membrane of doping, which all omits, not to be tested.
I）XRF two-dimensional imaging is tested
The test of XRF two-dimensional imaging has been carried out to embodiment 1, comparative example 1 and comparative example 2, has compared the first in film of three The microstructural differences of element distribution, if Fig. 1 is the alkali anion that Cu and Co binary transition metal ion dopings are made in embodiment 1 The XRF two-dimensional imaging figure of exchange membrane, Fig. 2 are the X ray that Co ion doping alkaline anion-exchange membranes are made in comparative example 1 Fluorescence two-dimensional imaging figure, Fig. 3 are the XRF two-dimensional imaging that Cu ion doping alkaline anion-exchange membranes are made in comparative example 2 Figure, three have notable difference.It will be seen from figure 1 that Cu and Co elements form core shell structure in film, wherein Cu is core, and Co is Shell, the nm of granular size about 500 of the binary transition metal ion formation of core shell structure, the diameter of Cu cores wherein in core shell structure It is 50-200 nm in the thickness for the shell that 200-300 nm, divalence Co, Ni ion are formed.Figure it is seen that single metal from The doping of son, Co easily form metallic particles cluster, about 2-3 μm of the size of cluster in organic film.From figure 3, it can be seen that Cu Disperse more uniform, the cluster size about 300-400 nm of formation in organic film.This explanation is in binary transition metal ion doping During into organic molecule chain, Co can be grown using less Cu particles as the nucleus of out-phase forming core, so as to be formed using Cu as core, Co is the binary transition metal ion doping structure of the core shell structure of shell；This core shell structure, also further increasing has The contact area of the Co ions of catalysis characteristics and the fuel infiltrated into film, improves its catalytic efficiency, so as to realize effective drop Low fuel permeability, the purpose for improving ion on-state rate and power generation performance.
II）The test of fuel permeability
Exchange membrane has been carried out to embodiment 1, embodiment 2, embodiment 3 and comparative example 1 at room temperature to fire alkaline sodium borohydride liquid The test of the permeability of material.The data of each embodiment and comparative example are as follows：
Table 1：The fuel permeability data of the alkaline anion-exchange membrane of preparation：
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Fuel permeability（×10-6 cm2/S） 2.5 2.6 2.6 2.7
III）The test of ionic conductivity
Alkaline anion-exchange membrane ionic conductivity at room temperature has been carried out to embodiment 1, embodiment 2, embodiment 3 and comparative example 1 Test.The data of each embodiment and comparative example are as follows：
Table 2：The ionic conductivity data of the alkaline anion-exchange membrane of preparation：
VI）Fuel battery performance is tested
Use each embodiment and compare alkaline anion-exchange membrane made from 1, alkaline sodium borohydride solution assembles respectively for fuel Into direct sodium borohydride fuel cell, such as the generating curve map of monocell that Fig. 4~Fig. 6 is assembling at different temperatures.Wherein, Fig. 4 is generating curve map of the monocell assembled using the exchange membrane of embodiment 1, comparative example 1 under 30 degrees Celsius, and Fig. 5 is real Apply example 1, comparative example 1 exchange membrane assembling monocell generating curve map at 60 c.It can be seen that in difference At a temperature of, relatively example, the alkali anion of Cu and Co core shell structures binary transition metal ion doping made from embodiment 1 The power generation performance of exchange membrane is best, and at 30 °C, its peak power output density is 190 mW cm-2, and at 60 °C, its maximum is defeated It is 303 mW cm to go out power density-2。
Fig. 6 is that the alkali anion of Cu and Co core shell structures binary transition metal ion doping made from embodiment 2 exchanges The power generation performance curve figure of the monocell of film assembling, at 30 °C, its peak power output density is 185 mW cm-2, and 60 ° During C, its peak power output density is 295 mW cm-2, it is suitable with embodiment 1.It can be seen that using Cu and Co core shell structures The fuel cell of the alkaline anion-exchange membrane of binary transition metal ion doping shows extraordinary power generation performance.
In addition, the swelling ratio and water absorption rate data phase of the alkaline anion-exchange membrane come measured by each embodiment and comparative example When without notable difference, the doping of two kinds of transition metal ions does not produce obvious influence to the water imbibition of film.

Claims (6)

  1. A kind of 1. preparation method of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping, it is characterised in that Comprise the following steps：
    1）First, divalence Cu salt is dissolved in deionized water, be stirred at room temperature, obtain Cu salting liquids；
    2）Pva powder is dissolved in step 1）In obtained Cu salting liquids, heat and stir, obtain the first colloidal sol；
    3）It is step 1 by mole）10%~20% ammoniacal liquor of middle Cu ions mole adds step 2）The first of middle acquisition is molten Glue, be sufficiently stirred, and it is static ageing 1~4 hour；
    4）Divalence Co inorganic salts or divalence Ni inorganic salts are dissolved in deionized water, obtain Co salt or Ni salting liquids；
    5）By step 4）Solution add step 3）The first colloidal sol after ageing, is sufficiently stirred, and obtains the second colloidal sol；
    6）Alkalescence anion-exchange resin is ground into fine powder and crosses screen cloth, is added to stirring to obtain suspension in deionized water, Suspension is added in the second colloidal sol, both carry out cross-linking reaction, form the first gel；And the first gel is stood 10~20 Minute, then by the bubble removal on surface；
    7）By the first gel film forming for removing blibbing on substrate, dry；
    8）Caustic dip pretreatment is carried out to the film after drying；The alkalescence of the core shell structure binary transition metal ion doping is made Anion-exchange membrane, be uniformly distributed in the film matrix of the alkaline anion-exchange membrane binary transition metal in core shell structure from Son, wherein the core of the core shell structure is divalence Cu ions, the shell of the core shell structure for the divalence Co with catalysis characteristics or Ni ions.
  2. 2. the preparation of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping according to claim 1 Method, it is characterised in that：The divalence Co inorganic salts are cobaltous dichloride or CoSO4, the divalence Cu salt is dichloride copper.
  3. 3. the preparation of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping according to claim 1 Method, it is characterised in that：According to the content of transition metal ions, step 1 is determined）Add divalence Cu salt and step 4）Add divalence The addition of Co inorganic salts or divalence Ni inorganic salts, the content of the transition metal ions are：0.1%~1%, the transition gold The content of category ion refers to the mass percent of transition metal ions and polyvinyl alcohol, and the transition metal ions includes step 1） The Cu ions and step 4 of addition）Co the or Ni ions of addition；And step 1）In divalence Cu ions and step 4）Middle Co or Ni The mass ratio of ion is 3:1~1:3.
  4. 4. the preparation of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping according to claim 1 Method, it is characterised in that：The step 6）Add alkalescence anion-exchange resin and the step 2）Add pva powder Mass ratio be 1：2.
  5. 5. the preparation of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping according to claim 1 Method, it is characterised in that：Step 2）Described in heating and temperature control at 80~95 degrees Celsius, stir 2.5~3 hours.
  6. 6. the preparation of the alkaline anion-exchange membrane of core shell structure binary transition metal ion doping according to claim 1 Method, it is characterised in that：The caustic dip pre-processes：The film dried is immersed in 1M KOH solutions 12~24 hours, taken out Rinsed repeatedly with deionized water.
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