CN107516743B - 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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CN107516743B
CN107516743B CN201710606468.9A CN201710606468A CN107516743B CN 107516743 B CN107516743 B CN 107516743B CN 201710606468 A CN201710606468 A CN 201710606468A CN 107516743 B CN107516743 B CN 107516743B
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transition metal
core
divalent
ion
shell structure
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CN107516743A (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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a kind of preparation methods of core-shell structure binary transition metal doping alkaline anion-exchange membrane.In preparation method, it is dispersed different in organic matter that present invention utilizes different transition metal ions, tiny nucleus is formed in organic matter using the high transition metal divalent Cu ion of dispersion degree, attract the transition metal ions of another doping to grow by out-phase forming core, forms the alkaline anion-exchange membrane of core-shell structure binary transition metal ion doping of the invention.The present invention is uniformly distributed the binary transition metal ion in core-shell structure in the matrix using alkaline anion-exchange membrane made from the method, center is divalent Cu ion, and shell is divalent Co or the Ni ion with catalysis characteristics.Core-shell structure improves the catalysis characteristics of film, and the fuel permeability of fuel cell is effectively reduced, improves the ion on-state rate of film；Excellent power generation performance is shown by the fuel cell that anion-exchange membrane produced by the present invention is assembled into.

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 fields, in particular to polymer dielectric film fuel cell and preparation method thereof.
Background technique
Polymer dielectric film fuel cell is that the chemical energy being stored in hydrogen and oxygen is directly converted to electricity by one kind Can energy conversion apparatus, have the characteristics that energy conversion efficiency height, can quick start and environmental-friendly at room temperature, be considered It has broad application prospects in terms of transport facility power supply, becomes the research hotspot of nearest power technique fields.
Polymer dielectric film fuel cell can be divided into the acid using proton exchange membrane generally according to the difference of conduction ion Property polymer dielectric film fuel cell (PEMFC) and using alkaline anion-exchange membrane alkaline polymer electrolyte membrane fuel Battery (AEMFC).Currently, with PEMFC technology scaleization and being commercialized deepening continuously for process, PEMFC technical application master It is faced with following four problem: (1) using expensive thin polymer film as amberplex；(2) it is urged using rare platinum Agent；(3) good dynamic water management is needed；(4) production, storage and transport of fuel hydrogen.
Direct akaline liquid fuel cell (DALFC) is that one kind directly uses akaline liquid to replace gaseous hydrogen as fuel AEMFC, studying relatively broad liquid fuel at present has basic methanol solution, hydrazine solution and sodium borohydride solution.With routine PEMFC compares, and akaline liquid fuel uses so that DALFC has following both sides outstanding advantage: (1) liquid fires Material has higher energy density, convenient for storage and transport, is conducive to the integrated level for improving battery；(2) alkaline working environment can To accelerate the catalytic kinetics of hydrogen reduction, it is expected to that battery cost is greatly reduced using non-platinum catalyst.Therefore, the research of DALFC To realize that the low cost of polymer-membrane fuel battery provides thinking with integrated.But the development of DALFC is equally faced with following bottle Neck is studied at present first is that the ionic conductivity of anion-exchange membrane used in DALFC (AEM) is low compared with proton exchange membrane How far 50 mscm are lower than-1；Second is that the infiltration of liquid fuel reduces the utilization rate of fuel when DALFC works, and produced in cathode Raw mixed potential reduces battery operating voltage or even Poisoning cathode catalyst, the serious output performance for damaging battery.
Currently, there is the research of various alkaline anion-exchange membranes to report that Zhang etc. causes free radical polymerization system by heating Enhance film for quaternized polystyrene type ptfe composite, 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 ZrO2It mixes quaternized poly (arylene ether) ether sulfone and prepares composite membrane, 80oIonic conductivity is increased to 41.4 under C mS·cm-1.The above result of study significantly improves ionic conductivity by the structure regulating of AEM.Amberplex is most important Characteristic is ionic conductivity, but the ionic conductivity of single raising AEM is still difficult to solve the infiltration of liquid fuel in DALFC and asks Topic, and as the raising of ionic conductivity can be further exacerbated by the infiltration of liquid fuel.Therefore, it studies a kind of with good Ionic conductivity and the simply inexpensive alkali anion of fuel power generation function performance, fuel-resistant permeance property and preparation process are handed over Changing film has good meaning to the development of polymer dielectric film fuel cell.
Summary of the invention
The technical issues of for existing alkaline ion exchange membrane, the present inventor has in view of transition metal ions Catalysis characteristics form core-shell structure using binary transition metal, and increasing, there is catalytic activity transition metal element to be distributed in film 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 ensureing the ionic conductivity for improving amberplex, to improve battery Power generation performance.There is good ionic conductivity, fuel cell hair simultaneously the object of the present invention is to provide a kind of as a result, The preparation method of electrical property and the alkaline anion-exchange membrane of fuel-resistant permeability.
To achieve 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, includes the following steps:
1) it firstly, divalent Cu salt is dissolved in deionized water, is stirred at room temperature, obtains Cu salting liquid；
2) pva powder is dissolved in Cu salting liquid made from step 1), heated and stirred, obtain the first colloidal sol；
3) the obtained in step 2 is added in 10%~20% ammonium hydroxide that mole is Cu ion mole in step 1) One colloidal sol, is sufficiently stirred, and static ageing 1~4 hour；
4) divalent Co inorganic salts or divalent Ni inorganic salts are dissolved in deionized water, obtain Co salt or Ni salting liquid；
5) the first colloidal sol after step 3) ageing is added in the solution of step 4), is sufficiently stirred, obtains the second colloidal sol；
6) alkalescence anion-exchange resin is ground into fine powder and crosses sieve, it is suspended to be add to deionized water stirring to obtain Suspension is added in the second colloidal sol by liquid, and the two carries out cross-linking reaction, forms the first gel；And the first gel is stood 10 ~20 minutes, then by the bubble removal on surface；
7) the first gel for removing blibbing is formed a film on substrate, is dried；
8) caustic dip pretreatment is carried out to the film after drying.
Further, divalent Co salt, preferably cobaltous dichloride or CoSO4, the divalent Cu salt is preferably dichloride copper.
Further, according to the content of transition metal ions, step 1) addition divalent Cu salt and step 4) addition two are determined The additive amount of valence Co inorganic salts or divalent Ni inorganic salts, the content of the transition metal ions are as follows: 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) Co the or Ni ion for Cu ion and the step 4) addition added；And in the divalent Cu ion in step 1) and step 4) Co or The mass ratio of Ni ion is 3:1~1:3.
Further, heating and temperature control described in step 2 stirs 2.5~3 hours at 80~95 degrees Celsius.
Further, the step 6) addition alkalescence anion-exchange resin and the step 2 add pva powder Mass ratio be 1:2.
Further, the caustic dip pretreatment are as follows: the film dried is immersed in 1M KOH solution 12~24 hours, is taken out With deionized water repeated flushing.
In above-mentioned preparation method, the present inventor through repeatedly the study found that Cu ion in organic matter it is opposite other Transition metal ions there is dispersibility well, highly uniform can be dispersed in organic matter；In the present invention, Cu ion There is high degree of dispersion in polyvinyl alcohol, due to the alkalescent of ammonium hydroxide after ammonium hydroxide is added, the hydroxyl of ionization divides with uniform The Cu ions binding being dispersed in polyvinyl alcohol, forms tiny nucleus in polyvinyl alcohol molecule；Add again later Co or Ni from Sub- solution, since Co, Ni, Cu belong to transition metal, chemical property is similar.Therefore Co the and Ni ion of subsequent addition preferentially exists On the Cu ion nucleating surface formed carry out the growth of out-phase forming core, form the shell of the core-shell structure, avoid Co or Ni ion itself forms coarse aggregate, reaches the work for improving the specific surface area of transition metal ions for the catalysis characteristics having With realizing the more effective fuel permeability for reducing fuel in amberplex, the ionic conductivity for improving amberplex, most The goal of the invention of the power generation performance of fuel cell is improved eventually.In addition, preparation method simple process of the invention, is applicable in 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 divalent Cu ion, and shell is the divalent with catalysis characteristics Co or Ni ion, wherein the diameter of Cu core is in 200~300nm, divalent Co or Ni the ion shell formed with a thickness of 50-200 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 excellent, and has good alcohol-rejecting ability.? The doping of binary transition metal ion has been carried out in film, and has passed through the doping of two kinds of binary transition metal ions, forms binary The heterogeneous core-shell structure of transition metal ions.Be utilized in preparation process different transition metal ions in organic matter dispersibility not Together, tiny nucleus is formed in organic matter using the high transition metal divalent Cu ion of dispersion degree, attract another doping transition gold Belong to ion such as divalent Co or the Ni ion with catalysis characteristics grown by out-phase forming core, formation using divalent Cu ion 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 ion 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 It is equally evenly distributed, to obtain the alkaline anion-exchange membrane of core-shell structure binary transition metal uniform ion distribution；And it keeps away When having exempted from the single doped transition metal ions with catalysis characteristics into film, dispersion degree is bad, gold is formed during doping Metal particles cluster, the non-uniform problem of the filming performance eventually led to；These equally distributed microfacies core-shell structures, can be effective The ionic conductivity for improving amberplex, reduces the resistivity of fuel cell, finally improves the power generation of fuel cell Energy.In an embodiment of the present invention, at 60 °C, the power generation peak power output density of amberplex obtained in embodiment For 303 mW cm-2, power generation performance is substantially better than the amberplex and currently on the market of single transition metal ion doping Proton exchange membrane 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, it can be in amberplex in time Catalysis reaction, to more effectively reduce fuel permeability of the fuel in amberplex.
Detailed description of the invention
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 doping of comparative example 1.
Fig. 3 is the fluorescence two-dimensional imaging figure of the alkaline anion-exchange membrane of the Cu ion doping of comparative example 2.
Fig. 4 is that the power generation performance of the monocell that is assembled using the exchange membrane of embodiment 1 and comparative example 1 under 30 degrees Celsius is bent Line chart.
Fig. 5 is the power generation performance song of the monocell that assemble using the exchange membrane of embodiment 1 and comparative example 1 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.
Specific embodiment
More specific detail is carried out to the present invention below with reference to specific embodiment.
Embodiment 1:
Prepare the process of the alkaline anion-exchange membrane of the core-shell structure binary transition metal ion doping of the present embodiment are as follows:
1) by the hydration of 0.027g bis- dichloride copper, (content of transition metal copper ion is 0.2 wt.%, i.e. transition metal copper The mass percent of ion and polyvinyl alcohol is 0.2%) it is added in 30 mL deionized waters, it is stirred at room temperature 5 minutes and obtains containing two The copper salt solution of first copper ion；
2) 5g polyvinyl alcohol (PVA) powder is dissolved in binary cobalt copper ion aqueous solution, is heated to 80 ~ 95 degrees Celsius, stirs It mixes and obtains within 2.5~3 hours the first copper ion doped colloidal sol of binary；
3) the obtained in step 2 is added in 10%~20% ammonium hydroxide that mole is Cu ion mole in step 1) One colloidal sol, is sufficiently stirred, and static ageing 1~4 hour；
4) by 0.04 g six hydration cobaltous dichloride, (content of transition metal cobalt ions is 0.2 wt.%, i.e. transition metals cobalt The mass percent of ion and polyvinyl alcohol is 0.2%, Co ion and the mass ratio of Cu ion is 1:1) it is added to deionized water In, form cobalt salt solution；
5) colloidal sol after step 3) ageing is added in the cobalt salt solution of step 4), is sufficiently stirred, obtains the second colloidal sol；
6) 2.5g alkalescence anion-exchange resin is taken to be ground into fine powder, the stainless steel mesh for crossing 120 mesh obtains uniform alkalinity Toner is added to stirring to obtain suspension in deionized water；Suspension is added in the second colloidal sol, the two is handed over Connection reaction, forms gel；And gel is stood 10~20 minutes, then by the bubble removal on surface；
7) gel for having removed blibbing is scraped on glass plate with blade applicator, sets film forming thickness as 1000 microns, Naturally dry；
8) film after drying is immersed in 1M KOH solution 12~24 hours, then takes out and is rushed repeatedly with deionized water It washes, the alkaline anion-exchange membrane of the core-shell structure binary transition metal ion doping of the present embodiment is made.
Embodiment 2
Prepare the process and reality of the core-shell structure binary transition metal ion doping alkaline anion-exchange membrane of the present embodiment The difference for applying example 1 is: the transition metal salt cobaltous dichloride of use is different with the additive amount of dichloride copper, the present embodiment step 1) In the addition quality of two hydration dichloride copper be 0.0405g, the addition quality of six hydration cobaltous dichlorides are 0.02 g in step 4), I.e. the mass ratio of Co ion and Cu ion is 1:3.
Embodiment 3
Prepare the process and reality of the core-shell structure binary transition metal ion doping alkaline anion-exchange membrane of the present embodiment The difference for applying example 1 is: the transition metal salt cobaltous dichloride of use is different with the additive amount of dichloride copper, the present embodiment step 1) In the quality of six hydration cobaltous dichlorides be 0.12 g, the quality of two hydration dichloride copper are 0.027g, i.e. Co ion and Cu ion Mass ratio be 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 Transition metal cobalt salt is replaced with the divalent nickel salt of transition metal by person, when the mass ratio of Co ion or Ni ion and Cu ion is 1: Between 3~3:1, the performance and each implementation of the alkaline anion-exchange membrane of core-shell structure binary transition metal ion doping obtained Example is quite.
Comparative example 1
Prepare the process of the ZnO thin film alkaline anion-exchange membrane of this comparative example are as follows:
1) 0.08 g six is hydrated cobaltous dichloride (content of transition metal ions is 0.4%, i.e. transition metal ions and poly- The mass percent of vinyl alcohol is 0.4%) to be added in 30 mL deionized waters, is stirred at room temperature 5 minutes and obtains containing divalent cobalt ion Aqueous solution；
2) 5g PVA powder is dissolved in divalent cobalt ion aqueous solution, is heated to 80 ~ 95 degrees Celsius, stirred 2.5 ~ 3 hours Obtain the PVA gel of divalent cobalt ion doping；
3) 2.5g alkalescence anion-exchange resin is taken to be ground into fine powder, the stainless steel mesh for crossing 120 mesh obtains uniform alkalinity Toner is add to deionized water to form solution, then solution is added to have been cooled to 50 degrees Celsius of divalent cobalt from The PVA gel of son doping, the two carry out cross-linking reaction, form the PVA-AER gel of transitional metal ion Co doping；
4) 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 solution 12 ~ 24 hours, is then taken out with deionized water repeated flushing.
Comparative example 2
Prepare the process of the copper ion doped alkaline anion-exchange membrane of this comparative example are as follows:
1) 0.053 g bis- is hydrated dichloride copper (content of transition metal ions is 0.4%, i.e. transition metal ions and poly- The mass percent of vinyl alcohol is 0.4%) to be added in 30 mL deionized waters, is stirred at room temperature 5 minutes and obtains containing bivalent cupric ion Aqueous solution；
2) 5g PVA powder is dissolved in bivalent cupric ion aqueous solution, is heated to 80 ~ 95 degrees Celsius, stirred 2.5 ~ 3 hours Obtain the PVA gel of bivalent cupric ion doping；
3) 2.5g alkalescence anion-exchange resin is taken to be ground into fine powder, the stainless steel mesh for crossing 120 mesh obtains uniform alkalinity Toner is add to deionized water to form solution, then solution is added to have been cooled to 50 degrees Celsius of cupric from The PVA gel of son doping, the two carry out cross-linking reaction, form the PVA-AER gel of transition metal ions Cu doping；
4) 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 solution 12 ~ 24 hours, is then taken out with deionized water repeated flushing.
More than, alkalescence anion-exchange resin used in each embodiment and comparative example is raw for U.S. Alfa Aesar company The IRA-402(OH of the Amberlite series of production) basic resin (AER resin).
Performance test:
Because in alkaline anion-exchange membrane Cu ion do not have catalysis characteristics, in addition to x-ray fluorescence two dimension at As test, the performance test that the subsequent catalysis characteristics by alkaline anion-exchange membrane obtained are influenced, to Cu made from comparative example 2 The anionic membrane of ion doping, which all omits, not to be tested.
I) x-ray fluorescence two-dimensional imaging is tested
To embodiment 1, comparative example 1 and comparative example 2 carried out x-ray fluorescence two-dimensional imaging test, compare three in film The microstructural differences of middle Elemental redistribution, if Fig. 1 is the alkalinity yin that Cu and Co binary transition metal ion doping is made in embodiment 1 The x-ray fluorescence two-dimensional imaging figure of amberplex, Fig. 2 are the X that Co ion doping alkaline anion-exchange membrane is made in comparative example 1 Ray fluorescence two-dimensional imaging figure, Fig. 3 are the x-ray fluorescence two dimension that Cu ion doping alkaline anion-exchange membrane is made in comparative example 2 Image, three have notable difference.It will be seen from figure 1 that Cu and Co element forms core-shell structure in film, wherein Cu is core, Co is shell, about 500 nm of granular size that the binary transition metal ion of core-shell structure is formed, wherein Cu core in core-shell structure Diameter is in 200-300 nm, divalent Co, Ni the ion shell formed with a thickness of 50-200 nm.Figure it is seen that single gold The doping of category ion, Co metallic particles cluster easy to form in organic film, about 2-3 μm of the size of cluster.It can from Fig. 3 Out, Cu disperses more uniform in organic film, the cluster size about 300-400 nm of formation.This explanation is in binary transition metal ion When being doped in organic molecule chain, Co can be grown using lesser Cu particle as the nucleus of out-phase forming core, to be formed with Cu For core, Co is the binary transition metal ion doping structure of the core-shell structure of shell；This core-shell structure, also further increases The contact area of Co ion and the fuel infiltrated into film with catalysis characteristics, improves its catalytic efficiency, so that realizing has The purpose that effect reduces fuel permeability, improves ion on-state rate and power generation performance.
II) the test of fuel permeability
Exchange membrane has been carried out at room temperature to alkaline sodium borohydride liquid to embodiment 1, embodiment 2, embodiment 3 and comparative example 1 The test of the permeability of fluid fuel.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 ion-conductance at room temperature has been carried out to embodiment 1, embodiment 2, embodiment 3 and comparative example 1 The test of conductance.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
Alkaline anion-exchange membrane made from using each embodiment and comparing 1, alkaline sodium borohydride solution is fuel difference It is assembled into direct sodium borohydride fuel cell, such as the monocell power generation curve graph at different temperatures that Fig. 4~Fig. 6 is assembling. Wherein, Fig. 4 is the power generation curve graph using the monocell of the exchange membrane assembling of embodiment 1, comparative example 1 under 30 degrees Celsius, Fig. 5 The monocell power generation curve graph at 60 c assembled for the exchange membrane of embodiment 1, comparative example 1.It can be seen that Under different temperatures, relatively example, the alkalinity yin of Cu and Co core-shell structure binary transition metal ion doping made from embodiment 1 The power generation performance of amberplex is best, and at 30 °C, peak power output density is 190 mW cm-2, and at 60 °C, most Big output power density is 303 mW cm-2。
Fig. 6 is the alkali anion exchange of Cu and Co core-shell structure binary transition metal ion doping made from embodiment 2 The power generation performance curve figure of the monocell of film assembling, at 30 °C, peak power output density is 185 mW cm-2, and 60 ° When C, peak power output density is 295 mW cm-2, suitable with embodiment 1.It can be seen that using Cu and Co core-shell structure 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, there is no the water imbibitions on film to generate apparent influence for the doping of two kinds of transition metal ions.

Claims (6)

1. a kind of preparation method of the alkaline anion-exchange membrane of core-shell structure binary transition metal ion doping, it is characterised in that Include the following steps:
1) it firstly, divalent Cu salt is dissolved in deionized water, is stirred at room temperature, obtains Cu salting liquid；
2) pva powder is dissolved in Cu salting liquid made from step 1), heated and stirred, obtain the first colloidal sol；
3) first obtained in step 2) is added in 10%~20% ammonium hydroxide that mole is Cu ion mole in step 1) Colloidal sol is sufficiently stirred, and static ageing 1~4 hour；
4) divalent Co inorganic salts or divalent Ni inorganic salts are dissolved in deionized water, obtain Co salt or Ni salting liquid；
5) the first colloidal sol after step 3) ageing is added in the solution of step 4), is sufficiently stirred, obtains the second colloidal sol；
6) alkalescence anion-exchange resin is ground into fine powder and crosses sieve, be add to deionized water stirring to obtain suspension, Suspension is added in the second colloidal sol, the two carries out cross-linking reaction, forms the first gel；And the first gel is stood 10~20 Minute, then by the bubble removal on surface；
7) the first gel for removing blibbing is formed a film on substrate, is dried；
8) caustic dip pretreatment is carried out to the film after drying；The alkalinity yin of the core-shell structure binary transition metal ion doping is made Amberplex, 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 divalent Cu ion, the shell of the core-shell structure be divalent Co with catalysis characteristics or Ni ion；
And the mass ratio of divalent Co or divalent Ni ion is 3:1~1:3 in the divalent Cu ion in step 1) and step 4).
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 divalent Co inorganic salts are cobaltous dichloride or CoSO4, the divalent Cu salt is dichloride copper.
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, determine step 1) addition divalent Cu salt and step 4) addition divalent The additive amount of Co inorganic salts or divalent Ni inorganic salts, the content of the transition metal ions are as follows: 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) Co the or Ni ion for Cu ion and step 4) addition added.
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: step 6) the addition alkalescence anion-exchange resin and the step 2) add pva powder Mass ratio be 1:2.
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: heating and temperature control described in step 2) stirs 2.5~3 hours at 80~95 degrees Celsius.
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 pretreatment are as follows: the film dried is immersed in 1M KOH solution 12~24 hours, is taken out With deionized water repeated flushing.
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