CN106972184B - A kind of in-situ treatment method for reducing amberplex and sodium borohydride fuel being permeated - Google Patents

A kind of in-situ treatment method for reducing amberplex and sodium borohydride fuel being permeated Download PDF

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CN106972184B
CN106972184B CN201710229547.2A CN201710229547A CN106972184B CN 106972184 B CN106972184 B CN 106972184B CN 201710229547 A CN201710229547 A CN 201710229547A CN 106972184 B CN106972184 B CN 106972184B
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transition metal
metal salt
amberplex
salt solution
cathode
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CN106972184A (en
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蒋伟
陈宇麒
刘锋
董泽熹
王紫旌
王宣程
吴睿知
盛欢欢
秦海英
褚雯
刘嘉斌
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Zhejiang University ZJU
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Zhejiang University ZJU
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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
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of reduction amberplexes to the method for sodium borohydride fuel infiltration in-situ treatment amberplex, includes the following steps.First by the components assembled battery such as amberplex and electrode, flow field, clamping plate, it is not passed through fuel and oxygen first, but transition metal salt solution first is passed through in cathode, transition metal salt solution concentration is 1M~5M, and transition metal salt solution is kept to fill up cathode flow field 5~30 minutes, so that the transition metal ions in transition metal salt is penetrated into the microchannel in amberplex, empties the transition metal salt solution later；Then it is passed through sodium borohydride solution in anode, is passed through oxygen in cathode, can normally started battery work, externally generate electricity.Wherein transition metal salt is cobalt chloride, copper chloride, cobaltous sulfate or iron chloride.Fuel permeability is significantly reduced since transition metal ions blocks microchannel by the amberplex that the present invention is handled, mixed potential reduction cell voltage is generated in cathode so as to avoid the fuel of infiltration, ensures that battery plays excellent performance.And method is simple.

Description

A kind of in-situ treatment method for reducing amberplex and sodium borohydride fuel being permeated
Technical field
The present invention relates to fuel cell fields, the in particular to place of polymer dielectric film fuel cell intermediate ion exchange membrane Reason method.
Background technique
Fuel cell as a kind of special device that chemical energy is converted to electric energy, due to it is high with energy conversion efficiency, The incomparable superiority of various other energy generating apparatus such as low pollution, the wide, low noise of ergastic substances range of choice, are considered It is most promising, environmental-friendly one of mechanism of new electrochemical power sources.Wherein, polymer dielectric film fuel cell has and quickly opens It is dynamic and the advantages that the quick responses of load variations, it receives more and more attention, becomes nearest research hotspot.
Polymer dielectric film fuel cell using polymer dielectric film as solid electrolyte, play segmentation yin-yang the two poles of the earth and Proton conducting (H+) or hydroxide ion (OH-) effect, be a critical component in polymer electrolyte fuel cells.It is poly- The performance quality of polymer electrolyte membrane play the role of to the power generation performance of polymer dielectric film fuel cell it is conclusive, because And the research and development of high-performance polymer dielectric film are just particularly important.
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 and using alkaline anion-exchange membrane alkaline polymer electrolyte membrane fuel cell.Mesh Before, commercialized proton exchange membrane for example DuPont Corporation production perfluorinated sulfonic acid (Nafion) film, due to high conductivity, Excellent chemistry, electrochemistry and mechanical stability is current business application polymer dielectric film most in fuel cell. But Nafion membrane preparation process is complicated, at high price, preparation process causes damages to environment, must use noble metal catalyst The problems such as, it is further commercially use to limit Proton Exchange Membrane Fuel Cells.And on the other hand, relative to proton exchange membrane Fuel cell, alkaline anion-exchange membrane fuel cell have a series of particular advantages: due to its alkaline environment, fuel cell tool There are the organic-fuels such as faster kinetics, the methanol that non-precious metal catalyst can be used and be readily transported or ethyl alcohol.
It is fuel that direct sodium borohydride fuel cell, which is directly using sodium borohydride aqueous solution, and oxygen or air are as oxidant A kind of new fuel cell.Its working principle is: in anode region, negative electrode active material sodium borohydride aqueous solution is through anode stream After field plate evenly distributes, is spread by anode diffusion layer and enter in anode catalyst layer (i.e. anode electrochemical active reaction area Domain), electrochemical oxidation reactions occur under the action of pallium-on-carbon elctro-catalyst, generate proton, electronics and metaboric acid root.It generates Proton moves to cathode by perfluoro sulfonic acid membrane polymer dielectric, and electronics is transmitted to cathode by external circuit, metaboric acid root from Anode export discharge；Cathodic region, positive active material oxygen or air pass through cathode diffusion layer after cathode flow field plate is uniformly matched It spreads and enters in cathode catalysis layer (i.e. negative electricity chemical activity conversion zone), under the action of pallium-on-carbon elctro-catalyst and from sun The proton that pole migration comes occurs electrochemical reducting reaction generation water and is discharged with reaction end gas from cathode outlet.Its electrode reaction is such as Under:
Anode reaction: BH4 -+2 H2O→BO2 -+8 H++ 8e；
Cathode reaction: 2O2+8 H+The H of+8e → 42O；
Overall reaction: BH4 -+2 O2→BO2 -+2 H2O 。
Sodium borohydride is liquid at room temperature, has very high energy density.However fuel infiltration is to influence direct boron hydrogen Change the critical issue of sodium fuel battery performance.When sodium borohydride through film to cathode after, generating mixed potential, to reduce battery total Voltage damages cell power generation efficiency.
Patent (publication number 105884948A) discloses a kind of fuel cell anionic membrane for blocking methanol crossover, and use is different Butylene, 1- chlorine iso-amylene and cross-linking monomer 2- trifluoromethyl -6- methyl -5- heptene acetic acid esters, by cationic pre-polymerization, amination, Quaternized, dehydration ethylene linkage, last free radical polymerization densification crosslinking is polyisobutene anionic membrane.Due to being the tertiary alkyl master of saturation Chain, will not highly basic degradation.With excellent alkali resistance and methanol blocking ability, room temperature membrane conductivity can reach >=80mS/cm.
Patent (publication number 105826584A) reduces Nafion membrane using the method for mixing sulfonated graphene in Nafion Methanol permeability.Patent (grant number ZL03137306.2), which discloses, belongs to being used for for fuel cell material technology of preparing range The aromatic heterocyclic polymer containing sulfonic acid lateral group of direct methanol fuel cell is doped preparation proton exchange membrane with inorganic material A kind of preparation method of methanol tolerance infiltration proton exchange membrane.Aromatic heterocyclic polymer by film matrix containing sulfonic acid lateral group is added to solvent In, after forming homogeneous mixture, inorganic matter is added, forms suspended matter.The suspended matter is crushed by nanometer crushing technology, Finely dispersed slurry is obtained, is film-made with casting.Its membrane structure formed is uniform, quite fine and close.It can not only resist well Methanol crossover also has good chemical stability and proton-conducting, and methanol permeability is less than 5%.
As described above, have some ion exchange membrane preparation methods about reduction methanol permeability at present, however about The ion exchange membrane processing method for reducing sodium borohydride fuel permeability is rarely reported.Methanol crossover mechanism and sodium borohydride permeate Mechanism is different, the former is molecule diffusion, and the latter is ionic conduction.Method suitable for reducing methanol permeability is not necessarily suitable Sodium borohydride system.Therefore it is necessary to develop a kind of ion exchange membrane processing method for reducing sodium borohydride permeability.
Summary of the invention
Above-mentioned mentioned amberplex in the prior art there are aiming at the problem that, the present invention is intended to provide a kind of reduction The ion exchange membrane processing method of sodium borohydride permeability.
The present invention provides a kind of reduction amberplexes to sodium borohydride fuel infiltration in-situ treatment amberplex Method includes the following steps:
(1) by the components assembled battery such as amberplex and electrode, flow field, clamping plate, it is not first passed through fuel and oxygen, but It first is passed through transition metal salt solution in cathode, and transition metal salt solution is kept to fill up cathode flow field 5~30 minutes, keeps transition golden Belong to the microchannel that the transition metal ions in salt penetrates into amberplex, empties the transition metal salt solution later；
(2) it then is passed through sodium borohydride solution in anode, is passed through oxygen in cathode, can normally start battery work, it is right Outer power generation.
Wherein the transition metal salt solution concentration in preferred steps (1) is 1M~5M.
Wherein preferred transition metal salt is cobalt chloride, copper chloride, cobaltous sulfate or iron chloride.
Core of the invention thinking is: no matter at present there is fuel infiltration in which kind of amberplex, basic former Because being that high-molecular polymerization membrane matrix inevitably has microchannel, if it is possible to block these microchannels, then can significantly subtract Few fuel infiltration.Being passed through transition metal salt solution in advance in cathode makes transition metal ions adsorption and diffusion in membrane micropore road, it Afterwards when anode is passed through sodium borohydride fuel, sodium borohydride will also attempt to penetrate into cathode by microchannel.When sodium borohydride with Reaction is generated into insoluble transition metal boride to transition metal ions is fixed on micro- when transition metal ions meets In duct and clogging microchannel makes subsequent sodium borohydride that can not continue to permeate, and realizing reduces permeability effect.
Key problem in technology of the invention is: the amount in transition metal ions infiltration membrane micropore road.If the transition in infiltration into microporous road Metal ion content deficiency can not then generate enough borides in subsequent reactions and be filled up completely microchannel to reach to reduce and seep Saturating rate effect.The present invention ensures that the ion for penetrating into membrane micropore road contains by control transition metal salt solution concentration and time of penetration Amount.
Beneficial effects of the present invention:
1) amberplex handled according to the present invention significantly reduces combustion since transition metal ions blocks microchannel Expect permeability, generates mixed potential reduction cell voltage in cathode so as to avoid the fuel of infiltration, it is excellent to ensure that battery is played Good performance；
2) processing method of the invention is simple and easy to do, and is progress in situ, is not necessarily to precision equipment, easy to accomplish.
Detailed description of the invention
Fig. 1 is the power spectrum test result of the carbon EDS maps near untreated preceding amberplex cross section microchannel, White bright spot indicates carbon signaling point in picture.
Fig. 2 is the energy using the cobalt element EDS maps near amberplex cross section microchannel handled by embodiment 1 Test result is composed, white bright spot indicates cobalt element signaling point in picture.
Specific embodiment
No matter at present there is fuel infiltration in which kind of amberplex, and basic reason is as amberplex Inevitably there is microchannel in high-molecular polymerization membrane matrix, as attached drawing 1 be at present conventional use of amberplex (without Processing method of the present invention processing) cross section microchannel near carbon EDS maps power spectrum test result, Bai Liang in picture Point indicate carbon signaling point, from this test result reflect microchannel in amberplex it is generally existing.
Below by specific embodiment, the present invention is described further.
Embodiment 1:
(1) by the components assembled battery such as amberplex and electrode, flow field, clamping plate, be not first passed through fuel and oxygen but First the cobalt chloride solution of 5 M concentration is continually fed into cathode and solution is kept to fill up cathode flow field 5 minutes, empties the chlorination later Cobalt liquor；
(2) it then is passed through sodium borohydride solution in anode, is passed through oxygen in cathode, can normally start battery work, it is right Outer power generation.
Embodiment 2:
The difference from embodiment 1 is that cobalt chloride is copper chloride substitution in step (1), other parameters are identical.
Embodiment 3:
The difference from embodiment 1 is that cobalt chloride is cobaltous sulfate substitution in step (1), other parameters are identical.
Embodiment 4:
The difference from embodiment 1 is that cobalt chloride is iron chloride substitution in step (1), other parameters are identical.
Embodiment 5:
The difference from embodiment 1 is that the concentration of cobalt chloride is 1 M in step (1), the retention time is 30 minutes, other Parameter is identical.
Comparative example 1:
With the difference of embodiment 1: the retention time is 1 minute in step (1), and other parameters are identical.
Comparative example 2:
With the difference of embodiment 1: cobalt chloride concentration is 0.1 M in step (1), and other parameters are identical.
Comparative example 3:
With the difference of embodiment 1: not including step (1), other parameters are identical.
Cell active area used in above-described embodiment and comparative example is 6 cm2, anode use Ni-Pd catalyst, loading For 10 mg/cm2, for cathode using Pt/C catalyst, loading is 5 mg/cm2, sodium borohydride solution 5wt.%NaBH4With 10wt.%NaOH mixed aqueous solution, oxidant are purity oxygen, and pressure is 0.2 MPa, and test temperature is 30 degrees Celsius.Pass through test Voltage under different discharge currents obtains battery peak power output density.By constant current discharge, cell voltage is tested at any time Between variation to evaluating cell performance decay rate.The experimental result that specific each test obtains is as shown in table 1.In addition, will implement The amberplex of example 1 takes out ultra-thin section and is divided with the transition metal ions of transmission electron microscope cooperation energy disperse spectroscopy test film cross section Cloth, as shown in Fig. 2.
Battery peak power output density after each embodiment and comparative example in-situ treatment of table 1, attenuation rate and open circuit electricity Pressure.
Sample Open-circuit voltage (V) Peak power output density (mW/cm2) Attenuation rate (300 mA continuous discharge 24 hours)
Embodiment 1 1.12 89 3.2
Embodiment 2 1.15 92 3.5
Embodiment 3 1.10 88 3.1
Embodiment 4 1.26 93 3.5
Embodiment 5 1.13 90 3.7
Comparative example 1 1.07 67 7.4
Comparative example 2 1.05 71 8.6
Comparative example 3 1.02 65 9.4
From the open-circuit voltage of table 1 can be seen that it is processed by the invention after battery open circuit voltage be generally higher than comparative example Open-circuit voltage, this exactly has benefited from proposed by the invention making fuel be difficult to seep by membrane micropore road again from blocking effect thinking Battery open circuit voltage is reduced to cathode thoroughly.Decaying of the present invention treated the cell voltage degradation rate also below comparative example simultaneously Rate reduces anticathode detrimental effect this is because proposed by the invention reduce fuel infiltration from blocking effect thinking, Ensure that battery performance is stablized.It is suppressed due to permeating, on the one hand makes battery total voltage higher, another aspect battery performance is steady It is fixed, to ensure that battery plays good power generation performance, therefore the embodiment of the present invention maximum power density obtained is aobvious It writes and is higher than comparative example.
It can be reacted from the visible common transition metal ions of Examples 1 to 4 with sodium borohydride and generate insoluble boride It is produced from blocking effect, and different anion influences less the processing method.
From the comparison of embodiment 1,5 and comparative example 1,2 as it can be seen that the penetration degree of transition metal ions is very crucial, transition gold Category salinity is too low or processing time too short be unable to reach adequately blocks effect certainly.
From the comparison of Examples 1 to 5 and comparative example 3 as it can be seen that directly being tested compared to battery shown in comparative example 3, surveying Increasing step (1) proposed by the invention before examination can significantly improve battery performance.

Claims (3)

1. a kind of in-situ treatment method for reducing amberplex and being permeated to sodium borohydride fuel, it is characterised in that including walking as follows It is rapid:
Step 1: by the component assembled battery including amberplex and electrode, flow field, clamping plate, not first being passed through fuel and oxygen, But it first is passed through transition metal salt solution in cathode, and transition metal salt solution is kept to fill up cathode flow field, later described in emptying Transition metal salt solution；
Step 2: being passed through sodium borohydride solution in anode, is passed through oxygen in cathode, can normally start battery work, to outgoing Electricity；
And transition metal salt described in step 1 is cobalt chloride, copper chloride, cobaltous sulfate or iron chloride；
The concentration of the transition metal salt solution is 1M~5M, and transition metal salt solution is kept to fill up 5~30 points of cathode flow field Clock.
2. a kind of in-situ treatment method for reducing amberplex and sodium borohydride fuel being permeated according to claim 1, Be characterized in that: the concentration of transition metal salt solution described in step 1 is 5M, and transition metal salt solution is kept to fill up cathode stream Field 5 minutes.
3. a kind of in-situ treatment method for reducing amberplex and sodium borohydride fuel being permeated according to claim 1, Be characterized in that: the concentration of transition metal salt solution described in step 1 is 1M, and transition metal salt solution is kept to fill up cathode stream Field 30 minutes.
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CN101587958A (en) * 2009-07-07 2009-11-25 重庆大学 Method for improving performance of direct sodium borohydride fuel cell
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