CN104716351A - Proton exchange membrane fuel cell self-humidifying membrane electrode and preparation method thereof - Google Patents

Proton exchange membrane fuel cell self-humidifying membrane electrode and preparation method thereof Download PDF

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Publication number
CN104716351A
CN104716351A CN201310690005.7A CN201310690005A CN104716351A CN 104716351 A CN104716351 A CN 104716351A CN 201310690005 A CN201310690005 A CN 201310690005A CN 104716351 A CN104716351 A CN 104716351A
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China
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membrane electrode
fuel cell
anode
inorganic hydrophilic
hydrophilic
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CN201310690005.7A
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Inventor
邵志刚
郭晓倩
肖宇
秦晓平
曾亚超
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • Y02E60/50—Fuel cells

Abstract

The present invention discloses a self-humidifying membrane electrode and a preparation method thereof. The method comprises: mixing a platinum-carbon catalyst, inorganic hydrophilic metal oxide nanoparticles, a perfluorosulfonic acid polymer and a low-boiling point solvent as an anode catalysis layer, coating on one side of a Nafion membrane, adopting a mixture of a platinum-carbon catalyst, a perfluorosulfonic acid polymer and a low-boiling point solvent as a cathode catalysis, coating on the other side of the Nafion membrane to prepare CCM, placing the anode catalysis layer of the CCM under an ultraviolet light lamp to carry out an ultraviolet illumination treatment, and then carrying out hot pressing with a diffusion layer so as to prepare the membrane electrode (MEA). According to the present invention, the hydrophilicity enhancing effect is more significant than the effect of the increase of the inorganic hydrophilic oxide, the hydrophilicity can be increased while the inorganic hydrophilic oxide nanoparticle content is not increased, the performance of the battery under the low humidity condition is improved, and the problem that the addition of the excessive hydrophilic substance causes the increased resistance and the decreased catalyst electrochemistry activity area are solved.

Description

One proton exchanging film fuel battery self-humidifying membrane electrode and preparation method thereof
Technical field
The present invention relates to field of fuel cell technology, belong to the preparation method of fuel cell from humidification, be specially proton exchanging film fuel battery self-humidifying membrane electrode and preparation method thereof.
Background technology
Fuel cell, with its high-energy-density and of low pollution, is hopeful to replace fossil energy to become main flow in the future.And PEMFC have room temperature start fast, without electrolyte loss, low noise advantages, there are the potentiality as portable power source, various compact power and uninterrupted power supply.In order to keep the high battery performance of PEMFC, dielectric film needs to make it completely saturated by extraneous humidification system, but unnecessary humidification system can increase the volume and weight of whole battery system, increase its complexity, so reach the particularly important in PEMFC system from humidification of MEA.
A lot of research recently is all absorbed in doping hydrophilic substance and is played water retention, and obtains researcher's favor because inorganic oxide has good hydrophily.
Inorganic matter or its oxidate powder are broken into the powder of 0.1 ~ 10 micron by " humidity preservation composite film of a kind of used in proton exchange membrane fuel cell and preparation method thereof " patent of invention [CN1442913A] of Tsing-Hua University's application, be coated in organic film matrix surface by after powder, the organic substance identical with organic film composition and organic solvent Homogeneous phase mixing form slurry, obtain humidity preservation composite film.But can gross distortion be there is because film runs into solvent, reduce battery performance.And what add is micron-sized hydrophilic inorganic oxide, and Water-saving effect is not good, and can increase the resistance of battery after adding too much hydrophilic substance, affects the transmission of gas.
Inorganic nano-particle is transferred to the fuel cell chip that the preparation of proton exchange membrane both sides has water retention property by hot pressing transfer method by " having the preparation method of the proton exchange film fuel cell chip of water retaining function " patent of invention [CN1719653A] of Wuhan University of Technology's application.The hydrophily that adds of nanoscale hydrophilic substance is better than micron order, but still there is the optimization problem of hydrophilic substance addition, and adding too much inorganic nano-particle still can increase cell resistance, affects catalyst and contacts with film.
The patented invention [CN101615677A] of " eelctro-catalyst and preparation method thereof and the fuel cell membrane electrode for fuel cell membrane electrode " of South China Science & Engineering University's application is then absorbed in Electrocatalytic Layer, improves contacting and proton conductivity of film and catalyst layer.It is characterized in that, using the carbon of water conservation electrodeposition substance as complex carrier, supporting noble metal as eelctro-catalyst.But water conservation electric conductivity of matter is poor, can cell resistance be increased as carrier, affect electrical conductivity.
Up to the present, while not needing to add too much hydrophilic substance, the desirable method from moisturization effect is not also reached.
Summary of the invention
The object of this invention is to provide and a kind ofly can improve the method for PEMFC anode-side from moisturization, ensure the fuel cell after assembling can under reaction gas not humidification conditions steady operation, and significantly improve its performance.The invention solves the increase of the cell resistance caused owing to adding too much hydrophilic substance, the shortcoming of the minimizing of catalyst electrochemical surface area.
To achieve these goals, the technical solution used in the present invention is:
1) inorganic hydrophilic oxide nano-particles is mixed evenly ultrasonic with Pt/C catalyst and proton exchange resins solution, obtained anode catalyst layer slurry, wherein inorganic hydrophilic oxide is 0% ~ 60% relative to the mass ratio of Pt/C, and in cathode inks, inorganic hydrophilic oxide content is 0%;
2) anode and cathode pulp spraying is coated in proton exchange membrane both sides, dry after making CCM;
3) carry out ultraviolet lighting process under the CCM containing inorganic hydrophilic oxide nano-particles being placed in ultraviolet source, wherein ultraviolet wavelength is less than 387nm, and light application time is 0.5h ~ 3h, and ultraviolet source is 3 ~ 10cm from sample distance;
4) by step 2) and the CCM of step 3) process and gas diffusion layers be hot pressed into membrane electrode, hot pressing temperature is 140 DEG C, time 2min, and pressure is 0.15MPa;
Described proton exchange membrane is the perfluorinated sulfonic resin with sulfonate group, as the Nafion212 film that du Pont company produces, and Nafion211 film or Nafion117 film; Described solvent is water or organic solvent, as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, ethyl acetate.
Described inorganic hydrophilic oxide nano-particles is TiO 2, SnO 2or W 2o 3, they have good water retention usually, and have the characteristic being caused hydrophily to strengthen by ultraviolet excitation.
Described ultraviolet lighting preparation method, is the anode-side containing inorganic hydrophilic oxide fixed on a glass upward, is placed in by glass plate and shrinks on lifting platform.Shrink lifting platform is vertically fixed with and carve graduated scale, be used for measuring the distance of ultraviolet source and sample surfaces.The ultraviolet wavelength that described control is different is that the filter by adding different wave length in ultraviolet lamp realizes.And ultraviolet source is faced sample center down and carry out photo-irradiation treatment.
The present invention is compared with background technology, the anode of fuel cell of preparation has better water retention property, its hydrophily can be increased while not increasing inorganic hydrophilic oxide, solve the problem that cell resistance increases and catalyst electro-chemical activity face reduces caused after adding too much inorganic hydrophilic oxide, and add the performance under low humidity better.
Accompanying drawing explanation
Fig. 1 is ultraviolet lighting preparation technology figure;
Fig. 2 is contact angle variation diagram;
Fig. 3 is for containing 20%TiO 2battery is performance change after ultraviolet lighting;
Fig. 4 is containing 20%TiO before and after 2000min 2positive contact angle changes;
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1: by 40wt%Pt/C (Johnson Matthey), 5wt% solution nano-TiO 2(21nm) be mixed into Anode inks with isopropyl alcohol, after being uniformly dispersed by its ultrasonic 40min, spray to Nafion212 side on film, by 40wt%Pt/C (Johnson Matthey), 5wt% solution be mixed into cathode inks with isopropyl alcohol 5g, after ultrasonic 40min is uniformly dispersed, the opposite side spraying to Nafion212 film makes thin layer Film electrode CCMs, wherein nano particle TiO in anode catalyst layer 2content be 0%, 10% and 40%(relative to the mass ratio of Pt/C).Anode-side is contained 10%TiO 2cCMs to be placed in wavelength be that under the uviol lamp of 350nm photo-irradiation treatment 1h(is as shown in Figure 1), light source 1 is undertaken being adjusted to 8cm(with the distance of sample 2 by support 3 and is indicated by scale 4).The anode-side of self-control CCMs is fixed on a glass upward, KRUSS DSA100 liquid form analytical system is adopted to measure contact angle, when room temperature, the distilled water of 3 μ L is dripped on CCMs at every turn, water droplet state is taken pictures at once, then utilize the contact angle of software analysis drop shape and sample surfaces.As shown in Figure 2,40%TiO is added 2after hydrophilic particle, contact angle is relative to not adding TiO 2traditional C CM reduce 15.68 °, and only containing 10%TiO 2cCM contact angle after ultraviolet lighting of hydrophilic particle reduces 20.46 °, so increase hydrophilic substance content, not adopt ultraviolet lighting method to carry out processing the hydrophilic effect obtained good.
Embodiment 2: by 40wt%Pt/C (Johnson Matthey), 5wt% solution 20% nano-TiO 2(21nm, the mass ratio relative to Pt/C) and isopropyl alcohol 6g are mixed into Anode inks, after its ultrasonic 40min dispersion, spray to Nafion212 film side, the preparation method of cathode catalysis layer is identical with embodiment 1, makes thin layer Film electrode CCMs.Homemade CCM is carried out ultraviolet lighting process, and method is identical with embodiment 1 with condition.And contact angle experiments test is carried out to it, method of testing is identical with embodiment 1.Then by homemade CCMs and gas diffusion layers at 140 DEG C, under 0.15MPa condition, hot pressing 2min obtains asymmetric membrane electrode (MEA).The effective active area of MEA is 5cm 2, be assembled into battery carry out low-humidification condition under performance evaluation.Find containing 20%TiO 2contact angle before and after CCM ultraviolet lighting is respectively 146.2 ° and 106.83 °.Under anode-side not humidification situation, as seen from Figure 3, relative to without ultraviolet lighting, the cell power density through ultraviolet lighting adds 106mW cm -2.
Embodiment 3: anode catalyst layer is identical with embodiment 2 with the preparation method of cathode catalysis layer, makes thin layer Film electrode CCMs.Homemade CCM is carried out ultraviolet lighting process, and method is identical with embodiment 1 with condition.And contact angle experiments test is carried out to it, method of testing is identical with embodiment 1.CCM through ultraviolet lighting process is placed in N 2under environment after 2000min, then contact angle experiments test is carried out to it.As can be seen from Figure 4, at N 2under environment, before and after 2000min, contact angle is substantially constant.So through N 2environmental testing, can infer that ultraviolet light induced hydrophily can remain unchanged under galvanic anode environment.

Claims (5)

1. one kind for the membrane electrode of fuel cell from humidification system, comprise anode diffusion layer, anode catalyst layer, proton exchange membrane, cathode catalyst layer, cathode diffusion layer successively, it is characterized in that: in anode catalyst layer, add inorganic hydrophilic oxide nano-particles, keep hydrophily; And antianode Catalytic Layer is processed by ultraviolet lighting method, increase its hydrophily, after assembling compacting, be the membrane electrode from humidification system.
2. according to claim 1 for the membrane electrode of fuel cell from humidification system, it is characterized in that: described inorganic hydrophilic oxide is the metal oxide with photic hydrophilic effects, as TiO 2, SnO 2or W 2o 3, nano particle refers to the metal oxide particle of particle size between 10 ~ 50nm.
3. according to claim 2 for the membrane electrode of fuel cell from humidification system, it is characterized in that: the metal oxide with photic hydrophilic effects is less than the UV-irradiation of 387nm at wavelength under, Lacking oxygen is produced after valence-band electrons is excited, water in air forms hydroxyl OH with Lacking oxygen reaction, makes surface hydrophilic.
4. according to claim 1 for the membrane electrode of fuel cell from humidification system, it is characterized in that: described ultraviolet lighting method carries out ultraviolet lighting process under the CCM anode-side containing inorganic hydrophilic oxide nano-particles is placed in ultraviolet source, wherein ultraviolet wavelength is for being less than 387nm, light application time is 0.5h ~ 3h, and ultraviolet source is 3 ~ 10cm from sample distance.
5. one kind for the preparation method of fuel cell from the membrane electrode of humidification system, it is characterized in that: by inorganic hydrophilic oxide nano-particles, 40wt%Pt/C catalyst mixes ultrasonic evenly obtained anode catalyst layer slurry with proton exchange resins solution, wherein inorganic hydrophilic oxide is 0% ~ 60% relative to the mass ratio of Pt/C, and in cathode inks, inorganic hydrophilic oxide content is 0%; Anode and cathode pulp spraying is coated in proton exchange membrane both sides, makes after CCM dry, after being hot pressed into membrane electrode with diffusion layer, carry out performance test under low-humidification.
CN201310690005.7A 2013-12-13 2013-12-13 Proton exchange membrane fuel cell self-humidifying membrane electrode and preparation method thereof Pending CN104716351A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109065923A (en) * 2018-07-06 2018-12-21 华南理工大学 Add the high-performance high power density membrane electrode and preparation method thereof of hydrophily carbon material preparation having from humidifying capacity
CN112424978A (en) * 2018-08-09 2021-02-26 三井金属矿业株式会社 Electrode catalyst layer for fuel cell and solid polymer fuel cell using same
CN113795611A (en) * 2019-05-05 2021-12-14 多伦多大学管理委员会 Conversion of carbonates to synthesis gas or C2+ products in an electrolytic cell
CN114665131A (en) * 2022-02-24 2022-06-24 南京工业大学 H for representing oxygen electrode material3O+Transmission method

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CN1941466A (en) * 2005-09-29 2007-04-04 株式会社东芝 Membrane electrode, membrane electrode assembly, fuel cell, method of manufacturing the membrane electrode
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CN101079487A (en) * 2006-05-26 2007-11-28 中国科学院大连化学物理研究所 Multi-layer moisture making compound film for proton exchange film fuel cell and its making method
CN101615677A (en) * 2009-07-24 2009-12-30 华南理工大学 Eelctro-catalyst that is used for fuel cell membrane electrode and preparation method thereof reaches fuel cell membrane electrode
CN102784638A (en) * 2011-05-20 2012-11-21 北京化工大学 New process for preparing Pt-M (Mo, au, ce)/C/TiO2fuel cell anode electrocatalyst by in-situ reduction with illumination

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1993854A (en) * 2004-09-27 2007-07-04 松下电器产业株式会社 Fuel cell system and method for operating fuel cell system
CN1881667A (en) * 2005-06-17 2006-12-20 中国科学院大连化学物理研究所 Multilayer composite proton exchange membrane and synthesizing method for self-humidifying fuel cell
CN1941466A (en) * 2005-09-29 2007-04-04 株式会社东芝 Membrane electrode, membrane electrode assembly, fuel cell, method of manufacturing the membrane electrode
CN101079487A (en) * 2006-05-26 2007-11-28 中国科学院大连化学物理研究所 Multi-layer moisture making compound film for proton exchange film fuel cell and its making method
CN101615677A (en) * 2009-07-24 2009-12-30 华南理工大学 Eelctro-catalyst that is used for fuel cell membrane electrode and preparation method thereof reaches fuel cell membrane electrode
CN102784638A (en) * 2011-05-20 2012-11-21 北京化工大学 New process for preparing Pt-M (Mo, au, ce)/C/TiO2fuel cell anode electrocatalyst by in-situ reduction with illumination

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109065923A (en) * 2018-07-06 2018-12-21 华南理工大学 Add the high-performance high power density membrane electrode and preparation method thereof of hydrophily carbon material preparation having from humidifying capacity
CN112424978A (en) * 2018-08-09 2021-02-26 三井金属矿业株式会社 Electrode catalyst layer for fuel cell and solid polymer fuel cell using same
CN113795611A (en) * 2019-05-05 2021-12-14 多伦多大学管理委员会 Conversion of carbonates to synthesis gas or C2+ products in an electrolytic cell
CN114665131A (en) * 2022-02-24 2022-06-24 南京工业大学 H for representing oxygen electrode material3O+Transmission method
CN114665131B (en) * 2022-02-24 2024-01-16 南京工业大学 H for representing oxygen electrode material 3 O + Method of transmissibility

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