CN104638274B - Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate - Google Patents
Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate Download PDFInfo
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- CN104638274B CN104638274B CN201510058931.1A CN201510058931A CN104638274B CN 104638274 B CN104638274 B CN 104638274B CN 201510058931 A CN201510058931 A CN 201510058931A CN 104638274 B CN104638274 B CN 104638274B
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a metal bipolar plate of a fuel cell with a polymer electrolyte membrane. A nano-TiO2 membrane with the thickness of 1-50mu m is arranged on the surface of a matrix, the corrosion rate is lower than 5mu A/cm＜2＞, the resistivity is lower than 0.01mohm.cm, and the gas permeability is lower than 1*10＜-4＞cm＜3＞/s.cm＜2＞. A method provided by the invention can be used for remarkably improving the corrosion resistance and battery performance of the metal bipolar plate under the condition that the strength of the bipolar plate is not influenced. The preparation method has the advantages of simple process, low cost, large-scale batch production and the like.
Description
Technical field
The invention belongs to field of fuel cell technology.Particularly to metal double polar plates of polymer electrolyte film fuel cell and
Its surface modification.
Background technology
Polymer dielectric film fuel cell has the features such as energy conversion efficiency height, life-span length, environmental friendliness, work in addition
Make temperature low and started quickly at low temperature can be realized, be particularly suitable as the power source of transport facility and build dispersion electricity
Stand, be a kind of general movable power source of the army and the people.However, the factors such as of a relatively high cost, weight and volume are very big
The scale commercialization application of polymer dielectric film fuel cell is unfavorable on degree.Therefore, its raw material and system how are reduced
Standby cost is always national governments and the hot issue of researcher concern.
As a kind of important multifunctional module, bipolar plates can not only separate reacting gas, afflux conduction, support membrane electricity
Pole, can also provide passage for reacting gas and so that it is evenly distributed, facilitate the hydro-thermal of set of cells to manage.Good due to having
Electric conductivity and chemical stability, graphite is considered as preferable polymer dielectric film fuel cell bipolar plate material always.But
By its fragility is big, low intensity and loose porous limited the fuel cell unit being difficult to prepare low weight, low volume.Additionally, in stone
Complex process and costly during black plate surface processing flow field, account for polymer dielectric film fuel cell cost 80% is left
Right.Metal material has good obdurability, electric conductivity and air-tightness, can be processed into the thick thin plate of 0.1～0.3mm, and can
With the method using machining and punching press in the variously-shaped flow field of its Surface Machining, occupy substantially excellent in terms of batch production
Gesture, is conducive to increasing substantially the quality specific power of polymer dielectric film fuel cell and volumetric specific power.Commonly use at present
Metallic bipolar plate materials mainly include ferrous alloy, nickel-base alloy and aluminum, titanium and its alloy etc..
In view of the particularity of the Partial digestion of PEM and technology for preparing electrode, in polymer dielectric film fuel electricity
SO is all contained in the working environment in pond4 2-、SO3 2-、CO3 2-、HSO4 -And HSO3 -Plasma.Therefore, metal double polar plates are in this bar
Electrochemical corrosion can occur under part unavoidably.Although the oxide in the formed passivating film of metal bipolar plate surface can effectively suppress
Metal corrodes further, but its semiconductor property can lead to surface contacted resistance to raise.All of these factors taken together certainly will cause
The consumption of electric energy and the reduction of fuel cell stack power output, thus affect the performance of set of cells.For this reason, passing through surface modification skill
Art meets its requirement in electric conductivity and corrosion resistance in metal bipolar plate surface preparation modified layer simultaneously and can yet be regarded as one kind effectively
Method, also will produce material impact to the development of polymer dielectric film fuel cell and extensive application.Obviously, noble metal changes
Property layer be unsuitable for because of its high cost produce low cost set of cells.Using the different method such as PVD, CVD, chemical plating and plating
The nitride of preparation and oxide coating then generate the micropore being difficult to avoid that and micro-crack etc. and lack because of the restriction of its preparation technology
Fall into, thus causing coating local corrosion and peeling off and substantially shorten with the service life of polymer dielectric film fuel cell.Due to
These methods are constantly present such or such deficiency, up to the present, also do not have any one by surface modification treatment
Metal double polar plates are able to the application of large-scale market.Therefore, develop the bipolar of inexpensive, high surface conductivity and good corrosion resistance
Plate is the inexorable trend of polymer dielectric film fuel cell, and also necessarily the commercialization to polymer dielectric film fuel cell is entered
Journey produces important impact.
Content of the invention
It is an object of the invention to provide a kind of low cost has excellent electric conductivity, corrosion resistance, is readily produced processing
And disclosure satisfy that the metal double polar plates of polymer electrolyte film fuel cell of scale market application requirement and preparation method thereof.
In order to reach above-mentioned purpose, the present invention employs the following technical solutions：
Metal double polar plates of polymer electrolyte film fuel cell provided by the present invention, be 0.1～3mm in thickness gold
Belong to and prepare nano-TiO on matrix2Modified film and obtain.The present invention is through nano-TiO2Modified metal double polar plates corrosion rate is less than 5
μA/cm2, less than 0.01m Ω cm, gas permeability is less than 1 × 10 for resistivity-4cm3/s·cm2.Currently preferred nanometer
TiO2Film thickness is 1～50 μm.
Nano-TiO of the present invention2Modified metal double polar plates of polymer electrolyte film fuel cell, described metallic matrix
Material is rustless steel, carbon steel and titanium or titanium alloy.Further, described rustless steel includes austenitic stainless steel, ferrite not
Rust steel and two phase stainless steel etc.；Described carbon steel includes 1020 carbon steels, 1010 carbon steels etc..
The nano-TiO that the present invention provides2Modified metal double polar plates of polymer electrolyte film fuel cell, according to following step
Suddenly nano-TiO is prepared on metallic matrix2Thin film：
A. it is added dropwise over deionization frozen water in the 100g titanium tetrachloride of cooling to 350ml and to shake up to prepare chlorination oxygen
Titanium；Chlorination oxygen titanium is added dropwise in 7～15ml glycolic, adds deionized water and to 350ml and shake up；This solution is in room
Temperature is lower to stand 10 days until forming precipitation；Precipitate water after described precipitation is filtered and alcohol washes, obtain particle mean size
TiO for 10～150nm2Powder；
B. by alkyd resin and hexamethyl tripolycyanamide according to mass ratio 7:After 3 mixing, add nano-TiO2Powder, fills
Nano-TiO is obtained after dividing mixing2Powdered substrate；
C. the metallic matrix that the thickness of pretreatment is 0.1～3mm is placed in well-mixed nano-TiO2In powdered substrate,
At the uniform velocity pull-up metallic matrix vertically upward repeatedly, you can form nano-TiO in metal base surface2Thin film.Described pretreatment step
Suddenly it is by metal base surface after oil removing, rust cleaning, grinding process, cleaned with acetone and redistilled water and be dried.
Nano-TiO of the present invention2Modified metal double polar plates of polymer electrolyte film fuel cell, described metallic matrix
The speed of pull-up vertically upward is 1～20cm/min.
Nano-TiO of the present invention2Modified metal double polar plates of polymer electrolyte film fuel cell, described metallic matrix
The number of times of pull-up vertically upward is 1～20 time.
The metal double polar plates advantage that the present invention provides is：Nano-TiO2Modified metal double polar plates can apply to be polymerized
Thing dielectric film fuel cell field.The nano-TiO of present invention preparation2Modified metal double polar plates disclosure satisfy that bipolar plates exist
Corrosion electric current density (16 μ A cm-2) and contact resistance (10m Ω cm2) aspect use requirement.The nanometer that the present invention provides
TiO2Modified metal double polar plates are the common metal preparations using relative low price, preparation process is simple, and processing cost is low
Honest and clean, it is easy to accomplish metal double polar plates mass production, wide for quickening metal double polar plates of polymer electrolyte film fuel cell
General application has important practical significance.
Specific embodiment
Embodiment 1
The nano-TiO that the present embodiment provides2Modified metal double polar plates of polymer electrolyte film fuel cell, according to following
Step prepares nano-TiO on 316L stainless steel base2Thin film：
A. it is added dropwise over deionization frozen water in the 100g titanium tetrachloride of cooling in condenser to 350ml and to shake up to prepare
Chlorination oxygen titanium.Chlorination oxygen titanium is added dropwise in 7ml glycolic, adds deionized water and to 350ml and shake up.This solution exists
Standing 10 days under room temperature is until form precipitation.Filter precipitate water and alcohol washes, you can obtain particle mean size be 10～
150nmTiO2Powder.
B. according to mass ratio 7:3 ratio is mixed and alkyd resin and hexamethyl tripolycyanamide as substrate, then
Nano-TiO2It is sufficiently mixed in powder addition substrate.
C.316L stainless steel surfaces, after oil removing, rust cleaning, grinding process, are cleaned with acetone and redistilled water and are dried.
The metallic matrix of pretreatment is placed in well-mixed nano-TiO2In powdered substrate, at the uniform velocity pull-up vertically upward, speed is
10cm/min.So it is repeated 3 times, you can obtain the nano-TiO that thickness is 1 μm2Thin film.
Nano-TiO manufactured in the present embodiment2Modified 316L bipolar plate of stainless steel, resistivity is 0.003m Ω cm, gas
Body permeability is 0.8 × 10-4cm3/s·cm2.Its corrosion rate in replica polymerization thing dielectric film fuel cell environment is
4.5μA/cm2.
Embodiment 2:
The nano-TiO that the present embodiment provides2Modified metal double polar plates of polymer electrolyte film fuel cell, according to following
Step prepares nano-TiO on plain steel2Thin film：
A. it is added dropwise over deionization frozen water in the 100g titanium tetrachloride of cooling in condenser to 350ml and to shake up to prepare
Chlorination oxygen titanium.Chlorination oxygen titanium is added dropwise in 10ml glycolic, adds deionized water and to 350ml and shake up.This solution
Standing 10 days is until form precipitation at room temperature.Filter precipitate water and alcohol washes, obtain particle mean size be 40～
150nm TiO2Powder.
B. according to mass ratio 7:3 ratio is mixed and alkyd resin and hexamethyl tripolycyanamide as substrate, then
Nano-TiO2It is sufficiently mixed in powder addition substrate.
C. carbon steel surface, after oil removing, rust cleaning, grinding process, is cleaned with acetone and redistilled water and is dried.To locate in advance
The metallic matrix of reason is placed in well-mixed nano-TiO2In powdered substrate, at the uniform velocity pull-up vertically upward, speed is 1cm/min.
So it is repeated 10 times, you can obtain the nano-TiO that thickness is 10 μm2Thin film.
Nano-TiO manufactured in the present embodiment2Modified carbon steel resistivity is 0.005m Ω cm, and gas permeability is 0.5
×10-4cm3/s·cm2.Its corrosion rate in replica polymerization thing dielectric film fuel cell environment is 3 μ A/cm2.
Embodiment 3:
The nano-TiO that the present embodiment provides2Modified metal double polar plates of polymer electrolyte film fuel cell, according to following
Step prepares nano-TiO on Titanium board matrix2Thin film：
A. it is added dropwise over deionization frozen water in the 100g titanium tetrachloride of cooling in condenser to 350ml and to shake up to prepare
Chlorination oxygen titanium.Chlorination oxygen titanium is added dropwise in 15ml glycolic, adds deionized water and to 350ml and shake up.This solution
Standing 10 days is until form precipitation at room temperature.Filter precipitate water and alcohol washes, obtain particle mean size be 70～
150nmTiO2Powder.
B. according to mass ratio 7:Alkyd resin and hexamethyl tripolycyanamide are mixed and as substrate by 3 ratio, so
Afterwards nano-TiO2It is sufficiently mixed in powder addition substrate.
C. Titanium board surface, after oil removing, rust cleaning, grinding process, is cleaned with acetone and redistilled water and is dried.Will be pre-
The metallic matrix processing is placed in well-mixed nano-TiO2In powdered substrate, at the uniform velocity pull-up vertically upward, speed is 5cm/
min.So it is repeated 20 times, you can obtain the nano-TiO that thickness is 50 μm2Thin film.
Nano-TiO manufactured in the present embodiment2Modified Titanium board resistivity is 0.008m Ω cm, and gas permeability is
0.2×10-4cm3/s·cm2.Its corrosion rate in replica polymerization thing dielectric film fuel cell environment is 1.5 μ A/cm2.
Claims (5)
1. nano-TiO2Modified metal double polar plates of polymer electrolyte film fuel cell, with metal material as matrix, its feature exists
In：Described matrix thickness is 0.1～3mm, and matrix surface is nano-TiO2Modified layer；Described nano-TiO2Modified electrostrictive polymer
The corrosion rate of solution membrane fuel cell metal double polar plates is less than 5 μ A/cm2, resistivity is less than 0.01m Ω cm, gas infiltration
Rate is less than 1 × 10-4cm3/s·cm2；Preparation method is as follows：
A. it is added dropwise over deionization frozen water in the 100g titanium tetrachloride of cooling in condenser to 350ml and to shake up to prepare chlorination
Oxygen titanium；Chlorination oxygen titanium is added dropwise in 7～15ml glycolic, adds deionized water and to 350ml and shake up；This solution exists
Standing 10 days under room temperature is until form precipitation；The precipitate water filtering and alcohol washes, acquisition particle mean size is 10～150nm
TiO2Powder；
B. by alkyd resin and hexamethyl tripolycyanamide according to mass ratio 7:3 ratio is mixed, and adds nano-TiO2Powder
End, obtains nano-TiO after being sufficiently mixed2Powdered substrate；
C. the metallic matrix through pretreatment is placed in the nano-TiO of step b acquisition2In powdered substrate, at the uniform velocity repeatedly vertically upward
Pull-up metallic matrix, you can form nano-TiO in metal base surface2Modified layer.
2. nano-TiO according to claim 12Modified metal double polar plates of polymer electrolyte film fuel cell, its feature exists
In：Described metal matrix material is rustless steel, carbon steel, titanium or titanium alloy.
3. nano-TiO according to claim 12Modified metal double polar plates of polymer electrolyte film fuel cell, its feature exists
In：Described nano-TiO2Film thickness is 1～50 μm.
4. nano-TiO according to claim 12Modified metal double polar plates of polymer electrolyte film fuel cell, its feature
Be metallic matrix pull-up vertically upward speed be 1～20cm/min.
5. nano-TiO according to claim 12Modified metal double polar plates of polymer electrolyte film fuel cell, its feature
Be metallic matrix pull-up vertically upward number of times be 1～20 time.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510058931.1A CN104638274B (en) | 2015-02-03 | 2015-02-03 | Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510058931.1A CN104638274B (en) | 2015-02-03 | 2015-02-03 | Nano-TiO2-modified metal bipolar plate of fuel cell with polymer electrolyte membrane and preparation method of nano-TiO2-modified metal bipolar plate |
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| CN104638274A CN104638274A (en) | 2015-05-20 |
| CN104638274B true CN104638274B (en) | 2017-02-22 |
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| CN113996517A (en) * | 2021-12-30 | 2022-02-01 | 广州仑擎能源科技有限公司 | Plating method of metal bipolar plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439742A (en) * | 2003-03-27 | 2003-09-03 | 厦门大学 | Metal surface anti-corrosion method based on surface nanometer construct |
| CN1893156A (en) * | 2005-06-30 | 2007-01-10 | 通用汽车环球科技运作公司 | Fuel cell contact element including a tio2 layer and a conductive layer |
| CN102629690A (en) * | 2012-04-20 | 2012-08-08 | 大连交通大学 | Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9821856D0 (en) * | 1998-10-08 | 1998-12-02 | Ici Plc | Bipolar plates for fuel cells |
| EP1494300A1 (en) * | 2003-07-04 | 2005-01-05 | Nisshinbo Industries, Inc. | Porous fuel cell separator, method of manufacture thereof, and solid polymer fuel cell |
| US9520600B2 (en) * | 2009-09-22 | 2016-12-13 | GM Global Technology Operations LLC | Conductive and hydrophilic bipolar plate coatings and method of making the same |
| US9647277B2 (en) * | 2011-01-26 | 2017-05-09 | GM Global Technology Operations LLC | Hydrolytically-stable hydrophilic coating for bipolar plates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1439742A (en) * | 2003-03-27 | 2003-09-03 | 厦门大学 | Metal surface anti-corrosion method based on surface nanometer construct |
| CN1893156A (en) * | 2005-06-30 | 2007-01-10 | 通用汽车环球科技运作公司 | Fuel cell contact element including a tio2 layer and a conductive layer |
| CN102629690A (en) * | 2012-04-20 | 2012-08-08 | 大连交通大学 | Chromium nitride modified metal bipolar plate for fuel cells and manufacturing method thereof |
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