CN107195909A - A kind of preparation method of fuel battery double plates and its surface titanium film - Google Patents
A kind of preparation method of fuel battery double plates and its surface titanium film Download PDFInfo
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- CN107195909A CN107195909A CN201710397593.3A CN201710397593A CN107195909A CN 107195909 A CN107195909 A CN 107195909A CN 201710397593 A CN201710397593 A CN 201710397593A CN 107195909 A CN107195909 A CN 107195909A
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- 239000010936 titanium Substances 0.000 title claims abstract description 107
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 104
- 239000000446 fuel Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000005137 deposition process Methods 0.000 claims abstract description 13
- 238000007733 ion plating Methods 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims description 54
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 53
- 229910052737 gold Inorganic materials 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 20
- 238000010891 electric arc Methods 0.000 claims description 18
- 239000002159 nanocrystal Substances 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000002161 passivation Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005240 physical vapour deposition Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 239000002114 nanocomposite Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical group [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 24
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 63
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 235000013339 cereals Nutrition 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- FXNGWBDIVIGISM-UHFFFAOYSA-N methylidynechromium Chemical compound [Cr]#[C] FXNGWBDIVIGISM-UHFFFAOYSA-N 0.000 description 3
- 239000002120 nanofilm Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009498 subcoating Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
Present invention is disclosed the preparation method of a kind of fuel battery double plates and its surface titanium film, belong to fuel cell field.Bipolar plates include matrix and the titanium nano compound film layer of matrix two sides, titanium nano compound film layer deposits to be formed using arc ion plating (aip) in matrix surface, in titanium film deposition process, by the control of filming parameter, the bipolar plates for being coated with titanium film are obtained.The present invention makes the corrosion resistance in analog fuel battery context improve 3 orders of magnitude under 0.6V voltages, and 2 orders of magnitude are improved under 1.36V, and contact resistance is reduced to 0.5m Ω cm2(0.2MPa pressure) below, after the anti-corrosion test of long-time simulated battery environment, possesses good corrosion stability, excellent electric conductivity, service requirement when meeting long in regeneratable fuel cell and Proton Exchange Membrane Fuel Cells.
Description
Technical field
The present invention relates to fuel cell field, more particularly, to a kind of fuel battery double plates and its surface titanium film
Preparation method.
Background technology
The chemical energy being stored in fuel and oxidant can be converted into electric energy by fuel cell (Fuel Cell), its
Transformation efficiency is high, environment-friendly, highly reliable, it is considered to be the efficient sustainable development power technology of 21 century first choice.
In each types of fuel cells, and regeneratable fuel cell (Regenerative Fuel Cell Sectem, referred to as
RFC it is) current specific energy highest energy-storage system, by water electrolysis (WE) pond and fuel cell (FC), two major parts are constituted,
It can have by electrolytic cell by water electrolysis Cheng Qing and oxygen and then further through hydrogen, oxygen are generated into water after fuel cell generation electric energy again
Reproducible feature is recycled, its power is in 10~1000Kw scopes, and specific energy is up to 400~1000WhKg-1, it is most
Several times of light secondary cell specific energy.Current regeneratable fuel cell is mainly developed and applied to spacecraft and space
Mixed tensor storage system and portable energy system of ship etc..
In addition, Proton Exchange Membrane Fuel Cells (Proton Exchange MembraneFuel Cell, abbreviation PEMFC)
It is also the Typical Representative in fuel cell family, it has the advantages that fast startup, long lifespan, specific power are high, except suitable for ground
Beyond power station, be also particularly well suited for removable power source and various portable power supplies, be electric car and other vehicles very
One of to the ideal source for being weapon carrying.Therefore the development of regeneratable fuel cell and Proton Exchange Membrane Fuel Cells is to whole
The development of field of new energy technologies is with very important effect.
Bipolar plates play a part of support, afflux and separate oxidant and reducing agent in a fuel cell, and guide
Oxidizing and Reducing Agents electrode surface in battery flows, and is the key components of fuel cell, accounts for the 70% of battery weight
More than, also accounted for close to half in battery totle drilling cost.Preferable bipolar plates should have very high electric conductivity, corrosion resistance, height
The features such as mechanical strength, high-gas resistance ability, low-cost and easy-to are processed.From general performance, metal is preferable fuel cell
Bipolar plate material, but the subject matter of metal is easily corroded under fuel cell environment, particularly in recyclable fuel
Under the electrolysis mode of battery, its operating voltage is higher, and typically in 1.2~1.5V, particularly electrolytic anode is due in oxic gas
Atmosphere and make it that its corrosive environment is more severe, its consequence, which is not only, makes bipolar plates disabler, but also battery can be caused overall
" poisoning " and paralyse.Some noble metals (such as gold Au, silver Ag, platinum Pt etc.) have simultaneously conductive, anti-corrosion composite performance, but directly
Being greatly improved for material cost can be brought using noble metal by connecing.
It is existing that rare noble metal is replaced with stainless steel or titanium plate virgin metal as bipolar plates scheme, with the excellent of low cost
Gesture, but because there is one layer of passivating film, although positive role is played to improving corrosion resisting property, but considerably increases bipolar plates
Contact resistance so that battery generates heat in the process of running, power reduction and corrosion accelerate.In addition, also have by multi sphere from
Sub- coating technology prepares carbon chromium nano compound film from pure titanium target and graphite target and is deposited on bipolar plate surfaces, and the program has one
Fixed cost advantage, is provided simultaneously with conductive and corrosion resisting property, but the resistance of the bipolar plate surfaces carbon chromium nano compound film is still
Larger 15m Ω cm2 (0.8MPa pressure), and after the anti-corrosion test 1000H of continuous analog resistance compared with initial resistance into multiplication
Long, electric conductivity declines and increased with etch resistant properties, causes heating, power drop in battery operation.
The content of the invention
It is an object of the invention to the defect for overcoming prior art, there is provided a kind of cost is controllable, material consumption quantity is low, high
Quality, be easy to batch production fuel battery double plates and its surface titanium film preparation method.
To achieve the above object, the present invention proposes following technical scheme：A kind of fuel battery double plates, including matrix and base
The modified film layer in body surface face, the modified film layer is covered on the two sides of matrix, and is connected with matrix, and the modification is thin
Film layer is titanium nano compound film layer.
Preferably, described matrix is sheet metal.
Preferably, the sheet metal is stainless steel plate or titanium plate.
Preferably, the thickness of described matrix is 0.05mm-1.0mm.
Preferably, the thickness of the titanium nano compound film layer is 0.05 μm -5 μm.
Preferably, titanium nano compound film layer be titanium or titanium nitride or gold or nitrogen it is nanocrystalline in any two kinds or
Three kinds of plural layers for being combined into.
Preferably, the titanium nano compound film layer is that titanium nitride and gold nanocrystals are distributed on nanocrystalline Ti matrix
Laminated film, the grain size of the titanium, titanium nitride and gold nanocrystals is 3nm-100nm.
Preferably, the titanium nano compound film layer is the compound of the distribution gold nanocrystals on the brilliant matrix of titanium nitride nano
Film, the grain size of the titanium nitride and gold nanocrystals is 3nm-100nm.
Preferably, the titanium nano compound film layer is distribution nitrogen and gold nanocrystals on the brilliant matrix of titanium nitride nano
Laminated film, the grain size of the titanium nitride, nitrogen and gold nanocrystals is 3nm-100nm.
Present invention also offers a kind of method for preparing fuel battery double plates surface titanium film, methods described is use
Arc ion plating (aip) comprises the following steps in matrix surface titanium deposition gold nano composite film layer：
S1, the matrix after cleaning, drying is put in PVD equipment vacuum drying oven, when vacuum chamber vacuum is extracted into 2 × 10-2Pa
When, vacuum chamber is heated, is heated to stopping heating at 150 DEG C；
S2, when vacuum chamber is evacuated to 4 × 10-3Working gas is filled with during Pa, operating air pressure is adjusted to 0.3~0.5Pa, and
Biasing starter cathode target electric arc starts bombardment described matrix and removes surface passivation layer, and the bombardment duration is 2~10 minutes；Its
In, the working gas is inert gas, and flow is 50~500sccm, and the amplitude of biasing is -300V~-800V, startup
Cathode target electric arc is pure titanium target electric arc, and arc stream is 50A~120A；
Bias sets are -50V~-300V by S3, and adjustment operating air pressure to 0.2Pa~1.0Pa starts pure titanium target intermediate frequency
Power supply and adjust its to setting power proceed by film deposition process, sedimentation time is 20min-150min；
S4, eventually passes after stove cooling, decontrols the bipolar plates that vacuum takes out plated film.
Preferably, in step S1, matrix be cleaned by ultrasonic and after drying and processing, is placed in PVD equipment vacuum drying oven,
Vacuum chamber vacuum is extracted into 2 × 10 by vacuum system-2Pa, now opens heating system and vacuum chamber is heated, temperature rises to 150
DEG C when stop heating.
Preferably, in the S2, substrate is bombarded by the way of Ions Bombardment and removes its surface passivation layer, Ions Bombardment
Ion mostlys come from the arc discharge gas ions of pure titanium target arc evaporation and the glow discharge gas ions of a small amount of inert gas.
Preferably, the working gas is inert gas argon.
Preferably, in the S3, in film deposition process, to reaction gas flow and pure titanium target, gold target power match
It is adjusted, wherein, start power after pure titanium target and be set to 5KW~15KW, it is 0.5KW~5KW to start power setting after gold target, thin
Pure titanium target described in film deposition process is constantly in opening, and the flow of reacting gas is adjusted 15 according to titanium target power bracket
~300sccm, and it adds to the follow-up continuation of insurance of setting maximum and keeps steady fixed, until film forming terminates, the reacting gas includes nitrogen.
Preferably, film deposition process includes in the S3：
Bias sets are -50~-150V by S31, start pure titanium target intermediate frequency power supply and adjust its to setting power 5~
15KW, starts the pure titanium layer of deposition film bottom；
S32, by bias sets be -50~-200V, be passed through corresponding reacting gas start deposition aerating cross film layer, repeatedly
Bias sets value is adjusted, continues amount of reactant gases after 30~60 minutes and adds to setting maximum；
S33, starts gold target intermediate frequency power supply, is that 0.5~5KW, now titanium target and gold target sputter base simultaneously by its power setting
Body, continues to close titanium target intermediate frequency power supply after 5~10 minutes, after gold target intermediate frequency power supply continues 10~25 minutes afterwards, closes successively
Its intermediate frequency power supply, bias, working gas.
Compared with prior art, the beneficial effects of the invention are as follows：By being received in bipolar plates matrix surface deposition synthesis titanium
Rice laminated film, increases the modified film of one layer of nanometer scale thickness, so, and the effect such as support, trapping is played by matrix；By table
Face mask layer plays the surface property that the effect such as anti-corrosion, conductive and hydrophobic changes metal double polar plates, makes in analog fuel battery context
Corrosion resistance 3 orders of magnitude are improved under 0.6V voltages, 2 orders of magnitude are improved under 1.36V, contact resistance is reduced to 0.5m
Ω·cm2(0.2MPa pressure) below, after the anti-corrosion test of long-time simulated battery environment, possesses good corrosion stability, excellent
Electric conductivity, service requirement when meeting long in regeneratable fuel cell and Proton Exchange Membrane Fuel Cells.
Brief description of the drawings
Fig. 1 is the structural representation of fuel battery double plates of the present invention；
Fig. 2 is the schematic flow sheet of the preparation method of fuel battery double plates surface titanium film of the present invention；
Fig. 3 is the schematic flow sheet of film deposition process of the embodiment of the present invention；
Fig. 4 is the waveform diagram of bipolar plate surfaces contact resistance of the present invention；
Fig. 5, Fig. 6 and Fig. 7 are OCP, dynamic electricity of the simulated battery solution environmental of the present invention to titanium nano thin-film respectively
Position and the electro-chemical test waveform diagram of 0.6V constant potentials.
Reference：
1st, matrix, 2, titanium nano compound film layer.
Embodiment
Below in conjunction with the accompanying drawing of the present invention, the technical scheme to the embodiment of the present invention carries out clear, complete description.
As shown in figure 1, a kind of fuel battery double plates disclosed in the embodiment of the present invention, including matrix and matrix surface
Titanium nano compound film layer, titanium nano compound film layer is covered on the two sides of matrix, and is connected with matrix.
Specifically, matrix plays support, trapping etc. as bipolar plates base material.In the present embodiment, matrix is metal foil
Plate, can be but be not limited to stainless steel plate or titanium plate, the thickness of sheet metal is 0.05mm~1.0mm.
Titanium nano compound film layer is located at matrix surface, and the effect such as corrosion-resistant, conductive and hydrophobic is played to matrix.This reality
Apply in example, the thickness of titanium nano compound film layer is 0.05 μm -5 μm, and be titanium or titanium nitride or gold or nitrogen it is nanocrystalline in
The plural layers being combined into for any two or three.
Specifically, if titanium nano compound film layer is that answering for titanium nitride and gold nanocrystals is distributed on nanocrystalline Ti matrix
Film is closed, wherein, the grain size of titanium, titanium nitride and gold nanocrystals is 3nm-100nm.
As interchangeable embodiment, titanium nano compound film layer may also be to be distributed on the brilliant matrix of titanium nitride nano
The laminated film of gold nanocrystals, the grain size of the titanium nitride and gold nanocrystals is 3nm-100nm.
As interchangeable another embodiment, titanium nano compound film layer is distributed on the brilliant matrix of titanium nitride nano
The laminated film of nitrogen and gold nanocrystals, the grain size of the titanium nitride, nitrogen and gold nanocrystals is 3nm-100nm.
To sum up, by increasing the modified film of one layer of nanometer scale thickness on bipolar plates base material, metal double polar plates are changed
Surface property, the corrosion resistance in analog fuel battery context is improved 3 orders of magnitude under 0.6V voltages, carried under 1.36V
High 2 orders of magnitude, contact resistance is reduced to 0.5m Ω cm2 (0.2MPa pressure) below, resistance in long-time simulated battery environment
Possesses good corrosion stability, excellent electric conductivity after erosion test.
As shown in Fig. 2 a kind of side for preparing fuel battery double plates surface titanium film disclosed in the embodiment of the present invention
Method, this method, in matrix surface titanium deposition gold nano composite film layer, specifically includes following steps using arc ion plating (aip)：
S1, the matrix after cleaning, drying is put in PVD equipment vacuum drying oven, when vacuum chamber vacuum is extracted into 2 × 10-2Pa
When, vacuum chamber is heated, is heated to stopping heating at 150 DEG C.
Specifically, matrix is cleaned by ultrasonic, after drying and processing, is fixed and be put into PVD equipment vacuum drying oven using fixture,
The pure titanium target of cylinder and cylinder proof gold target are installed on negative electrode target position；Open evacuation system to vacuumize vacuum drying oven, be when evacuating
Vacuum chamber pressure is evacuated to 2 × 10 by system-2During Pa, open heating system and vacuum drying oven is heated, vacuum room temperature is heated to
Heating system is closed at 150 DEG C.
S2, when vacuum chamber is evacuated to 4 × 10-3Working gas is filled with during Pa, operating air pressure is adjusted to 0.3~0.5Pa, and
Biasing starter cathode target electric arc starts bombardment described matrix and removes surface passivation layer, and the bombardment duration is 2~10 minutes；Its
In, the working gas is inert gas, and flow is 50~500sccm, and the amplitude of biasing is -300V~-800V, startup
Cathode target electric arc is pure titanium target electric arc, and arc stream is 50A~120A.
Specifically, when vacuum chamber vacuum is extracted into 4 × 10-3During Pa, working gas is filled with, adjustment operating air pressure to 0.3~
0.5Pa, the pulsed bias of opening, starter cathode cylindrical target electric arc starts bombardment substrate and removes surface passivation layer, bombardment continues
Time is 2~10 minutes.In the present embodiment, carry out bombardment substrate by the way of Ions Bombardment or sputtering, Ions Bombardment from
Son mostlys come from the arc discharge plasma of metallic target arc evaporation and the glow discharge plasma of a small amount of inert gas
Body.Working gas is inert gas, such as argon, and argon flow amount is 50~500sccm, and the cathode arc of startup is pure titanium metal target electricity
Arc, arc stream is 50A~120A, and the amplitude of biasing is -300V~-800V.
Bias sets are -50V~-300V by S3, and adjustment operating air pressure to 0.2Pa~1.0Pa starts pure titanium target intermediate frequency
Power supply and adjust its to setting power proceed by film deposition process, sedimentation time is 20min-150min.
Specifically, in film deposition process, reaction gas flow and pure titanium target, gold target power match are adjusted,
Wherein, start power after pure titanium target and be set to 5KW~15KW, it is 0.5KW~5KW, thin film deposition to start power setting after gold target
Pure titanium target is constantly in opening in journey, and the flow of reacting gas is adjusted in 15~300sccm according to titanium target power bracket, and
It, which adds to the follow-up continuation of insurance of setting maximum and kept steady, determines, until film forming terminates.In the present embodiment, reacting gas includes nitrogen.
Wherein, as shown in figure 3, film deposition process specifically includes following steps：
Bias sets are -50~-150V by S31, start pure titanium target intermediate frequency power supply and adjust its to setting power 5~
15KW, starts the pure titanium layer of deposition film bottom；
S32, by bias sets be -50~-200V, be passed through corresponding reacting gas start deposition aerating cross film layer, repeatedly
Bias sets value is adjusted, continues 30~60 minutes reacting gas and adds to setting maximum；
S33, starts gold target intermediate frequency power supply, is that 0.5~5KW, now titanium target and gold target sputter base simultaneously by its power setting
Body, continues to close titanium target intermediate frequency power supply after 5~10 minutes, gold target intermediate frequency power supply closes it successively after continuing 10~25 minutes afterwards
Intermediate frequency power supply, bias, working gas (including inert gas and reacting gas).
S4, eventually passes after stove cooling, decontrols the bipolar plates that vacuum takes out plated film.
Specifically, cooling is evacuated 10 minutes in stove, and inflatable open fire door takes out plated film bipolar plates.
Below by two specific embodiments, further describe the present invention and prepare fuel battery double plates surface titanium film
Method flow.
Embodiment 1
After the premenstrual cleaning of bipolar plate of stainless steel, drying and processing, fixed and be put into PVD equipment vacuum drying oven using fixture,
The pure titanium target of cylinder and cylinder proof gold target are installed on negative electrode target position；When vacuum is that pressure is evacuated to 2 × 10 by evacuation system-2During Pa,
Open when vacuum room temperature is heated to 150 DEG C by heating system and close heating system；When being evacuated to 4 × 10-3During Pa, argon gas is filled with
Pressure is to 0.30pa, and argon flow amount is 50sccm, opens the pulsed bias of -300 × 40KHZ × 75%, and starter cathode cylinder is pure
Titanium target electric arc, arc stream is 120A, is put using the arc discharge plasma of target arc evaporation and the aura of a small amount of inert gas
Electro-plasma bombardment (sputtering) substrate removal surface passivation layer, continue after 10 minutes by bias drop to -100 × 40KHZ ×
75%, the pure titanium target arc power of cylinder is closed, magnetic control cylinder titanium target intermediate frequency power supply is opened, power setting 5KW starts deposition film
The pure titanium layer of bottom；Bias is dropped into -50 × 40KHZ × 50%, N is passed through2Start deposition aerating and cross film layer, then bias is dropped to-
150 × 40KHZ × 50%, adjusts bias sets value, continues N after 60 minutes repeatedly2Amount adds to the last value of setting, opens gold target intermediate frequency
Power supply, power setting 0.5KW, now titanium target and gold target sputter simultaneously, stablize after 10 minutes closing titanium target intermediate frequency power supply, a karat gold
Cooling is evacuated 10 minutes in intermediate frequency power supply, bias, working gas successively after target intermediate frequency power supply continues 25 minutes, stove, inflatable open
Fire door takes out plated film bipolar plates.Now, the chromium carbon nanocapsule thin film thickness of bipolar plate surfaces is 1.0um, with reference to Fig. 5~Fig. 7 institutes
Show, nano-hardness improvement >=15Gpa (6mN loads), shake friction testing >=2H, contact resistance≤0.5m Ω cm2(0.2MPa
Pressure) possess superior electrical conductivity, in simulated battery solution environmental, under the conditions of high potential accelerated corrosion, the corrosion current measured
0~0.1 μm of density, shows good corrosion resistance.
Embodiment 2
After the premenstrual cleaning of bipolar plate of stainless steel, drying and processing, fixed and be put into PVD equipment vacuum drying oven using fixture,
The pure titanium target of cylinder and cylinder proof gold target are installed on negative electrode target position；When vacuum is that pressure is evacuated to 2 × 10 by evacuation system-2During Pa,
Open when vacuum room temperature is heated to 150 DEG C by heating system and close heating system；When being evacuated to 4 × 10-3During Pa, argon gas is filled with
Pressure is to 0.40pa, and argon flow amount is 300sccm, opens the pulsed bias of -800 × 40KHZ × 50%, and starter cathode cylinder is pure
Titanium arc target, arc stream is 50A, utilizes glow discharge of arc discharge plasma and a small amount of inert gas of target arc evaporation etc.
Gas ions bombardment (sputtering) substrate removes surface passivation layer, continues after 2 minutes bias dropping to -150 × 40KHZ × 75%, pass
Close post arc target power supply and open magnetic control cylinder titanium target intermediate frequency power supply, power setting 13KW starts the pure titanium layer of deposition film bottom；Will be inclined
Pressure drop is passed through N to -100 × 40KHZ × 50%2Start deposition aerating and cross film layer, then by bias drop to -200 × 40KHZ ×
50%, bias sets value is adjusted repeatedly, continues N after 30 minutes2Amount adds to the last value of setting, opens gold target intermediate frequency power supply, power is set
Determine 5.0KW, now titanium target and gold target are sputtered simultaneously, stablize closing titanium target intermediate frequency power supply, a karat gold target intermediate frequency power supply after 10 minutes
Continue film forming intermediate frequency power supply, bias, working gas, interior cooling evacuation of stove 10 minutes successively after 25 minutes, inflatable open fire door takes
Go out plated film bipolar plates.Now the titanium nano film thickness of bipolar plate surfaces is 1.0um, with reference to shown in Fig. 5~Fig. 7, surface
Nano hardness >=15Gpa (6mN loads), shakes friction testing >=2H, contact resistance≤0.5m Ω cm2(0.2MPa pressure) has
Standby superior electrical conductivity, in simulated battery solution environmental, under the conditions of high potential accelerated corrosion, the corrosion electric current density 0 measured~
0.1 μm, show good corrosion resistance.
Embodiment 3
After the premenstrual cleaning of bipolar plate of stainless steel, drying and processing, fixed and be put into PVD equipment vacuum drying oven using fixture,
The pure titanium target of cylinder and cylinder proof gold target are installed on negative electrode target position；When vacuum is that pressure is evacuated to 2 × 10 by evacuation system-2During Pa,
Open when vacuum room temperature is heated to 150 DEG C by heating system and close heating system；When being evacuated to 4 × 10-3During Pa, argon gas is filled with
Pressure is to 0.50pa, and argon flow amount is 500sccm, opens the pulsed bias of -500 × 40KHZ × 75%, and starter cathode cylinder is pure
Titanium target electric arc, arc stream is 80A, utilizes the glow discharge of the arc discharge plasma and a small amount of inert gas of target arc evaporation
Plasma bombardment (sputtering) substrate removes surface passivation layer, continues after 5 minutes bias dropping to -50 × 40KHZ × 75%, closes
The pure titanium target arc power of cylinder is closed, magnetic control cylinder titanium target intermediate frequency power supply is opened, power setting 15KW starts deposition film bottom pure
Titanium layer；Bias is remained into -100 × 40KHZ × 50%, N is passed through2Start deposition aerating and cross film layer, then bias is added to -200
× 40KHZ × 50%, adjusts bias sets value, continues N after 40 minutes repeatedly2Amount adds to the last value of setting, opens gold target medium frequency electric
Source, power setting 2.5KW, now titanium target and gold target sputter simultaneously, stablize after 8 minutes closing titanium target intermediate frequency power supply, a karat gold target
Intermediate frequency power supply is closed cooling in intermediate frequency power supply, bias, working gas, stove and evacuated 10 minutes successively after continuing 15 minutes, inflation is beaten
Blow-on door takes out plated film bipolar plates.Now, the titanium nano film thickness of bipolar plate surfaces is 1.0um, with reference to Fig. 5~Fig. 7
Shown, nano-hardness improvement >=15Gpa (6mN loads) shakes friction testing >=2H, contact resistance≤0.5m Ω cm2
(0.2MPa pressure) possesses superior electrical conductivity, in simulated battery solution environmental, under the conditions of high potential accelerated corrosion, the corruption measured
0~0.1 μm of current density is lost, good corrosion resistance is shown.
The technology contents and technical characteristic of the present invention have revealed that as above, but those skilled in the art still may base
Make a variety of replacements and modification without departing substantially from spirit of the present invention, therefore, the scope of the present invention in teachings of the present invention and announcement
The content disclosed in embodiment should be not limited to, and various replacements and modification without departing substantially from the present invention should be included, and is this patent Shen
Please claim covered.
Claims (10)
1. a kind of fuel battery double plates, it is characterised in that it includes the modified film layer of matrix and matrix surface, the modification
Film layer is covered on the two sides of matrix, and is connected with matrix, and the modified film layer is titanium nano compound film layer.
2. fuel battery double plates according to claim 1, it is characterised in that the thickness of the titanium nano compound film layer
Spend for 0.05 μm -5 μm.
3. fuel battery double plates according to claim 1, it is characterised in that the titanium nano compound film layer is titanium
Titanium nitride or gold or nitrogen it is nanocrystalline in the plural layers being combined into for any two or three.
4. fuel battery double plates according to claim 3, it is characterised in that the titanium nano compound film layer be
The laminated film of titanium nitride and gold nanocrystals is distributed on nanocrystalline Ti matrix, the crystal grain of the titanium, titanium nitride and gold nanocrystals is big
Small is 3nm-100nm.
5. fuel battery double plates according to claim 3, it is characterised in that the titanium nano compound film layer be
The laminated film of gold nanocrystals is distributed on titanium nitride nano crystalline substance matrix, the grain size of the titanium nitride and gold nanocrystals is
3nm-100nm。
6. fuel battery double plates according to claim 3, it is characterised in that the titanium nano compound film layer be
The laminated film of distribution nitrogen and gold nanocrystals on titanium nitride nano crystalline substance matrix, the crystal grain of the titanium nitride, nitrogen and gold nanocrystals is big
Small is 3nm-100nm.
7. a kind of method of the fuel battery double plates surface titanium film prepared described in claim 1, it is characterised in that described
Method is, in matrix surface titanium deposition gold nano composite film layer, to comprise the following steps using arc ion plating (aip)：
S1, the matrix after cleaning, drying is put in PVD equipment vacuum drying oven, when vacuum chamber vacuum is extracted into 2 × 10-2It is right during Pa
Vacuum chamber is heated, and is heated to stopping heating at 150 DEG C；
S2, when vacuum chamber is evacuated to 4 × 10-3Working gas, adjustment operating air pressure to 0.3~0.5Pa, and biasing are filled with during Pa
Pressure starter cathode target electric arc starts bombardment described matrix and removes surface passivation layer, and the bombardment duration is 2~10 minutes；Wherein,
The working gas is inert gas, and flow is 50~500sccm, and the amplitude of biasing is -300V~-800V, the moon of startup
Pole target electric arc is pure titanium target electric arc, and arc stream is 50A~120A；
Bias sets are -50V~-300V by S3, and adjustment operating air pressure to 0.2Pa~1.0Pa starts pure titanium target intermediate frequency power supply
And adjust its to setting power proceed by film deposition process, sedimentation time is 20min-150min；
S4, eventually passes after stove cooling, decontrols the bipolar plates that vacuum takes out plated film.
8. method according to claim 7, it is characterised in that in the S2, matrix is bombarded by the way of Ions Bombardment
Remove its surface passivation layer, the ion used in Ions Bombardment comes from the arc discharge gas ions of pure titanium target arc evaporation and lazy
The glow discharge gas ions of property gas.
9. method according to claim 7, it is characterised in that in the S3, in film deposition process, to reacting gas
Flow and pure titanium target, gold target power match are adjusted, wherein, start power after pure titanium target and be set to 5KW~15KW, start gold target
Power setting is 0.5KW~5KW afterwards, and pure titanium target described in film deposition process is constantly in opening, the stream of reacting gas
Amount is adjusted in 15~300sccm according to titanium target power bracket, and it adds to the follow-up continuation of insurance of setting maximum and kept steady and determines, until film forming
Terminate, the reacting gas includes nitrogen.
10. method according to claim 9, it is characterised in that film deposition process includes in the S3：
Bias sets are -50~-150V by S31, are started pure titanium target intermediate frequency power supply and are adjusted it to setting 5~15KW of power, open
The beginning pure titanium layer of deposition film bottom；
S32, by bias sets be -50~-200V, be passed through corresponding reacting gas start deposition aerating cross film layer, adjust repeatedly
Bias sets value, continues amount of reactant gases after 30~60 minutes and adds to setting maximum；
S33, starts gold target intermediate frequency power supply, is 0.5~5KW, now titanium target and gold target sputtered substrate simultaneously by its power setting, holds
Titanium target intermediate frequency power supply is closed after continuous 5~10 minutes, after gold target intermediate frequency power supply continues 10~25 minutes afterwards, its intermediate frequency is closed successively
Power supply, bias, working gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108390075A (en) * | 2018-01-24 | 2018-08-10 | 上海交通大学 | Anticorrosive conductive film and its pulsed bias replace magnetron sputtering deposition methods and applications |
| CN109856037A (en) * | 2019-01-08 | 2019-06-07 | 浙江锋源氢能科技有限公司 | A kind of measuring method of metal double polar plates long-time stability |
| CN112467161A (en) * | 2020-10-28 | 2021-03-09 | 浙江工业大学 | TiN coating surface modified titanium alloy bipolar plate and liquid ion nitriding method thereof |
| CN113588525A (en) * | 2021-04-16 | 2021-11-02 | 上海大学 | Method for rapidly evaluating electrochemical corrosion resistance of metal bipolar plate coating of fuel cell |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108390075A (en) * | 2018-01-24 | 2018-08-10 | 上海交通大学 | Anticorrosive conductive film and its pulsed bias replace magnetron sputtering deposition methods and applications |
| CN108390075B (en) * | 2018-01-24 | 2019-04-02 | 上海交通大学 | Anticorrosive conductive film and its pulsed bias alternating magnetron sputtering deposition method and application |
| CN109856037A (en) * | 2019-01-08 | 2019-06-07 | 浙江锋源氢能科技有限公司 | A kind of measuring method of metal double polar plates long-time stability |
| CN109856037B (en) * | 2019-01-08 | 2021-09-10 | 浙江锋源氢能科技有限公司 | Method for measuring long-term stability of metal bipolar plate |
| CN112467161A (en) * | 2020-10-28 | 2021-03-09 | 浙江工业大学 | TiN coating surface modified titanium alloy bipolar plate and liquid ion nitriding method thereof |
| CN113588525A (en) * | 2021-04-16 | 2021-11-02 | 上海大学 | Method for rapidly evaluating electrochemical corrosion resistance of metal bipolar plate coating of fuel cell |
| CN113588525B (en) * | 2021-04-16 | 2022-07-12 | 上海大学 | Method for rapidly evaluating electrochemical corrosion resistance of metal bipolar plate coating of fuel cell |
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