CN105239050A - Method for preparing spinel oxide protective coating of stainless steel connector of solid oxide fuel battery - Google Patents
Method for preparing spinel oxide protective coating of stainless steel connector of solid oxide fuel battery Download PDFInfo
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- CN105239050A CN105239050A CN201510771263.7A CN201510771263A CN105239050A CN 105239050 A CN105239050 A CN 105239050A CN 201510771263 A CN201510771263 A CN 201510771263A CN 105239050 A CN105239050 A CN 105239050A
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Abstract
The invention relates to a method for preparing a spinel oxide protective coating of a stainless steel connector of a solid oxide fuel battery, and aims at solving the problems of many pores and poor adhesion of a protective coating film prepared by use of a traditional method and the failure of the traditional method in preparing a spinel oxide film with an appropriate thickness. The method comprises the following steps: 1, ultrasonic cleaning; 2, pre-sputtering treatment; 3, alloy film preparation; and 4, protective coating preparation. The film prepared by use of the method is dense and good in adhesive, and adjustable in coating thickness; besides, the film is good in high temperature oxidization resistance, low in interface resistance and good in Cr blocking property, and further capable of effectively preventing cathode poisoning. The method is used for coating the stainless steel connector of the solid oxide fuel battery with a protective layer.
Description
Technical field
The present invention relates to a kind of preparation method of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat.
Background technology
Solid Oxide Fuel Cell (SolidOxideFuelCell, SOFC) be a kind of can be directly the energy device of electric energy by chemical energy, as a kind of all solid state high-temperature fuel cell, there is not the risk of electrolyte leakage, operating temperature is high, cheap metal oxide can be adopted to substitute precious metal as catalytic material, there is energy conversion efficiency in addition high, suitability of fuel is wide, Environmental compatibility waits remarkable advantage well, in distributed power station, Household hot chp system, and as boats and ships, the electrical source of power of vehicle etc. has a wide range of applications, become the new energy technology that various countries competitively develop.
According to the principle of work of hydrogen-oxygen fuel cell, SOFC cell only can provide the voltage of about 0.7 ~ 0.8V, for meeting the voltage request of practical application, needs cell to be together in series formation battery pile.Between two cells, adopt fine and close linker to connect, linker plays conduction current on the one hand, can also isolate fuel gas and oxic gas on the other hand, and the groove that surface exists plays the effect providing gas passage.Because Solid Oxide Fuel Cell working temperature is higher, therefore require higher for metallic interconnect materials, except it has good electroconductibility, also need that there is stability, resistance to air loss, thermal conductivity, and its thermal expansivity should match with other assembly of battery, anti-oxidant, chromium preferably should be had in addition and poison ability, at high temperature there is the performances such as sufficiently high intensity and creep-resistant property and plasticity-are good.
Along with SOFC working temperature is reduced to middle low temperature (600 ~ 800 DEG C) from high temperature (1000 DEG C), have superior electrical conductivity, high strength, low cost, the stainless material of better processing characteristics causes extensive concern as metallic interconnect materials.Particularly the electrode materials of ferrite base stainless material (SUS430, SUS441, ZMG232L, ZMG232J3, ZMG232G10, APU22 etc.) and SOFC, electrolyte and sealing material have good thermal matching and chemical stability, and its resistance of oxidation is better, cost is lower, is the preferred material of SOFC linker.But under SOFC working temperature, stainless steel linker rate of oxidation is higher, and zone of oxidation easily comes off, and the Cr element playing antioxygenation in the middle of stainless material can volatilize in the course of the work, cause negative electrode to occur Cr intoxicating phenomenon, thus have impact on the performance of battery pile.By preparing protective layer on stainless steel linker surface; the resistance of oxidation of stainless steel linker can be improved, the interface resistance between linker and electrode can also be reduced, and the volatilization of Cr element can be stopped in the course of the work; prevent negative electrode from poisoning, improve the permanent stability of battery pile.
Spinel oxide material (Co3O4; (Mn; Co) 3O4; (Cu; Mn) 3O4) there is higher electroconductibility, with ferritic stainless steel matched coefficients of thermal expansion, the diffusion of Cr element under high temperature, can well be stopped; can better protecting negative electrode, be a kind of SOFC stainless steel linker supercoat material of excellence.Traditional supercoat preparation method has silk screen print method, spraying method, electrochemical co-deposition method etc.Supercoat hole prepared by silk screen printing or spraying method is more, poor with basal body binding force, not easily obtains film, and in the long-term test process of high temperature, the oxidation film layer of matrix surface is thicker, reduces membranous layer binding force, is unfavorable for the permanent stability of SOFC.The difficulty of electrochemical co-deposition is comparatively large, cannot prepare the supercoat film of suitable thickness.
Summary of the invention
The present invention will solve that supercoat film hole prepared by traditional method is many, bonding force is poor; the problem of the spinel oxide film of applicable thickness can not be prepared, and a kind of preparation method of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat is provided.
One, ultrasonic cleaning: ferrite base stainless steel being put into acetone is ultrasonic cleaning twice under the condition of 40kHz in ultrasonic frequency, and each ultrasonic cleaning time is 8min ~ 15min, obtains the ferrite base stainless steel after supersound process;
Two, pre-sputtering process: the ferrite base stainless steel after supersound process step one obtained is put on the sample bench in vacuum chamber, being evacuated to vacuum tightness is 1.0 × 10
-4pa ~ 1.0 × 10
-3pa, carries out pre-sputter cleaning 10min ~ 30min under be 100V ~ 200V and air pressure being the condition of 10Pa, obtain the ferrite base stainless steel after pre-sputtering process at voltage;
Three, alloy firm preparation: alloy target material is fixed on target position, then the stainless deposited on silicon alloy firm of ferrite base after the pre-sputtering process adopting high power pulsed source to obtain step 2, voltage be 500V ~ 700V, electric current is 10A ~ 120A, ar pressure is 0.5 ~ 1.5Pa, pulsewidth deposits under being the condition of 50 μ s ~ 200 μ s and frequency 100Hz ~ 500Hz, depositing time is 0.5h ~ 5h, be cooled to room temperature after having deposited, obtain the ferrite base stainless steel that surface deposition has alloy firm;
Four, supercoat preparation: surface deposition step 3 obtained has the ferrite base stainless steel of alloy firm to be placed in air furnace, be under the condition of 3 DEG C/min at temperature rise rate, temperature in air furnace is incubated 1h after room temperature to 750 DEG C, then be under the condition of 3 DEG C/min at rate of temperature fall, temperature in air furnace is cooled to 100 DEG C from 750 DEG C, then cool to room temperature with the furnace, obtain the ferrite base stainless steel that surface is covered with spinel oxide supercoat; The thickness that described surface is covered with the spinel oxide supercoat of the ferrite base stainless steel surface of spinel oxide supercoat is 0.1 μm ~ 10 μm.
The invention has the beneficial effects as follows:
The present invention prepares alloy film by using the method for high-power impulse magnetron sputtering, and prepares spinel oxide supercoat by anneal, and prepared densification, bonding force is good, the supercoat that thickness is adjustable (0.1 μm ~ 10 μm).The present invention has the following advantages:
1, prepared densification, bonding force is good, the supercoat that coat-thickness is adjustable; Supercoat is fine and close, does not have hole, adopts different parameters, can prepare the film of different thickness, from nano level to micron order.
2, high-temperature oxidation resistance is good, and interface resistance is low.
3, hinder Cr performance good, effectively prevent the poisoning of cathode; By film prepared by the present invention, at 750 DEG C, work after 500 hours, film surface Cr content is 0, effectively prevents Cr from volatilizing, protection negative electrode.
Accompanying drawing explanation
Fig. 1 is the stainless surface topography map of ferrite base that surface that embodiment one obtains is covered with spinel oxide supercoat.
Embodiment
Embodiment one: the preparation method of a kind of Solid Oxide Fuel Cell stainless steel of present embodiment linker spinel oxide supercoat carries out according to the following steps:
One, ultrasonic cleaning: ferrite base stainless steel being put into acetone is ultrasonic cleaning twice under the condition of 40kHz in ultrasonic frequency, and each ultrasonic cleaning time is 8min ~ 15min, obtains the ferrite base stainless steel after supersound process;
Two, pre-sputtering process: the ferrite base stainless steel after supersound process step one obtained is put on the sample bench in vacuum chamber, being evacuated to vacuum tightness is 1.0 × 10
-4pa ~ 1.0 × 10
-3pa, carries out pre-sputter cleaning 10min ~ 30min under be 100V ~ 200V and air pressure being the condition of 10Pa, obtain the ferrite base stainless steel after pre-sputtering process at voltage;
Three, alloy firm preparation: alloy target material is fixed on target position, then the stainless deposited on silicon alloy firm of ferrite base after the pre-sputtering process adopting high power pulsed source to obtain step 2, voltage be 500V ~ 700V, electric current is 10A ~ 120A, ar pressure is 0.5 ~ 1.5Pa, pulsewidth deposits under being the condition of 50 μ s ~ 200 μ s and frequency 100Hz ~ 500Hz, depositing time is 0.5h ~ 5h, be cooled to room temperature after having deposited, obtain the ferrite base stainless steel that surface deposition has alloy firm;
Four, supercoat preparation: surface deposition step 3 obtained has the ferrite base stainless steel of alloy firm to be placed in air furnace, be under the condition of 3 DEG C/min at temperature rise rate, temperature in air furnace is incubated 1h after room temperature to 750 DEG C, then be under the condition of 3 DEG C/min at rate of temperature fall, temperature in air furnace is cooled to 100 DEG C from 750 DEG C, then cool to room temperature with the furnace, obtain the ferrite base stainless steel that surface is covered with spinel oxide supercoat; The thickness that described surface is covered with the spinel oxide supercoat of the ferrite base stainless steel surface of spinel oxide supercoat is 0.1 μm ~ 10 μm.
Present embodiment prepares alloy film by using the method for high-power impulse magnetron sputtering, and prepares spinel oxide supercoat by anneal, and prepared densification, bonding force is good, the supercoat that thickness is adjustable (0.1 μm ~ 10 μm).Present embodiment has the following advantages:
1, prepared densification, bonding force is good, the supercoat that coat-thickness is adjustable; Supercoat is fine and close, does not have hole, adopts different parameters, can prepare the film of different thickness, from nano level to micron order.
2, high-temperature oxidation resistance is good, and interface resistance is low.
3, hinder Cr performance good, effectively prevent the poisoning of cathode; By film prepared by the present invention, at 750 DEG C, work after 500 hours, film surface Cr content is 0, effectively prevents Cr from volatilizing, protection negative electrode.
Embodiment two: present embodiment and embodiment one unlike: the stainless steel of ferrite base described in step one is SUS430 stainless steel, SUS441 stainless steel, ZMG232L stainless steel, ZMG232J3 stainless steel, ZMG232G10 stainless steel or APU22 stainless steel.Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: carry out pre-sputter cleaning 20min under be 100V ~ 200V and air pressure being the condition of 10Pa at voltage in step 2.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: alloy target material described in step 3 is CoMn alloys target, and wherein Co constituent content is 10% ~ 90%, Mn constituent content is 10% ~ 90%.Other are identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: alloy target material described in step 3 is CuMn alloys target, and wherein Cu constituent content is 10% ~ 90%, Mn constituent content is 10% ~ 90%.Other are identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: alloy target material described in step 3 is 67Co33Mn target.Other are identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: in step 3 voltage be 600V, electric current is 80A, ar pressure is 1Pa, pulsewidth is under the condition of 100 μ s and frequency 200Hz.Other are identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: in step 3, depositing time is 3h.Other are identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: in step 3, depositing time is 4h.Other are identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the thickness that described surface is covered with the spinel oxide supercoat of the ferrite base stainless steel surface of spinel oxide supercoat is 5 μm.Other are identical with one of embodiment one to nine.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: a kind of preparation method of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat carries out according to the following steps:
One, ultrasonic cleaning: SUS430 stainless steel being put into acetone is ultrasonic cleaning twice under the condition of 40kHz in ultrasonic frequency, and each ultrasonic cleaning time is 10min, obtains the SUS430 stainless steel after supersound process;
Two, pre-sputtering process: the SUS430 stainless steel after supersound process step one obtained is put on the sample bench in vacuum chamber, being evacuated to vacuum tightness is 1.0 × 10
-4pa ~ 1.0 × 10
-3pa, carries out pre-sputter cleaning 10min ~ 30min under be 100V ~ 200V and air pressure being the condition of 10Pa, obtain the SUS430 stainless steel after pre-sputtering process at voltage;
Three, alloy firm preparation: alloy target material is fixed on target position, then the stainless deposited on silicon alloy firm of SUS430 after the pre-sputtering process adopting high power pulsed source to obtain step 2, voltage be 500V ~ 700V, electric current is 10A ~ 120A, ar pressure is 0.5 ~ 1.5Pa, pulsewidth is deposit under the condition of 50 μ s ~ 200 μ s and frequency 100Hz ~ 500Hz, depositing time is 0.5h ~ 1.5h, be cooled to room temperature after having deposited, obtain the SUS430 stainless steel that surface deposition has alloy firm;
Four, supercoat preparation: surface deposition step 3 obtained has the SUS430 stainless steel of alloy firm to be placed in air furnace, be under the condition of 3 DEG C/min at temperature rise rate, temperature in air furnace is incubated 1h after room temperature to 750 DEG C, then be under the condition of 3 DEG C/min at rate of temperature fall, temperature in air furnace is cooled to 100 DEG C from 750 DEG C, then cool to room temperature with the furnace, obtain the SUS430 stainless steel that surface is covered with spinel oxide supercoat; The thickness that described surface is covered with the spinel oxide supercoat of the SUS430 stainless steel surface of spinel oxide supercoat is 0.1 μm ~ 10 μm.
Fig. 1 is the stainless surface topography map of ferrite base that surface that embodiment one obtains is covered with spinel oxide supercoat; The present invention has prepared densification as can be seen from Figure 1, and bonding force is good, the supercoat that coat-thickness is adjustable; Supercoat is fine and close, does not have hole.
The surface that embodiment one obtains is covered with the SUS430 stainless steel of spinel oxide supercoat after oxidation 500h, spinel oxide supercoat resistance 800 DEG C time is 0.022ohm/cm
2, SUS430 stainless steel resistance 800 DEG C time that surface is covered with spinel oxide supercoat is 0.088ohm/cm
2.
Claims (10)
1. a preparation method for Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat, is characterized in that a kind of preparation method of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat carries out according to the following steps:
One, ultrasonic cleaning: ferrite base stainless steel being put into acetone is ultrasonic cleaning twice under the condition of 40kHz in ultrasonic frequency, and each ultrasonic cleaning time is 8min ~ 15min, obtains the ferrite base stainless steel after supersound process;
Two, pre-sputtering process: the ferrite base stainless steel after supersound process step one obtained is put on the sample bench in vacuum chamber, being evacuated to vacuum tightness is 1.0 × 10
-4pa ~ 1.0 × 10
-3pa, carries out pre-sputter cleaning 10min ~ 30min under be 100V ~ 200V and air pressure being the condition of 10Pa, obtain the ferrite base stainless steel after pre-sputtering process at voltage;
Three, alloy firm preparation: alloy target material is fixed on target position, then the stainless deposited on silicon alloy firm of ferrite base after the pre-sputtering process adopting high power pulsed source to obtain step 2, voltage be 500V ~ 700V, electric current is 10A ~ 120A, ar pressure is 0.5 ~ 1.5Pa, pulsewidth deposits under being the condition of 50 μ s ~ 200 μ s and frequency 100Hz ~ 500Hz, depositing time is 0.5h ~ 5h, be cooled to room temperature after having deposited, obtain the ferrite base stainless steel that surface deposition has alloy firm;
Four, supercoat preparation: surface deposition step 3 obtained has the ferrite base stainless steel of alloy firm to be placed in air furnace, be under the condition of 3 DEG C/min at temperature rise rate, temperature in air furnace is incubated 1h after room temperature to 750 DEG C, then be under the condition of 3 DEG C/min at rate of temperature fall, temperature in air furnace is cooled to 100 DEG C from 750 DEG C, then cool to room temperature with the furnace, obtain the ferrite base stainless steel that surface is covered with spinel oxide supercoat; The thickness that described surface is covered with the spinel oxide supercoat of the ferrite base stainless steel surface of spinel oxide supercoat is 0.1 μm ~ 10 μm.
2. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1, is characterized in that the stainless steel of ferrite base described in step one is SUS430 stainless steel, SUS441 stainless steel, ZMG232L stainless steel, ZMG232J3 stainless steel, ZMG232G10 stainless steel or APU22 stainless steel.
3. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1, it is characterized in that be 100V ~ 200V and air pressure be the condition of 10Pa at voltage in step 2 under carry out pre-sputter cleaning 20min.
4. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1; it is characterized in that alloy target material described in step 3 is CoMn alloys target; wherein Co constituent content is 10% ~ 90%, Mn constituent content is 10% ~ 90%.
5. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1; it is characterized in that alloy target material described in step 3 is CuMn alloys target; wherein Cu constituent content is 10% ~ 90%, Mn constituent content is 10% ~ 90%.
6. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1, is characterized in that alloy target material described in step 3 is 67Co33Mn target.
7. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1; it is characterized in that in step 3 voltage be 600V, electric current is 80A, ar pressure is 1Pa, pulsewidth is under the condition of 100 μ s and frequency 200Hz.
8. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1, is characterized in that in step 3, depositing time is 3h.
9. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1, is characterized in that in step 3, depositing time is 4h.
10. the preparation method of a kind of Solid Oxide Fuel Cell stainless steel linker spinel oxide supercoat according to claim 1, is characterized in that the thickness that described surface is covered with the spinel oxide supercoat of the ferrite base stainless steel surface of spinel oxide supercoat is 5 μm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111201652A (en) * | 2017-10-20 | 2020-05-26 | 株式会社Lg化学 | Interconnector for solid oxide fuel cell, method for producing same, and solid oxide fuel cell |
| CN112195444A (en) * | 2020-08-17 | 2021-01-08 | 徐州华清智能装备有限公司 | Preparation method of solid oxide fuel cell stack connector protective coating |
| CN112331893A (en) * | 2020-10-28 | 2021-02-05 | 华中科技大学 | Flat-plate type solid oxide fuel cell and sealing method thereof |
| CN114318248A (en) * | 2021-12-17 | 2022-04-12 | 国家能源集团新能源有限责任公司 | Preparation method and application of manganese-cobalt spinel coating |
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| US20090035561A1 (en) * | 2007-08-02 | 2009-02-05 | The Trustees Of Boston University | Protective oxide coatings for SOFC interconnections |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111201652A (en) * | 2017-10-20 | 2020-05-26 | 株式会社Lg化学 | Interconnector for solid oxide fuel cell, method for producing same, and solid oxide fuel cell |
| CN112195444A (en) * | 2020-08-17 | 2021-01-08 | 徐州华清智能装备有限公司 | Preparation method of solid oxide fuel cell stack connector protective coating |
| CN112331893A (en) * | 2020-10-28 | 2021-02-05 | 华中科技大学 | Flat-plate type solid oxide fuel cell and sealing method thereof |
| CN112331893B (en) * | 2020-10-28 | 2022-02-15 | 华中科技大学 | Flat-plate type solid oxide fuel cell and sealing method thereof |
| CN114318248A (en) * | 2021-12-17 | 2022-04-12 | 国家能源集团新能源有限责任公司 | Preparation method and application of manganese-cobalt spinel coating |
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