CN117778939A - Preparation method of connector coating, connector and battery or electrolytic cell group - Google Patents
Preparation method of connector coating, connector and battery or electrolytic cell group Download PDFInfo
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- CN117778939A CN117778939A CN202410218081.6A CN202410218081A CN117778939A CN 117778939 A CN117778939 A CN 117778939A CN 202410218081 A CN202410218081 A CN 202410218081A CN 117778939 A CN117778939 A CN 117778939A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 75
- 238000005422 blasting Methods 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 60
- 238000007750 plasma spraying Methods 0.000 claims abstract description 40
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical group [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000446 fuel Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims description 45
- 238000005488 sandblasting Methods 0.000 claims description 34
- 238000005507 spraying Methods 0.000 claims description 33
- 238000004321 preservation Methods 0.000 claims description 29
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 10
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- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 5
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 5
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Classifications
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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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- Fuel Cell (AREA)
Abstract
The invention belongs to the field of fuel cells, and relates to a preparation method of a connector coating, a connector and a cell or an electrolytic cell group. The preparation method comprises the steps of carrying out plasma spraying on the side of the groove of the thin-wall connector, wherein the side of the groove of the thin-wall connector and the plane of the thin-wall connector respectively form an included angle of 40-50 degrees and 130-140 degrees, so as to obtain a precoat, wherein the sprayed powder is manganese cobalt oxide powder with the grain size of nanometers; when the precoat is not cooled to room temperature, carrying out shot blasting treatment on the precoat, wherein the included angles between the shot blasting angle and the plane of the thin-wall connector are 40-50 degrees and 130-140 degrees respectively, so as to obtain a shot-blasted coating; and carrying out heat treatment on the shot-blasted coating at the temperature of 400-600 ℃ to obtain the connector coating. The coating continuously covers the side of the groove of the thin-wall connector, and has high surface evenness and high compactness.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a connector coating, the coating, a connector and a cell or an electrolytic cell group.
Background
A Solid Oxide Fuel Cell (SOFC) belongs to a third generation fuel cell, is an all-solid-state chemical power generation device for directly converting chemical energy stored in fuel and oxidant into electric energy at medium and high temperature with high efficiency and environmental friendliness, and is an important development direction of the fuel cell because of high power generation efficiency, slow attenuation and excellent comprehensive performance. The anode material, the electrolyte material and the cathode material constitute a single cell unit of a Solid Oxide Fuel Cell (SOFC), the power of which is limited, and in order to obtain a high power stack several single cells need to be connected together with a connector material. The Solid Oxide Electrolytic Cell (SOEC) is a reverse running device of a solid oxide fuel cell, has the same structural form as an SOFC, and can be used for preparing hydrogen by high-temperature water electrolysis, preparing carbon monoxide by carbon dioxide electrolysis and the like.
The Solid Oxide Fuel Cell (SOFC) and electrolytic cell (SOEC) connectors are mainly classified into ceramic connectors and metal connectors, and there is a trend to use metal connectors having high electrical conductivity, high thermal conductivity, easy processing into complex shapes, low manufacturing cost, and excellent mechanical properties, as compared with conventional ceramic connectors. However, the metal material is easily damaged by oxidation corrosion, which results in an increase in the impedance of the connector, and in order to improve the high-temperature oxidation resistance of the metal, it is proposed to add Cr element to the metal matrix, however, cr is easily volatilized, and can poison the cathode, resulting in degradation of the SOFC performance, and at present, a conductive protective coating is generally sprayed on the connector to inhibit these phenomena.
Because the connector often has a groove structure for circulating gas, the conductive protective coating needs to cover all surfaces of the groove, which puts a high requirement on the coating preparation process. Although the deposition method represented by magnetron sputtering can uniformly deposit the coating, the method has the problems of excessively slow coating deposition speed, low preparation efficiency, high cost and the like. When the spraying method represented by plasma spraying is used for preparing a coating on a connector with a groove structure, the problems of poor coating continuity, low surface flatness and low compactness exist.
Disclosure of Invention
The invention aims to overcome the defects of poor coating continuity, low surface flatness and low density in the preparation of a thin-wall connector coating of a fuel cell or an electrolytic cell by a plasma spraying method in the prior art, and provides a preparation method of the connector coating, the coating, a connector and a cell or an electrolytic cell group.
In order to achieve the above object, in a first aspect, the present invention provides a method for preparing a coating of a thin-walled connection body of a fuel cell or an electrolytic cell, the thin-walled connection body being provided with grooves extending from one side to the other side, the method comprising:
plasma spraying is carried out on the side where the groove of the thin-wall connector is located, a precoat is obtained, the plasma spraying comprises plasma spraying with the included angles between the flame flow axis direction and the plane where the thin-wall connector is located being 40-50 degrees and 130-140 degrees respectively, and the plasma spraying conditions comprise: the spraying powder is manganese cobalt oxide powder, and the grain size of the manganese cobalt oxide powder is nano-scale;
when the precoat is not cooled to room temperature, carrying out shot blasting on the precoat to obtain a shot-blasted coating, wherein the shot blasting comprises shot blasting with the included angles of a shot blasting angle and a plane of the thin-wall connector being 40-50 degrees and 130-140 degrees respectively;
and carrying out heat treatment on the shot-blasting post-coating to obtain a connector coating, wherein the heat treatment conditions comprise: the temperature of the heat preservation is 400-600 ℃.
In some preferred embodiments, the preparation method further comprises, before the plasma spraying, performing sand blasting on the side where the groove of the thin-wall connector is located, obtaining a connector after sand blasting, and performing straightening treatment on the connector after sand blasting;
the sand blasting comprises sand blasting with included angles of 40-50 degrees and 130-140 degrees between the sand blasting direction and the plane of the thin-wall connector;
the conditions of the heat treatment further include: and applying preset pressure in the vertical direction to the surface of the thin-wall connector.
Preferably, the blasting conditions include: the sand blasting pressure is 0.15-0.35 MPa, and the gravel flow is 10-30 g/min.
In some preferred embodiments, the plasma spraying conditions further comprise: when the average granularity of the manganese cobalt oxide powder is 10-25 mu m, the spraying power is 40-45 kW, the spraying distance is 50-100 mm, and when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the spraying power is 46-50 kW, and the spraying distance is 95-150 mm.
In some preferred embodiments, the conditions of the peening process further include: the shot is steel shot, the diameter of the shot is 0.3 mm-1 mm, and the shot blasting pressure is 0.2 MPa-0.3 MPa.
In some preferred embodiments, the conditions of the heat treatment further comprise: and the temperature of the thin-wall connector is raised to the heat preservation temperature along with the furnace, the temperature is reduced after heat preservation, the heating rate and the cooling rate are 5 ℃/min-15 ℃/min, and the heat preservation time is 0.5 h-1 h.
Preferably, when the average granularity of the manganese cobalt oxide powder is 10-25 mu m, the heat preservation temperature of the heat treatment is 400-500 ℃, the heating rate and the cooling rate are 10-15 ℃/min, and the heat preservation time is 0.5-0.75 h;
when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the heat preservation temperature of the heat treatment is 500-600 ℃, the heating rate and the cooling rate are 5-10 ℃/min, and the heat preservation time is 0.7-1 h.
In a second aspect, the present invention provides a fuel cell or cell thin-walled connector coating made by the method of making a fuel cell or cell thin-walled connector coating of the first aspect.
In a third aspect, the invention provides a thin-walled fuel cell or electrolyser connector, the side of the groove of the thin-walled connector is provided with a connector coating prepared by the preparation method in the first aspect.
In a fourth aspect, the present invention provides a fuel cell or an electrolytic cell group, which comprises monomers of the fuel cell or the electrolytic cell, wherein the monomers are connected through a thin-wall connector, and the side of a groove of the thin-wall connector is provided with a connector coating prepared by the preparation method in the first aspect.
According to the preparation method of the thin-wall connector coating, plasma spraying comprises plasma spraying with the included angles between the flame flow axis direction and the plane of the thin-wall connector being 40-50 degrees and 130-140 degrees respectively, a continuous pre-coating with flat and compact surface can be obtained on the whole inner surface of a groove and the surface of the connector at the edge of the groove, spraying powder of the plasma spraying is manganese cobalt oxide powder with the grain size of nanometers, and the pre-coating obtained after the spraying has a micro-nano grain structure; after plasma spraying, when the precoat is not cooled to room temperature, shot blasting is carried out on the precoat, so that on one hand, the flatness and compactness of the precoat can be further improved, and on the other hand, microstress is introduced into the precoat, and the grain structure of the precoat is further refined; the heat treatment is carried out on the coating after shot blasting, so that the internal stress of the thin-wall connector including the micro stress introduced in the shot blasting process can be released, and the stress elimination and the closure of microcrack defects in the coating in the heat treatment process can be promoted and the crack defects of the coating are reduced because the grain size of the coating after shot blasting is very small and rich grain boundaries exist in the coating.
According to the invention, the manganese cobalt oxide powder with the grain size of nanometer grade is adopted for plasma spraying, and shot blasting and heat treatment are carried out, so that a continuous coating with smooth and compact surface and fully removed stress can be obtained, and the defect of the coating is reduced.
The coating after shot blasting has rich grain boundaries, can promote stress elimination and crack defect closure in the heat treatment process, can adopt lower temperature for heat treatment, and can avoid oxidation of the thin-wall connector in the heat treatment process when the base material of the thin-wall connector adopts metal.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic illustration of a plasma spraying process of the preparation method of the present invention.
Fig. 2 is a process flow diagram of one embodiment of a straightening process of the present invention.
FIG. 3 is a scanning electron micrograph of a groove sidewall of a coated thin-walled connector prepared by the method of example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The inventor of the invention researches and discovers that the thin-wall connector coating of the fuel cell or the electrolytic cell prepared by adopting a plasma spraying method has poor coating continuity and low surface evenness and compactness.
In this regard, in a first aspect, and referring to fig. 1, the present invention provides a method for preparing a coating of a thin-walled connector for a fuel cell or an electrolytic cell, the thin-walled connector being provided with a groove extending from one side to the other, the method comprising:
plasma spraying is carried out on the side where the groove of the thin-wall connector is located, a precoat is obtained, the plasma spraying comprises plasma spraying with the included angles between the flame flow axis direction and the plane where the thin-wall connector is located being 40-50 degrees and 130-140 degrees respectively, and the plasma spraying conditions comprise: the spraying powder is manganese cobalt oxide powder, and the grain size of the manganese cobalt oxide powder is nano-scale;
when the precoat is not cooled to room temperature, carrying out shot blasting on the precoat to obtain a shot-blasted coating, wherein the shot blasting comprises shot blasting with the included angles of a shot blasting angle and a plane of the thin-wall connector being 40-50 degrees and 130-140 degrees respectively;
and carrying out heat treatment on the shot-blasting post-coating to obtain a connector coating, wherein the heat treatment conditions comprise: the temperature of the heat preservation is 400-600 ℃.
When the thin-wall connector with the groove extending from one side to the other side is sprayed with a coating by adopting a plasma spraying method, plasma spraying is carried out on the thin-wall connector, wherein the included angles between the flame flow axis direction and the plane of the thin-wall connector are 40-50 degrees and 130-140 degrees respectively, and a continuous pre-coating with flat and compact surface can be obtained on the whole inner surface of the groove and the surface of the connector at the edge of the groove, wherein the included angles between 40-50 degrees and 130-140 degrees are the same in opening direction. According to the invention, the flatness and compactness of the precoat can be further improved, when the precoat is not cooled to room temperature, the peening is performed, the peening effect can be further improved, the peening with angles of 40-50 degrees and 130-140 degrees with the plane of the thin-wall connector is performed, and the peening can be uniformly performed on the whole inner surface of the groove and the surface of the connector at the edge of the groove, wherein the angles of 40-50 degrees and the opening directions of 130-140 degrees are the same.
The plasma spraying process adopts the manganese cobalt oxide powder with the grain size of nanometers, the precoat with the micro-nano grain structure is obtained after the plasma spraying, when the precoat is not cooled to room temperature, the precoat is subjected to shot blasting treatment, the grain structure of the precoat can be further refined by introducing micro-stress into the precoat, the coating after shot blasting is subjected to heat treatment, the internal stress of a thin-wall connector including the micro-stress introduced in the shot blasting process can be released, and because the grain size of the coating after shot blasting is very small, rich grain interfaces exist in the coating, the stress elimination of the coating and the closure of microcrack defects in the heat treatment process can be promoted, and the crack defects of the coating are reduced. Because of the abundant grain boundaries of the coating after shot blasting, stress elimination and crack defect closing are facilitated, the heat treatment can be performed at a lower temperature of 400-600 ℃, when the base material of the thin-wall connector is metal, oxidation of the thin-wall connector in the heat treatment process can be avoided, the heat treatment temperature is not lower than 400 ℃, stress and defect removal is facilitated, the heat treatment temperature is not higher than 600 ℃, and oxidation of the thin-wall connector is avoided. According to the invention, the metal thin-wall connector which is free from oxidation and has the advantages of sufficiently removed stress and remarkably reduced defects can be obtained by adopting the manganese cobalt oxide powder with the grain size of nano-scale for plasma spraying and performing shot blasting and heat treatment. The coating after shot blasting has a fine grain structure, rich grain boundaries, and the heat-treated coating has a finer grain structure and a rich grain boundaries, and can improve the conductivity of the thin-wall connector coating.
The thin-wall connector coating of the fuel cell or the electrolytic cell prepared by the invention has the porosity less than 5 percent.
The included angle between the flame flow axis direction and the plane of the thin-wall connector and the included angle between the shot blasting angle and the plane of the thin-wall connector can be, for example, 40 °, 42 °, 44 °, 46 °, 48 °, 50 °, 130 °, 132 °, 134 °, 136 °, 138 ° and 140 °, and the heat-insulating temperature of the heat treatment can be, for example, 400 ℃, 440 ℃, 480 ℃, 520 ℃, 560 ℃ and 600 ℃.
The invention does not limit the preparation method and structural parameters of the manganese cobalt oxide powder with the grain size of nanometer grade. Preferably by the method of preparation of ceramic powders in the applicant's prior patent CN 116082022B; the preparation method comprises the steps of dispersing the manganous oxide powder and the cobaltosic oxide powder in a solvent through ball milling according to the mass ratio of the manganous oxide powder to the cobaltosic oxide powder of 0.8:1-1:0.8 to obtain first slurry, separating and treating the first slurry to obtain suspension and precipitate of the manganous oxide powder and the cobaltosic oxide powder, wherein the particle size of the suspension is smaller than 50nm, spray drying the suspension to obtain agglomerated powder, sintering the agglomerated powder to obtain the ceramic powder, and the sintering temperature is 1120-1200 ℃ and the sintering time is 10 min-1 h. Preferably the ceramic powder of said prior patent, the grain size of the ceramic powder preferably being less than 100nm.
The plasma spraying with the included angle of 40-50 degrees and the plasma spraying with the included angle of 130-140 degrees can be simultaneously carried out or can be carried out separately, and the shot blasting with the included angle of 40-50 degrees and the shot blasting with the included angle of 130-140 degrees can be simultaneously carried out or can be carried out separately.
The cross-sectional shape of the groove is not particularly limited in the present invention, and may be, for example, rectangular, circular arc, trapezoid, or the like.
In some preferred embodiments, the preparation method further includes, before the plasma spraying, performing sand blasting on the side where the groove of the thin-wall connector is located, obtaining a connector after sand blasting, and performing alignment treatment on the connector after sand blasting;
the sand blasting comprises sand blasting with included angles of 40-50 degrees and 130-140 degrees between the sand blasting direction and the plane of the thin-wall connector;
the conditions of the heat treatment further include: and applying preset pressure in the vertical direction to the surface of the thin-wall connector.
According to the method, the side of the groove of the thin-wall connector is subjected to sand blasting before plasma spraying, the surface of the rough connector can be obtained, the plasma spraying process is facilitated, the binding force between the precoat and the thin-wall connector matrix is improved, sand blasting is conducted in the sand blasting direction and the included angle between the plane of the thin-wall connector and the included angle between the sand blasting direction and the plane of the thin-wall connector are respectively 40-50 degrees and 130-140 degrees, the sand blasting effect is improved, and even sand blasting is conducted on the whole inner surface of the groove and the surface of the connector at the edge of the groove, wherein the included angle between 40-50 degrees and the opening direction of the included angle between 130-140 degrees are the same. While the surface of the connector is roughened by sand blasting, small-amplitude bending deformation of the thin-wall connector may occur. The straightening method is not limited by the invention, and referring to fig. 2, specifically, the method can be that the concave surface of the thin-wall connector is placed downwards on the arc base with the radian close to the deformation radian of the thin-wall connector, downward pressure is applied to the thin-wall connector, the concave surface of the thin-wall connector contacts the arc base, the pressure is released after the thin-wall connector stays for preset seconds, the thin-wall connector is straightened, if the thin-wall connector still has small-amplitude bending deformation, the process of applying the pressure to the pressure release is repeated, and the straightening and/or the pressure stay time is repeated. In the heat treatment process, the preset pressure in the vertical direction is applied to the surface of the thin-wall connector, and the heat treatment process can further ensure the flat shape of the thin-wall connector while eliminating the internal stress in the thin-wall connector. It will be appreciated that a plurality of thin-walled connectors may be stacked together for heat treatment, with a predetermined vertical pressure applied to the upper surface of the thin-walled connector stack, with the lowermost connector bearing a pressure preferably no greater than 50kPa.
The sand blasting direction and the plane of the thin-wall connector can be simultaneously performed at an included angle of 40-50 degrees and at an included angle of 130-140 degrees, or can be separately performed.
In some preferred embodiments, the blasting conditions include: the sand blasting pressure is 0.15-0.35 MPa, and the gravel flow is 10-30 g/min. Under the preferred scheme, the sand blasting pressure is not lower than 0.15MPa, the gravel flow is not lower than 10g/min, the sand blasting effect is improved, the binding force between the coating and the thin-wall connector matrix is improved, the continuous, compact and flat coating is obtained, the sand blasting pressure is not higher than 0.35MPa, the gravel flow is not higher than 30g/min, and the bending deformation degree of the thin-wall connector is reduced.
In some preferred embodiments, the plasma spraying conditions further comprise: when the average granularity of the manganese cobalt oxide powder is 10-25 mu m, the spraying power is 40-45 kW, the spraying distance is 50-100 mm, and when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the spraying power is 46-50 kW, and the spraying distance is 95-150 mm. Under the preferred scheme, when the average granularity of the manganese cobalt oxide powder is smaller, particularly 10-25 mu m, the spraying power is not lower than 40kW, the spraying distance is not lower than 50mm and not higher than 100mm, powder particles can be well melted, a compact coating with high binding force can be better obtained, when the average granularity of the manganese cobalt oxide powder is larger, particularly 26-45 mu m, the spraying power is not lower than 46kW, the spraying distance is not lower than 95mm and not higher than 150mm, powder particles can be well melted, a compact coating with high binding force can be better obtained, the spraying power is not higher than 50kW, the overheat deformation of a workpiece can be better avoided, and the powder loss is reduced. The average particle size of the manganese cobalt oxide powder of the present invention may be, for example, 41kW, 42kW, 43kW, 44kW and 45kW, the spraying distance may be, for example, 60mm, 70mm, 80mm, 90mm, and the average particle size of the manganese cobalt oxide powder may be, for example, 46kW, 47kW, 48kW, 49kW and 50kW, and the spraying distance may be, for example, 100mm, 110mm, 120mm, 130mm and 140mm.
In some preferred embodiments, the conditions of the peening process further include: the shot is steel shot, the diameter of the shot is 0.3 mm-1 mm, and the shot blasting pressure is 0.2 MPa-0.3 MPa. The pre-coating obtained after plasma spraying has a micro-nano grain structure based on the manganese cobalt oxide powder with the crystal size of nanometer, and under the preferable scheme, the shot is steel shot, the shot blasting pressure is not less than 0.2MPa, the coating is tamped, the compactness of the coating is improved, the grain structure in the coating is further refined, the diameter of the shot is not more than 1mm, the shot conveying is facilitated, the shot conveying difficulty is avoided, the shot blasting effect is influenced, the grain refinement and the improvement of the compactness of the coating are influenced, the shot blasting pressure is not more than 0.3MPa, and the erosion damage of the coating caused by overload is avoided.
In some preferred embodiments, the conditions of the heat treatment further comprise: and the temperature of the thin-wall connector is raised to the heat preservation temperature along with the furnace, the temperature is reduced after heat preservation, the heating rate and the cooling rate are 5 ℃/min-15 ℃/min, and the heat preservation time is 0.5 h-1 h. Based on the precoat with a micro-nano grain structure, the shot blasting further refines the grain structure of the precoat, under the preferred scheme, the heating rate and the cooling rate are not higher than 15 ℃/min, which is more favorable for preventing the coating from cracking and peeling due to the action of thermal stress, fully releasing stress, the heating rate and the cooling rate are not lower than 5 ℃/min, which is more favorable for inhibiting the growth of grains in the coating, retaining the micro-nano grain structure, improving the conductivity of the thin-wall connector coating, keeping the temperature for not lower than 0.5h, fully releasing the stress and obviously reducing the crack defect of the coating, keeping the temperature for not higher than 1h, and being more favorable for inhibiting the growth of grains in the coating, retaining the micro-nano grain structure and improving the conductivity of the thin-wall connector coating.
Further preferably, when the average particle size of the manganese cobalt oxide powder is 10-25 mu m, the heat preservation temperature of the heat treatment is 400-500 ℃, the heating rate and the cooling rate are 10-15 ℃/min, and the heat preservation time is 0.5-0.75 h; when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the heat preservation temperature of the heat treatment is 500-600 ℃, the heating rate and the cooling rate are 5-10 ℃/min, and the heat preservation time is 0.7-1 h. Based on the spray powder is nano-sized manganese cobalt oxide powder, the pre-coating obtained after plasma spray has a micro-nano grain structure, and the grain structure of the pre-coating is further refined by shot blasting, under the preferred scheme, the average grain size of the nano-sized manganese cobalt oxide powder is smaller, particularly 10-25 μm, the lower heat treatment heat preservation temperature is adopted, the higher heating and cooling rate is adopted, the shorter heat preservation time is more beneficial to inhibiting the growth of grains in the coating, the micro-nano grain structure is reserved, the conductivity of the thin-wall connector coating is improved, the higher heat treatment heat preservation temperature is adopted, particularly 26-45 μm, the lower heating and cooling rate is adopted, the longer heat preservation time is more beneficial to fully releasing stress and remarkably reducing the crack defect of the coating, and the cracking and peeling of the coating due to the thermal stress are prevented. When the average particle size of the manganese cobalt oxide powder is 10-25 μm, the heat treatment temperature can be, for example, 410 ℃, 430 ℃, 450 ℃, 470 ℃ and 490 ℃, the heating rate and the cooling rate can be, for example, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min and 15 ℃/min, the heat preservation time can be, for example, 0.5h, 0.55h, 0.6h, 0.65h, 0.7h and 0.75h, and when the average particle size of the manganese cobalt oxide powder is 26-45 μm, the heat treatment temperature can be, for example, 510 ℃, 530 ℃, 550 ℃, 570 ℃ and 590 ℃, the heating rate and the cooling rate can be, for example, 6 ℃/min, 7 ℃/min, 8 ℃/min and 9 ℃/min, and the heat preservation time can be, for example, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h and 1h.
In a second aspect, the present invention provides a fuel cell or cell thin-walled connector coating made according to the method of making a fuel cell or cell thin-walled connector coating of the first aspect.
The thin-wall connector coating is prepared by the preparation method of the first aspect, is continuous, compact and good in flatness, and has the advantages of fully removed stress and obviously reduced crack defects.
In a third aspect, the invention provides a thin-walled fuel cell or electrolyser connector, the side of the groove of the thin-walled connector is provided with a connector coating prepared by the preparation method in the first aspect.
In a fourth aspect, the present invention provides a fuel cell or an electrolytic cell group, which comprises monomers of the fuel cell or the electrolytic cell, wherein the monomers are connected through a thin-wall connector, and the side of a groove of the thin-wall connector is provided with a connector coating prepared by the preparation method in the first aspect.
The invention will be further described in detail with reference to specific examples.
The preparation method of the manganese cobalt oxide powder with the grain size of nanometer grade comprises the following steps: adding 400g of manganous oxide powder, 500g of cobaltosic oxide powder, 500g of deionized water and 80g of polyvinyl alcohol binder into a ball milling device, and performing ball milling to obtain first slurry, wherein the average particle size of the manganous oxide powder is 0.1 mu m, and the average particle size of the cobaltosic oxide powder is 0.1 mu m; filtering the first slurry with a 5 μm screen to obtain a second slurry containing fine particles, and naturally precipitating the second slurry for 10 hours to obtain an upper suspension and a lower precipitate; granulating the upper suspension serving as a spray drying raw material in a spray drying device to obtain agglomerated powder, wherein the particle size of the agglomerated powder is 10-45 mu m; and sintering the agglomerated powder in a muffle furnace at 1120 ℃ for 1h to obtain ceramic powder. The grain size of the ceramic powder is less than 100nm.
Example 1
A preparation method of a fuel cell or electrolytic cell thin-wall connector coating, wherein the connector is a stainless steel metal thin-wall connector, a groove extending from one side to the other side is arranged on the connector, the cross section of the groove is rectangular, and the preparation method comprises the following steps:
step one: carrying out sand blasting on the side of the groove of the thin-wall connector to obtain a sand blasted connector, sequentially carrying out sand blasting with an included angle of 45 degrees between the sand blasting direction and the plane of the thin-wall connector and an included angle of 135 degrees between the sand blasting direction and the plane of the thin-wall connector, wherein the sand blasting pressure is 0.25MPa, the gravel flow is 20g/min, and carrying out small-amplitude bending deformation on the sand blasted thin-wall connector; straightening the sandblasted connecting body, placing the concave surface of the sandblasted thin-wall connecting body downwards on an arc base with the radian close to the deformation radian of the thin-wall connecting body, applying downward pressure on the thin-wall connecting body to enable the concave surface of the thin-wall connecting body to contact the arc base, and releasing the pressure after staying for 5 seconds to obtain a flat sandblasted connecting body;
step two: carrying out plasma spraying on the side of the groove of the sandblasted connecting body to obtain a precoat, and sequentially carrying out twice plasma spraying on the side of the groove of the sandblasted connecting body, wherein the included angle between the flame flow axis direction and the plane of the thin-wall connecting body is 45 degrees, and the included angle between the flame flow axis direction and the plane of the thin-wall connecting body is 135 degrees, wherein the spraying powder is manganese cobalt oxide powder with the grain size smaller than 100nm, the granularity of the spraying powder is 10-25 mu m, the spraying power is 42kW, and the spraying distance is 75mm; detecting the grain size of the precoating, wherein the average grain size of the precoating is 600nm;
step three: when the precoat is not cooled to room temperature, carrying out shot blasting treatment on the precoat to obtain a shot-blasted coating, and sequentially carrying out two shot blasting treatments of which the included angle between the shot blasting angle and the plane of the thin-wall connector is 45 degrees and the included angle between the shot blasting angle and the plane of the thin-wall connector is 135 degrees, wherein shot-blasted pellets are steel pellets, the diameter of each shot pellet is 0.5 mm-0.8 mm, and the shot blasting pressure is 0.25MPa; detecting the grain size of the coating after shot blasting, wherein the average grain size of the coating after shot blasting is 300nm;
step four: after stacking and placing 10 thin-wall connectors, applying pressure in the vertical direction on the upper surface of the thin-wall connector stack, wherein the pressure is 1kpa. And (3) carrying out heat treatment on the shot-blasted coating, and preserving heat for 0.6h in a high-temperature furnace at 450 ℃ to obtain a connector coating, wherein the temperature of the thin-wall connector is increased and decreased along with the furnace, and the temperature increasing and decreasing rates are respectively 12 ℃/min.
Referring to fig. 3, after the spraying, the bottom and the side walls of the groove of the thin-walled connector, and the surface of the thin-walled connector around the groove are continuously and smoothly coated with a coating. The porosity of the coating of the connector of this example was 1.9% and the stresses in the coating were sufficiently removed with minimal crack defects.
Example 2
The preparation method of the reference example 1 is carried out, except that in the second step, the granularity of the spraying powder is 26-45 mu m, the spraying power is 48kW, the spraying distance is 120mm, in the fourth step, the heat is preserved for 0.8h in a high-temperature furnace at 550 ℃, the temperature of the thin-wall connector is increased and decreased along with the furnace, and the temperature increasing and decreasing rates are 7.5 ℃/min respectively. The porosity of the coating of the connector of this example was 2.5% and the stresses in the coating were sufficiently removed with minimal crack defects.
Example 3
The process of example 1 was followed, except that in the third step, the shot peening pressure was 0.15MPa. The porosity of the coating of the connector of this example was 4.1%, the average grain size of the coating after shot blasting was 450nm, the stress in the coating was sufficiently removed, and the crack defects were extremely small.
Example 4
The preparation method of example 1 was used, except that in the third step, the pellet diameter was 0.8mm to 1.2mm. The porosity of the coating of the connector of this example was 3.6%, the average grain size of the coating after shot blasting was 400nm, the stress in the coating was sufficiently removed, and the crack defects were extremely small.
Example 5
The procedure of example 2 was followed, except that in step four, the heat was maintained in a high temperature furnace at 450℃for 0.8h. The porosity of the coating of the connector of this example was 3.4% with minimal stress removal and less crack defects in the coating.
Comparative example 1
The production method of example 1 was conducted except that the shot blasting of step three was not conducted. The porosity of the coating of the connector of this comparative example was 5.9% with a small residual stress in the coating and more crack defects.
Comparative example 2
The procedure of example 1 was followed, except that in the second step, the spray powder was manganese cobalt oxide powder having a grain size of 1. Mu.m. The porosity of the coating of the connector of this comparative example was 6.7%, the average grain size of the coating after shot blasting was 1.2 μm, and there were few residual stresses in the coating and many crack defects.
Comparative example 3
The procedure of example 1 was followed, except that in the second step, the spray powder was a manganese cobalt oxide powder having a grain size of 1. Mu.m, and the shot blasting in the third step was not performed. The porosity of the coating of the connector of this comparative example was 7.1% with more residual stress in the coating and more crack defects.
Comparative example 4
The procedure of example 1 was followed, except that in step four, the temperature was maintained in a high-temperature furnace at 350℃for 0.6h. The porosity of the coating of the connector of this comparative example was 7.6% with more residual stress in the coating and more crack defects.
In the comparative examples 1 and 1-3, the spray powder is manganese cobalt oxide powder with a nano-scale grain size, the grain size of the coating after shot blasting is small, stress elimination of the coating and closure of microcrack defects in the heat treatment process can be promoted, the compactness of the coating can be improved, the grain size is refined, stress elimination and defect closure in the heat treatment process are promoted, and in the comparative examples 1 and 4, the heat treatment temperature is not lower than 400 ℃, and stress and defects are more favorably removed.
In comparative examples 1, 3 and 4, the pellet diameter is 0.3 mm-1 mm, the shot blasting pressure is 0.2 MPa-0.3 MPa, the compaction of the coating is facilitated, the compactness of the coating is improved, the grain structure in the coating is further refined, and in comparative examples 2 and 5, when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the heat preservation temperature of heat treatment is not lower than 500 ℃, and the sufficient stress release and the remarkable reduction of the crack defect of the coating are facilitated.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method of preparing a coating for a thin-walled fuel cell or electrolyser connector provided with grooves extending from one side to the other, the method comprising:
plasma spraying is carried out on the side where the groove of the thin-wall connector is located, a precoat is obtained, the plasma spraying comprises plasma spraying with the included angles between the flame flow axis direction and the plane where the thin-wall connector is located being 40-50 degrees and 130-140 degrees respectively, and the plasma spraying conditions comprise: the spraying powder is manganese cobalt oxide powder, and the grain size of the manganese cobalt oxide powder is nano-scale;
when the precoat is not cooled to room temperature, carrying out shot blasting on the precoat to obtain a shot-blasted coating, wherein the shot blasting comprises shot blasting with the included angles of a shot blasting angle and a plane of the thin-wall connector being 40-50 degrees and 130-140 degrees respectively;
and carrying out heat treatment on the shot-blasting post-coating to obtain a connector coating, wherein the heat treatment conditions comprise: the temperature of the heat preservation is 400-600 ℃.
2. The method according to claim 1, further comprising, before the plasma spraying, blasting the side of the thin-walled connector where the groove is located to obtain a blasted connector, and straightening the blasted connector;
the sand blasting comprises sand blasting with included angles of 40-50 degrees and 130-140 degrees between the sand blasting direction and the plane of the thin-wall connector;
the conditions of the heat treatment further include: and applying preset pressure in the vertical direction to the surface of the thin-wall connector.
3. The method according to claim 2, wherein the blasting conditions include: the sand blasting pressure is 0.15-0.35 MPa, and the gravel flow is 10-30 g/min.
4. The method of claim 1, wherein the plasma spraying conditions further comprise: when the average granularity of the manganese cobalt oxide powder is 10-25 mu m, the spraying power is 40-45 kW, the spraying distance is 50-100 mm, and when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the spraying power is 46-50 kW, and the spraying distance is 95-150 mm.
5. The method according to claim 1, wherein the conditions of the shot blasting include: the shot is steel shot, the diameter of the shot is 0.3 mm-1 mm, and the shot blasting pressure is 0.2 MPa-0.3 MPa.
6. The method according to claim 1, wherein the conditions of the heat treatment further comprise: and the temperature of the thin-wall connector is raised to the heat preservation temperature along with the furnace, the temperature is reduced after heat preservation, the heating rate and the cooling rate are 5 ℃/min-15 ℃/min, and the heat preservation time is 0.5 h-1 h.
7. The preparation method according to claim 6, wherein when the average particle size of the manganese cobalt oxide powder is 10-25 μm, the heat-preserving temperature of the heat treatment is 400-500 ℃, the heating rate and the cooling rate are 10-15 ℃/min, and the heat-preserving time is 0.5-0.75 h;
when the average granularity of the manganese cobalt oxide powder is 26-45 mu m, the heat preservation temperature of the heat treatment is 500-600 ℃, the heating rate and the cooling rate are 5-10 ℃/min, and the heat preservation time is 0.7-1 h.
8. A fuel cell or electrolyser thin wall connector coating made by the method of making a fuel cell or electrolyser thin wall connector coating as claimed in any one of claims 1-7.
9. A fuel cell or electrolyser thin-walled connector, characterized in that the side of the groove of the thin-walled connector is provided with a connector coating prepared by the preparation method according to any of claims 1-7.
10. A fuel cell or cell stack comprising fuel cell or cell cells connected by a thin-walled connector having a connector coating on the side of the groove of the thin-walled connector prepared by the method of any one of claims 1-7.
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