CN116454524A - Explosion-proof valve and preparation method and application thereof - Google Patents
Explosion-proof valve and preparation method and application thereof Download PDFInfo
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- CN116454524A CN116454524A CN202310637337.2A CN202310637337A CN116454524A CN 116454524 A CN116454524 A CN 116454524A CN 202310637337 A CN202310637337 A CN 202310637337A CN 116454524 A CN116454524 A CN 116454524A
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- proof valve
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- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 130
- 239000011248 coating agent Substances 0.000 claims abstract description 129
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 92
- 239000010410 layer Substances 0.000 claims description 57
- 238000005507 spraying Methods 0.000 claims description 43
- 229910052759 nickel Inorganic materials 0.000 claims description 40
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 32
- 238000003466 welding Methods 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000004544 sputter deposition Methods 0.000 claims description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 23
- 238000007750 plasma spraying Methods 0.000 claims description 21
- 238000005516 engineering process Methods 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000004880 explosion Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 14
- 230000003111 delayed effect Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010959 steel 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
- H01M50/317—Re-sealable arrangements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Gas Exhaust Devices For Batteries (AREA)
Abstract
The invention belongs to the technical field of battery preparation, and particularly relates to an explosion-proof valve and a preparation method and application thereof. The explosion-proof valve comprises a valve body, wherein a coating is arranged on the inner surface of the valve body, and the coating comprises a first coating and a second coating; the second coating comprises a component that can react to produce a third coating; the third coating is an anti-corrosion film. The explosion-proof valve provided by the invention is not easy to be corroded by HF acid in the use process, especially the notch is not easy to be corroded, the valve opening time of the explosion-proof valve is delayed, and the service life of a battery can be prolonged when the explosion-proof valve is applied to the battery.
Description
Technical Field
The invention belongs to the technical field of battery preparation, and particularly relates to an explosion-proof valve and a preparation method and application thereof.
Background
The explosion-proof valve is a safety accessory in the battery, is installed on the cover plate or the shell, and can quickly relieve pressure in time under the conditions of overcharging and the like of the battery, so that the explosion of the battery core is avoided.
Because the electrolyte contains LiPOF 6 And an additive, liPOF 6 HF can be generated when water (including water in air) is encountered, so that an HF acid solution is formed, and electrolyte is prevented from contacting the explosion-proof valve by increasing the distance between the liquid injection hole on the cover plate and the explosion-proof valve, or adding ribs between the liquid injection hole and the explosion-proof valve, or increasing the height of the edge of the explosion-proof valve hole, or adding grooves on the edge of the explosion-proof valve hole, and the like due to corrosiveness to the explosion-proof valve (aluminum and steel). The outside of the explosion-proof valve is contacted with electrolyte, so that the explosion-proof valve is easy to observe and clean, and the outside of the explosion-proof valve is usually protected in the prior art, for example, a protective film is arranged, but in the use process, the explosion-proof valve still has the problems of corrosion and the like.
As the thinnest notch of the explosion-proof valve is as low as 0.1mm, the explosion-proof valve is easy to be corroded by HF acid, electrolyte is corroded by HF acid solution generated by a small amount of water contained in a pole piece, a diaphragm or the electrolyte, and in the use process of a battery, the HF acid solution contacts the explosion-proof valve due to vibration of the battery, so that the explosion-proof valve is corroded, the explosion-proof valve is opened too early, and the service life of the battery is shortened.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that an explosion-proof valve, particularly a notch position in the prior art is easy to be corroded by HF acid, the valve is opened prematurely, the service life of a battery is shortened and the like, and further provides the explosion-proof valve, a preparation method and application thereof.
For this purpose, the invention provides the following technical scheme.
The invention provides an explosion-proof valve, which comprises a valve body;
the inner surface of the valve body is provided with a coating;
the second coating comprises a component that can react to produce a third coating;
the third coating is an anti-corrosion film.
The inner surface of the valve body is the surface close to the inner side of the battery cell.
The outer surface of the explosion-proof valve is provided with a notch;
preferably, the coating is positioned at the projection position of the notch on the inner surface of the valve body; and/or the number of the groups of groups,
the coating is arranged in the welding area of the explosion-proof valve and the cover plate.
The thickness of the coating is 10nm-20 mu m;
preferably, the porosity of the coating is less than or equal to 5%;
preferably, the thickness of the first coating is 2nm-5 μm;
preferably, the thickness of the second coating layer is 8nm-15 μm.
The components in the second coating layer comprise metal;
preferably, the second coating is a nickel layer;
preferably, the explosion-proof valve is an aluminum alloy;
preferably, the first coating is a nickel aluminum layer.
In addition, the invention provides a preparation method of the explosion-proof valve, which comprises the following steps:
and spraying by adopting a plasma spraying technology or a magnetron sputtering technology, and forming the first coating and the second coating on the inner surface of the valve body.
The technological parameters of the plasma spraying technology comprise: the powder feeding speed is 10-25g/min; the speed of the spray gun is 500-600mm/s. Preferably, the powder feeding speed is 10-20g/min, and the spray gun speed is 500-560mm/s; more preferably, the powder feed rate is 13g/min and the spray gun speed is 550mm/s.
The technological parameters of the plasma spraying technology further comprise: the spraying current is 500-600A; the spraying voltage is 70-90V; the nitrogen flow is 10-15L/min; argon flow is 10-25L/min; the spraying distance is 100-110mm. Preferably, the spray current is 510-580A; the spraying voltage is 70-85V; more preferably, the spray current 550A; the spraying voltage was 75V.
The technological parameters of the magnetron sputtering are as follows: sputtering power of 2-5w/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Sputtering air pressure is 0.2-1Pa; argon flow is 40-60sccm. Preferably, the sputtering power is 3-4w/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Sputtering air pressure is 0.2-0.5Pa; more preferably, the sputtering power is 3.5w/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The sputtering air pressure was 0.3Pa.
The sprayed material is nickel powder and/or nickel alloy powder.
Further, the invention also provides a battery comprising the explosion-proof valve or the explosion-proof valve manufactured by the manufacturing method.
The technical scheme of the invention has the following advantages:
1. the invention provides an explosion-proof valve, which comprises a valve body, wherein the inner surface of the valve body is provided with a coating, and the coating comprises a first coating and a second coating; the second coating comprises a component that can react to produce a third coating; the third coating is an anti-corrosion film. The explosion-proof valve provided by the invention is not easy to be corroded by HF acid in the use process, especially the notch is not easy to be corroded, the valve opening time of the explosion-proof valve is delayed, and the service life of a battery can be prolonged when the explosion-proof valve is applied to the battery. The inventor finds that in the application process of the explosion-proof valve, the corrosion phenomenon still occurs after the protective film is arranged on the outer surface of the explosion-proof valve in the prior art, because electrolyte splashes to the inner surface of the explosion-proof valve in the use process, and the explosion-proof valve is easy to corrode due to thinner nick positions, so that the explosion-proof valve is opened prematurely. The invention is provided with the coating on the inner surface of the explosion-proof valve, and part of components in the second coating, such as metallic nickel and the like, can react with HF to generate a third coating, and the third coating is a compact anti-corrosion protective film and is attached to the surface of the second coating, so that the inner surface of the valve body is prevented from being corroded, the content of HF acid in a battery cell can be reduced, and the service performance of the cell can be improved.
When the explosion-proof valve is stamped, the thickness of the notch area is reduced from 0.5mm to 0.1mm, the deformation is large, a large number of crystal defects appear, the internal energy of the crystal is increased along with the deformation, and the temperature is transferred to the notch part when the explosion-proof valve is welded, so that the grain size is further increased, and the pressure resistance value of the explosion-proof valve is reduced. The invention is provided with the coating on the inner surface of the valve body, and the coating and the valve body can form firm self-bonding in a micro metallurgical bonding mode or a physical bonding method, so that the reduction of the pressure resistance value is compensated, and the service life of the battery is prolonged.
2. Compared with polymer material coatings such as PP and PE in the prior art, the explosion-proof valve provided by the invention has the advantages that the second coating is a nickel layer, and nickel can react with HF acid in electrolyte to generate NiF 2 The dense protective layer, namely the third coating, can avoid the premature opening of the valve caused by corrosion of the weakest notch of the explosion-proof valve,the content of HF acid in the electrolyte is also reduced; in addition, the adhesion between the coating of the high polymer materials such as PP, PE and the like and the aluminum alloy is poor, and the coating is easy to fall off when the battery works normally, so that the corrosion resistance is invalid.
The specific coating thickness of the invention does not influence the function of the explosion-proof valve, can protect the explosion-proof valve from being corroded to fail in advance, and controls the variation of the explosion-proof valve within 0.4 MPa.
3. The preparation method of the explosion-proof valve provided by the invention can control the thickness of the coating to be 5-20 mu m by controlling the technological parameters of the plasma spraying technology, the porosity is not higher than 5%, and the plasma spraying can enable the coating and the valve body to form firm self-bonding in a micro metallurgical bonding mode. The spraying current, voltage, gas flow and spraying distance mainly influence the ability of melting powder, and the speed of a spray gun and the speed of powder feeding have great influence on the thickness and the porosity of a coating.
The preparation method can control the thickness of the coating to be 10-300nm by controlling the technological parameters of magnetron sputtering, the porosity is not higher than 2%, the magnetron sputtering can enable the coating and the valve body to form firm self-bonding in a physical bonding mode, the sputtering power and the sputtering air pressure mainly influence the coating efficiency, the coating adhesion, the coating thickness and the porosity, and the argon flow mainly prevents oxidation and influences the coating thickness and the porosity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIGS. 1-3 are schematic structural views of an explosion-proof valve in an embodiment of the present invention;
FIG. 4 is a schematic diagram of the structure of the explosion-proof valve according to the embodiment of the present invention after the valve is applied to HF liquid;
1-a valve body; 101-scoring; a 2-nickel layer; 201-nickel aluminum layer; 202-a nickel layer; 203-a third coating; and a welding area of the 3-explosion-proof valve and the cover plate.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
It can be understood that the point value data of the present invention is a test reference value, and may have a certain measurement error or instrument error in the actual operation or detection process, so that a certain amplitude of fluctuation may occur. For example, in the practical experimental process, the gas flow is a floating value, which meets the requirements of the invention.
Example 1
The embodiment provides an explosion-proof valve, as shown in fig. 1-3, the explosion-proof valve comprises a valve body 1, a notch 101 is arranged on the outer surface of the valve body, a coating 2 is arranged on the inner surface of the valve body, fig. 1 is the outer surface of the valve body, fig. 2 is the inner surface of the valve body, 3 in fig. 2 is a welding area of the explosion-proof valve and a cover plate, the welding area is an edge of the lower surface of the valve body, and the width of the welding area is not larger than the welding melting width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 3.3%, the thickness of the nickel layer is 13.8 mu m, the thickness of the nickel aluminum layer is 3.4 mu m, and the coating is positioned at the projection position of the notch on the inner surface of the valve body; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting a plasma spraying technology to form a coating; wherein, the technological parameters of the plasma spraying technology are as follows: the spraying current is 600A, the spraying voltage is 70V, the nitrogen flow is 10-15L/min, the argon flow is 10-15L/min, the powder feeding speed is 20g/min, the spraying gun speed is 580mm/s, and the spraying distance is 110mm. And nickel sprayed on the inner surface of the valve body reacts with aluminum in the valve body to generate nickel-aluminum alloy, and the nickel-aluminum layer is connected with the inner surface of the valve body.
Example 2
The embodiment provides an explosion-proof valve, as shown in fig. 1-3, the explosion-proof valve comprises a valve body 1, a notch 101 is arranged on the outer surface of the valve body, a coating 2 is arranged on the inner surface of the valve body, fig. 1 is the outer surface of the valve body, fig. 2 is the inner surface of the valve body, 3 is a welding area of the explosion-proof valve and a cover plate, the welding area is an edge of the lower surface of the valve body, and the width of the welding area is not larger than the welding melting width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 2.2%, the thickness of the nickel layer is 12.7 mu m, the thickness of the nickel aluminum layer is 3.2 mu m, and the coating is arranged in a welding area of the valve body and the cover plate and in a projection position of the notch on the inner surface of the valve body; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting a plasma spraying technology to form a nickel coating; wherein, the technological parameters of the plasma spraying technology are as follows: spraying current 580A, spraying voltage 70V, nitrogen flow 10-15L/min, argon flow 15-20L/min, powder feeding rate 16g/min, spray gun speed 570mm/s and spraying distance 110mm.
Example 3
The embodiment provides an explosion-proof valve, as shown in fig. 1-3, the explosion-proof valve comprises a valve body 1, a notch 101 is arranged on the outer surface of the valve body, a coating 2 is arranged on the inner surface of the valve body, fig. 1 is the outer surface of the valve body, fig. 2 is the inner surface of the valve body, 3 is a welding area of the explosion-proof valve and a cover plate, the welding area is an edge of the lower surface of the valve body, and the width of the welding area is not larger than the welding melting width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 1.7%, the thickness of the nickel layer is 110nm, the thickness of the nickel aluminum layer is 9nm, and the coating is positioned at the projection position of the notch corresponding to the inner surface; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting magnetron sputtering to form a nickel coating; wherein, the technological parameters of the magnetron sputtering are as follows: sputtering power 3.5w/cm 2 Sputtering pressure was 0.2Pa, and argon flow was 50sccm.
Example 4
The embodiment provides an explosion-proof valve, as shown in fig. 1-3, the explosion-proof valve comprises a valve body 1, a notch 101 is arranged on the outer surface of the valve body, a coating 2 is arranged on the inner surface of the valve body, fig. 1 is the outer surface of the valve body, fig. 2 is the inner surface of the valve body, 3 is a welding area of the explosion-proof valve and a cover plate, the welding area is an edge of the lower surface of the valve body, and the width of the welding area is not larger than the welding melting width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity is 1.1%, the thickness of the nickel layer is 155nm, the thickness of the nickel aluminum layer is 13nm, and the coating is arranged on the whole inner surface of the valve body and comprises a welding area and a projection position of a notch corresponding to the inner surface; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting magnetron sputtering to form a nickel coating; wherein, the technological parameters of the magnetron sputtering are as follows: sputtering power 5w/cm 2 Sputtering pressure was 0.3Pa, and argon flow was 50sccm.
Example 5
The embodiment provides an explosion-proof valve, the explosion-proof valve includes valve body 1, and the valve body surface is provided with nick 101, and the valve body internal surface is provided with coating 2, and figure 1 is the surface of valve body, and figure 2 is the internal surface of valve body, and 3 in figure 2 are explosion-proof valve and apron welded area, and this welded area is the edge of valve body lower surface, and welded area's width is not greater than the welding width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 2.1 percent, the thickness of the nickel layer is 8.1 mu m, the thickness of the nickel aluminum layer is 2.4 mu m, and the coating is arranged in a welding area of the valve body and the cover plate and the projection position of the notch on the inner surface of the valve body; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting a plasma spraying technology to form a coating; wherein, the technological parameters of the plasma spraying technology are as follows: the spraying current is 550A, the spraying voltage is 75V, the nitrogen flow is 10-15L/min, the argon flow is 15-20L/min, the powder feeding speed is 13g/min, the spraying gun speed is 550mm/s, and the spraying distance is 110mm. And nickel sprayed on the inner surface of the valve body reacts with aluminum in the valve body to generate nickel-aluminum alloy, and the nickel-aluminum layer is connected with the inner surface of the valve body.
Example 6
The embodiment provides an explosion-proof valve, the explosion-proof valve includes valve body 1, and the valve body surface is provided with nick 101, and the valve body internal surface is provided with coating 2, and figure 1 is the surface of valve body, and figure 2 is the internal surface of valve body, and 3 in figure 2 are explosion-proof valve and apron welded area, and this welded area is the edge of valve body lower surface, and welded area's width is not greater than the welding width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 3.1 percent, the thickness of the nickel layer is 10.1 mu m, the thickness of the nickel aluminum layer is 3.0 mu m, and the coating is positioned at the projection position of the notch on the inner surface of the valve body; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting a plasma spraying technology to form a coating; wherein, the technological parameters of the plasma spraying technology are as follows: spraying current 560A, spraying voltage 80V, nitrogen flow 10-15L/min, argon flow 20-25L/min, powder feeding speed 10g/min, spray gun speed 530mm/s and spraying distance 100mm. And nickel sprayed on the inner surface of the valve body reacts with aluminum in the valve body to generate nickel-aluminum alloy, and the nickel-aluminum layer is connected with the inner surface of the valve body.
Example 7
The embodiment provides an explosion-proof valve, the explosion-proof valve includes valve body 1, and the valve body surface is provided with nick 101, and the valve body internal surface is provided with coating 2, and figure 1 is the surface of valve body, and figure 2 is the internal surface of valve body, and 3 in figure 2 are explosion-proof valve and apron welded area, and this welded area is the edge of valve body lower surface, and welded area's width is not greater than the welding width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 2.7%, the thickness of the nickel layer is 14.8 mu m, the thickness of the nickel aluminum layer is 4.5 mu m, and the coating is arranged on the whole inner surface of the valve body and comprises a welding area and a projection position of a notch corresponding to the inner surface; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting a plasma spraying technology to form a coating; wherein, the technological parameters of the plasma spraying technology are as follows: the spraying current is 600A, the spraying voltage is 85V, the nitrogen flow is 10-15L/min, the argon flow is 20-25L/min, the powder feeding rate is 25g/min, the spraying gun speed is 600mm/s, and the spraying distance is 105mm. And nickel sprayed on the inner surface of the valve body reacts with aluminum in the valve body to generate nickel-aluminum alloy, and the nickel-aluminum layer is connected with the inner surface of the valve body.
Example 8
The embodiment provides an explosion-proof valve, the explosion-proof valve includes valve body 1, and the valve body surface is provided with nick 101, and the valve body internal surface is provided with coating 2, and figure 1 is the surface of valve body, and figure 2 is the internal surface of valve body, and 3 is explosion-proof valve and apron welded area, and this welded area is the edge of valve body lower surface, and welded area's width is not greater than the welding width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 1.9%, the thickness of the nickel layer is 118nm, the thickness of the nickel aluminum layer is 16nm, and the coating is arranged in a welding area of the valve body and the cover plate and in a projection position of the notch on the inner surface of the valve body; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting magnetron sputtering to form a nickel coating; wherein, the technological parameters of the magnetron sputtering are as follows: sputtering power 3.5w/cm 2 Sputtering pressure was 0.3Pa, and argon flow was 50sccm.
Example 9
The embodiment provides an explosion-proof valve, the explosion-proof valve includes valve body 1, and the valve body surface is provided with nick 101, and the valve body internal surface is provided with coating 2, and figure 1 is the surface of valve body, and figure 2 is the internal surface of valve body, and 3 is explosion-proof valve and apron welded area, and this welded area is the edge of valve body lower surface, and welded area's width is not greater than the welding width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 1.5%, the thickness of the nickel layer is 131nm, the thickness of the nickel aluminum layer is 19nm, and the coating is positioned at the projection position of the notch corresponding to the inner surface; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting magnetron sputtering to form a nickel coating; wherein, the technological parameters of the magnetron sputtering are as follows: sputtering power 4w/cm 2 Sputtering pressure was 0.5Pa, and argon flow was 60sccm.
Example 10
The embodiment provides an explosion-proof valve, the explosion-proof valve includes valve body 1, and the valve body surface is provided with nick 101, and the valve body internal surface is provided with coating 2, and figure 1 is the surface of valve body, and figure 2 is the internal surface of valve body, and 3 is explosion-proof valve and apron welded area, and this welded area is the edge of valve body lower surface, and welded area's width is not greater than the welding width. In this example, the score had a thickness of 0.1mm; the coating comprises a nickel layer 202 and a nickel aluminum layer 201, the porosity of the coating is 1.2%, the thickness of the nickel layer is 83nm, the thickness of the nickel aluminum layer is 14nm, and the coating is arranged on the whole inner surface of the valve body and comprises a welding area and a projection position of a notch corresponding to the inner surface; the explosion-proof valve is 1 series aluminum.
The preparation method of the explosion-proof valve comprises the following steps:
spraying nickel powder on the inner surface of the valve body by adopting magnetron sputtering to form a nickel coating; wherein, the technological parameters of the magnetron sputtering are as follows: sputtering power 2w/cm 2 Sputtering pressure was 0.2Pa, and argon flow was 40sccm.
Comparative example 1
The present comparative example provides an explosion-proof valve, which is different from example 1 in that the explosion-proof valve in the present comparative example is not provided with a coating layer.
Comparative example 2
This comparative example provides an explosion-proof valve differing from example 1 in that PP is used as a coating. 10 parts by weight of PP (trade name: 4150), 60 parts by weight of methyl isobutyl ketone and 30 parts by weight of benzoyl peroxide were mixed to form a mixed solution, which was coated on the inner surface of the valve body of the explosion-proof valve to form a coating layer having a thickness of 62. Mu.m.
Test examples
The test example provides performance tests of the explosion-proof valves prepared in each example and comparative example, and the performance test is specifically as follows:
the explosion-proof valve was placed in a cell of about 100ppm HF acid solution electrolyte, 1C charged at 45C, 2C discharged, and cycled 200-2000 times or capacity decayed to 20% soh, and the results are shown in table 1.
The explosion pressure detection method of the explosion-proof valve comprises the following steps: disassembling a cover plate assembly in a battery, arranging an explosion-proof valve in the cover plate assembly, testing the explosion pressure of the explosion-proof valve, putting the cover plate assembly into an explosion-proof tester, clamping by a clamp in the tester, starting the test, filling 0.2Mpa air pressure into the tester, keeping 30s free of air leakage, and then raising the air pressure until the explosion-proof valve is exploded, and checking the maximum explosion pressure value. Wherein, the closer the burst pressure value is to the standard value of 0.6+/-0.2 MPa, the better the performance of the explosion-proof valve is.
Table 1 test results of the explosion-proof valves of examples and comparative examples
When the explosion-proof valve is placed in HF acid solution electrolyte, part of nickel in the second coating on the inner surface of the valve body of the explosion-proof valve in the embodiment can react with HF acid to generate NiF 2 The third coating 203 is attached to the surface of the second coating, as shown in fig. 4, and the third coating is a dense protective film, so that corrosion of the notch can be prevented, and the development time of the explosion-proof valve can be delayed.
The results show that the coating is arranged on the surface of the valve body of the explosion-proof valve, so that the explosion-proof valve can be prevented from being abnormal, and the explosion-proof valve cannot be broken, and the battery core cannot bulge. The explosion-proof valve of comparative example 1 was broken during the test; comparative example 2 the explosion-proof valve was coated with PP, and the explosion-proof valve was broken during the test, and the coating was peeled off. None of comparative examples 1-2 was able to test the burst pressure value of the explosion proof valve.
The porosity, the nickel layer thickness and the nickel aluminum layer thickness of the coating are determined by the process parameters of plasma spraying and magnetron sputtering, and after the process parameters of plasma spraying and magnetron sputtering are determined, the porosity, the nickel layer thickness and the nickel aluminum layer thickness of the coating are determined, and as can be seen from the table 1, the performance of the explosion-proof valve adopting the magnetron sputtering is superior to that of the explosion-proof valve adopting the plasma treatment, and the explosion pressure of the explosion-proof valve adopting the magnetron sputtering is closer to the standard value.
Further, by comparing the plasma spraying process parameters, it was found that in example 5, when the powder feeding rate was 13g/min, the spray gun speed was 550mm/s, the spraying current was 550A, and the spraying voltage was 75V, the burst pressure of the explosion-proof valve was closer to the standard value, which indicates that the valve opening time of the explosion-proof valve obtained under the specific condition was delayed, and the specific condition was the optimum process of plasma spraying.
By comparing magnetron sputtering process parameters, it was found that the burst pressure values of the explosion-proof valves obtained in example 8 and example 9 were closest to the standard values, and the delay in the opening time of the two explosion-proof valves was the best for the explanation, but the coating of example 10 was located on the whole inner surface of the valve body, which was more costly than that of example 8, so that the sputtering power was 3.5w/cm in example 8 2 The method comprises the steps of carrying out a first treatment on the surface of the The sputtering air pressure of 0.3Pa is the optimal process of magnetron sputtering.
In summary, the coating is arranged on the inner surface of the valve body, the second coating comprises components capable of generating the third coating by reaction, and the third coating is an anti-corrosion film, for example, the second coating is a nickel layer, so that the anti-explosion valve is not easy to be corroded by HF acid in the use process, particularly the notch is not easy to be corroded, the valve opening time of the anti-explosion valve is delayed, and the service life of the battery can be prolonged when the anti-explosion valve is applied to the battery; preferably a magnetron sputtering process, especially when the sputtering power is 3.5w/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the When the sputtering air pressure is 0.3Pa, the performance of the explosion-proof valve is optimal and the cost is lowest.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. An explosion-proof valve, characterized in that the explosion-proof valve comprises a valve body;
the inner surface of the valve body is provided with a coating;
the coating comprises a first coating and a second coating;
the second coating comprises a component that can react to produce a third coating;
the third coating is an anti-corrosion film.
2. The explosion proof valve of claim 1, wherein an outer surface of the explosion proof valve is provided with scores;
preferably, the coating is positioned at the projection position of the notch on the inner surface of the valve body; and/or the number of the groups of groups,
the coating is arranged in the welding area of the explosion-proof valve and the cover plate.
3. The explosion-proof valve according to claim 1 or 2, wherein the thickness of the coating is 10nm-20 μm;
preferably, the porosity of the coating is less than or equal to 5%;
preferably, the thickness of the first coating is 2nm-5 μm;
preferably, the thickness of the second coating layer is 8nm-15 μm.
4. The explosion protection valve according to any one of claims 1-3, wherein the components in the second coating layer comprise a metal;
preferably, the second coating is a nickel layer;
preferably, the explosion-proof valve is an aluminum alloy;
preferably, the first coating is a nickel aluminum layer.
5. A method of manufacturing an explosion-proof valve as claimed in any one of claims 1 to 4, comprising the steps of: and spraying by adopting a plasma spraying technology or a magnetron sputtering technology, and forming the first coating and the second coating on the inner surface of the valve body.
6. The method of claim 5, wherein the process parameters of the plasma spray technique include: the powder feeding speed is 10-25g/min, and the spray gun speed is 500-600mm/s.
7. The method of claim 6, wherein the process parameters of the plasma spraying technique further comprise: the spraying current is 500-600A; the spraying voltage is 70-90V; the nitrogen flow is 10-15L/min; argon flow is 10-25L/min; the spraying distance is 100-110mm.
8. The method according to claim 5, wherein the process parameters of the magnetron sputtering are as follows: sputtering power of 2-5w/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Sputtering air pressure is 0.2-1Pa; argon flow is 40-60sccm.
9. The method according to any one of claims 5 to 8, wherein the material sprayed in the spraying step is nickel powder and/or nickel alloy powder.
10. A battery comprising an explosion-proof valve according to any one of claims 1 to 4 or an explosion-proof valve produced by the production method according to any one of claims 5 to 9.
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| CN116454524B (en) | 2024-05-24 |
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