CN116463632A - Corrosion inhibition complexing agent for hydrogen fuel cell cooling liquid and preparation method and application thereof - Google Patents
Corrosion inhibition complexing agent for hydrogen fuel cell cooling liquid and preparation method and application thereof Download PDFInfo
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- CN116463632A CN116463632A CN202310474122.3A CN202310474122A CN116463632A CN 116463632 A CN116463632 A CN 116463632A CN 202310474122 A CN202310474122 A CN 202310474122A CN 116463632 A CN116463632 A CN 116463632A
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- 230000007797 corrosion Effects 0.000 title claims abstract description 100
- 238000005260 corrosion Methods 0.000 title claims abstract description 100
- 230000005764 inhibitory process Effects 0.000 title claims abstract description 95
- 239000008139 complexing agent Substances 0.000 title claims abstract description 79
- 239000000446 fuel Substances 0.000 title claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 72
- 239000001257 hydrogen Substances 0.000 title claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000110 cooling liquid Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 69
- -1 silane fatty acid ester Chemical class 0.000 claims abstract description 43
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 41
- 229930195729 fatty acid Natural products 0.000 claims abstract description 41
- 239000000194 fatty acid Substances 0.000 claims abstract description 41
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004202 carbamide Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 17
- 150000007980 azole derivatives Chemical class 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 239000002826 coolant Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- NDAURKDIFHXVHE-UHFFFAOYSA-N 5-phenyl-1,3,4-oxathiazol-2-one Chemical compound S1C(=O)OC(C=2C=CC=CC=2)=N1 NDAURKDIFHXVHE-UHFFFAOYSA-N 0.000 claims description 8
- QVSRWXFOZLIWJS-UHFFFAOYSA-N trimethylsilyl propanoate Chemical compound CCC(=O)O[Si](C)(C)C QVSRWXFOZLIWJS-UHFFFAOYSA-N 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 230000002401 inhibitory effect Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 3
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 19
- 238000007710 freezing Methods 0.000 abstract description 15
- 230000008014 freezing Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007769 metal material Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 5
- 238000005536 corrosion prevention Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04029—Heat exchange using liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of fuel cell cooling liquid, and relates to a corrosion inhibition complexing agent for hydrogen fuel cell cooling liquid, and a preparation method and application thereof. The corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid prepared by the invention comprises the following components in percentage by weight: 0.1 to 0.5 percent of silane fatty acid ester; 0.1% of azole derivative; 0.001% -0.01% of defoaming agent; 20% -95% of ethylene glycol; the balance being water. The corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid adopts the novel additives, namely the silyl fatty acid ester and the urea, and the addition of the additives improves the corrosion inhibition performance of the glycol/water system cooling liquid, maintains the conductivity of the system at a lower level, and synchronously realizes the effects of temperature control, corrosion inhibition and electric energy loss inhibition. The cooling liquid corrosion inhibition complexing agent prepared by the invention has the characteristics of low electric conduction, high heat transfer, low freezing point and high boiling point, has good corrosion prevention and inhibition effects on metal materials in the hydrogen fuel cell, is beneficial to fully playing the service performance of equipment and prolonging the service life of the equipment.
Description
Technical Field
The invention belongs to the technical field of fuel cell cooling liquid, and relates to a corrosion inhibition complexing agent for hydrogen fuel cell cooling liquid, and a preparation method and application thereof.
Background
The hydrogen fuel cell can directly convert chemical energy of hydrogen and oxygen into electric energy, and is a clean green energy technology. The principle of hydrogen fuel cell operation is based on an electrochemical redox reaction, where hydrogen diffuses out through the anode and reacts with the electrolyte, after which electrons are released and an electric current is formed through the externally loaded electrons to the cathode. Based on the above process, the hydrogen fuel cell only generates water and heat during operation, does not generate dust, greenhouse gases and the like, and has the advantage of environmental friendliness. Therefore, the hydrogen fuel cell has wide application prospect. The method has the advantages that the method is applied to the fields of aerospace and new energy automobiles, and has good application potential in the fields of charging piles, portable power supplies, emergency power supplies and the like.
The hydrogen fuel cells are commonly used as a power generation unit, and a battery pack is formed by stacking the hydrogen fuel cells. In such a laminated structure, cooling plates having a cooling liquid inside are installed in each of the sub-cells to achieve a temperature control effect. Therefore, when the hydrogen fuel cell works, namely, in the process of converting chemical energy into electric energy, additionally generated heat can be circularly taken away by the cooling liquid, so that the safe work and stable use of the hydrogen fuel cell are ensured. Therefore, the high quality coolant is required to have good heat transfer properties, which is important for research and application of hydrogen fuel cells. Also, since the coolant circulates between the inside of the battery pack performing power generation and the sub-battery pack, the antifreeze must have low conductivity (insulating property) to prevent leakage of electricity to the outside of the battery pack, resulting in a roll-off of power generation efficiency.
Moreover, the coolant is required to have good protection to metallic materials in the thermal management system and ideal adaptability to nonmetallic materials. Thus, the cooling liquid with temperature control and corrosion resistance can be used as the cooling liquid corrosion inhibition complexing agent. Taking a vehicle hydrogen fuel cell module as an example, the cooling liquid corrosion inhibition complexing agent needs to have good protection effect on metal materials such as aluminum alloy, cast iron, steel, brass, soldering tin, red copper and the like, and has compatibility and adaptability on non-metal materials such as silicon rubber, fluororubber, ethylene Propylene Diene Monomer (EPDM), polytetrafluoroethylene and the like, which are consistent with the cooling liquid for the traditional fuel vehicle engine. At present, the cooling liquid corrosion inhibition complexing agent for the main stream fuel vehicle engine at home and abroad is usually a mixture of glycol and water. The ethylene glycol and water are easy to obtain, and the cost is low. By reasonable blending, the system is easy to realize the characteristics of low freezing point, high boiling point and high heat conduction. And a proper amount of silicate additive is matched, so that the oxidation reaction of ethylene glycol at high temperature can be further inhibited, the corrosion of the cooling liquid to metal is avoided, and the corrosion inhibition and corrosion prevention properties of the cooling liquid are further enhanced. However, silicate type glycol/water coolant corrosion inhibition systems, which are widely used in temperature control systems for fuel engines, are not suitable for hydrogen fuel cell stacks. The reason for this is that this type of complexing agent has a relatively high electrical conductivity and that after a long period of operation the electrical conductivity increases further. This will result in power loss from the hydrogen fuel cell, reduce the power capacity of the stack, and also reduce the life of the stack, thereby affecting the endurance mileage of the equipped system, such as a hydrogen fuel cell vehicle, and the stability of the stack.
Therefore, the characteristics of the hydrogen fuel cell are combined with the purposes of temperature control and corrosion prevention, and the nonionic cooling liquid corrosion inhibition complexing agent is developed and simultaneously meets the following conditions: 1) High heat transfer, freeze protection, boiling prevention and bubble suppression; 2) Protecting metallic and non-metallic materials; 3) The conductivity is low enough to be suitable for a high-performance hydrogen fuel cell thermal management system, and has important scientific research significance and practical application value.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cooling liquid corrosion inhibition complexing agent and a preparation method thereof aiming at the defects of the prior art so as to meet the use requirement of a high-performance hydrogen fuel cell.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention discloses a corrosion inhibition complexing agent for a hydrogen fuel cell cooling liquid, which comprises the following components in percentage by weight:
0.1 to 0.5 percent of silane fatty acid ester;
0.1% of azole derivative;
0.001% -0.01% of defoaming agent;
20% -95% of ethylene glycol;
the balance being water.
In some embodiments, preferably, the hydrogen fuel cell coolant corrosion inhibition complexing agent comprises the following components in weight percent:
0.2% of a silyl fatty acid ester;
0.1% of azole derivative;
0.01% of defoaming agent;
ethylene glycol 56.21%;
the balance being water.
In some embodiments, preferably, the hydrogen fuel cell coolant corrosion inhibition complexing agent comprises the following components in weight percent:
0.2% of a silyl fatty acid ester;
0.1% of azole derivative;
0.01% of defoaming agent;
50.00% of ethylene glycol;
the balance being water.
Wherein, the proportion of the glycol and the ultrapure water is prepared according to the actual freezing point requirement.
In some embodiments, the silyl fatty acid ester is any one or a combination of several of trimethylsilyl acetate, trimethylsilyl propionate, and trimethylsilyl butyrate; the azole derivative is urea (1, 2, 4-triazolidine-3, 5-dione); the defoaming agent is modified siloxane defoaming agent.
In some embodiments, the water is ultrapure water; the conductivity of the ultrapure water is less than 10 -2 μS/cm。
Wherein the ultrapure water is prepared by an ion exchange system.
Wherein the trimethylsilyl acetate has the following structural formula:
wherein the trimethylsilyl propionate has the following structural formula:
wherein the trimethylsilyl butyrate has the following structural formula:
the invention further discloses a preparation method of the corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid, which comprises the steps of uniformly mixing glycol and water, adding silane fatty acid ester and azole derivatives into a system, uniformly stirring, finally adding a defoaming agent into the system, and uniformly mixing to obtain the corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid.
In the process of adding the silane fatty acid ester and the azole derivative into the system and uniformly stirring, steam heating can be used as appropriate according to the dissolution condition of the raw materials in the system to increase the solubility of the raw materials and the miscibility among the components.
Before adding the defoaming agent into the system, the physical and chemical properties such as pH value and freezing point of the mixed system need to be detected, and then the defoaming agent is added into the system after meeting the standard requirements.
The application of the hydrogen fuel cell cooling liquid corrosion inhibition complexing agent in the hydrogen fuel cell is also within the protection scope of the invention.
In some embodiments, the hydrogen fuel cell coolant corrosion inhibition complexing agent has a conductivity of less than 0.3 μS/cm.
In some embodiments, the hydrogen fuel cell coolant corrosion inhibition complexing agent has a protective corrosion inhibition function on metal and non-metal materials.
The beneficial effects are that:
the corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid adopts the novel additives, namely the silyl fatty acid ester and the urea, and the addition of the additives improves the corrosion inhibition performance of the glycol/water system cooling liquid, maintains the conductivity of the system at a lower level, and synchronously realizes the effects of temperature control, corrosion inhibition and electric energy loss inhibition. The coolant corrosion inhibition complexing agent based on the novel component formula has the characteristics of low conductivity, high heat transfer, low freezing point and high boiling point, is matched with a hydrogen fuel cell for use, meets the requirement of temperature control and cooling of the hydrogen fuel cell, has good corrosion inhibition effect on metal materials in the hydrogen fuel cell, is favorable for fully playing the service performance of equipment and prolonging the service life of the equipment.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a graph comparing glassware corrosion test data for various coolant corrosion inhibiting complexing agents having freezing points of-45 ℃ and different compositions.
FIG. 2 is a graph comparing glassware corrosion test data for various coolant corrosion inhibition complexing agents having freezing points of-35 ℃ and different compositions.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
The purity of the ethylene glycol used in the embodiment of the invention is more than 99.9 percent.
The defoamer used in the examples of the present invention was a MUNZING FOAM BAN EC type defoamer.
The ultrapure water used in the embodiment of the invention has the conductivity less than 10 -2 μS/cm。
The data testing method in the embodiment of the invention refers to national standards and petrochemical/electric industry standards.
Example 1: preparation of cooling liquid corrosion inhibition complexing agent with freezing point of-45℃ standard
The corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid comprises the following components in percentage by weight:
0.2% of trimethylsilyl propionate;
0.1% of urea;
0.01% of defoaming agent;
ethylene glycol 56.21%;
43.48% of ultrapure water.
The preparation method of the corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid comprises the following steps: mixing 56.21% of ethylene glycol and 43.48% of ultrapure water uniformly, adding 0.2% of trimethylsilyl propionate and 0.1% of urea into the system, stirring uniformly, detecting that each physical and chemical parameter of the mixed system meets the standard requirement, adding 0.01% of defoamer into the system, and mixing uniformly to obtain the corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid.
The cooling liquid corrosion inhibition complexing agent obtained in example 1 is tested according to national standards and various industry standards, and the specific physicochemical indexes and the corresponding conditions of the detection index reference values are shown in table 1.
TABLE 1 physicochemical index data table of Cooling liquid Corrosion inhibiting complexing agent obtained in example 1
As can be seen from the data in Table 1, the cooling liquid corrosion inhibition complexing agent prepared according to the measured proportion and the preparation method accords with the national standard. It is worth noting that the addition of the silane-based fatty acid ester/urea additive composition has lower conductivity of the corrosion inhibition complexing agent, can effectively insulate, inhibit the electric energy loss of the hydrogen fuel cell and improve the working efficiency. According to the method guided by GB/T6682, the cooling liquid corrosion inhibition complexing agent has ideal conductivity as low as 0.22 mu S/cm.
Meanwhile, the performance of the cooling liquid corrosion inhibition complexing agent prepared in the example 1 is further characterized, and various data are shown in Table 2.
TABLE 2 characterization data sheet for the corrosion inhibition complexing agent for Cooling liquid obtained in example 1
From the characterization data in table 2, it can be seen that: based on the addition of the silicane fatty acid ester/urea composition additive, the cooling liquid corrosion inhibition complexing agent has ideal protection effect on metals and non-metals in the system, and has good foam inhibition characteristic. From the data in tables 1 and 2, it can be seen that the prepared coolant corrosion inhibition complexing agent has excellent performance and can efficiently meet the use requirement of a hydrogen fuel cell.
Example 2: preparation of cooling liquid corrosion inhibition complexing agent with freezing point of-35℃ standard
The corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid comprises the following components in percentage by weight:
0.2% of trimethylsilyl butyrate;
0.1% of urea;
0.01% of defoaming agent;
50% of ethylene glycol;
49.69% of ultrapure water.
The preparation method of the cooling liquid corrosion inhibition complexing agent comprises the following steps: after 50% of ethylene glycol and 49.69% of ultrapure water are uniformly mixed, 0.2% of trimethylsilyl butyrate and 0.1% of urea are added into the system and uniformly stirred, after each physical and chemical parameter of the mixed system is detected to meet the standard requirement, finally, 0.01% of defoamer is added into the system, and the mixture is uniformly mixed, so that the corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid is obtained.
The performance of the coolant corrosion inhibition complexing agent prepared in example 2 was further characterized, and various data are shown in Table 3.
TABLE 3 characterization data sheet for the performance of the Cooling liquid Corrosion inhibiting Complex obtained in example 2
The freezing point of the cooling liquid corrosion inhibition complexing agent can be definitely regulated and controlled by regulating the proportion of the ethylene glycol to the ultrapure water. From the data in Table 3, the formulation has good repeatability in improving the performance of the complexing agent, and the scientificity and reliability of the formulation are proved.
Example 3: optimizing the proportion of silane-based fatty acid ester and urea in the cooling liquid corrosion inhibition complexing agent
In addition, the adding proportion of the silyl fatty acid ester and the urea in the additive is optimized and adjusted systematically. The effect of different mass fractions of the silyl fatty acid ester and the urea on the corrosion inhibition performance of the complexing agent based on the cooling liquid corrosion inhibition complexing agent at-35 ℃ and-45 ℃ is shown in table 4.
TABLE 4 summary of the effects of different additive compositions on conductivity and glassware corrosion tests
From the experimental results of comparative example 1 with control groups 1,2, and example 2 with control groups 3, 4, it can be found that: when the adding proportion of the silyl fatty acid ester is increased from 0.1% to 0.2%, the corrosion inhibition performance of the complexing agent is obviously improved, and the conductivity is stable. In addition, when the proportion of the urea component is increased from 0.1% to 0.2%, the corrosion inhibition performance change is not particularly obvious, but the conductivity is obviously increased to more than three times of the original value. Therefore, from the viewpoints of improving corrosion inhibition performance, maintaining low conductivity, simplifying the formula and reducing the cost, the adding proportion of the silyl fatty acid ester and the urea is finally determined to be 0.2 percent and 0.1 percent respectively.
Example 4: comparison of the Performance of Cooling liquids based on different Components
Blank coolant group: the preparation method was the same as in example 1 and example 2, except that no silyl fatty acid ester (trimethylsilyl propionate or trimethylsilyl butyrate) and no urea were added, and a blank coolant having a freezing point of-45 ℃ and a blank coolant having a freezing point of-35 ℃ were obtained, respectively.
Group of individual silyl fatty acid ester coolants: the preparation method was the same as in example 1 and example 2, except that no urea was added, and a single trimethylsilyl propionate coolant with a freezing point of-45 ℃ and a trimethylsilyl butyrate coolant with a freezing point of-35 ℃ were obtained, respectively.
Group of individual urea cooling solutions: the preparation method was the same as in example 1 and example 2, respectively, except that no silyl fatty acid ester (trimethylsilyl propionate or trimethylsilyl butyrate) was added, and an individual urea cooling liquid at-45℃was obtained without adding a silyl fatty acid ester, and an individual urea cooling liquid at-35℃without adding a silyl fatty acid ester.
The blank cooling liquid, the independent silane-based fatty acid ester cooling liquid and the independent urea cooling liquid prepared by the method are subjected to corrosion inhibition performance characterization, and specific data are shown in tables 5-7.
TABLE 5 data sheet for characterization of corrosion inhibition complexing agent for blank coolant set
TABLE 6 Performance characterization data sheet for Corrosion inhibition complexing agents for Individual Silyl fatty acid ester Cooling fluid sets
TABLE 7 Performance characterization data sheet for Corrosion inhibition complexing agent for individual urazole coolant groups
From the data in tables 5 to 7, it can be seen that: (1) The ethylene glycol/water blank, although having minimal conductivity, showed the worst protection performance of the system to metals as demonstrated by the glassware corrosion test results; (2) When a single silyl fatty acid ester component is added, the conductivity of the cooling liquid corrosion inhibition complexing agent only generates small floating, and the corrosion inhibition performance is greatly enhanced, thus proving the beneficial effect of the silyl fatty acid ester; (3) After the single urea component is added, the corrosion inhibition performance is improved, and the protection capability of the urea component to metal is demonstrated; in addition, the conductivity of the system fluctuates greatly with the introduction of the urea component.
The advantages of the silane-based fatty acid ester and the urea component are combined, the adding proportion of the silane-based fatty acid ester and the urea is optimized, the corrosion inhibition performance of the cooling liquid corrosion inhibition complexing agent on the metal material is further enhanced, the conductivity is maintained at a relatively low level, and the conductivity is only increased to 0.22 mu S/cm. The difference in corrosion inhibition performance of metals in hydrogen fuel cell systems with simultaneous addition of a silyl fatty acid ester and a urea additive can be clearly demonstrated in figures 1 and 2 of the specification. The comparative test proves that the composition of the silane-based fatty acid ester and the urea is an efficient additive, can effectively enhance the corrosion inhibition performance of the cooling liquid corrosion inhibition complexing agent, maintains stable and lower conductivity, and proves the advancement and innovation of the combined additive.
The invention discloses a novel formula and a preparation method of a cooling corrosion inhibition complexing agent for a hydrogen fuel cell, which are characterized in that an additive containing silyl fatty acid ester and urea is used. Based on a classical glycol/water system, the composition with low freezing point, high boiling point and ideal heat conducting property is realized by adjusting the proportion of each component in the cooling liquid corrosion inhibition complexing agent. Next, the silyl fatty acid ester and the urea additive are introduced, so that the corrosion inhibition property of the cooling liquid corrosion inhibition complexing agent is improved, and the conductivity of the system is maintained at a sufficiently low level. In particular, the cooling liquid corrosion inhibition complexing agent based on the silicane fatty acid ester and the urea additive has good protection, corrosion prevention and corrosion inhibition capability on metal materials involved in a hydrogen fuel cell application system, such as brass, red copper, stainless steel 304, stainless steel 316L, aluminum 3A21, aluminum 4043, aluminum 5A05, aluminum 6063 and the like. The silyl fatty acid ester component can effectively protect aluminum alloy in the battery, and macromolecule colloid is not easy to form, so that a cooling loop is blocked. Meanwhile, the silyl fatty acid ester is favorable for inhibiting the oxidation of glycol at high temperature and maintaining the pH value of the cooling liquid corrosion inhibition complexing agent, so that the service life of the complexing agent is prolonged, and the hydrogen fuel cell is protected for a longer time. In addition, the urea molecule contains active hydrogen with a plurality of sites, which can form coordination bonds with copper, aluminum and the like and weak intermolecular interaction, thereby forming multi-dimensional 'net-shaped' chemical protection and further realizing corrosion prevention, rust prevention and corrosion inhibition properties on the metal surface. The method has ideal adaptability to nonmetallic materials in the system and has certain protection capability. More importantly, the non-ionic additive and the formula make up the conductivity of the complexing agent to be maintained within a good level lower than 0.3 mu S/cm, which is beneficial to inhibiting the electric energy loss of the hydrogen fuel cell. Meanwhile, the cooling liquid slow release agent system has the characteristics of excellent anti-foaming and foam inhibition properties and stable color. In summary, the coolant corrosion inhibition complexing agent for the hydrogen fuel cell can meet the use requirement of the hydrogen fuel cell, realize high-efficiency temperature control, protect metals and nonmetal in the hydrogen fuel cell, ensure low conductivity at a lower level to inhibit electric energy loss, thereby enhancing the working efficiency of the hydrogen fuel cell and prolonging the service life of the hydrogen fuel cell.
In conclusion, the patent develops a novel cooling liquid corrosion inhibition complexing agent for the hydrogen fuel cell. The complexing agent is based on a classical glycol/water system, and by adding a novel silyl fatty acid ester and an urea composition additive, the corrosion inhibition effect of the complexing agent on system metal is effectively improved by utilizing the compatibility of multiple components in the system, and the effects of temperature control and metal protection are synchronously realized. Meanwhile, the addition of the additive of the composition effectively controls the conductivity of the complexing agent at a lower level, and inhibits the electric energy loss of the hydrogen fuel cell. Therefore, the cooling liquid corrosion inhibition complexing agent based on the silicane fatty acid ester and the urea composition additive is beneficial to protecting a battery pack, guaranteeing the high-efficiency work of the battery pack, prolonging the service life of the battery pack, meeting the use requirement of a hydrogen fuel cell, realizing the aim of realizing double carbon in China by efficiently utilizing hydrogen energy, and having positive propulsion effect and application value.
The invention provides a hydrogen fuel cell cooling liquid corrosion inhibition complexing agent, a preparation method and an application thought and method thereof, and particularly the method and the way for realizing the technical scheme are a plurality of methods, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by a person of ordinary skill in the art without departing from the principle of the invention, and the improvements and the modifications are also regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (9)
1. The corrosion inhibition complexing agent for the hydrogen fuel cell cooling liquid is characterized by comprising the following components in percentage by weight:
0.1 to 0.5 percent of silane fatty acid ester;
0.1% of azole derivative;
0.001% -0.01% of defoaming agent;
20% -95% of ethylene glycol;
the balance being water.
2. The hydrogen fuel cell coolant corrosion inhibition complexing agent of claim 1, comprising the following components in percentage by weight:
0.2% of a silyl fatty acid ester;
0.1% of azole derivative;
0.01% of defoaming agent;
ethylene glycol 56.21%;
the balance being water.
3. The hydrogen fuel cell coolant corrosion inhibition complexing agent of claim 1, comprising the following components in percentage by weight:
0.2% of a silyl fatty acid ester;
0.1% of azole derivative;
0.01% of defoaming agent;
50.00% of ethylene glycol;
the balance being water.
4. The hydrogen fuel cell coolant corrosion inhibition complexing agent according to any one of claims 1 to 3, characterized in that the silyl fatty acid ester is any one or a combination of several of trimethylsilyl acetate, trimethylsilyl propionate and trimethylsilyl butyrate; the azole derivative is urea; the defoaming agent is modified siloxane defoaming agent.
5. A hydrogen fuel cell coolant corrosion inhibition complexing agent according to any one of claims 1 to 3 wherein the water is ultra-pure water; the conductivity of the ultrapure water is less than 10 -2 μS/cm。
6. The method for preparing the corrosion inhibition complexing agent for the cooling liquid of the hydrogen fuel cell according to any one of claims 1 to 3, which is characterized in that after ethylene glycol and water are uniformly mixed, silane-based fatty acid ester and azole derivatives are added into the system and uniformly stirred, and finally, a defoaming agent is added into the system and uniformly mixed, so that the corrosion inhibition complexing agent for the cooling liquid of the hydrogen fuel cell is obtained.
7. Use of a hydrogen fuel cell coolant corrosion inhibiting complexing agent according to any one of claims 1 to 3 in a hydrogen fuel cell.
8. The use according to claim 7, wherein the hydrogen fuel cell coolant corrosion inhibition complexing agent has a conductivity of less than 0.3 μs/cm.
9. The use according to claim 7, wherein the hydrogen fuel cell coolant corrosion inhibition complexing agent has a protective corrosion inhibition function for metallic and nonmetallic materials.
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