Leak-proof long-life energy storage battery cooling concentrate, method of making and use thereof

Abstract

The application discloses a leakage-proof long-service-life energy storage battery cooling concentrate as well as a preparation method and application thereof. The leakage-proof long-service-life energy storage battery cooling concentrate comprises the following components: ethylene glycol, a surface tension improver, a buffer, a benzotriazole compound and an organic acid. The cooling concentrate has excellent heat conduction performance, metal corrosion resistance, acid resistance, leakage prevention performance and super-long service life, and the cooling concentrate also has good environmental protection performance. By using the cooling concentrate, the performance and service life of the energy storage battery can be effectively improved, the operation and maintenance cost is reduced, and a powerful guarantee is provided for the safe and stable operation of a power system.

Description

Technical Field

[0001] This invention relates to the field of energy storage battery technology, specifically to a leak-proof, long-life energy storage battery cooling concentrate, its preparation method, and its application. Background Technology

[0002] As a key component of energy storage and conversion, energy storage batteries have been widely used in power systems and other fields due to the transformation of the global energy structure and the rapid development of renewable energy. However, energy storage batteries generate a large amount of heat during operation. If heat cannot be dissipated in a timely and effective manner, the battery temperature will rise, affecting the performance, lifespan, and safety of the energy storage battery. Furthermore, energy storage power stations are generally built in conjunction with wind and solar power systems and are located in remote areas. Frequent replacement of the liquid cooling medium will increase maintenance costs. Even worse, used liquid cooling media may be hazardous waste, further increasing waste liquid treatment costs.

[0003] Currently, most mainstream energy storage battery coolants on the market are traditional ethylene glycol aqueous solutions. These coolants can effectively absorb and dissipate the heat generated by the battery during initial use, but during long-term operation, due to chemical reactions such as oxidation and acidification, the performance of the coolant will gradually decline, and even produce corrosion and deposits, leading to blockage or leakage in the cooling system, thereby causing energy storage battery performance degradation, shortened lifespan, and safety hazards.

[0004] Furthermore, traditional coolants typically have a short lifespan, requiring replacement every 3-5 years. This not only increases the maintenance costs of energy storage systems, but frequent replacements can also damage the battery system. More importantly, the thermal management system of energy storage power stations, especially the liquid cooling plates, has defects such as micro-cracks due to structural and design reasons, creating seepage channels. Coolants with low surface tension are more prone to leakage, leading to short circuits in the system circuitry and posing a potential risk of arcing.

[0005] Therefore, effective thermal management of energy storage batteries, especially the development of a long-life, leak-proof energy storage battery coolant, is of great practical significance for improving the safety and reliability of energy storage batteries, extending their service life, and reducing operation and maintenance costs. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a leak-proof, long-life energy storage battery cooling concentrate, its preparation method, and its applications. The cooling concentrate of this invention employs a special formulation design, exhibiting excellent thermal conductivity, metal corrosion resistance, acid resistance, leak-proof performance, and an ultra-long service life, predicted to exceed 10 years. Furthermore, this cooling concentrate also possesses good environmental performance. By using the cooling concentrate of this invention, the performance and lifespan of energy storage batteries can be effectively improved, operation and maintenance costs reduced, and a strong guarantee provided for the safe and stable operation of power systems.

[0007] One of the objectives of this invention is to provide a leak-proof, long-life energy storage battery cooling concentrate, comprising the following components: ethylene glycol, surface tension enhancer, buffer, benzotriazole compound, and organic acid.

[0008] In a preferred embodiment of the present invention,

[0009] The surface tension enhancer is one or both of glycerol and potassium carbonate.

[0010] In a preferred embodiment of the present invention,

[0011] The buffer is boric acid.

[0012] In a preferred embodiment of the present invention,

[0013] The benzotriazole compounds are one or more of benzotriazole and its derivatives, preferably one or two of methylbenzotriazole and benzotriazole.

[0014] In a preferred embodiment of the present invention,

[0015] The organic acid is one or more of monocarboxylic acids and dicarboxylic acids having 5-12 carbon atoms, preferably one or more of azelaic acid, isodecanoic acid, and octanoic acid, more preferably a mixture of azelaic acid, isodecanoic acid, and octanoic acid; even more preferably...

[0016] The weight ratio of azelaic acid, isodecanoic acid and octanoic acid in the mixture is (2-5):(1-3):1, preferably (3-4):(1.5-2.5):1.

[0017] In a preferred embodiment of the present invention,

[0018] The leak-proof, long-life energy storage battery cooling concentrate also contains a pH adjuster; preferably,

[0019] The pH adjuster is at least one of alkali metal hydroxides, preferably at least one of sodium hydroxide and potassium hydroxide; the alkali metal hydroxide can also be used dissolved in an aqueous solution; and / or

[0020] The pH adjuster adjusts the pH value of the leak-proof, long-life energy storage battery cooling concentrate to 7.5-11.0, preferably 7.5-10.0, and more preferably 7.9-9.0.

[0021] In a preferred embodiment of the present invention,

[0022] The components of the leak-proof, long-life energy storage battery cooling concentrate are calculated based on ethylene glycol as 100 parts by weight.

[0023] 5-60 parts by weight of surface tension improver; preferably 10-50 parts by weight; more preferably 10-35 parts by weight; and even more preferably, when the surface tension improver includes potassium carbonate, the amount of potassium carbonate is less than or equal to 20 parts by weight.

[0024] The buffer is 0.5-3.0 parts by weight; preferably 0.5-2.0 parts by weight; more preferably 1.0-1.8 parts by weight.

[0025] The benzotriazole compound is used in an amount of 0.05-2.0 parts by weight; preferably 0.15-1.5 parts by weight; more preferably 0.15-0.5 parts by weight.

[0026] The organic acid is 1.0-5.0 parts by weight; preferably 1.5-4.5 parts by weight; more preferably 1.5-3.8 parts by weight.

[0027] A second objective of this invention is to provide a method for preparing a leak-proof, long-life energy storage battery cooling concentrate, which is one of the objectives of this invention. The method includes a step of mixing components comprising ethylene glycol, a surface tension enhancer, a buffer, a benzotriazole compound, and an organic acid; preferably,

[0028] The mixture includes components such as ethylene glycol, surface tension enhancer, buffer, benzotriazole compound, and organic acid, and further includes a step of adding a pH adjuster to adjust the pH value. The pH adjuster adjusts the pH value of the leak-proof, long-life energy storage battery cooling concentrate to 7.5-11.0, preferably 7.5-10.0, and more preferably 7.9-9.0.

[0029] The third objective of this invention is to provide a leak-proof, long-life energy storage battery coolant, comprising the leak-proof, long-life energy storage battery coolant concentrate of objective one of this invention or the leak-proof, long-life energy storage battery coolant concentrate obtained by the preparation method of objective two of this invention, and water; the freezing point of the leak-proof, long-life energy storage battery coolant of this invention is determined according to the lowest local temperature where the energy storage power station is located, and generally the freezing point should be (5-10)℃ lower than the local lowest temperature. The freezing point is mainly obtained by mixing the leak-proof, long-life energy storage battery coolant concentrate with water in different proportions; the method of mixing the coolant concentrate with water to obtain a specific freezing point is a conventional method in the art and is not specifically limited in this invention; preferably, the volume ratio of the leak-proof, long-life energy storage battery coolant concentrate to water is 1:(0.5-9), more preferably 1:(0.5-2.5).

[0030] The fourth objective of this invention is to provide a leak-proof, long-life energy storage battery coolant as described in the first objective of this invention, or a leak-proof, long-life energy storage battery coolant prepared by the second objective of this invention, or a leak-proof, long-life energy storage battery coolant as described in the third objective of this invention, for use in the field of energy storage batteries.

[0031] In the leak-proof, long-life energy storage battery coolant of this invention, organic acids and benzotriazole compounds synergistically protect metals such as copper, brass, steel, and aluminum in the form of an adsorption film or oxide film. The addition of a surface tension enhancer increases the surface tension of the coolant by altering the imbalance of molecular attraction at the liquid surface layer, preventing leakage through the micropores of the liquid cooling plate. Buffers, in synergy with organic acids, provide a higher reserve alkalinity to resist acidification during ethylene glycol use, ensuring pH stability and thus extending the coolant's service life.

[0032] The leak-proof, long-life energy storage battery coolant of this invention features high reserve alkalinity, excellent leak-proof performance, and environmentally friendly properties. Compared with existing technologies, the beneficial effects of the technical solution adopted in this invention are reflected in:

[0033] 1. Excellent alkalinity reserve performance solves the problem of pH drop caused by ethylene glycol oxidation and acidification. Buffers and other substances play a role in corrosion inhibition and provide a pH environment to ensure excellent performance over a long period of time.

[0034] 2. Excellent anti-leakage performance, which improves the surface tension of the coolant in the energy storage battery, prevents micro-leakage, and enhances the safety performance of the energy storage power station.

[0035] 3. Excellent environmental performance: The selected components do not contain non-environmentally friendly ingredients such as silicon, phosphorus, amine, chromium, nitrite, and nitrate. Detailed Implementation

[0036] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0037] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0038] Example 1

[0039] The leak-proof, long-life energy storage battery cooling concentrate of Example 1 has the following composition by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 2.2 parts azelaic acid, 10 parts glycerol, and 1 part boric acid. The components are stirred evenly, and the pH of the solution is adjusted to 8.3 with sodium hydroxide to obtain the leak-proof, long-life energy storage battery cooling concentrate.

[0040] Example 2

[0041] The leak-proof, long-life energy storage battery cooling concentrate of Example 2 has the following components by weight: 100 parts ethylene glycol, 0.2 parts methylbenzotriazole, 0.1 parts benzotriazole, 2.2 parts azelaic acid, 10 parts glycerol, 2 parts potassium carbonate, and 1.8 parts boric acid. The components are stirred evenly, and the pH of the solution is adjusted to 8.5 with sodium hydroxide to obtain the leak-proof, long-life energy storage battery cooling concentrate.

[0042] Example 3

[0043] The leak-proof, long-life energy storage battery cooling concentrate of Example 3 has the following components by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 2.2 parts isodecanoic acid, 1 part octanoic acid, 30 parts glycerol, 2 parts potassium carbonate, and 1.2 parts boric acid. All components are stirred evenly, and the pH of the solution is adjusted to 8.6 with sodium hydroxide to obtain the leak-proof, long-life energy storage battery cooling concentrate.

[0044] Example 4

[0045] The leak-proof, long-life energy storage battery cooling concentrate of Example 4 has the following components by weight: 100 parts ethylene glycol, 0.5 parts methylbenzotriazole, 1 part azelaic acid, 1.2 parts isodecanoic acid, 0.6 parts n-octanoic acid, 18 parts glycerol, and 1.5 parts boric acid. All components are stirred evenly, and the pH of the solution is adjusted to 8.7 with potassium hydroxide to obtain the leak-proof, long-life energy storage battery cooling concentrate.

[0046] Example 5

[0047] The leak-proof, long-life energy storage battery cooling concentrate of Example 5 has the following components by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 1.2 parts azelaic acid, 0.7 parts isodecanoic acid, 0.35 parts octanoic acid, 30 parts glycerol, 20 parts potassium carbonate, and 1.4 parts boric acid. All components are stirred evenly, and the pH of the solution is adjusted to 8.5 with potassium hydroxide to obtain the leak-proof, long-life energy storage battery cooling concentrate.

[0048] Example 6

[0049] The leak-proof, long-life energy storage battery cooling concentrate of Example 6 has the following components by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 1.2 parts azelaic acid, 0.7 parts isodecanoic acid, 0.35 parts n-octanoic acid, 30 parts glycerol, 2 parts potassium carbonate, and 1.4 parts boric acid. All components are stirred evenly, and the pH of the solution is adjusted to 8.5 with sodium hydroxide to obtain the leak-proof, long-life energy storage battery cooling concentrate.

[0050] Comparative Example 1

[0051] The cooling concentrate of Comparative Example 1 has the following composition by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 1.2 parts azelaic acid, 0.7 parts isodecanoic acid, 0.35 parts octanoic acid, and 1.4 parts boric acid. All components are stirred until homogeneous, and the pH of the solution is adjusted to 8.5 with sodium hydroxide to obtain the cooling concentrate. Compared to Example 6, it does not contain glycerol or potassium carbonate.

[0052] Comparative Example 2

[0053] The cooling concentrate of Comparative Example 2 has the following components by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 1.2 parts azelaic acid, 0.7 parts isodecanoic acid, 0.35 parts n-octanoic acid, 30 parts glycerol, and 2 parts potassium carbonate. All components are stirred thoroughly, and the pH of the solution is adjusted to 8.5 with sodium hydroxide to obtain the cooling concentrate. Compared to Example 6, it does not contain boric acid.

[0054] Comparative Example 3

[0055] The cooling concentrate of Comparative Example 3 has the following composition by weight: 100 parts ethylene glycol, 0.25 parts methylbenzotriazole, 30 parts glycerol, 2 parts potassium carbonate, and 3.65 parts boric acid. All components were stirred until homogeneous, and the pH of the solution was adjusted to 8.5 with sodium hydroxide to obtain the cooling concentrate. Compared to Example 6, it does not contain organic acids, and the amount of boric acid added is 3.65 parts.

[0056] Comparative Example 4

[0057] The coolant concentrate provided in Comparative Example 4 is glysantin G30, which is an organic carboxylic acid technology coolant with a service life of 5 years when used in energy storage power stations.

[0058] Comparative Example 5

[0059] The coolant concentrate provided in Comparative Example 5 is Shell Long Life OAT coolant, which is an organic carboxylic acid technology coolant with a service life of 5 years when used in energy storage power stations.

[0060] The leak-proof, long-life energy storage battery coolant concentrates from Examples 1-6 were mixed with laboratory grade tertiary water to prepare a leak-proof, long-life energy storage battery coolant with a freezing point of -35°C.

[0061] Each comparative proportion of the cooling concentrate was mixed with laboratory grade tertiary water to prepare a cooling solution with a freezing point of -35°C.

[0062] According to SH / T 0069 "Determination of pH value of engine antifreeze, rust inhibitor and coolant", SH / T 0091 "Determination of reserve alkalinity of engine coolant and rust inhibitor", NB / SH / T 6047 "Electric vehicle coolant" SH / T0085 "Determination of corrosion of engine coolant (glassware method)" and QB / T 1323-1991 "Determination of surface tension of detergent by ring pulling liquid film method", the pH value, reserve alkalinity, metal corrosion performance and surface tension of the above coolant were tested. The specific test results are shown in Table 1 and Table 2.

[0063] Table 1. Coolant performance test results of Examples 1-6

[0064]

[0065] Table 2. Coolant performance test results for Comparative Examples 1–5

[0066]

[0067] As can be seen from Example 6 and Comparative Example 1, Example 6 of the present invention, compared with Comparative Example 1, can effectively increase the surface tension of the coolant due to the addition of surface tension enhancers such as glycerol and potassium carbonate, which can reduce leakage in microchannels, improve the intrinsic safety of the coolant, and prevent leakage. In addition, as can be seen from Examples 5 and 6, although the increase of surface tension enhancer can effectively improve surface tension and better prevent leakage, excessive dosage, especially excessive dosage of potassium carbonate, will cause poor corrosion resistance. Therefore, in the present invention, the preferred dosage of surface tension enhancer is 5-60 parts by weight, preferably 10-50 parts by weight (based on 100 parts by weight of ethylene glycol).

[0068] As can be seen from Example 6 and Comparative Examples 2-3: Comparative Example 2, due to the absence of boric acid, experienced a significant decrease in its reserve alkalinity and a reduction in its corrosion resistance (especially against aluminum); Comparative Example 3, by replacing the organic acid with the same mass of boric acid, showed a decrease in both reserve alkalinity and corrosion resistance; while Example 6 of the present invention, by using organic acid and boric acid simultaneously, effectively improved both reserve alkalinity and corrosion resistance, especially providing superior protection for aluminum, indicating that organic acid and boric acid have a synergistic effect in the present invention.

[0069] Furthermore, the coolant in Comparative Example 5 had a reserve alkalinity of 2.0 ml and a service life of 5 years. The coolant in Examples 1-6 of the present invention all had a reserve alkalinity of >4 ml, so it can be inferred that they have an extremely long service life. Even compared with Comparative Example 4, the coolant in Examples 1-6 of the present invention has a reserve alkalinity that is at least 31.5% higher, which has a significant ability to resist pH changes, improves the ability to resist acidification, and can effectively extend the service life.

[0070] Therefore, the high reserve alkalinity and high surface tension characteristics of the leak-proof, long-life energy storage battery coolant of the present invention effectively extend the service life of the energy storage battery coolant, prevent leakage problems such as those caused by tiny channels in welds, improve the safety performance of power batteries, and are applicable to non-direct contact temperature control systems with cold plates for lithium-ion batteries in energy storage power stations.

[0071] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

[0072] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0073] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0074] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0075] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

[0076] Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

Claims

1. A leak-proof, long-life energy storage battery cooling concentrate, comprising the following components: ethylene glycol, surface tension enhancer, buffer, benzotriazole compound, and organic acid.

2. The leak-proof, long-life energy storage battery cooling concentrate as described in claim 1, characterized in that: The surface tension enhancer is one or both of glycerol and potassium carbonate.

3. The leak-proof, long-life energy storage battery cooling concentrate as described in claim 1, characterized in that: The buffer is boric acid.

4. The leak-proof, long-life energy storage battery cooling concentrate as described in claim 1, characterized in that: The benzotriazole compounds are one or more of benzotriazole and its derivatives, preferably one or two of methylbenzotriazole and benzotriazole.

5. The leak-proof, long-life energy storage battery cooling concentrate as described in claim 1, characterized in that: The organic acid is one or more of monocarboxylic acids and dicarboxylic acids having 5-12 carbon atoms, preferably one or more of azelaic acid, isodecanoic acid, and octanoic acid.

6. The leak-proof, long-life energy storage battery cooling concentrate as described in claim 1, characterized in that: The leak-proof, long-life energy storage battery cooling concentrate also contains a pH adjuster; preferably, The pH adjuster is at least one of alkali metal hydroxides, preferably at least one of sodium hydroxide and potassium hydroxide; and / or, The pH adjuster adjusts the pH value of the leak-proof, long-life energy storage battery cooling concentrate to 7.5-11.0, preferably 7.5-10.

0.

7. The leak-proof, long-life energy storage battery cooling concentrate as described in any one of claims 1-6, characterized in that: The components of the leak-proof, long-life energy storage battery cooling concentrate are calculated based on ethylene glycol as 100 parts by weight. 5-60 parts by weight of surface tension enhancer; preferably 10-50 parts by weight; The buffer is 0.5-3.0 parts by weight; preferably 0.5-2.0 parts by weight. 0.05-2.0 parts by weight of benzotriazole compounds; preferably 0.15-1.5 parts by weight; 1.0-5.0 parts by weight of organic acid; preferably 1.5-4.5 parts by weight.

8. A method for preparing a leak-proof, long-life energy storage battery cooling concentrate as described in any one of claims 1-7, comprising the step of mixing components including ethylene glycol, a surface tension enhancer, a buffer, a benzotriazole compound, and an organic acid; preferably, The mixture includes components such as ethylene glycol, surface tension enhancer, buffer, benzotriazole compound and organic acid, and also includes a step of adding pH adjuster to adjust the pH value.

9. A leak-proof, long-life energy storage battery coolant, comprising the leak-proof, long-life energy storage battery coolant concentrate according to any one of claims 1-7 or the leak-proof, long-life energy storage battery coolant concentrate obtained by the preparation method according to claim 8, and water.

10. The application of a leak-proof long-life energy storage battery coolant as described in any one of claims 1-7, or a leak-proof long-life energy storage battery coolant obtained by the preparation method described in claim 8, or a leak-proof long-life energy storage battery coolant as described in claim 9, in the field of energy storage batteries.

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