CN115404046A - Flexible composite phase change material suitable for battery thermal management and preparation method and application thereof - Google Patents
Flexible composite phase change material suitable for battery thermal management and preparation method and application thereof Download PDFInfo
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- CN115404046A CN115404046A CN202211057954.7A CN202211057954A CN115404046A CN 115404046 A CN115404046 A CN 115404046A CN 202211057954 A CN202211057954 A CN 202211057954A CN 115404046 A CN115404046 A CN 115404046A
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- 239000012782 phase change material Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000007726 management method Methods 0.000 title description 20
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000012188 paraffin wax Substances 0.000 claims abstract description 37
- 239000005639 Lauric acid Substances 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/066—Cooling mixtures; De-icing compositions
-
- 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
-
- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
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- Materials Engineering (AREA)
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Abstract
The invention discloses a flexible composite phase change material suitable for battery thermal management and a preparation method and application thereof, and belongs to the technical field of lithium ion batteries. The flexible composite phase change material consists of lauric acid, paraffin and expanded graphite, wherein the mixture of the lauric acid and the paraffin phase change material provides a cooling effect by virtue of a lower melting point of the mixture, and the expanded graphite not only improves the thermal conductivity, but also prevents the lauric acid and the paraffin from leaking. The two side surfaces with the largest area of the single battery are covered by the flexible composite phase change material. The invention fully utilizes the latent heat of phase change of the phase change material to store energy, and satisfies the requirement that the lithium ion battery controls the highest temperature and the maximum temperature difference within the safe range under different working conditions.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a flexible composite phase change material suitable for battery thermal management and a preparation method and application thereof.
Background
Currently, the development of green energy storage and electric vehicles using renewable energy has become an inevitable trend in the future. However, the safety issues of lithium ion batteries have hindered their large scale application, especially the thermal runaway problem. In practical application, temperature is one of the key factors influencing the electrochemical performance of the lithium battery, and when the heat generated inside the battery cannot be released in time under the conditions of overcharge or internal short circuit, the temperature of the battery can rise rapidly, so that thermal runaway is caused, and finally, the battery is ignited and even explodes. To address the risk of thermal runaway propagation, the temperature of the lithium battery should be maintained between 20-50 ℃ during charging and discharging. In addition, the temperature difference in the battery pack must be controlled to be within 5 ℃, because the uneven distribution of the cell temperature may aggravate the decrease in the transport capacity and seriously deteriorate the cell performance. Therefore, it is very necessary to reliably protect the lithium ion battery from thermal runaway.
Phase change materials are of great interest because of their simple structure, stable performance, low cost and no additional consumption. Phase change materials can not only store and release large amounts of energy in the opposite form of latent heat, but also maintain a constant temperature during the solid-liquid phase change. The paraffin and the fatty acid have good thermal properties, such as strong heat storage capacity, relatively stable chemical properties, no toxicity, no corrosion and low price, so that the paraffin and the fatty acid become widely used heat storage materials and become research hotspots. However, the application of the single phase change material in a battery thermal management system is limited due to the problems of low thermal conductivity, high phase change temperature, easy leakage and the like of the single phase change material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a flexible composite phase change material suitable for battery thermal management and a preparation method and application thereof, so as to solve the technical problems that a single phase change material in the prior art is low in thermal conductivity coefficient, too high in phase change temperature and easy to leak, and cannot be suitable for a battery thermal management system.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a flexible composite phase change material suitable for battery thermal management, which is prepared from lauric acid, paraffin and expanded graphite according to the weight ratio of 42.5:42.5:15, and the weight ratio is 15.
The invention also discloses a preparation method of the flexible composite phase change material suitable for battery thermal management, which comprises the following steps:
1) Mixing lauric acid and paraffin, heating, and fully and uniformly stirring after completely melting to obtain a mixed system;
2) Adding expanded graphite into the mixed system prepared in the step 1), continuously stirring uniformly to uniformly distribute lauric acid and paraffin in the expanded graphite to obtain a powdery sample, and cooling and pressing into a sheet to obtain the flexible composite phase change material suitable for battery heat management.
Preferably, in step 1), lauric acid is mixed with paraffin wax and then heated to be completely melted under the condition of oil bath at 60 ℃.
Preferably, in step 1), the mixture is stirred thoroughly with a magnetic stirrer for at least 1 hour.
Preferably, in step 2), stirring is continued for at least 1 hour by using a magnetic stirrer.
Preferably, in step 2), the cooling time is 1 hour.
The invention discloses a battery heat management device made of the flexible composite phase change material suitable for battery heat management, which comprises a battery, wherein the flexible composite phase change material suitable for battery heat management is attached to two sides with the largest battery area.
Preferably, the battery is a single soft package lithium ion battery.
The invention also discloses application of the flexible composite phase change material suitable for battery thermal management in preparation of a temperature control material of a lithium ion single battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a flexible composite phase-change material suitable for battery thermal management, which consists of lauric acid, paraffin and expanded graphite, wherein the mixture of the lauric acid and the paraffin phase-change material provides a cooling effect with a lower melting point, and the expanded graphite not only improves the thermal conductivity, but also prevents the lauric acid and the paraffin from leaking. When the flexible composite phase-change material is applied to battery thermal management, the flexible composite phase-change material is attached to two sides with the largest area of a single battery, the flexible composite phase-change material absorbs heat emitted by the battery to enable the temperature of the battery to be rapidly reduced to a safe temperature range, the lauric acid and paraffin organic solid-liquid phase-change material is subjected to phase change after absorbing the heat emitted by the battery and is changed from a solid state to a liquid state, but because the expanded graphite serving as a supporting material has open and irregular reticular pores and superposed graphite flakes, the specific surface area of the pores with different sizes and shapes is increased, and enough space is provided for the permeation of the liquid paraffin and the lauric acid, so that the condition of the whole leakage of the phase-change material cannot occur. The invention makes full use of the latent heat of phase change of the phase change material to store energy, and satisfies the requirement that the lithium ion battery controls the highest temperature and the maximum temperature difference within the safe range under different working conditions, thereby being widely applied to the battery thermal management system, controlling the temperature of the battery during operation within the safe temperature range, and ensuring the performance and the service life of the battery.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a flexible composite phase-change material according to the present invention;
FIG. 2 is a schematic diagram of thermal management of a flexible composite phase change material;
FIG. 3 is a differential scanning calorimeter curve and thermal conductivity for a phase change material; in the figure, PA is a 100% lauric acid sample, SA is a 100% paraffin sample, (A1 (40% paraffin 60% lauric acid), A2 (50% paraffin 50% lauric acid), A3 (60% paraffin 40% lauric acid), B1 (5% expanded graphite 47.5% paraffin 47.5% lauric acid), B2 (10% expanded graphite 45% paraffin 45% lauric acid), B3 (15% expanded graphite 42.5% paraffin 42.5% lauric acid), B4 (20% expanded graphite 40% paraffin 40% lauric acid)); wherein a is a differential scanning thermogravimetric graph of the PA, SA, A1, A2 and A3 samples; b is the thermogravimetric plot of B1, B2, B3, B4; c is a graph of enthalpy value and melting temperature of the PA, SA, A1, A2 and A3 samples; d is a graph of enthalpy and melting temperature of B1, B2, B3 and B4; e is a thermal conductivity graph of the PA, SA, A1, A2 and A3 samples; f is a thermal conductivity diagram of B1, B2, B3 and B4;
FIG. 4 is a leakage curve and a cycle curve of a lauric acid-paraffin-expanded graphite composite phase-change material; wherein a is a leakage curve; b is a circulation curve;
fig. 5 is a temperature profile of a battery module with and without phase change cooling at different discharge rates (0.5, 1, 1.5C) and different ambient temperatures (20 ℃, 25 ℃, 30 ℃, and 35 ℃); wherein a is 0.5C; b is 1.0C; c is 1.5c; d is the temperature difference (difference between the highest and lowest temperatures) of the battery module at different discharge rates (0.5C, 1.0C, 1.5C).
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, which is a schematic view of a preparation process of the flexible composite phase change material of the present invention, paraffin and lauric acid are mixed, heated and melted in an oil bath, then fully and uniformly stirred, and then expanded graphite is added to continue to be uniformly stirred, and after standing, flexible composite phase change material powder is obtained, and then the mixture is pressed into a sheet, such that a block sample of the flexible composite phase change material is obtained.
Referring to fig. 2, which is a schematic diagram of a thermal management of a flexible composite phase change material, the composite phase change material is composed of lauric acid, paraffin and expanded graphite, a mixture of the lauric acid and the paraffin phase change material provides a cooling effect with a lower melting point, and the expanded graphite not only improves thermal conductivity, but also prevents leakage of the lauric acid and the paraffin. The flexible composite phase change material is pasted on two side faces with the largest area of the single battery, and the characteristics of phase change latent heat energy storage of the phase change material can be utilized, so that the highest temperature and the maximum temperature difference of the lithium ion battery are controlled within a safety range under different working conditions.
A preparation method of a flexible composite phase change material suitable for battery thermal management comprises the following steps:
step one, weighing 5g of lauric acid and 5g of paraffin wax according to the mass ratio of 1:1, putting the lauric acid and the paraffin wax into a beaker, putting the beaker into an oil bath pan at 60 ℃ for oil bath heating, and stirring for 1 hour by a magnetic stirrer after the lauric acid and the paraffin wax are completely molten;
in the second step, 1.75g mass of expanded graphite was then added to the beaker and further stirred for 1 hour to uniformly distribute the lauric acid and paraffin wax in the expanded graphite. The obtained powdery sample was cooled for 1 hour and compressed into a tablet by a tablet press to obtain a block-shaped sample.
The flexible composite phase change material prepared in the embodiment is detected, and as a result, referring to fig. 3 and 4, when the mass ratio of lauric acid to paraffin is controlled to be 1:1, the enthalpy value of the lauric acid-paraffin composite material reaches a maximum value of 223.1J/g. When the lauric acid-paraffin composite material (the mass ratio is 1:1) is added into the expanded graphite matrix, as the mass fraction of the expanded graphite is increased from 5 percent to 20 percent, the enthalpy value of the lauric acid-paraffin-expanded graphite is gradually reduced from 178.7J/g to 125.8J/g, and the leakage rate is reduced from 1.452 percent to 0.238 percent. In comprehensive comparison, the lauric acid-paraffin-expanded graphite composite phase-change material (B3) with an expanded graphite content of 15% is the most effective. After 100 cycles, the melting temperature of sample B3 was still maintained at 36.5 deg.C, an enthalpy of 122.7J/g, and a loss per cycle of 0.0016%, indicating good stability.
When the flexible composite phase-change material works, the mixing ratio of the lauric acid to the paraffin is determined to be 1:1, then the mass fraction of the synthetic expanded graphite is determined to be 15%, and the materials are mixed to prepare the flexible composite phase-change material. The flexible composite phase change material is attached to a battery provided with a thermocouple, and is connected with a charge-discharge instrument through a lead and placed in a thermostat until the temperature of the thermocouple is consistent with that of the thermostat for experiment. The temperature of the incubator (20 ℃, 25 ℃, 30 ℃, 35 ℃) and the discharge rate (0.5C, 1.0C, 1.5C) were varied to obtain the desired temperature rise curves.
Referring to fig. 5, the battery temperature rises sharply when there is no phase change cold, and particularly when the discharge rate is higher than 1.0C, the battery temperature exceeds the safety temperature threshold of 50℃, which is not favorable for the continuous safety discharge of the battery. In sharp contrast, batteries using phase change cooling exhibit good cooling performance, maintaining temperatures at about 40 ℃, thereby improving safety and extending the cycle life of the battery. In addition, the cell temperature difference is another important indicator of cell thermal management. Without phase change cooling, the cell temperature difference (high and low temperature differences between the five measurement points) is as high as 9.33 ℃, which would impair cell performance. However, under the phase change cooling system, the temperature difference of the battery is controlled within 2 ℃, which shows that the phase change material not only can effectively control the discharge temperature of the lithium battery, but also can uniformly manage the temperature of the battery.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (9)
1. A flexible composite phase change material suitable for battery thermal management is characterized in that the flexible composite phase change material is prepared from lauric acid, paraffin and expanded graphite according to a weight ratio of 42.5:42.5:15, and the weight ratio is 15.
2. The method for preparing the flexible composite phase change material suitable for battery thermal management according to claim 1, comprising the following steps:
1) Mixing lauric acid and paraffin, heating, and fully and uniformly stirring after completely melting to obtain a mixed system;
2) Adding expanded graphite into the mixed system prepared in the step 1), continuously stirring uniformly to uniformly distribute lauric acid and paraffin in the expanded graphite to obtain a powdery sample, and pressing the powdery sample into a sheet after cooling to prepare the flexible composite phase change material suitable for battery thermal management.
3. The method for preparing the flexible composite phase change material suitable for battery thermal management according to claim 2, wherein in the step 1), the lauric acid is mixed with the paraffin and then heated to be completely molten under the condition of oil bath at 60 ℃.
4. The preparation method of the flexible composite phase change material suitable for battery thermal management according to claim 2, wherein in the step 1), the mixture is fully stirred for at least 1 hour by using a magnetic stirrer.
5. The preparation method of the flexible composite phase change material suitable for battery thermal management according to claim 2, wherein in the step 2), the mixture is continuously stirred uniformly for at least 1 hour by using a magnetic stirrer.
6. The preparation method of the flexible composite phase change material suitable for battery thermal management according to claim 2, wherein in the step 2), the cooling time is 1 hour.
7. A battery thermal management device made of the flexible composite phase change material suitable for battery thermal management according to claim 1, wherein the device comprises a battery, and the flexible composite phase change material suitable for battery thermal management is attached to two sides of the largest area of the battery.
8. The battery thermal management device of claim 8, wherein the battery is a single pouch lithium ion battery.
9. The application of the flexible composite phase change material suitable for battery thermal management in preparing a temperature control material of a lithium ion single battery according to claim 1.
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|---|---|---|---|---|
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2022
- 2022-08-30 CN CN202211057954.7A patent/CN115404046A/en active Pending
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