CN108288739B - Thermal management module for cylindrical battery, preparation method of thermal management module and battery pack - Google Patents
Thermal management module for cylindrical battery, preparation method of thermal management module and battery pack Download PDFInfo
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- CN108288739B CN108288739B CN201611127547.3A CN201611127547A CN108288739B CN 108288739 B CN108288739 B CN 108288739B CN 201611127547 A CN201611127547 A CN 201611127547A CN 108288739 B CN108288739 B CN 108288739B
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- 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
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
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- 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
- H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
- H01M10/625—Vehicles
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- 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
- H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
- H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a thermal management module for a cylindrical battery, a preparation method thereof and a battery pack, wherein the thermal management module comprises a thermal management material forming body, and a plurality of cylindrical holes for accommodating the cylindrical battery are formed in the thermal management material forming body; the heat management material forming body is made of a heat management material through a forming method; the heat management material comprises the following components in percentage by mass: 55-90% of phase-change material; 4-20% of heat-conducting filler; 4-20% of a flame retardant; 2-10% of short fibers. The chopped fibers are added into the heat management module, so that the heat management module can play an effective reinforcing role, the content of the phase-change material in the heat management material can be improved to a greater extent, the heat storage capacity of the heat management module is further improved, and the temperature regulation and control of the heat management module are more stable.
Description
Technical Field
The invention relates to the technical field of battery thermal management, in particular to a thermal management module for a cylindrical battery, a preparation method of the thermal management module and a battery pack.
Background
Batteries, such as secondary batteries, have been widely used as energy sources for wireless mobile devices, for example, as power sources for electric vehicles, hybrid electric vehicles, and plug-in hybrid electric vehicles, etc., in order to solve problems, such as air pollution, caused by vehicles using petroleum fuel. A small-sized wireless mobile device may use one or more battery cells, while a middle-or large-sized wireless device, such as a vehicle, may use a middle-or large-sized battery module including a plurality of battery cells electrically connected with each other, such middle-or large-sized battery module is generally manufactured to have as small a size and weight as possible, and thus the integration of the battery cells stacked in the battery module is very high.
The charging characteristics of the battery vary at elevated temperatures and can lead to a significant reduction in battery cycle life if charged at excessive temperatures. For example, the cycle life of some lithium-based batteries decreases by more than 50% if repeatedly charged at about 50 ℃. Since cycle life can be greatly reduced, the life cost of the battery can be greatly increased if the charging temperature is not controlled within appropriate limits. Moreover, some high performance batteries exhibit reduced performance and may be damaged if charged or operated at too low a temperature, e.g., below about-30 ℃. In addition, batteries and battery arrays may experience thermal events that permanently damage or destroy the batteries, and may even cause safety-related events such as fires, explosions, etc. when temperature conditions are exceeded. If the temperature of the working environment is too high, the side surface of the battery case of the cylindrical battery inevitably swells, which not only causes problems such as difficulty in mounting the battery to a machine using the battery, but also causes problems such as an increase in dead space due to the provision of the swelling space. Therefore, thermal management of the battery is generally required to control the operating ambient temperature of the battery.
Currently, battery thermal management systems are generally classified into air-cooled and water-cooled types. The air-cooled type also comprises a natural air-cooled type and a forced air-cooled type, wherein the natural convection cooling mode is adopted for heat dissipation of the battery in the former mode, and the forced convection cooling mode of an electronic fan is generally adopted for heat dissipation in the latter mode. The scheme of the air-cooled heat management device is single, the heat dissipation of the battery is considered more, and the preheating function of the battery in cold starting is blank. Moreover, the prior art has the following problems: (1) the forced convection cooling mode has a remarkable cooling and heat dissipation effect on the power battery close to the electronic fan due to the fact that a ventilating duct is not designed, but the power battery far away from the electronic fan is difficult to effectively cool and dissipate, so that the internal temperature of each battery monomer in the battery box is uneven, and the power battery cannot be efficiently cooled due to the natural convection cooling mode; (2) the preheating function is not provided, and the service life of the power battery can be seriously influenced after the battery is forcibly cold started; (3) the air quantity entering the battery modules has large difference, and the heat generation and heat dissipation environments of the modules are different, so that the battery modules work at different environmental temperatures, the temperature difference among the modules is increased rapidly, the temperature difference among the modules causes the inconsistency of the battery performance, and the performance and the service life of the whole battery module are influenced finally. At present, the battery rarely uses a water-cooling method to realize heat management, because the water-cooling structure is often more complicated and has higher cost, and the danger of leakage of condensed water also exists.
Phase Change Materials (PCMs) are smart materials that absorb or emit heat when a substance undergoes a phase change, while the substance itself does not change or does not change much in temperature. Due to the unique functions of self-adaptive environmental temperature regulation and control and the like, the solar energy heat-storage air conditioner is widely applied to the fields of energy sources, materials, aerospace, textiles, electric power, medical instruments, buildings and the like, such as solar energy utilization, industrial waste heat and waste heat recovery, building energy conservation, constant-temperature clothes, cold and heat storage air conditioners, constant temperature of electric devices and the like.
Phase change materials can be mainly classified into solid-solid phase change materials, solid-liquid phase change materials, solid-gas phase change materials, and liquid-gas phase change materials according to their phase change processes. The volume change is large during solid-gas phase change and liquid-gas phase change, the device is complex during use, the practical application is not facilitated, and the research is less at present. The solid-liquid phase change has small volume change, larger latent heat, good energy storage and wide phase change temperature range, and is widely applied in practice. Solid-liquid phase change materials, however, suffer from serious problems of melt flow and migration by infiltration and must therefore be packaged in containers for use, thereby increasing the cost of the system and greatly limiting its applicability. From the practical application point of view, the solid-solid phase change does not need a complex using device, does not need a packaging container with good sealing performance, and has wider application occasions and relatively lower system cost. Therefore, it has been proposed to use phase change materials to achieve battery thermal management.
Phase change composites comprising: A) 30-65% of phase-change material, which is low-melting-point paraffin and/or dodecanol with a melting point of 25-45 ℃; B) 25-45% of a carrier material which is high density polyethylene and/or ethylene-vinyl acetate copolymer; C) 5-15% of inorganic filler which is porous substance and is selected from one or more of expanded perlite and expanded graphite; D) 1-10% of a thermal conductivity enhancer; and E) 1-10% of a flame retardant, wherein the phase change material, the inorganic filler, the thermal conductivity enhancer and the flame retardant are dispersed in a spatial network structure formed by the carrier material. However, the phase-change composite material disclosed by the patent contains porous inorganic filler and has high carrier material content, so that the phase-change material content is relatively low, the heat storage capacity is poor, and the phase-change composite material is only suitable for being used as a building material such as a wall heat-insulating material.
Therefore, the use of phase change materials for battery thermal management still has many problems, such as low thermal conductivity and poor thermal conductivity, which easily cause the following problems:
1) when a certain single battery is overheated, heat cannot be effectively removed, so that temperature unevenness among the single batteries in the battery pack is easily caused;
2) when the temperature of the battery pack is continuously increased, the temperature of the whole battery pack exceeds the tolerance temperature, so that the battery module is accelerated to deteriorate, the service life is further shortened, and some battery packs even catch fire or explode to bring about greater potential safety hazards;
3) if the battery pack works at a high temperature for a long time, the output power of the battery pack is greatly reduced along with the increase of the temperature, so that the battery pack cannot fully exert the maximum performance.
In addition, these thermal management materials have problems of poor flame retardancy, easy combustion, poor shape stability and cycle stability of the resulting module, and easy bleeding of the surface of the module. Therefore, a cylindrical battery is highly in need of a battery thermal management solution capable of solving the above problems.
Disclosure of Invention
In order to solve one or more of the above problems, the present invention provides a thermal management module for a cylindrical battery, a method of manufacturing the same, and a battery pack.
The purpose of the invention is realized by the following technical scheme:
1. a thermal management module for a cylindrical battery comprising a shaped body of thermal management material having a plurality of cylindrical holes formed therein for receiving cylindrical batteries; the heat management material forming body is made of a heat management material through a forming method; the heat management material comprises the following components in percentage by mass:
2. the thermal management module of claim 1, wherein:
the phase change material is one material selected from the group consisting of higher aliphatic hydrocarbons having 18 to 26 carbon atoms, higher aliphatic alcohols having 12 to 18 carbon atoms, paraffin-type paraffin having a melting point of 25 to 55 ℃, and polyethylene glycol having a molecular weight of 800 to 20000; preferably, the phase change material is selected from the group consisting of higher aliphatic hydrocarbons having 18 to 26 carbon atoms and paraffin type paraffins having a melting point of 30 to 55 ℃; more preferably, the phase change material is paraffin type wax having a melting point of 30 to 55 ℃; and/or
The content of the phase-change material is 66-90%, and more preferably 70-90%; and/or
The heat-conducting filler is selected from the group consisting of aluminum powder, copper powder, graphite powder, nano aluminum nitride, heat-conducting carbon fiber, graphene and expanded graphite; preferably, the thermally conductive filler is selected from the group consisting of thermally conductive carbon fibers, graphene, expanded graphite; more preferably, the thermally conductive filler is selected from the group consisting of graphene and expanded graphite; and/or
The content of the heat-conducting filler is 5-10%; and/or
The flame retardant is selected from the group consisting of decabromodiphenyl ether, ammonium polyphosphate, silicone flame retardant, ammonium polyphosphate/montmorillonite nanocomposite, pentaerythritol, zinc borate, terpene resin, antimony trioxide and melamine; preferably, the flame retardant is made of decabromodiphenyl ether, antimony trioxide and terpene resin; and/or
The content of the flame retardant is 5-20%, and more preferably 10-15%; and/or
The chopped fiber is selected from the group consisting of chopped carbon fiber, chopped glass fiber, chopped quartz fiber, chopped mullite fiber, chopped aramid fiber, chopped nylon fiber, chopped polyester fiber and the like; preferably, the chopped fibers are selected from the group consisting of chopped carbon fibers, chopped glass fibers, and chopped quartz fibers; more preferably, the chopped fibers are selected from the group consisting of chopped glass fibers and chopped quartz fibers; and/or
The content of the chopped fibers is 2-5%; and/or the length of the chopped fiber is 2-10 mm, and more preferably 3-5 mm; and/or the diameter of the chopped fiber is 2-50 mu m.
3. The heat management module according to claim 1, wherein the heat management material further comprises 0-20% by mass of an oil absorbent.
4. The thermal management module of claim 3, wherein the oil absorbent is a hydrogenated styrene-butadiene-styrene elastomer and/or high density polyethylene; and/or the content of the oil absorbent is 5-15%.
5. The thermal management module of claim 1, wherein the cylindrical bore is in interference fit with the received cylindrical battery; the hole center distance L of the cylindrical hole and the hole diameter D meet the following relation:
L＝D+T；
wherein the value of T is 1-10 mm.
6. The thermal management module of any of claims 1-5, further comprising a graphite sealing layer on the upper and lower surfaces of the thermal management material form.
7. The thermal management module of claim 6, wherein the sealing layer of graphite is formed by direct molding of vermicular expanded graphite in a molding process of the thermal management material molding, and the sealing layer of graphite is left open in the region corresponding to the cylindrical holes.
8. The thermal management module according to claim 6, wherein the outer surface of the thermal management module is further covered with an insulating layer, and an opening is reserved in an area of the insulating layer corresponding to the cylindrical hole.
9. The method for manufacturing a thermal management module for a cylindrical battery according to any one of claims 1 to 8, comprising the steps of:
(1) laying the thermal management material in the inner cavity of the mold; optionally, when the graphite sealing layer is arranged, firstly paving a layer of graphite powder at the bottom of the inner cavity of the mold, then paving the heat management material, and then paving a layer of graphite powder on the heat management material;
(2) placing the die in an oven for preheating after die assembly;
(3) pressing and forming;
(4) and (4) after cooling, disassembling the die, taking out the prefabricated block, and optionally wrapping an insulating film on the outer surface to obtain the thermal management module for the cylindrical battery.
10. A battery pack comprising a thermal management module for cylindrical batteries according to any of claims 1 to 8, and a plurality of cylindrical batteries received in cylindrical holes of the thermal management module.
The implementation of the thermal management module for the cylindrical battery, the preparation method thereof and the battery pack has the following beneficial effects:
(1) the thermal management module for the cylindrical battery has good heat conducting performance and a temperature control function, can be used for thermal management of power batteries, communication base station batteries and battery packs of other cylindrical batteries, and when the single batteries in the battery packs are overheated, the thermal management material can effectively absorb heat and conduct and diffuse rapidly, so that the temperature uniformity among the single batteries in the battery packs is ensured.
(2) When the overall temperature of the battery pack is too high, the heat management module can absorb excessive heat to play a role in preventing overtemperature; when the temperature of the battery pack is too low, the heat management module can release the heat energy stored in the heat management module, and the battery pack is prevented from reducing the efficiency of the battery due to the too low temperature. Therefore, the thermal management module can ensure that the operating temperature of the battery pack does not exceed the tolerance temperature, prolong the service life and improve the safety of the battery pack.
(3) According to the invention, the temperature of the battery pack is regulated and controlled by the thermal management module, so that the battery pack can operate within a rated temperature range, and the overall efficiency of the battery pack is improved.
(4) According to the invention, the upper surface and the lower surface of the thermal management material forming body are sealed by adopting the expanded graphite, so that on one hand, the heat conduction from the square battery to the thermal management material can be promoted, and on the other hand, the problem that the phase change material in the thermal management material seeps out after the phase change material is melted and changed is solved.
(5) The heat management material adopted by the invention contains the chopped fibers, can play an effective reinforcing role, and can resist the destructive effect caused by volume expansion and shrinkage in the processes of repeated melting, solidification and phase change of the module; therefore, the content of the phase-change material in the heat management material can be greatly improved, and the heat storage capacity of the heat management material is further improved, so that the temperature regulation and control of the heat management material are more stable.
(6) The heat management material components adopted by the invention contain the efficient flame retardant, so that the combustion problem of the battery pack caused by accidents can be effectively prevented, and the safety performance of the battery pack is greatly improved.
(7) The heat management material component adopted by the invention can be added with or without an oil absorbent, and when high oil absorption resins such as hydrogenated styrene-butadiene-Styrene Elastomer (SEBS) and/or High Density Polyethylene (HDPE) and the like are adopted, the high oil absorption resins can play a shaping role in the phase change material, so that the problems of serious flowing and exudation after the melting phase change of the high oil absorption resins are avoided.
(8) The efficient heat management material and the efficient heat management module belong to passive heat management, do not need additional energy consumption and have the advantage of energy conservation; and the performance is excellent, the preparation process is simple, and the mass production is easy.
Drawings
Fig. 1 is a perspective view illustrating a thermal management module for a prismatic battery according to a first embodiment of the present invention;
fig. 2 is a top view of a thermal management module for a prismatic battery provided in accordance with a first embodiment of the present invention;
FIG. 3 is a cross-sectional view taken along line A-A of FIG. 2;
fig. 4 is a perspective view illustrating a thermal management module for a prismatic battery according to a second embodiment of the present invention;
fig. 5 is a cross-sectional view of a thermal management module for a prismatic battery provided in accordance with a second embodiment of the present invention;
fig. 6 is a perspective view illustrating a thermal management module for prismatic batteries according to a third embodiment of the present invention;
fig. 7 is a cross-sectional view of a thermal management module for a prismatic battery provided in accordance with a third embodiment of the present invention;
fig. 8 is a pictorial picture of a thermal management module for a cylindrical battery made in accordance with the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As described above, the present invention provides in a first aspect a thermal management module for a cylindrical battery. Referring to fig. 1 to 3, fig. 1 and 2 are a perspective view and a top view of a thermal management module for a cylindrical battery according to a first embodiment of the present invention, respectively, and fig. 3 is a cross-sectional view taken along line a-a in fig. 2. As shown in the drawing, the thermal management module for a cylindrical battery provided by this embodiment includes a thermal management material molding body 1.
Wherein, the heat management material forming body 1 is prepared from a heat management material by a forming method; preferably, the mold is pressed in a predetermined mold by a press molding method. The thermal management material comprises a phase change material, a thermally conductive filler, a flame retardant, and chopped fibers. The shaped body 1 of thermal management material is provided with a plurality of cylindrical holes 11 for receiving cylindrical batteries. Preferably, the cylindrical holes 11 are perpendicular to the upper and lower surfaces of the thermal management material shaped body 1. The thickness of the shaped body 1 of thermal management material can be set as desired.
In some preferred embodiments, the heat management material molded body 1 is formed by molding heat management material powder, and the heat management material comprises the following components in percentage by mass:
in some preferred embodiments, the phase change material employed in the present invention has a melt phase transition temperature of 25 to 55 ℃ (e.g., 25, 30, 35, 40, 45, 50, or 55 ℃) and/or a latent heat of phase change of 160 to 270kJ/kg (e.g., 160, 180, 200, 240, or 270 kJ/kg).
In some more preferred embodiments, the phase change material is one selected from the group consisting of higher aliphatic hydrocarbons having 18 to 26 carbon atoms (e.g., 18, 20, 22, 24, or 26 carbon atoms), higher aliphatic alcohols having 12 to 18 carbon atoms (e.g., 12, 14, 16, 17, or 18 carbon atoms), paraffin-type paraffins having a melting point of 25 to 55 ℃ (e.g., 25, 30, 35, 40, 45, 50, or 55 ℃), polyethylene glycols having a molecular weight of 800 to 20000 (e.g., a molecular weight of 800, 1000, 5000, 15000, or 20000). Preferably, the phase change material is selected from the group consisting of higher aliphatic hydrocarbons having 18 to 26 carbon atoms (e.g., having 18, 20, 22, 24, or 26 carbon atoms) and paraffin-type paraffins having a melting point of 30 to 55 ℃ (e.g., having a melting point of 30, 35, 40, 45, 50, or 55 ℃); more preferably, the phase change material is an alkane type paraffin having a melting point of 30 to 55 ℃ (e.g., melting point of 30, 35, 40, 45, 50 or 55 ℃).
In some preferred embodiments, the phase change material is present in the thermal management material at 66-90% (e.g., 66%, 70%, 75%, 80%, 85%, or 90%) by mass. Preferably, the phase change material is 70 to 90% (e.g., 70%, 75%, 80%, 85%, or 90%) by mass, and more preferably 75 to 85% (e.g., 75%, 80%, or 85%) by mass. The heat management material adopted by the invention has higher content of the phase change material, and can absorb excessive heat to the maximum extent to play a role in preventing overtemperature when the temperature of the battery pack is overhigh; when the temperature of the battery pack is too low, the heat energy stored in the battery pack can be released, and the battery pack is prevented from reducing the efficiency of the battery due to too low temperature. Therefore, the efficient thermal management module has high thermal conductivity, can effectively control the temperature difference between the single batteries in the battery pack within a certain range, and improves the overall efficiency of the battery pack.
In some preferred embodiments, the thermally conductive filler is selected from the group consisting of aluminum powder, copper powder, graphite powder, nano aluminum nitride, thermally conductive carbon fiber, graphene, expanded graphite; preferably, the thermally conductive filler is selected from the group consisting of thermally conductive carbon fibers, graphene, expanded graphite; more preferably, the thermally conductive filler is selected from the group consisting of graphene and expanded graphite. More preferably, the mass percentage of the heat conductive filler is 5-10% (e.g., 5%, 8%, or 10%).
In some preferred embodiments, the flame retardant is selected from the group consisting of decabromodiphenyl oxide (DBDPO), ammonium polyphosphate (APP), silicone flame retardants, ammonium polyphosphate/montmorillonite (APP/MMT) nanocomposites, Pentaerythritol (PER), zinc borate, terpene resins, antimony trioxide (Sb), and mixtures thereof2O3) Melamine (MA). The flame retardant can be a single substance or a flame retardant system consisting of a plurality of substances. For example, one of decabromodiphenyl oxide (DBDPO), ammonium polyphosphate (APP), silicone flame retardant, and ammonium polyphosphate/montmorillonite (APP/MMT) nanocomposite is used alone as a flame retardant. For example, decabromodiphenyl oxide (DBDPO) is used as a main component of the flame retardant, and antimony trioxide (Sb) is added2O3) As synergist, improve the flame retardant efficiency of decabromodiphenyl oxide (DBDPO), wherein the decabromodiphenyl oxide (DBDPO) and antimony trioxide (Sb)2O3) The mass ratio of (A) to (B) is 3: 1. As another example, intumescent flame retardant systems are used, typically consisting of a gas source, an acid source and a char-forming agent, for example, ammonium polyphosphateAPP) is used as an acid source and also can play a role of a gas source, and Pentaerythritol (PER) is used as a carbon forming agent. Wherein the char-forming agent may also be replaced by zinc borate or a terpene resin, and the gas source may also be provided by Melamine (MA). More preferably, the flame retardant in the present invention is made of decabromodiphenyl ether, antimony trioxide and terpene resin, wherein decabromodiphenyl ether (DBDPO), antimony trioxide (Sb)2O3) The mass ratio of the terpene resin to the terpene resin is preferably (2-3):1:1, more preferably 3:1: 1. Experiments prove that the flame retardant with the mass ratio can obtain better flame retardant effect.
In some preferred embodiments, the flame retardant is present in the heat management material in an amount of 5 to 20% (e.g., 5%, 10%, 12%, 15%, or 20%) by weight, and more preferably 10 to 15% (e.g., 10%, 12%, or 15%) by weight. The efficient flame retardant added in the material components can effectively prevent the combustion problem of the battery pack caused by accidents, and greatly improve the safety performance of the battery pack.
In some preferred embodiments, the chopped fibers are selected from the group consisting of chopped carbon fibers, chopped glass fibers, chopped quartz fibers, chopped mullite fibers, chopped aramid fibers, chopped nylon fibers, chopped polyester fibers, and the like. Preferably, the chopped fibers are selected from the group consisting of chopped carbon fibers, chopped glass fibers, and chopped quartz fibers; the chopped carbon fibers can be heat-conducting carbon fibers or non-heat-conducting carbon fibers, and the non-heat-conducting carbon fibers are more preferably used. Compared with the thermal conductive carbon fiber, the chopped fiber is made of the non-thermal conductive carbon fiber, so that the raw material cost of the thermal management material can be effectively reduced, and the thermal management material is added with the thermal conductive filler with the mass percentage of 4-20%, so that the thermal conductive performance requirement of the whole thermal management material can be met by adopting the non-thermal conductive carbon fiber. More preferably, the chopped fibers are selected from the group consisting of chopped glass fibers and chopped quartz fibers.
In some preferred embodiments, the chopped fibers are present in the thermal management material in an amount of 2 to 5% (e.g., 2%, 4%, or 5%) by weight; the length of the adopted chopped fiber is 2-10 mm (such as 2, 4, 6, 8 or 10mm), and more preferably 3-5 mm; the chopped fibers have a diameter of 2 to 50 μm (e.g., 2, 10, 20, 30, 40, or 50 μm). The chopped fibers contained in the heat management material can play an effective reinforcing role and resist the damage caused by volume expansion and shrinkage in the processes of repeated melting, solidification and phase change of the heat management material in use.
In some more preferred embodiments, the thermal management material for a cylindrical battery of the present invention further comprises 0 to 20% (e.g., 0, 1%, 5%, 10%, 15%, or 20%) by mass of an oil absorbent, more preferably 5 to 15% (e.g., 5%, 10%, or 15%). Preferably, the oil absorbent is a hydrogenated styrene-butadiene-Styrene Elastomer (SEBS) and/or High Density Polyethylene (HDPE). According to the invention, the high oil absorption resin such as hydrogenated styrene-butadiene-Styrene Elastomer (SEBS) and/or High Density Polyethylene (HDPE) is added, so that the phase change material can be shaped, and the problems of serious flow and seepage after the melting phase change of the phase change material are avoided. Further, the inventors have found that when a substance having a strong electrical conductive property such as expanded graphite is selected as the heat conductive filler, the heat management material is liable to cause short-circuiting between the cells during application. Therefore, the invention adds a certain amount of oil absorbent on the basis of adopting the heat-conducting filler such as the expanded graphite, and the like, and can play a role in further wrapping and insulating the expanded graphite and the like, so that the resistivity of the prepared heat management material is improved to 10 from a few ohms7And the ohm level meets the application requirement.
More preferably, the oil absorbent is made of hydrogenated styrene-butadiene-Styrene Elastomer (SEBS) and High Density Polyethylene (HDPE) in a mass ratio of 1:2 to 1:3, enabling optimal material properties to be achieved. On the one hand, the phase-change material is changed into a liquid state after melting and phase-changing, and loses strength and shape. In order to solve the problem, the invention adopts a method of adding High Density Polyethylene (HDPE) into a phase-change material such as paraffin, and forms a high molecular alloy by utilizing the similar compatibility principle of the HDPE and the paraffin. In the specific application process, the phase change material is melted and phase-changed at 40-50 ℃, and the high-melting-point HDPE (the melting point is more than 170 ℃) is not melted, so that the liquid paraffin phase change material is supported by the framework, and the paraffin phase change material is shaped and maintained in strength. On the other hand, the phase-change material is changed into liquid after melting and phase-changing, and is easy to seep out from the surface of a component, thereby seriously influencing the product performance and quality reliability. Aiming at the problem, the invention adopts a method of adding the oil-absorbing resin SEBS into the phase-change material such as paraffin, and utilizes the high oil-absorbing property of the SEBS to absorb and encapsulate the liquid phase-change material, thereby solving the problem of the surface seepage of the phase-change material member and meeting the application requirement.
In some more preferred embodiments, the thermal management material for a cylindrical battery is made from the following raw materials: 75-85% of phase change material, 5-10% of heat conducting filler, 5-15% of flame retardant, 2-5% of chopped fiber and 3-13% of oil absorbent. The heat management material with the mass ratio has the advantages of high heat conductivity, good temperature uniformity of the battery pack, good flame retardant property, high shape stability and difficult seepage.
According to the invention, by adding a proper amount of chopped fibers, the deformation of the material caused by volume expansion or contraction can be effectively prevented, so that the content of the phase-change material in the heat management material can be greatly improved, the heat storage capacity of the heat management material is further improved, and the temperature regulation and control of the heat management material are more stable. On the other hand, the invention can realize the function of the carrier by short-cut fibers without adding oil absorbent or adding a small amount of oil absorbent, thereby effectively reducing the volume of the material and improving the heat-conducting property and the mechanical strength of the product.
In some preferred embodiments of the invention, the cylindrical hole of the shaped body 1 of thermal management material is sized to match the size of the cylindrical battery to be housed, with an interference fit. The number of cylindrical holes is determined by the number of single cells of the battery pack, and an X Y array (X, Y ≧ 1) is formed, as shown in FIG. 2. The invention can provide thermal management modules of various specifications, such as 13 × 10 and 30 × 40. Preferably, the hole center distance L of the cylindrical hole and the hole diameter D satisfy the following relationship:
L＝D+T；
wherein the value of T is 1-10 mm; that is, the thickness of the hole wall between the holes in the molded heat management material 1 is 1 to 10mm (for example, 1, 3, 5, 8, or 10 mm). The size of the cylindrical hole is designed to be the optimal size, and the cylindrical battery can be well equalized in temperature.
Referring to fig. 4 to 5, fig. 4 and 5 are a perspective view and a cross-sectional view of a thermal management module for a cylindrical battery according to a second embodiment of the present invention, respectively. As shown in the drawing, the second embodiment provides a thermal management module for a cylindrical battery which is substantially the same as the first embodiment except that the thermal management module includes a thermal management material molded body 1 and graphite sealing layers 2 on the upper and lower surfaces of the thermal management material molded body 1.
The sealing layer 2 of graphite is preferably formed by direct compression moulding of vermicular expanded graphite in the compression moulding of the shaped body of thermal management material. The graphite sealing layer 2 is opened in the region corresponding to the cylindrical hole. The diameter of the pores of the expanded graphite is 10-100 nm, and the expanded graphite is a good sealing material. The graphite sealing layer 12 preferably has a thickness of 20 to 100 μm (e.g., 20, 40, 60, 80, or 100 μm). The graphite sealing layer 2 made of the expanded graphite can well seal the heat management material forming body 1 and prevent the phase change material from leaking in the heat absorption process. It is also possible to promote heat conduction between the prismatic battery 2 and the thermal management material, and to improve thermal conductivity. In addition, the content of the phase-change material in the thermal management material is high, so that the thermal management module 1 has high thermal conductivity, the temperature difference between the single batteries in the battery pack can be effectively controlled within a certain range, and the overall efficiency of the battery pack is improved.
Referring to fig. 6 and 7, a perspective structural view and a sectional view of a thermal management module for a cylindrical battery according to a third embodiment of the present invention are respectively provided. As shown in fig. 6 and 7, the thermal management module for a cylindrical battery of this battery pack is substantially the same as the second embodiment except that the entire external surface of the thermal management module is covered with the insulating film 3, that is, the insulating film 3 is covered on the graphite sealing layer 2 on the side surface and the upper and lower surfaces of the thermal management material molded body 1. And the insulating layer is left open in the region corresponding to the cylindrical hole 11 to facilitate the subsequent mounting of the cylindrical battery. Preferably, the insulating film 3 is formed by sticking and wrapping a film with an insulating property and a single-sided tape. The thickness of the insulating film is 25 to 100 μm (for example, 25, 40, 50, 65, 80 or 100 μm). The insulating film 13 is selected from the group consisting of polyethylene terephthalate (PET), polyvinyl chloride (PVC), Polyimide (PI), Polyethylene (PE), polyvinylidene fluoride (PVDF), and Polytetrafluoroethylene (PTFE). More preferably polyethylene terephthalate (PET) or polyvinyl chloride (PVC). The insulating film 13 can perform an effective insulating function to prevent the battery pack from being dangerous due to leakage during storage and use.
The present invention provides, in a second aspect, a method for manufacturing a thermal management module for a cylindrical battery according to the first aspect, comprising the steps of:
(1) laying the thermal management material in the inner cavity of the mold; preferably, a core is provided in the mold in a position corresponding to the cylindrical hole.
(2) Placing the die in an oven for preheating after die assembly; preferably, the preheating is to above 10 ℃ above the melting point of the phase change material, preferably from 10 to 20 ℃ above the melting point of the phase change material, when no oil absorbent is added to the heat management material. When an oil absorbent is added to the heat management material, it is preheated to 10 ℃ or more above the melting point of the oil absorbent, preferably 10 to 20 ℃ above the melting point of the oil absorbent.
(3) Pressing and forming;
(4) and (4) after cooling, disassembling the die, taking out the prefabricated block, and optionally wrapping an insulating film on the outer surface to obtain the thermal management module for the cylindrical battery. Preferably, the insulating film may be opened in advance with an opening corresponding to the position of the cylindrical hole. In this step the temperature is reduced to 10 to 20 ℃ below the melting point of the phase change material.
Optionally, when a graphite sealing layer is arranged, a layer of graphite powder is uniformly paved at the bottom of the inner cavity of the mold in the step (1); then, uniformly paving the powder of the heat management material; and finally, uniformly paving a layer of graphite powder again.
The invention also provides a preparation method of the heat management material, which comprises the following steps:
(1) heating and melting the phase change material, optionally adding an oil absorbent, and uniformly stirring;
(2) adding the heat-conducting filler and the chopped fibers into the material obtained in the step (1), and uniformly stirring and mixing;
(3) adding a flame retardant into the material obtained in the step (2) and uniformly stirring;
(4) discharging, cooling and sieving to prepare the heat management material. For example, after discharging, the material is cooled to normal temperature, and then a sieve with 10-20 meshes is adopted to sun-dry larger lumps to obtain the heat management material.
Preferably, when no oil absorbent is added in step (1), the phase change material is heated to 10 ℃ or more, preferably 10 to 20 ℃ or more, above the melting point of the phase change material when melted by heating. When the oil absorbent is added in step (1), the phase change material is heated to 10 ℃ or more above the melting point of the oil absorbent, preferably 10 to 20 ℃ above the melting point of the oil absorbent when melted by heating.
The present invention provides in a third aspect a battery pack constructed using the thermal management module for cylindrical batteries, which includes a thermal management module for cylindrical batteries, and a plurality of cylindrical batteries received in the cylindrical holes 11 of the thermal management module. Cylindrical batteries in the battery pack are arranged in an array shape, so that the battery pack with high integration level is realized. It should be noted that although a specific number of cylindrical batteries is shown in the drawings of the present invention, it should not be construed as a limitation on the number of cylindrical batteries, and the battery pack of the present invention may be assembled with several cylindrical batteries as needed to form a highly integrated stacked battery array.
The present invention will be further described below in the form of examples, but since the inventor is unlikely and not necessarily exhaustive to show all technical solutions obtained based on the inventive concept, the scope of the present invention should not be limited to the following examples, but should include all technical solutions obtained based on the inventive concept.
Example 1
(1) Paving a layer of heat management material in the inner cavity of the mold; wherein the composition of the thermal management material is as shown in table 1; wherein the composition of the thermal management material is as shown in table 1;
(2) placing the die in an oven for preheating after die assembly;
(3) pressing and forming;
(4) after cooling, disassembling the die, and taking out the prefabricated block to obtain the thermal management module for the cylindrical battery; as shown in the live shot of fig. 8.
(5) The cylindrical battery is fitted into the cylindrical hole of the thermal management module to obtain a battery pack.
Examples 2 to 30
Examples 2 to 30 were performed in the same manner as example 1 except for the contents shown in table 1 below. And the enthalpy value, the phase transition temperature and the thermal conductivity of the thermal management material were measured, and the measurement results are shown in table 1.
In table 1: a1 represents paraffin wax having a melting point of 45 ℃, A2 represents paraffin wax having a melting point of 55 ℃, A3 represents higher aliphatic hydrocarbon having 18 carbon atoms, a4 represents higher aliphatic hydrocarbon having 22 carbon atoms, a5 represents higher aliphatic hydrocarbon having 26 carbon atoms, a6 represents higher aliphatic alcohol having 12 carbon atoms, a7 represents higher aliphatic alcohol having 18 carbon atoms, A8 represents polyethylene glycol having a molecular weight of 10000, a9 represents polyethylene glycol having a molecular weight of 20000, and a10 represents higher aliphatic acid having 14 carbon atoms; b1 represents graphene, B2 represents copper powder, B3 represents graphite powder, B4 represents nano aluminum nitride, B5 represents heat conductive carbon fiber, B6 represents aluminum powder, and B7 represents expanded graphite; c1 represents a flame retardant formulated with decabromodiphenyl ether, antimony trioxide and terpene resin in a mass ratio of 3:1:1, C2 represents a flame retardant formulated with decabromodiphenyl ether, antimony trioxide and terpene resin in a mass ratio of 2.5:1:1, C3 represents a flame retardant formulated with decabromodiphenyl ether, antimony trioxide and terpene resin in a mass ratio of 2:1:1, C4 represents a flame retardant formulated with decabromodiphenyl ether and antimony trioxide in a mass ratio of 3:1, C5 represents a flame retardant formulated with ammonium polyphosphate (APP) and Pentaerythritol (PER) in a mass ratio of 3:1, C6 represents a flame retardant formulated with ammonium polyphosphate (APP), Pentaerythritol (PER) and Melamine (MA) in a mass ratio of 3:2:1, C7 represents a flame retardant formulated with ammonium polyphosphate (APP), zinc borate and Melamine (MA) in a mass ratio of 3:2:1, c8 represents a silicone flame retardant, C9 represents an ammonium polyphosphate/montmorillonite (APP/MMT) nanocomposite; d1 represents chopped glass fibers, D2 represents chopped carbon fibers, D3 represents chopped quartz fibers, D4 represents chopped mullite fibers, D5 represents chopped aramid fibers, D6 represents chopped nylon fibers, and D7 represents chopped polyester fibers; e1 denotes hydrogenated styrene-butadiene-Styrene Elastomer (SEBS), E2 denotes High Density Polyethylene (HDPE), E3 is made of SEBS and HDPE in a mass ratio of 1:2, E4 is made of SEBS and HDPE in a mass ratio of 1:3, and E5 is made of SEBS and HDPE in a mass ratio of 1: 5.
In the experimental process, the inventor finds that when the higher fatty acid with 14 carbon atoms is adopted in the example 29, the heat management material is easy to absorb moisture, and the fatty acid is corrosive and has great influence on the stability and the temperature equalization performance of the material. Compared with the prior art, when the higher aliphatic hydrocarbon with 18 to 26 carbon atoms, the higher aliphatic alcohol with 12 to 18 carbon atoms, the alkane type paraffin with the melting point of 25 to 55 ℃ or the polyethylene glycol with the molecular weight of 800 to 20000 are selected as the phase-change material, the prepared heat management material is more stable in the environment and has better overall performance.
Example 31
Example 31 is substantially the same as example 1 except that in step (1), a layer of expanded graphite powder is uniformly spread on the bottom of the cavity of the mold; then, uniformly paving the powder of the heat management material; and finally, uniformly spreading a layer of expanded graphite powder again. Thereby, a graphite sealing layer 12 is formed on the upper and lower surfaces of the thermal management material molded body 11.
Example 32
Example 32 is substantially the same as example 1 except that the insulating film 13 made of polyethylene terephthalate (PET) was entirely wrapped on the outside of the thermal management material molded body 11 and the graphite sealing layer 12.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except for the thermal management mold of the battery packThe blocks are made of different thermal management materials. The thermal management material adopted in the comparative example 1 is a phase change composite material, and the specific preparation process is as follows: paraffin wax with a melting point of 44 ℃, ethylene-vinyl acetate copolymer particles with a vinyl acetate monomer unit content of 14 weight percent and a melting point of 90 ℃, and inorganic filler with a bulk density of 45kg/m3And the expanded perlite with the average grain diameter of 3.0mm and the interior of the expanded perlite in a honeycomb structure, graphite serving as a heat conduction reinforcing agent, and the compound flame retardant of magnesium hydroxide and aluminum hydroxide with the average grain diameter of 200nm (wherein the magnesium hydroxide and the aluminum hydroxide respectively account for 45 wt% and 55 wt%) are weighed according to the proportion of 50%, 32%, 10%, 5% and 3%. Adjusting the temperature of a temperature-controllable heating furnace to 48 +/-1 ℃, adding paraffin into the temperature-controllable heating furnace to melt the paraffin into liquid, removing the paraffin into a mixer, immediately adding the EVA particles at room temperature into the paraffin, stirring the mixture for 1 to 2 minutes by a stirrer at a stirring speed of 100 revolutions per minute, and cooling the mixture to the room temperature to obtain the EVA particles coated by the paraffin. And then adding the obtained coated particles and a compound flame retardant of expanded perlite, graphite, nano-scale magnesium hydroxide and aluminum hydroxide into a double-screw extruder for melt blending extrusion, wherein the rotating speed of a screw of the extruder is 180 revolutions per minute, the temperature is controlled at 120 ℃, and the phase-change composite particles with the average particle size of 1mm are obtained through granulation. The enthalpy value of the phase change composite material is 90J/g, the phase change temperature is 44 ℃, and the thermal conductivity is 0.5W/mK. It can be seen that the enthalpy and thermal conductivity of the materials of the thermal management modules prepared according to examples 1-20 of the present invention are significantly better than the phase change composite material prepared according to comparative example 1.
Claims (15)
1. A thermal management module for a cylindrical battery, comprising:
the heat management module comprises a heat management material forming body, wherein the heat management material forming body is made of a heat management material through a forming method;
a plurality of cylindrical holes for accommodating cylindrical batteries are formed in the thermal management material forming body;
the cylindrical hole is in interference fit with the accommodated cylindrical battery; the hole center distance L of the cylindrical hole and the hole diameter D meet the following relation: l = D + T, wherein T is 1-10 mm;
the thermal management module further comprises a graphite sealing layer on the upper and lower surfaces of the thermal management material molded body;
the outer surface of the thermal management module is covered with an insulating layer;
the heat management material comprises the following components in percentage by mass:
66-90% of phase-change material;
4-20% of heat-conducting filler;
4-20% of a flame retardant;
2-10% of short-cut fibers;
the heat management material also comprises 5-15% of oil absorbent by mass;
the oil absorbent is prepared from hydrogenated styrene-butadiene-styrene elastomer and high-density polyethylene according to the weight ratio of 1: (2-3) by mass;
the phase change material is one material selected from the group consisting of higher aliphatic hydrocarbons having 18 to 26 carbon atoms, higher aliphatic alcohols having 12 to 18 carbon atoms, paraffin type paraffin having a melting point of 25 to 55 ℃, and polyethylene glycol having a molecular weight of 800 to 20000.
2. The thermal management module of claim 1, wherein:
the content of the phase-change material is 70-90%; and/or
The heat-conducting filler is selected from the group consisting of aluminum powder, copper powder, graphite powder, nano aluminum nitride, heat-conducting carbon fiber, graphene and expanded graphite; and/or
The content of the heat-conducting filler is 5-10%; and/or
The flame retardant is selected from the group consisting of decabromodiphenyl ether, ammonium polyphosphate, silicone flame retardant, ammonium polyphosphate/montmorillonite nanocomposite, pentaerythritol, zinc borate, terpene resin, antimony trioxide and melamine; and/or
The content of the flame retardant is 5-20%; and/or
The chopped fibers are selected from the group consisting of chopped carbon fibers, chopped glass fibers, chopped quartz fibers, chopped mullite fibers, chopped aramid fibers, chopped nylon fibers and chopped polyester fibers; and/or
The content of the chopped fibers is 2-5%; and/or the length of the chopped fiber is 2-10 mm; and/or the diameter of the chopped fiber is 2-50 mu m.
3. The thermal management module of claim 1, wherein:
the phase change material is selected from the group consisting of higher aliphatic hydrocarbons having 18 to 26 carbon atoms and paraffin type paraffins having a melting point of 30 to 55 ℃.
4. The thermal management module of claim 3, wherein:
the phase change material is an alkane type paraffin having a melting point of 30 to 55 ℃.
5. The thermal management module of claim 2, wherein:
the thermally conductive filler is selected from the group consisting of thermally conductive carbon fibers, graphene, expanded graphite.
6. The thermal management module of claim 5, wherein:
the thermally conductive filler is selected from the group consisting of graphene and expanded graphite.
7. The thermal management module of claim 2, wherein:
the flame retardant is prepared from decabromodiphenyl ether, antimony trioxide and terpene resin.
8. The thermal management module of claim 2, wherein:
the content of the flame retardant is 10-15%.
9. The thermal management module of claim 2, wherein:
the chopped fibers are selected from the group consisting of chopped carbon fibers, chopped glass fibers, and chopped quartz fibers.
10. The thermal management module of claim 9, wherein:
the chopped fibers are selected from the group consisting of chopped glass fibers and chopped quartz fibers.
11. The thermal management module of claim 2, wherein:
the length of the chopped fiber is 3-5 mm.
12. The thermal management module of claim 1, wherein the sealing layer of graphite is molded directly from the vermicular expanded graphite during molding of the thermal management material form, and the sealing layer of graphite is left open in the areas corresponding to the cylindrical holes.
13. The thermal management module of claim 1, wherein the insulating layer is open in correspondence with the area of the cylindrical hole.
14. The method of making a thermal management module for a cylindrical battery of any of claims 1-13, comprising the steps of:
(1) paving the heat management material in the inner cavity of the mold, wherein a layer of graphite powder is paved at the bottom of the inner cavity of the mold, then the heat management material is paved, and then a layer of graphite powder is paved on the heat management material;
(2) placing the die in an oven for preheating after die assembly;
(3) pressing and forming;
(4) and (5) after cooling, disassembling the die, taking out the prefabricated block, and wrapping the insulating film on the outer surface to obtain the thermal management module for the cylindrical battery.
15. A battery pack comprising a thermal management module for cylindrical batteries according to any of claims 1 to 13, and a plurality of cylindrical batteries housed in cylindrical holes of the thermal management module.
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| PCT/CN2017/089971 WO2018103305A1 (en) | 2016-12-09 | 2017-06-26 | Thermal management material and applications thereof in thermal management module of cylindrical battery |
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| CN111261974A (en) * | 2020-01-21 | 2020-06-09 | 广东工业大学 | Phase change material module for battery thermal management system and preparation method and application thereof |
| CN111607362A (en) * | 2020-07-01 | 2020-09-01 | 广东工业大学 | Preparation method of high-thermal-conductivity flexible phase change material and battery module |
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| CN114621733A (en) * | 2022-01-21 | 2022-06-14 | 中国石油大学(华东) | Flame-retardant phase change material capable of inhibiting thermal runaway of lithium ion battery, preparation method and application thereof, and lithium ion battery |
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