CN119009068A - Lithium ion battery with high and low temperature resistance and preparation method thereof - Google Patents
Lithium ion battery with high and low temperature resistance and preparation method thereof Download PDFInfo
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- CN119009068A CN119009068A CN202411206052.4A CN202411206052A CN119009068A CN 119009068 A CN119009068 A CN 119009068A CN 202411206052 A CN202411206052 A CN 202411206052A CN 119009068 A CN119009068 A CN 119009068A
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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- 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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- 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
- H01M10/655—Solid structures for heat exchange or heat conduction
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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
- H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
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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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
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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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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Abstract
本发明公开了一种具有耐高低温性能的锂离子电池及其制备方法，该锂离子电池，包括电芯以及封装电芯的壳体；壳体外表面设置有第一凹槽和第二凹槽，且第一凹槽和第二凹槽并排嵌设于壳体外表面，第一凹槽和第二凹槽分别由壳体外表面的中心向壳体外表面的边缘呈回形弯折延伸；第一凹槽设置有耐低温材料层，耐低温材料层的相变温度为‑12℃～‑15℃；第二凹槽设置有耐高温材料层，耐高温材料层的相变温度为57℃～62℃；耐低温材料层的厚度与第一凹槽的深度相同，耐高温材料层的厚度与第二凹槽的深度相同；且耐低温材料层、耐高温材料层和壳体三者的外表面处于同一水平面上。本发明提供的锂离子电池能够在极端高低温条件下仍能保持稳定性能。
The present invention discloses a lithium ion battery with high and low temperature resistance and a preparation method thereof, the lithium ion battery comprising a battery cell and a shell for encapsulating the battery cell; the outer surface of the shell is provided with a first groove and a second groove, and the first groove and the second groove are embedded in the outer surface of the shell side by side, and the first groove and the second groove are respectively extended from the center of the outer surface of the shell to the edge of the outer surface of the shell in a zigzag shape; the first groove is provided with a low temperature resistant material layer, and the phase change temperature of the low temperature resistant material layer is ‑12°C to ‑15°C; the second groove is provided with a high temperature resistant material layer, and the phase change temperature of the high temperature resistant material layer is 57°C to 62°C; the thickness of the low temperature resistant material layer is the same as the depth of the first groove, and the thickness of the high temperature resistant material layer is the same as the depth of the second groove; and the outer surfaces of the low temperature resistant material layer, the high temperature resistant material layer and the shell are on the same horizontal plane. The lithium ion battery provided by the present invention can still maintain stable performance under extreme high and low temperature conditions.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery with high and low temperature resistance and a preparation method thereof.
Background
Lithium ion batteries are widely used in consumer electronics, electric vehicles, and large-scale energy storage systems due to their high energy density, long cycle life, and environmental friendliness as key components in modern energy applications. However, with diversification and extreme application scenarios, the performance limitation of the conventional lithium ion battery in the high-low temperature environment is increasingly prominent, and the conventional lithium ion battery becomes a bottleneck for restricting further development of the conventional lithium ion battery.
Under low temperature conditions, lithium ion batteries face serious performance degradation problems. When the temperature is lowered, the viscosity of the electrolyte increases significantly, resulting in a significant decrease in the migration rate of lithium ions. This causes not only an increase in the internal impedance of the battery but also a sharp decrease in the charge-discharge efficiency. The method is characterized in that the charging time is prolonged, the discharge capacity is reduced, and the actual use effect of the battery in cold areas or low-temperature application scenes is seriously influenced. For example, in an environment below-15 ℃, the discharge capacity of conventional lithium ion batteries may drop below 50% at room temperature.
On the other hand, high temperature environments also pose significant challenges to the performance and safety of lithium ion batteries. The temperature rise accelerates side reactions inside the battery, such as electrolyte decomposition, structural changes of anode and cathode materials, and the like. These reactions not only lead to rapid decay of battery capacity and significant reduction in cycle life, but may also raise more serious safety concerns. For example, in a high temperature environment above 60 ℃, the battery may be out of control, resulting in safety accidents such as battery expansion, smoke and even explosion.
In the prior art, in order to improve the temperature adaptability of lithium ion batteries, researchers have tried various methods such as developing new electrolyte additives, improving electrode material structures, optimizing battery management systems, and the like. However, these methods often only improve the performance of the battery in a specific temperature range to some extent, and it is difficult to simultaneously satisfy the use requirements in high and low temperature environments. In addition, certain improvements may increase the manufacturing cost of the battery or reduce other performance metrics (e.g., energy density).
Therefore, the development of the lithium ion battery which can keep stable performance in a wide temperature range and can still work efficiently under extremely high and low temperature conditions is of great significance in expanding the application field of the battery, improving the user experience and guaranteeing the use safety.
Disclosure of Invention
The main purpose of the invention is that: aiming at the defect that the existing lithium ion battery cannot meet the use under the high-low temperature condition, the lithium ion battery with high-low temperature resistance and the preparation method thereof are provided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a lithium ion battery having high and low temperature resistance, comprising: a cell and a housing encapsulating the cell;
the shell comprises a shell body and is characterized in that a first groove and a second groove are formed in the outer surface of the shell body, the first groove and the second groove are embedded in the outer surface of the shell body side by side, and the first groove and the second groove are bent and extended in a shape of a return from the center of the outer surface of the shell body to the edge of the outer surface of the shell body;
The first groove is provided with a low-temperature-resistant material layer, and the phase transition temperature of the low-temperature-resistant material layer is-12 ℃ to-15 ℃; the second groove is provided with a high-temperature-resistant material layer, and the phase transition temperature of the high-temperature-resistant material layer is 57-62 ℃;
The thickness of the low-temperature-resistant material layer is the same as the depth of the first groove, and the thickness of the high-temperature-resistant material layer is the same as the depth of the second groove; and the outer surfaces of the low temperature resistant material layer, the high temperature resistant material layer and the shell are positioned on the same horizontal plane.
Preferably, the low temperature resistant material layer comprises the following components in parts by weight: 40-50 parts of n-tridecane, 25-35 parts of n-dodecane, 10-15 parts of 2-methylpentane, 3-5 parts of polyvinyl alcohol, 2-4 parts of graphene, 1-2 parts of nano alumina and 0.5-1 part of silica aerogel.
Preferably, the high-temperature resistant material layer comprises the following components in parts by weight: 45-55 parts of glyceryl stearate, 20-25 parts of palmitic acid, 4000 10-15 parts of polyethylene glycol, 3-5 parts of carbon nano tubes, 2-3 parts of boron nitride nano sheets, 1-2 parts of expanded graphite and 0.5-1 part of nano magnesium oxide.
Preferably, the depth of the first groove is H1, the depth of the second groove is H2, the thickness of the low temperature resistant material layer is H1, the thickness of the high temperature resistant material layer is H2, and the wall thickness of the shell is H; wherein H, H, H2, H1 and H2 satisfy the relationship: h1 =h2=h 1=h2; h1 is more than or equal to 0.2H less than or equal to 0.6H; h2 is more than or equal to 0.2H 2 less than or equal to 0.6H.
Preferably, the forward projection area of the low temperature resistant material layer is S1, the forward projection area of the high temperature resistant material layer is S2, and the forward projection area of the shell is S; wherein S1, S2 and S satisfy the relationship: s is more than or equal to 0.6S and less than or equal to S1+ S2.
Preferably, a third groove is further formed in the outer surface of the shell, the third groove is embedded between the first groove and the second groove side by side, and the third groove is bent and extended in a shape of a loop from the center of the outer surface of the shell to the edge of the outer surface of the shell;
The third groove is provided with a buffer heat-conducting material layer; the thickness of the buffer heat-conducting material layer is larger than that of the low-temperature-resistant material layer or the high-temperature-resistant material layer, and the buffer heat-conducting material layer protrudes out of the outer surface of the shell;
The buffer heat-conducting material layer comprises a first aluminum foam, a second aluminum foam and a third aluminum foam which are sequentially arranged from outside to inside, wherein the density ρ1 of the first aluminum foam, the density ρ2 of the second aluminum foam and the density ρ3 of the third aluminum foam satisfy the relation: ρ1 > ρ2 > ρ3; and the first aluminum foam, the second aluminum foam and the third aluminum foam are all provided with air hole structures which are arranged in a staggered way, and the porosity Q1 of the first aluminum foam, the porosity Q2 of the second aluminum foam and the porosity Q3 of the third aluminum foam satisfy the relation: q1 is less than Q2 and less than Q3.
Preferably, the density rho 1 of the first foamed aluminum is 0.8-1.2 g/cm 3; the density rho 2 of the second foamed aluminum is 0.5-0.8 g/cm 3; the density rho 3 of the third foamed aluminum is 0.2-0.5 g/cm 3;
the porosity Q1 of the first foamed aluminum is 45% -60%; the porosity Q2 of the second foamed aluminum is 60% -75%; the third foamed aluminum has a porosity Q3 of 75-90%.
Preferably, a third groove is further formed in the outer surface of the shell, the third groove is embedded between the first groove and the second groove side by side, and the third groove is bent and extended in a shape of a loop from the center of the outer surface of the shell to the edge of the outer surface of the shell;
the third groove is provided with a heat-insulating buffer material layer, the thickness of the heat-insulating buffer material layer is larger than that of the low-temperature-resistant material layer or the high-temperature-resistant material layer, and the heat-insulating buffer material layer protrudes out of the outer surface of the shell;
The heat insulation buffer material layer is made of ceramic silica gel foam, and the ceramic silica gel foam comprises the following components in parts by weight: 30-40 parts of vinyl silicone oil, 10-20 parts of white carbon black, 20-50 parts of nano ceramic powder, 0.1-1.0 part of ethynyl cyclohexanol, 1-10 parts of hydrogen-containing silicone oil, 1-10 parts of hydroxyl silicone oil, 0.1-1.0 part of platinum catalyst, 10-20 parts of beta-eucryptite and 1-8 parts of halloysite nanotube.
Preferably, a third groove is further formed in the outer surface of the shell, the third groove is embedded between the first groove and the second groove side by side, and the third groove is bent and extended in a shape of a loop from the center of the outer surface of the shell to the edge of the outer surface of the shell;
The third groove is provided with modified heat conduction silica gel, the porosity of the modified heat conduction silica gel is 65% -85%, the thickness of the modified heat conduction silica gel is larger than that of the low temperature resistant material layer or the high temperature resistant material layer, and the modified heat conduction silica gel protrudes out of the outer surface of the shell.
In addition, the invention also provides a preparation method of the lithium ion battery with high and low temperature resistance, which comprises the following steps:
1) The outer surface of the shell is provided with a first groove and a second groove in a laser engraving, etching or stamping mode;
2) Respectively preparing low-temperature-resistant material layer slurry and high-temperature-resistant material layer slurry;
3) Coating the slurry of the low-temperature-resistant material layer on the first groove, and coating the slurry of the high-temperature-resistant material layer on the second groove;
4) And drying the outer surface of the shell, and packaging the battery core in the shell to obtain the lithium ion battery.
Compared with the prior art, the invention has at least the following beneficial effects:
1) According to the invention, the low-temperature-resistant material layer and the high-temperature-resistant material layer are respectively arranged on the outer surface of the battery shell, so that the performance problem of the lithium ion battery at extreme temperature is effectively solved, and the service temperature range of the battery is greatly expanded. The design of the low temperature resistant material layer can absorb or release heat in a specific temperature range, so that the lithium ion battery can stably work in the temperature range from minus 15 ℃ to 62 ℃.
2) According to the invention, the first groove and the second groove which are embedded side by side are arranged on the outer surface of the shell, the first groove and the second groove are respectively bent and extended in a shape of a loop from the center of the outer surface of the shell to the edge of the outer surface of the shell, the low temperature resistant material layer and the high temperature resistant material layer are respectively arranged on the first groove and the second groove, the outer surfaces of the low temperature resistant material layer, the high temperature resistant material layer and the shell are positioned on the same horizontal plane, the flatness and the aesthetic property of the appearance of the battery are ensured through the structural design, the wall thickness of the shell of the battery is not required to be additionally increased, the high temperature resistance and the low temperature resistance of the battery are effectively improved under the condition that the volume energy density of the battery is not lost, and the heat exchange area is increased through the loop bending design of the first groove and the second groove, and the temperature adjusting efficiency is improved.
Drawings
Fig. 1 is a schematic structural diagram of a lithium ion battery according to an embodiment of the invention;
Fig. 2 is a top view of a lithium-ion battery in an embodiment of the invention;
Fig. 3 is a schematic structural diagram of a lithium ion battery according to another embodiment of the present invention;
FIG. 4 is a cross-sectional view of a cushioning, thermally conductive material layer in another embodiment of the present invention;
fig. 5 is a schematic structural diagram of a lithium ion battery according to another embodiment of the present invention;
fig. 6 is a schematic structural diagram of a lithium ion battery according to another embodiment of the invention.
In the figure: 1. a housing; 2. a low temperature resistant material layer; 3. a high temperature resistant material layer; 4. buffering the heat conducting material layer; 41. a first aluminum foam; 42. a second aluminum foam; 43. a third aluminum foam; 5. a layer of insulating buffer material; 6. modified heat conducting silica gel.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-2, a lithium ion battery with high and low temperature resistance provided in this embodiment includes: a battery cell and a housing 1 for packaging the battery cell; the battery cell comprises a positive plate, a diaphragm and a negative plate which are sequentially laminated and wound; wherein, the shell material can be aluminum shell, steel shell or aluminum alloy material;
the outer surface of the shell 1 is provided with a first groove and a second groove, the first groove and the second groove are embedded in the outer surface of the shell 1 side by side, and the first groove and the second groove respectively extend from the center of the outer surface of the shell 1 to the edge of the outer surface of the shell 1 in a back-shaped bending way;
the first groove is provided with a low-temperature-resistant material layer 2, and the phase transition temperature of the low-temperature-resistant material layer 2 is-12 ℃ to-15 ℃; the second groove is provided with a high temperature resistant material layer 3, and the phase transition temperature of the high temperature resistant material layer 3 is 57-62 ℃;
The thickness of the low-temperature resistant material layer 2 is the same as the depth of the first groove, and the thickness of the high-temperature resistant material layer 3 is the same as the depth of the second groove; and the outer surfaces of the low temperature resistant material layer 2, the high temperature resistant material layer 3 and the shell 1 are positioned on the same horizontal plane.
In one implementation according to the application, the low temperature resistant material layer 2 comprises the following components in parts by weight: 40-50 parts of n-tridecane, 25-35 parts of n-dodecane, 10-15 parts of 2-methylpentane, 3-5 parts of polyvinyl alcohol, 2-4 parts of graphene, 1-2 parts of nano alumina and 0.5-1 part of silica aerogel.
The n-tridecane and n-dodecane are used as main phase change materials, provide low-temperature phase change capability, and can adjust the phase change temperature and reduce the freezing point when being used in a mixed mode; 2-methylpentane further reduces the solidifying point of the mixture, increases the fluidity of the material, and improves the low-temperature performance; polyvinyl alcohol (PVA) is used as a thickener and a structural stabilizer, so that the mechanical strength and the shape stability of the material are improved; the graphene obviously improves the thermal conductivity of the material and improves the distribution of heat in the phase change material; the nano aluminum oxide reinforced material has high thermal stability, and improves the thermal conductivity and the mechanical strength; the silica aerogel provides excellent heat preservation performance, reduces heat loss and improves the efficiency of the phase change material. The phase transition temperature of the low temperature resistant material layer 2 is-12 ℃ to-15 ℃, and when the phase transition temperature is reached, heat can be quickly released, the temperature of the battery can be effectively regulated, and the low temperature resistance of the battery can be improved.
The preparation method of the low-temperature-resistant material layer 2 comprises the following steps:
(1) Mixing n-tridecane, n-dodecane and 2-methylpentane according to a proportion, and uniformly stirring at room temperature;
(2) Dissolving polyvinyl alcohol (PVA) in a small amount of deionized water, heating to 60 ℃, and stirring until the PVA is completely dissolved;
(3) Slowly adding the solution in the step (2) into the mixture in the step (1), and uniformly dispersing for 30 minutes by using a high-speed shearing machine;
(4) Dispersing graphene in a small amount of ethanol, and carrying out ultrasonic treatment for 20 minutes;
(5) Sequentially adding the suspension in the step (4), the nano alumina and the silica aerogel into the mixture in the step (3), and continuously shearing at a high speed for 15 minutes to obtain low-temperature-resistant material layer slurry;
(6) And (3) coating the slurry of the low-temperature-resistant material layer on the first groove, and drying to obtain the low-temperature-resistant material layer 2 with the required shape and thickness.
In one embodiment according to the application, the refractory material layer 3 comprises the following components in parts by weight: 45-55 parts of glyceryl stearate, 20-25 parts of palmitic acid, 4000 10-15 parts of polyethylene glycol, 3-5 parts of carbon nano tubes, 2-3 parts of boron nitride nano sheets, 1-2 parts of expanded graphite and 0.5-1 part of nano magnesium oxide.
The glyceryl stearate and the palmitic acid are used as main phase-change materials, high-temperature phase-change capacity is provided, and the phase-change temperature range can be adjusted by mixed use; the polyethylene glycol 4000 adjusts the phase transition temperature, increases the heat capacity of the material and improves the heat storage capacity; the carbon nano tube remarkably improves the heat conductivity of the material and improves the rapid distribution of heat in the phase change material; the boron nitride nano-sheet further enhances heat conduction and improves the heat stability of the material; the specific surface area of the material is increased by the expanded graphite, the heat exchange efficiency is improved, and the heat conductivity and flame retardance of the material are improved; the nano magnesium oxide enhances the thermal stability and flame retardance of the material and improves the structural integrity of the material at high temperature. The phase transition temperature of the high temperature resistant material layer 3 is 57-62 ℃, and when the phase transition temperature is reached, the heat can be quickly absorbed, the temperature of the battery can be effectively regulated, and the high temperature resistance of the battery can be improved.
The preparation method of the high temperature resistant material layer 3 comprises the following steps:
(1) Mixing the glyceryl stearate and the palmitic acid according to a proportion, heating and melting in an oil bath at 85-95 ℃, and uniformly stirring;
(2) Adding polyethylene glycol 4000 into the molten mixture in the step (1), and continuously stirring until the polyethylene glycol 4000 is completely dissolved;
(3) Dispersing the carbon nano tube and the boron nitride nano sheet in a small amount of N-methyl pyrrolidone (NMP), and carrying out ultrasonic treatment for 30 minutes;
(4) Slowly adding the suspension in the step (3) into the molten mixture in the step (2), and stirring at a high speed for 45 minutes;
(5) Adding the expanded graphite and the nano magnesium oxide, and continuing stirring at a high speed for 20 minutes to obtain high-temperature-resistant material layer slurry;
(6) And coating the slurry of the high-temperature-resistant material layer on the second groove, and drying to obtain the high-temperature-resistant material layer 3 with the required shape and thickness.
In one embodiment according to the present application, the depth of the first groove is H1, the depth of the second groove is H2, the thickness of the low temperature resistant material layer 2 is H1, the thickness of the high temperature resistant material layer 3 is H2, and the wall thickness of the housing 1 is H; wherein H, H, H2, H1 and H2 satisfy the relationship: h1 =h2=h 1=h2; h1 is more than or equal to 0.2H less than or equal to 0.6H; h2 is more than or equal to 0.2H 2 less than or equal to 0.6H. Through the dimensional proportion relation of the first groove, the second groove, the low temperature resistant material layer 2, the high temperature resistant material layer 3 and the shell 1, the overall structural strength and the high and low temperature resistant performance of the battery are ensured to be effectively exerted. If the depth of the groove is too small, the heat-resistant material layer is difficult to bear, and if the depth of the groove is too large, the strength of the shell 1 is affected; therefore, the dimension proportion combination design ensures that the temperature resistant material layer does not influence the integral integration of the battery, and can fully play the function of the battery.
In an implementation according to the present application, the forward projection area of the low temperature resistant material layer 2 is S1, the forward projection area of the high temperature resistant material layer 3 is S2, and the forward projection area of the housing 1 is S; wherein S1, S2 and S satisfy the relationship: s is more than or equal to 0.6S and less than or equal to S1+ S2. By controlling the sum of the forward projected areas of the low temperature resistant material layer 2 and the high temperature resistant material layer 3 to satisfy the above-described relationship, it is ensured that the coverage area of the material layers is sufficiently large to effectively adjust the temperature of the entire casing 1.
In an implementation according to the present application, as shown in fig. 3 to 4, the outer surface of the housing 1 is further provided with a third groove, the third groove is embedded between the first groove and the second groove side by side, and the third groove is bent and extended in a shape of a loop from the center of the outer surface of the housing 1 to the edge of the outer surface of the housing 1;
The third groove is provided with a buffer heat conducting material layer 4; the thickness of the buffer heat-conducting material layer 4 is larger than that of the low-temperature-resistant material layer 2 or the high-temperature-resistant material layer 3, and the buffer heat-conducting material layer 4 protrudes out of the outer surface of the shell 1;
The cushioning and heat-conducting material layer 4 includes a first aluminum foam 41, a second aluminum foam 42, and a third aluminum foam 43, which are sequentially provided from the outside to the inside, and the density ρ1 of the first aluminum foam 41, the density ρ2 of the second aluminum foam 42, and the density ρ3 of the third aluminum foam 43 satisfy the relation: ρ1 > ρ2 > ρ3; and the first aluminum foam 41, the second aluminum foam 42 and the third aluminum foam 43 are all provided with air hole structures which are arranged in a staggered manner, and the porosity Q1 of the first aluminum foam 41, the porosity Q2 of the second aluminum foam 42 and the porosity Q3 of the third aluminum foam 43 satisfy the relation: q1 is less than Q2 and less than Q3.
Wherein, each foamed aluminum layer can be arranged in the third groove of the shell 1 in a spray coating, 3D printing and other modes. The foamed aluminum is a novel light functional material with metal and bubble characteristics, can have excellent energy absorption buffer effect and heat conduction effect, effectively absorbs the expansion force of a battery, and simultaneously reduces the overall quality of the battery pack to the greatest extent; when the batteries are grouped, the three-layer foamed aluminum structural design with gradual density and porosity can effectively absorb and disperse impact energy and has good heat conduction and heat dissipation effects, so that excellent buffer protection and heat conduction and heat dissipation performances are provided. Wherein, the first aluminum foam 41 with high density and lower porosity can firstly receive and disperse external impact energy, and reduce the impact force to be directly transmitted to the inside; the medium density and higher porosity secondary aluminum foam 42 is capable of further absorbing and dispersing the remaining impact energy. The low-density and high-porosity third aluminum foam 43 has extremely high energy absorbing capability, and can finally absorb and disperse the residual impact energy to protect the battery cell. The application can realize the effect of absorbing and dispersing impact energy layer by creatively combining the porosity and the density of each layer, thereby obviously improving the buffer protection performance of the lithium ion battery and ensuring the safety and the reliability of the battery pack.
In one embodiment according to the application, the density ρ1 of the first aluminum foam 41 is 0.8-1.2 g/cm 3, preferably 0.95g/cm 3; the density ρ2 of the second aluminum foam 42 is 0.5 to 0.8g/cm 3, preferably 0.65g/cm 3; the density ρ3 of the third aluminum foam 43 is 0.2 to 0.5g/cm 3, preferably 0.35g/cm 3;
the porosity Q1 of the first aluminum foam 41 is 45% -60%, preferably 55%; the second aluminum foam 42 has a porosity Q2 of 60% to 75%, preferably 70%; the porosity Q3 of the third aluminum foam 43 is 75% to 90%, preferably 85%.
In an embodiment according to the present application, as shown in fig. 5, a third groove is further disposed on the outer surface of the housing 1, the third groove is embedded between the first groove and the second groove side by side, and the third groove extends from the center of the outer surface of the housing 1 to the edge of the outer surface of the housing 1 in a shape of a loop;
The third groove is provided with a heat-insulating buffer material layer 5, the thickness of the heat-insulating buffer material layer 5 is larger than that of the low-temperature-resistant material layer 2 or the high-temperature-resistant material layer 3, and the heat-insulating buffer material layer 5 protrudes out of the outer surface of the shell 1;
The heat insulation buffer material layer 5 is made of ceramic silica gel foam, and the ceramic silica gel foam comprises the following components in parts by weight: 30-40 parts of vinyl silicone oil, 10-20 parts of white carbon black, 20-50 parts of nano ceramic powder, 0.1-1.0 part of ethynyl cyclohexanol, 1-10 parts of hydrogen-containing silicone oil, 1-10 parts of hydroxyl silicone oil, 0.1-1.0 part of platinum catalyst, 10-20 parts of beta-eucryptite and 1-8 parts of halloysite nanotube.
The ceramic silica gel foam provided by the invention has good elasticity in a normal working state, and can play a good role in buffering and protecting batteries when the batteries are grouped; and at high temperature, the ceramic silica gel foam can rapidly form a foam ceramic body with a self-supporting structure, can maintain a high degree of cell structure retention rate, thereby playing an excellent heat insulation and flame retardation effect, can resist the burning of flames above 1300 ℃ for a long time, can effectively isolate the transmission and temperature transmission of fire, and can control the firing range in a single battery interval to avoid the firing of adjacent batteries.
Wherein, the vinyl silicone oil is used as a main polymerization matrix, and the vinyl silicone oil provides required elasticity and flexibility in a foaming system; the material can form a cross-linked structure through an addition reaction with hydrogen-containing silicone oil, so that the mechanical strength of the material is enhanced. The white carbon black is used as a reinforcing agent, so that the tear strength and the wear resistance of the composite material are improved, and the compression resistance of the silicon rubber is improved, so that the material is not easy to deform even under higher load. The nano ceramic powder plays a role of a flame retardant, and can promote the surface of a material to form a hard ceramic layer at high temperature, so that further propagation of flame and heat is effectively prevented. The ethynyl cyclohexanol is used as an inhibitor, and the compound can control the rate of polymerization reaction and avoid unstable structure caused by too fast reaction. The hydrogen-containing silicone oil is used as a cross-linking agent and reacts with vinyl silicone oil to generate a silicone rubber network structure, so that the overall mechanical property and the thermal stability of the material are enhanced. The hydroxy silicone oil acts as a foaming agent in the system, and the hydroxy silicone oil is decomposed to generate gas when heated to form a foam structure, thereby providing good buffering performance and low density. The platinum catalyst catalyzes the addition crosslinking reaction of vinyl silicone oil and hydrogen-containing silicone oil, so that the efficiency and uniformity of the reaction are improved, and the consistency of the material performance is ensured. The beta-eucryptite is used as a porcelain forming agent, so that the transformation from the silicon rubber to the ceramic body can be promoted at high temperature, and the high temperature resistance and the structural stability of the material are enhanced. The halloysite nanotube is used as a cell structure stabilizer, can form a uniformly distributed supporting structure in the material, enhances the stability of the cell structure, and avoids collapse at high temperature or under mechanical pressure.
Therefore, through the specific components and the synergistic effect of the specific components, the silica gel foam not only maintains excellent elasticity and flexibility and effectively protects the battery cells, but also remarkably improves the performance of the material under extreme conditions. Particularly, under the thermal runaway firing scene, the material can quickly form a self-supporting foam ceramic body, and greatly improves the heat insulation and flame retardance. The foam ceramic body can maintain the structural integrity and flame retardance when being subjected to high temperature or direct flame irradiation, unlike the traditional silica gel foam, the foam can crack, deform, collapse cells and even pulverize under the same conditions, so that the protective capability is lost.
The preparation method of the ceramic silica gel foam comprises the following steps:
s1, adding vinyl silicone oil, white carbon black, nano ceramic powder and beta-eucryptite into a kneader, kneading into a mass at 100-150 ℃, and cooling to obtain base rubber;
Step S2, stirring and mixing hydroxyl silicone oil and halloysite nanotubes to obtain a foaming mixture; wherein, the rotation speed of stirring and mixing is 23000-26000 r/min, and the mixing time is 10-25 s;
S3, adding the foaming mixture, ethynyl cyclohexanol, hydrogen-containing silicone oil and a platinum catalyst into the base adhesive, and uniformly mixing to obtain the adhesive;
And S4, vulcanizing and foaming the sizing material by adopting casting, calendaring or mould pressing processes to obtain the ceramic silica gel foam.
The ceramic silica gel foam prepared by the method has the following advantages:
1) Excellent mechanical properties and elasticity: because of the cross-linking structure of vinyl silicone oil and hydrogen-containing silicone oil and the reinforcing effect of white carbon black, the silica gel foam of the invention has good elasticity and mechanical stress resistance, so that the silica gel foam can still maintain the original shape and function after long-term use or repeated compression.
2) High-efficiency flame-retardant and heat-insulating capability: the addition of the nano ceramic powder and the beta-eucryptite ensures that the material can quickly form a protective ceramic layer when being subjected to high temperature or flame attack, and the structure of the layer can not only effectively isolate flame, but also reduce heat transfer and protect the internal structure from damage.
3) High stability foam structure: the foam structure formed by the gas generated by the decomposition of the hydroxyl silicone oil is enhanced by the halloysite nanotube, so that the foam is not easy to collapse even at high temperature, and the higher retention rate of the foam structure is maintained.
4) Excellent heat resistance: the uniform formation and stability of the silicon rubber network structure are ensured by controlling the polymerization rate of the ethynyl cyclohexanol and the high-efficiency catalysis of the platinum catalyst, so that the performance can be maintained under an extremely high-temperature environment.
In an implementation according to the present application, as shown in fig. 6, a third groove is further disposed on the outer surface of the housing 1, the third groove is embedded between the first groove and the second groove side by side, and the third groove extends from the center of the outer surface of the housing 1 to the edge of the outer surface of the housing 1 in a shape of a loop;
The third groove is provided with modified heat conduction silica gel 6, the porosity of the modified heat conduction silica gel 6 is 65% -85%, the thickness of the modified heat conduction silica gel 6 is larger than that of the low temperature resistant material layer 2 or the high temperature resistant material layer 3, and the modified heat conduction silica gel 6 protrudes out of the outer surface of the shell 1.
The modified heat-conducting silica gel 6 with the porosity of 65-85% is arranged in the third groove, so that the modified heat-conducting silica gel has good heat-conducting property and good energy absorption and buffer effects; in addition, when the batteries are grouped, the modified heat-conducting silica gel 6 can fix two adjacent batteries and absorb the expansion force of the batteries, and the heat conductivity of the modified heat-conducting silica gel can reach 6-10W/(m.k), so that the heat conduction and dissipation of the battery pack at high temperature can be accelerated, and the temperature inside the battery pack can be reduced.
The preparation method of the modified heat-conducting silica gel 6 comprises the following steps:
1) Boron nitride and KH570 silane coupling agent were dispersed in 100ml of aqueous solution at a mass ratio of 10:1 at concentrations of 40mg/ml and 4mg/ml, respectively. And (3) placing the mixed dispersion liquid in water bath ultrasonic, carrying out ultrasonic treatment at 0 ℃ for 40min, centrifuging to remove redundant solvent, and carrying out cold drying to obtain modified boron nitride powder.
2) Mixing modified boron nitride powder with graphene in a ratio of 1:5, dispersing the graphene slurry in a mixed solvent with alcohol water of 4:1 in mass ratio, wherein the concentration is 1.2mg/ml and 6mg/ml respectively, simultaneously adding 2mg/ml of carbon nano tube, and performing ultrasonic treatment for 10min under 1200W power by using an ultrasonic cell grinder to obtain the graphene slurry.
3) The polyurethane foam is immersed in 2mol/L NaOH solution, treated in warm water at 40 ℃ for 3.5 hours, then put into 5mg/ml aniline methyltriethoxysilane aqueous solution, and immersed for 24 hours, thus obtaining the modified polyurethane foam.
4) And (3) immersing the modified polyurethane porous foam structure in the prepared uniform graphene slurry, and carrying out water bath ultrasonic treatment for 20min at the temperature of 0 ℃. Drying the material at 60 ℃, then keeping the temperature for 30min at a temperature rising rate of 15 ℃ per minute from 60 ℃ to 200 ℃ and a temperature rising rate of 3 ℃ per minute from 200 ℃ to 380 ℃, and removing the porous material to obtain the three-dimensional porous graphene-boron nitride composite material.
5) Immersing the obtained three-dimensional porous graphene-boron nitride composite material into silica gel (Wake SEMICOSIL 9212,9212), vacuumizing to remove bubbles, and placing into a 125 ℃ oven for curing for 15min to obtain the modified heat-conducting silica gel 6.
In addition, the invention also provides a preparation method of the lithium ion battery with high and low temperature resistance, which comprises the following steps:
1) The outer surface of the shell 1 is provided with a first groove and a second groove by means of laser engraving, etching or stamping;
2) Respectively preparing low-temperature-resistant material layer slurry and high-temperature-resistant material layer slurry;
3) Coating the slurry of the low-temperature-resistant material layer on the first groove, and coating the slurry of the high-temperature-resistant material layer on the second groove;
4) And (3) drying the outer surface of the shell 1, packaging the battery cell in the shell, injecting liquid, and forming to obtain the lithium ion battery.
According to the preparation method, the grooves are formed in the outer surface of the shell in a laser engraving, etching or stamping mode, so that the size and shape of the grooves can be accurately controlled, and the uniform coating of the material layer is ensured; the process of coating the low-temperature-resistant material layer slurry and the high-temperature-resistant material layer slurry can be adjusted and optimized according to the needs, so that the quality and performance of the material layer are ensured; and finally, through a drying and packaging process, the tight combination of the material layer and the shell is ensured, and the overall performance and reliability of the battery are improved.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120270075A1 (en) * | 2011-04-22 | 2012-10-25 | Hidekazu Fujimura | Secondary battery module and secondary battery pack |
| CN115020862A (en) * | 2022-06-29 | 2022-09-06 | 广东畅能达科技发展有限公司 | Battery shell, manufacturing method and power battery |
| CN220324564U (en) * | 2023-07-18 | 2024-01-09 | 江苏正力新能电池技术有限公司 | Battery shell, battery and electric equipment |
| CN118448770A (en) * | 2024-05-31 | 2024-08-06 | 广东嘉尚新能源科技有限公司 | Heat dissipation protection structure of lithium ion battery pack |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120270075A1 (en) * | 2011-04-22 | 2012-10-25 | Hidekazu Fujimura | Secondary battery module and secondary battery pack |
| CN115020862A (en) * | 2022-06-29 | 2022-09-06 | 广东畅能达科技发展有限公司 | Battery shell, manufacturing method and power battery |
| CN220324564U (en) * | 2023-07-18 | 2024-01-09 | 江苏正力新能电池技术有限公司 | Battery shell, battery and electric equipment |
| CN118448770A (en) * | 2024-05-31 | 2024-08-06 | 广东嘉尚新能源科技有限公司 | Heat dissipation protection structure of lithium ion battery pack |
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