WO2020147367A1 - 一种相变乳液传热工质及其制备方法和电池热管理系统 - Google Patents

一种相变乳液传热工质及其制备方法和电池热管理系统 Download PDF

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WO2020147367A1
WO2020147367A1 PCT/CN2019/113794 CN2019113794W WO2020147367A1 WO 2020147367 A1 WO2020147367 A1 WO 2020147367A1 CN 2019113794 W CN2019113794 W CN 2019113794W WO 2020147367 A1 WO2020147367 A1 WO 2020147367A1
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phase change
battery
heat transfer
working fluid
heat
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English (en)
French (fr)
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张正国
王方娴
凌子夜
方晓明
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to GB2111617.3A priority Critical patent/GB2595152B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • 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
    • 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
    • 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
    • H01M10/617—Types of temperature control for achieving uniformity or desired distribution of temperature
    • 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
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6552—Closed pipes transferring heat by thermal conductivity or phase transition, e.g. heat pipes
    • 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
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • 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
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6554—Rods or plates
    • H01M10/6555—Rods or plates arranged between the cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Definitions

  • the present invention relates to the technical field of battery thermal management, in particular to a phase change emulsion heat transfer working fluid and a preparation method thereof, and a battery thermal management system using the phase change emulsion heat transfer working fluid.
  • Lithium-ion batteries have the advantages of high energy density, high working voltage, and good cycle performance. They are one of the main power sources for new energy vehicles. However, the performance of lithium-ion batteries is greatly affected by temperature. Too high or too low a temperature will significantly reduce the effective capacity and cycle life of the battery. Lithium-ion batteries will generate a lot of heat during collisions, overcharge/discharge, etc., causing the battery temperature to become too high and reducing the battery life.
  • the current battery thermal management system can be divided into four categories according to the heat transfer medium: air thermal management, heat pipe thermal management, phase change material thermal management and liquid thermal management.
  • the liquid thermal management system has the advantages of good shape adaptability, high convection heat transfer coefficient, and relatively good temperature consistency of the battery pack, and has received extensive attention in recent years.
  • the commonly used heat transfer working fluids for liquid thermal management systems are water, glycol aqueous solution, and heat transfer oil (CN1 02832425 A ⁇ CN102881959A and CN205992580U).
  • the utility model patent of the publication number CN205992580 U provides a battery pack that uses thermal oil for thermal management, and the temperature of each battery is balanced through the convection effect of the thermal oil.
  • the heat transfer fluid used in the system is heat transfer oil, which has problems such as low energy storage density, low thermal conductivity and high viscosity, and its heat dissipation effect is very limited, which limits its practical application.
  • the present invention provides a method for preparing a phase change emulsion heat transfer working fluid and a battery thermal management system thereof, which efficiently regulates the temperature of the battery pack and improves battery performance and reliability
  • a battery thermal management system includes a battery pack composed of a number of batteries, a cooling pipe is arranged in the gap between the battery cells, and a forced convection phase change emulsion heat transfer working medium is arranged in the cooling pipe.
  • the battery is a cylindrical battery, a rectangular battery or a soft pack battery.
  • the battery pack is a battery pack composed of several batteries arranged in a parallel or staggered arrangement.
  • the electrodes of the plurality of batteries are connected by spot welding nickel sheets or busbar lock screws.
  • the material of the cooling tube includes copper, aluminum oxide and stainless steel.
  • phase change emulsion heat transfer working fluid used in a battery thermal management system wherein the phase change emulsion heat transfer working fluid is calculated by mass percentage and includes:
  • phase change material 5 to 30% of phase change material, 0.5 to 10% of surface active agent, 0 to 5% of nucleating agent and 55 to 94.5% of deionized water.
  • the phase change material is an aliphatic hydrocarbon or aliphatic alcohol with a phase change melting temperature of 25 to 45°C; and/or the phase change latent heat of the phase change material is 150 to 260
  • the surfactant includes sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB), polyethylene Glycol sorbitol laurate (Tw een 20), polyoxyethylene sorbitan monostearate (Tween 60), polyoxyethylene sorbitan Monooleate (Tween 80), Sorbitan Monolaurate (Span 20), Sorbitan Stearate (Span 60), Sorbitan Oleate (Span 80), Triton X- One or more of 100 (Triton X-100), polyvinyl alcohol (PVA) and polyethylene glycol (PEG).
  • SDBS sodium dodecylbenzene sulfonate
  • SDS sodium dodecyl sulfate
  • CTAB cetyltrimethylammonium bromide
  • polyethylene Glycol sorbitol laurate Tw een 20
  • the nucleating agent includes nano graphite powder, graphene, graphene oxide, carbon nanotubes, carbon-coated nickel, nano copper, alumina, silica, and paraffin wax with a melting point of 50 to 80° C.
  • PVA polyvinyl alcohol
  • a method for preparing the heat transfer working fluid of the phase change emulsion includes the steps:
  • the phase change emulsion as a liquid heat transfer working medium, is characterized in that when the temperature is higher than the phase change temperature of the phase change material, the phase change material undergoes a solid-liquid phase transition.
  • This phase change process has a constant phase transition temperature,
  • the advantage of large variable latent heat can significantly increase the effective specific heat capacity of the heat transfer fluid.
  • the heat transfer performance of the phase change emulsion working fluid is significantly better than that of heat transfer fluids in which water and heat transfer oil store heat in the form of sensible heat.
  • phase change emulsion heat transfer working fluid when the battery is thermally managed, the phase change emulsion heat transfer working fluid with high energy storage density absorbs the heat released by the battery and stores it in the form of latent heat. Compared with the traditional liquid working fluid, the phase change emulsion heat transfer working fluid absorbs the heat. The change is small, so that the temperature difference between the battery packs is also reduced. Therefore, the use of phase change emulsion heat transfer working fluid can not only effectively enhance heat transfer, improve the heat dissipation capacity of the battery, but also improve the temperature consistency of the battery pack, thereby achieving efficient control of the temperature of the battery pack, and improving battery performance and reliability Brief description of the drawings
  • FIG. 1 is a schematic structural diagram of a battery thermal management system using a phase change emulsion heat transfer working fluid according to Embodiment 1 of the present invention
  • Example 2 is a differential scanning calorimetry (DSC) curve of the heat transfer working fluid of the phase change emulsion obtained in Example 2 of the present invention.
  • DSC differential scanning calorimetry
  • FIG. 3 is a schematic diagram of the particle size distribution of the phase change emulsion heat transfer working fluid obtained in Example 2 of the present invention.
  • FIG. 4 is a graph showing the variation of the maximum temperature difference of the battery pack with the discharge rate when the heat transfer working fluid and water of the phase change emulsion obtained in Example 2 of the present invention are used as the cooling liquid respectively.
  • a battery thermal management system includes a battery pack composed of 20 lithium-ion batteries 1, and a cooling pipe 2 of aluminum oxide with an inner diameter of 4 mm is arranged in the gap between the battery cells. ,
  • the cooling pipe 2 is provided with a forced convection phase change emulsion heat transfer working medium 3.
  • the battery is a cylindrical battery, a rectangular battery or a soft pack battery.
  • the battery pack is a battery pack composed of several batteries arranged in parallel or in a staggered manner.
  • 20 lithium-ion batteries are connected to form a battery pack by spot welding nickel sheets.
  • the heat transfer performance of the phase change emulsion working fluid is significantly better than heat transfer fluids that store heat in the form of sensible heat such as heat transfer oil and water.
  • the phase change emulsion heat transfer refrigerant with high energy storage density absorbs the heat released by the battery and stores it in the form of latent heat.
  • the phase change emulsion heat transfer refrigerant absorbs the heat. The change is small, so that the temperature difference between the battery packs is also reduced.
  • phase change emulsion heat transfer working fluid can not only effectively enhance heat transfer, improve the heat dissipation capacity of the battery, but also improve the temperature consistency of the battery pack, thereby achieving efficient control of the temperature of the battery pack, and improving battery performance and reliability .
  • Example 2 A method for preparing a phase change emulsion heat transfer working fluid, including the steps:
  • SDBS sodium dodecylbenzene sulfonate
  • OP28E phase change material is heated to 50°C in a constant temperature water bath and melted into a liquid phase change material, and then added to the aqueous solution of sodium dodecylbenzene sulfonate (SDBS), and ultrasonic emulsification is carried out for 3 minutes at a power of 1000 W.
  • SDBS sodium dodecylbenzene sulfonate
  • the heat transfer working fluid of OP28E/water phase change emulsion with a mass fraction of 10% is obtained.
  • FIG. 2 is the DSC curve of the OP28E/water phase change emulsion obtained in Example 2.
  • the phase change temperature of the phase change emulsion is
  • FIG. 3 is a schematic diagram of the particle size distribution of the OP28E/water phase change emulsion obtained in Example 2.
  • the particle size distribution of the phase change emulsion is unimodal, and the average particle size is 180.9 nm.
  • the OP28E/water phase change emulsion heat transfer working fluid prepared in this embodiment was injected into the alumina cooling tube with an inner diameter of 4 mm in Example 1, and the OP28E/water phase change emulsion heat transfer working fluid and water were respectively inside the cooling tube Forced convection, while recording the maximum temperature and maximum temperature difference of the battery pack with discharge time under different discharge rates.
  • Figure 4 shows the change of the maximum temperature difference of the battery pack with the discharge rate when the coolant volume flow rate is 200 mL/min. Under different discharge rate conditions, the maximum temperature difference of the battery pack using the phase change emulsion heat transfer medium as the cooling liquid is smaller than the maximum temperature difference of the battery pack using water as the cooling liquid.
  • the maximum temperature difference of the battery pack is 3.3°C when the OP28E/water phase change emulsion heat transfer working medium with a mass fraction of 10% is used as the coolant compared to the battery pack using water as the coolant. Reduced by 0.8°C.
  • the OP28E/water phase change emulsion heat transfer working fluid in this embodiment has a high energy storage density, and the temperature change of the phase change emulsion heat transfer working fluid after absorbing heat is small, so that the temperature difference between the battery packs is also reduced. Therefore, the use of phase change emulsion heat transfer working fluid can not only effectively enhance heat transfer, improve the heat dissipation capacity of the battery, but also improve the temperature consistency of the battery pack, thereby achieving efficient control of the temperature of the battery pack, and improving battery performance and reliability .
  • a method for preparing a phase change emulsion heat transfer working fluid including the steps:
  • SDBS sodium dodecylbenzene sulfonate
  • 4% by mass of sodium dodecylbenzene sulfonate (SDBS) was added to 76% by mass of deionized water, and under a constant temperature water bath of 50° C., magnetic stirring was performed for 300 r/min to obtain Sodium dodecyl benzene sulfonate (SDBS) aqueous solution; 20% OP28E phase change material is heated to 50°C in a constant temperature water bath to melt into a liquid The phase change material is added to the aqueous solution of sodium dodecyl benzene sulfonate (SDBS), and the heat transfer process of OP28E/water phase change emulsion with a mass fraction of 20% is obtained by sonicating for 10 minutes at a power of 760 W. quality.
  • SDBS sodium dodecylbenzene sulfonate
  • the OP28E/water phase change emulsion heat transfer working fluid obtained above was measured by DSC, and its phase transition temperature was 26.2°C, and the phase transition enthalpy was 44.1 J/g; measured by Malvern Nanoparticle Size Analyzer, OP28E /Water phase change emulsion heat transfer working fluid particle size is about 191.4 nm.
  • the discharge rate is 2C
  • the maximum temperature difference of the battery pack is 2.5°C when the OP28E/water phase change emulsion heat transfer working medium with a mass fraction of 20% is used as the coolant compared to the battery pack using water as the coolant.
  • the decrease of 1.6°C indicates that the OP28E/water phase change emulsion heat transfer working fluid can not only effectively enhance the heat dissipation capacity of the battery thermal management system, but also improve the temperature consistency of the battery pack, so as to achieve efficient control of the temperature of the battery pack and increase Battery performance and reliability.
  • a method for preparing a phase change emulsion heat transfer working fluid including the steps:
  • the above-obtained OP35E/water phase change emulsion heat transfer working fluid was measured by DSC, and its phase transition temperature was 32.8°C, and the phase transition enthalpy was 22.3 J/g; measured by a Malvern nanoparticle size analyzer, OP35E /Water phase change emulsion heat transfer working fluid particle size is about 232.5 nm.
  • the discharge rate is 2C
  • the maximum temperature difference of the battery pack is 3.0°C when the OP35E/water phase change emulsion heat transfer working medium with a mass fraction of 10% is used as the coolant compared to the battery pack using water as the coolant.
  • the decrease of 0.9°C indicates that the OP35E/water phase change emulsion heat transfer working fluid can not only effectively enhance the heat dissipation capacity of the battery thermal management system, but also improve the temperature consistency of the battery pack, so as to achieve efficient control of the temperature of the battery pack and increase Battery performance and reliability.
  • a method for preparing a phase change emulsion heat transfer working fluid including the steps:
  • the OP44E/water phase change emulsion heat transfer working fluid obtained above was measured by DSC, and its phase transition temperature was 39.2°C, and the phase transition enthalpy was 48.6J/g; measured by a Malvern nanoparticle size analyzer, OP44E /Water phase change emulsion heat transfer working fluid particle size is about 176.4nm.
  • the maximum temperature difference of the battery pack is 1.8°C when the OP44E/water phase change emulsion heat transfer working medium with a mass fraction of 20% is used as the coolant compared to the battery pack using water as the coolant.
  • the decrease of 1.6°C indicates that the OP44E/water phase change emulsion heat transfer working fluid can not only effectively enhance the heat dissipation capacity of the battery thermal management system, but also improve the temperature consistency of the battery pack, so as to realize the efficient control of the temperature of the battery pack and increase Battery performance and reliability.
  • a method for preparing a phase change emulsion heat transfer working fluid including the steps:
  • the above-obtained normal octadecane/water phase change emulsion heat transfer working fluid was measured by DSC, and its phase transition temperature was 27.8 ° C, and the phase transition enthalpy was 48.3 J/g; by the Malvern nano particle size analyzer According to the measurement, the particle size of the heat transfer working fluid of the octadecane/water phase change emulsion is about 196.7 nm.
  • the maximum temperature difference of the battery pack is 2.7°C when the 10% mass fraction of the positive eighteen yakitorian/water phase change emulsion heat transfer working fluid is used as the coolant ,
  • the maximum temperature difference is reduced by 1.4°C, indicating that the positive eighteen-yellow/water phase change emulsion heat transfer working fluid can not only effectively enhance the heat dissipation capacity of the battery thermal management system, but also improve the temperature consistency of the battery pack, thereby Realize the efficient control of the temperature of the battery pack, and improve the battery performance and reliability.
  • a method for preparing a phase change emulsion heat transfer working fluid including the steps:
  • the above-obtained n-ecosine/water phase change emulsion heat transfer working fluid was measured by DSC, and its phase transition temperature was 36.5° C., and the phase transition enthalpy was 49.1 J/g; by the Malvern nano particle size analyzer According to the measurement, the particle size of the heat transfer working fluid of the phase change emulsion is about 208.4 nm.
  • the discharge rate is 2C, compared with the battery pack that uses water as the cooling liquid, the mass fraction of 20% is used.
  • the maximum temperature difference of the battery pack is 2.0°C, and the maximum temperature difference is reduced by 1.4°C, indicating that the positive twenty ⁇ /water phase change emulsion heat transfer working fluid can effectively strengthen the battery
  • the heat dissipation capacity of the thermal management system can also improve the temperature consistency of the battery pack, thereby achieving efficient control of the temperature of the battery pack, and improving battery performance and reliability.
  • 2% by mass polyvinyl alcohol (PVA) and 2% polyethylene glycol 600 (PEG 600) were added to 74% by mass deionized water, and magnetically stirred under a constant temperature water bath of 80° C. Stir uniformly at 500 r/min to obtain a mixed surfactant aqueous solution; Heat the n-tetradecanol phase change material with a mass percentage of 20% in a constant temperature water bath to 80°C to melt it into a liquid phase change material, and then add it to the mixed surface active In the aqueous solution of solvent, ultrasonic emulsification for 10 min under the power of 800 W, the heat transfer working fluid of the n-tetradecanol/water phase change emulsion with a mass fraction of 20% is obtained.
  • PVA polyvinyl alcohol
  • PEG 600 polyethylene glycol 600
  • n-tetradecyl alcohol/water phase change emulsion heat transfer working fluid was measured by DSC, and its phase transition temperature was 36.9° C., and the phase transition enthalpy was 43.8 J/g; It was determined that the particle size of the heat transfer working fluid of the n-tetradecanol/water phase change emulsion was about 381.6 nm.
  • the maximum temperature difference of the battery pack is 2.3°C when the 20% mass fraction n-tetradecanol/water phase change emulsion heat transfer working fluid is used as the coolant, and the maximum temperature difference is reduced by 1.2°C, indicating that n-tetradecanol/
  • the water phase change emulsion heat transfer working fluid can not only effectively strengthen the heat dissipation capacity of the battery thermal management system, but also improve the temperature consistency of the battery pack, thereby realizing efficient control of the temperature of the battery pack, and improving battery performance and reliability.

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Abstract

本发明公开了一种相变乳液传热工质及其制备方法和电池热管理系统，所述电池热管理系统包括由若干电池组成的电池组，电池单体之间缝隙内设置有冷却管，所述冷却管内设置有强制对流的相变乳液传热工质。所述相变乳液传热工质以质量百分比计，包括：5~30%的相变材料，0.5~10%的表面活性剂，0~5%的成核剂和55~94.5%的去离子水。所述相变乳液传热工质通过超声乳化法制备得到。本发明应用相变乳液传热工质的相变潜热吸收热量，强化电池热管理系统的散热能力，提升电池组的温度一致性，实现对电池组的温度高效调控。

Description

一种相变 液传热工质及其制备方法和电池热管理系统 技术领域
[0001] 本发明涉及电池热管理技术领域， 特别涉及一种相变乳液传热工质及其制备方 法和采用所述相变乳液传热工质的电池热管理系统。
背景技术
[0002] 交通运输业作为“能源消耗大户”， 在消耗大量化石燃料的同时还排放大量的温 室气体， 加剧温室效应。 新能源汽车是降低石油消耗量， 减少温室气体排放的 有效途径之一。 锂离子电池具有能量密度高、 工作电压大、 循环性能好等优点 ， 是新能源汽车的主要动力源之一。 然而， 锂离子电池的性能受温度的影响很 大， 温度过高或过低会显著降低电池的有效容量和循环寿命。 锂离子电池在发 生碰撞， 过充 /放电等过程中会产生大量的热量， 造成电池温度过高， 降低电池 的使用寿命。 过高的温度甚至会引发电池内部严重的热失控， 导致火灾、 爆炸 等安全问题。 此外， 电池组的温度一致性也是影响电池性能的关键因素。 如果 电池之前的温差过大， 不同电池的反应速率、 充电或放电速率差别也较大， 部 分电池的充电或放电过程可能会提前结束， 导致电池组的容量不能完全充满或 释放， 从而降低了电池组的有效容量。 为了预防上述的问题， 需要对电池进行 有效的热管理， 保证电池高效、 安全工作。 目前电池热管理系统按照传热介质 可以分四类： 空气热管理、 热管热管理和相变材料热管理和液体热管理。 其中 ， 液体热管理系统具有形状适应性好， 对流换热系数高， 电池组温度一致性相 对较好等优点， 近年来受到了人们的广泛关注。
[0003] 目前， 液体热管理系统常用的传热工质是水， 乙二醇水溶液和导热油等 (CN1 02832425 A ^ CN102881959A和 CN205992580U) 。 其中， 在公告号 CN205992580 U的实用新型专利中， 提供了一种使用导热油进行热管理的电池组， 通过导热油 的对流作用平衡各电池的温度。 但是系统所采用的传热流体是导热油， 其存在 储能密度低， 导热系数低和粘度较大等问题， 散热效果十分有限， 这都限制了 其实际应用。 这些液体工质在换热过程中完全以显热形式传导热量， 与电池换 热吸收热量后， 其自身温度逐渐升高， 且电池发热量越大， 相同流量下液体工 质的温升也越高。 由于液体工质温度变化大导致电池组之间的温度一致性下降 ， 从而影响了电池组的性能。
发明概述
技术问题
问题的解决方案
技术解决方案
[0004] 针对以上技术的一个或多个问题， 本发明提供了一种相变乳液传热工质的制备 方法及其电池热管理系统， 对电池组的温度高效调控， 提高电池性能和可靠性
[0005] 本发明的目的至少通过如下技术方案之一实现。
[0006] 一种电池热管理系统， 包括由若干电池组成的电池组， 电池单体之间缝隙内设 置有冷却管， 所述冷却管内设置有强制对流的相变乳液传热工质。
[0007] 优选的， 所述电池为圆柱形电池、 矩形电池或软包电池。
[0008] 优选的， 所述电池组为若干电池通过平行或交错排布方式组成的电池组。
[0009] 优选的， 所述若干电池的电极通过点焊镍片或母排锁螺丝方式进行连接。
[0010] 优选的， 所述冷却管材质包括铜， 氧化铝和不锈钢。
[0011] 一种用于电池热管理系统的相变乳液传热工质， 所述相变乳液传热工质以质量 百分比计， 包括：
[0012] 5~30%的相变材料， 0.5~10%的表面活性齐 U， 0~5%的成核剂和 55~94.5%的去离 子水。
[0013] 优选的， 所述相变材料为相变熔化温度为 25~45°C的脂肪烃或脂肪醇； 和 /或所 述相变材料的相变潜热为 150~260
J/g。 包括熔点为 25~45°C的石错， 比如德国 RUBITHERM生产的石蜡 （相变温度 为 28， 31， 35， 42与 44°C） 中的至少一种。
[0014] 优选的， 所述表面活性剂包括十二焼基苯磺酸钠 （SDBS） 、 十二焼基硫酸钠 （SDS） 、 十六烷基三甲基溴化铵 （CTAB） 、 聚乙二醇山梨糖醇月桂酸酯 （Tw een 20） 、 聚氧乙烯脱水山梨醇单硬脂酸酯 （Tween 60） 、 聚氧乙烯山梨糖醇酐 单油酸酯 （Tween 80） 、 失水山梨醇单月桂酸酯 （Span 20） 、 失水山梨醇硬脂 酸酯 （Span 60） 、 油酸山梨醇酯 （Span 80） 、 曲拉通 X-100 （Triton X-100） 、 聚乙烯醇 （PVA） 和聚乙二醇（PEG）中的一种或两种以上。
[0015] 优选的， 所述成核剂包括纳米石墨粉， 石墨稀， 氧化石墨稀， 碳纳米管， 碳包 镍， 纳米铜， 氧化铝， 二氧化硅， 熔点为 50~80°C的石蜡和聚乙烯醇 （PVA） 中 的一种或两种以上。
[0016] 一种如所述相变乳液传热工质的制备方法， 包括步骤：
[0017] 将以质量百分比计为 0.5~10%表面活性剂 （一种或两种以上） 加入 55~94.5%去 离子水中， 50°C~70°C恒温水浴加热， 在 200~800 r/min条件下搅拌， 得到第一混 合溶液；
[0018] 将以质量百分比计为 5~30%相变材料 （一种或两种以上） 和 0~5%成核剂按一定 比例混合， 恒温水浴加热至温度高于相变材料熔点但低于 80°C， 在 200~800 r/min 条件下搅拌使其充分混合或熔化， 得到第二混合溶液；
[0019] 50°C~70°C恒温水浴条件下， 将所述第二混合溶液加入到所述第一混合溶液中
， 再在功率 300~1000 W条件下超声乳化 3~30 min， 制得相变乳液传热工质。 发明的有益效果
有益效果
[0020] 相对现有技术， 本发明的具有以下优点及有益效果：
[0021] 相变乳液作为液体传热工质， 其特点是温度高于相变材料的相变温度时， 相变 材料发生固-液相变， 这种相变过程具有相变温度恒定、 相变潜热大的优点， 能 显著地提高传热流体的有效比热容。 根据对流传热原理， 比热容的提高， 在相 同操作条件下， 相变乳液工质的传热性能显著优于水和导热油以显热形式存储 热量的传热流体。 此外， 对电池进行热管理时， 高储能密度的相变乳液传热工 质吸收电池释放的热量是以潜热的形式存储， 对比传统液体工质， 相变乳液传 热工质吸收热量后温度变化很小， 使得电池组之间的温差也减小。 因此， 采用 相变乳液传热工质， 既能有效强化传热， 提高电池的散热能力， 又能改善电池 组的温度一致性， 从而实现对电池组的温度高效调控， 提高电池性能和可靠性 对附图的简要说明
附图说明
[0022] 图 1是本发明实施例 1的应用相变乳液传热工质的电池热管理系统的结构示意图
[0023] 图 2为本发明实施例 2所得相变乳液传热工质的差示扫描量热 (DSC) 曲线。
[0024] 图 3为本发明实施例 2所得相变乳液传热工质的粒径分布示意图。
[0025] 图 4为本发明实施例 2所得相变乳液传热工质和水分别作为冷却液时， 电池组的 最大温差随放电倍率的变化图。
[0026] 附图中的标记为： 1-电池， 2 -冷却管， 3 -相变乳液传热工质。
发明实施例
本发明的实施方式
[0027] 下面通过具体实施例对本发明作进一步详细的描述， 但本发明的实施方式不限 于此。
[0028] 实施例 1
[0029] 如图 1所示， 一种电池热管理系统， 包括由 20个锂离子的电池 1组成的电池组， 电池单体之间缝隙内设置有内径为 4 mm的氧化铝的冷却管 2, 所述冷却管 2内设 置有强制对流的相变乳液传热工质 3。
[0030] 所述电池为圆柱形电池、 矩形电池或软包电池。
[0031] 所述电池组为若干电池通过平行或交错排布方式组成的电池组。
[0032] 本实施例中 20个锂离子电池通过点焊镍片连接组成电池组。
[0033] 相同操作条件下， 相变乳液工质的传热性能显著优于导热油、 水等以显热形式 存储热量的传热流体。 此外， 对电池进行热管理时， 高储能密度的相变乳液传 热工质吸收电池释放的热量是以潜热的形式存储， 对比传统液体工质， 相变乳 液传热工质吸收热量后温度变化很小， 使得电池组之间的温差也减小。 因此， 采用相变乳液传热工质， 既能有效强化传热， 提高电池的散热能力， 又能改善 电池组的温度一致性， 从而实现对电池组的温度高效调控， 提高电池性能和可 靠性。
[0034] 实施例 2 [0035] 一种相变乳液传热工质的制备方法， 包括步骤：
[0036] 将质量百分比为 2%的十二烷基苯磺酸钠 (SDBS) 加入质量百分比为 88%的去 离子水溶解， 在 50°C恒温水浴下， 磁力搅拌 300 r/min搅拌均匀， 得到十二烷基苯 磺酸钠 (SDBS) 水溶液； 将质量百分比 10%的
OP28E相变材料恒温水浴加热到 50°C熔化成液态相变材料， 再将其加入到所述十 二烷基苯磺酸钠 (SDBS) 水溶液中， 在功率 1000 W条件下超声乳化 3 min， 即 得到质量分数为 10%的 OP28E/水相变乳液传热工质。
[0037] 图 2为实施例 2得到的 OP28E/水相变乳液的 DSC曲线。 该相变乳液的相变温度为
26.2°C 相变焓为 21.6 J/g
[0038] 图 3为实施例 2得到的 OP28E/水相变乳液的粒径分布示意图。 该相变乳液的粒径 分布呈单峰， 平均粒径为 180.9 nm。
[0039] 将本实施例制备的 OP28E/水相变乳液传热工质注入实施例 1内径为 4 mm的氧化 铝冷却管内， OP28E/水相变乳液传热工质和水分别在冷却管内部强制对流， 同 时记录不同放电倍率下电池组的最高温度和最大温差随放电时间变化曲线。 图 4 是冷却液体积流量为 200 mL/min时， 电池组的最大温差随放电倍率的变化。 不 同放电倍率条件下， 应用相变乳液传热工质作为冷却液的电池组的最大温差均 小于应用水作为冷却液的电池组的最大温差。 放电倍率为 2C时， 相对于使用水 作为冷却液的电池组， 以质量分数为 10%的 OP28E/水相变乳液传热工质作为冷 却液时电池组的最大温差为 3.3°C， 最大温差降低了 0.8°C。
[0040] 本实施例中的 OP28E/水相变乳液传热工质的储能密度大， 相变乳液传热工质吸 收热量后温度变化很小， 使得电池组之间的温差也减小。 因此， 采用相变乳液 传热工质， 既能有效强化传热， 提高电池的散热能力， 又能改善电池组的温度 一致性， 从而实现对电池组的温度高效调控， 提高电池性能和可靠性。
[0041] 实施例 3
[0042] 一种相变乳液传热工质的制备方法， 包括步骤：
[0043] 将质量百分比为 4%的十二烷基苯磺酸钠 (SDBS) 加入质量百分比为 76%的去 离子水， 在 50°C恒温水浴下， 磁力搅拌 300 r/min搅拌均匀， 得到十二烷基苯磺酸 钠 (SDBS) 水溶液； 将 20%的 OP28E相变材料恒温水浴加热到 50°C熔化成液态 相变材料， 再将其加入到十二烷基苯磺酸钠 （SDBS） 水溶液中， 在功率 760 W 条件下超声 10 min， 即得到质量分数为 20%的 OP28E/水相变乳液传热工质。
[0044] 上述所得到的 OP28E/水相变乳液传热工质经 DSC测定， 其相变温度为 26.2°C， 相变焓为 44.1 J/g; 经马尔文纳米粒度分析仪的测定， OP28E/水相变乳液传热工 质的粒径约为 191.4 nm。 放电倍率为 2C时， 相对于使用水作为冷却液的电池组， 以质量分数为 20%的 OP28E/水相变乳液传热工质作为冷却液时电池组的最大温 差为 2.5°C， 最大温差降低了 1.6°C， 说明 OP28E/水相变乳液传热工质既能有效强 化电池热管理系统的散热能力， 又能改善电池组的温度一致性， 从而实现对电 池组的温度高效调控， 提高电池性能和可靠性。
[0045] 实施例 4
[0046] 一种相变乳液传热工质的制备方法， 包括步骤：
[0047] 将质量百分比为 0.8%的聚氧乙烯脱水山梨醇单硬脂酸酯 （Tween 60） 、 质量百 分比为 1.1%的失水山梨醇硬脂酸酯 （Span 60） 和 0.1%的聚乙烯醇 （PVA） 加入 质量百分比为 88%的去离子水中， 在 70°C恒温水浴下， 磁力搅拌 300 r/min搅拌均 匀， 得到混合表面活性剂水溶液； 将质量百分比为 10%的 OP35E相变材料恒温水 浴加热到 70°C熔化成液态相变材料， 再将其加入到混合表面活性剂水溶液中， 在 功率 650 W条件下超声乳化 10 min, 即得到质量分数为 10%的 OP35E/水相变乳液 传热工质。
[0048] 上述所得到的 OP35E/水相变乳液传热工质经 DSC测定， 其相变温度为 32.8°C， 相变焓为 22.3 J/g; 经马尔文纳米粒度分析仪的测定， OP35E/水相变乳液传热工 质的粒径约为 232.5 nm。 放电倍率为 2C时， 相对于使用水作为冷却液的电池组， 以质量分数为 10%的 OP35E/水相变乳液传热工质作为冷却液时电池组的最大温 差为 3.0°C， 最大温差降低了 0.9°C， 说明 OP35E/水相变乳液传热工质既能有效强 化电池热管理系统的散热能力， 又能改善电池组的温度一致性， 从而实现对电 池组的温度高效调控， 提高电池性能和可靠性。
[0049] 实施例 5
[0050] 一种相变乳液传热工质的制备方法， 包括步骤：
[0051] 将质量百分比为 4%的十二烷基硫酸钠 （SDS） 加入质量百分比为 74%的去离子 水中， 在 70°C恒温水浴下， 磁力搅拌 300
r/min搅拌均匀， 得到十二烷基硫酸钠 (SDS) 水溶液； 将质量百分比为 20%的 OP44E相变材料和 2%的纳米石墨粉在 70°C恒温水浴条件下， 磁力搅拌 600 r/min 搅拌均匀， 得到含纳米石墨粉的液态相变材料， 再将其加入到十二烷基硫酸钠 (SDS) 水溶液中， 在功率 760 W条件下超声乳化 30
min， 即得到质量分数为 20%的 OP44E/水相变乳液传热工质。
[0052] 上述所得到的 OP44E/水相变乳液传热工质经 DSC测定， 其相变温度为 39.2°C， 相变焓为 48.6J/g; 经马尔文纳米粒度分析仪的测定， OP44E/水相变乳液传热工 质的粒径约为 176.4nm。 放电倍率为 2C时， 相对于使用水作为冷却液的电池组， 以质量分数为 20%的 OP44E/水相变乳液传热工质作为冷却液时电池组的最大温 差为 1.8°C， 最大温差降低了 1.6°C， 说明 OP44E/水相变乳液传热工质既能有效强 化电池热管理系统的散热能力， 又能改善电池组的温度一致性， 从而实现对电 池组的温度高效调控， 提高电池性能和可靠性。
[0053] 实施案例 6
[0054] 一种相变乳液传热工质的制备方法， 包括步骤：
[0055] 将质量百分比为 1.0%的十六烷基三甲基溴化铵 (CTAB) 、 质量百分比为 1.0% 十二烷基苯磺酸钠 (SDBS) 和质量百分比为 0.1 %的氧化石墨烯加入质量百分比 为 87.9%的去离子水中， 在 70°C恒温水浴和功率为 400 W条件下， 超声 5 min， 得 到含氧化石墨烯的混合表面活性剂水溶液； 将质量百分比为 10%的正十八烷相变 材料和在 70°C恒温水浴条件下熔化成液态相变材料， 再将其加入到含氧化石墨烯 的混合表面活性剂水溶液， 在功率 760 W条件下超声乳化 10 min， 即得到质量分 数为 10%的正十八焼 /水相变乳液传热工质。
[0056] 上述所得到的正十八焼 /水相变乳液传热工质经 DSC测定， 其相变温度为 27.8°C ， 相变焓为 48.3 J/g; 经马尔文纳米粒度分析仪的测定， 正十八焼 /水相变乳液传 热工质的粒径约为 196.7 nm。 放电倍率为 2C时， 相对于使用水作为冷却液的电池 组， 以质量分数为 10%的正十八焼 /水相变乳液传热工质作为冷却液时电池组的 最大温差为 2.7°C， 最大温差降低了 1.4°C， 说明正十八焼 /水相变乳液传热工质既 能有效强化电池热管理系统的散热能力， 又能改善电池组的温度一致性， 从而 实现对电池组的温度高效调控， 提高电池性能和可靠性。
[0057] 实施案例 7
[0058] 一种相变乳液传热工质的制备方法， 包括步骤：
[0059] 将质量百分比为 1.5%的聚氧乙烯山梨糖醇酐单油酸酯 (Tween 80) 、 质量百分 比为 2.5%油酸山梨醇酯 (Span
80) 加入质量百分比为 75.4%的去离子水溶解， 在 70°C恒温水浴下， 磁力搅拌 30 O r/min搅拌均勻， 得到混合表面活性剂水溶液； 将质量百分比为 20%的正二十烷 相变材料和 0.6%的碳纳米管在 70°C恒温水浴条件下， 磁力搅拌 600 r/min搅拌均匀 ， 得到含碳纳米管的液态正二十烷相变材料， 再将其加入混合表面活性剂水溶 液中， 在功率 800 W条件下超声乳化 10 min 即得到质量分数为 20%的正二十焼 / 水相变乳液传热工质。
[0060] 上述所得到的正二十焼 /水相变乳液传热工质经 DSC测定， 其相变温度为 36.5°C ， 相变焓为 49.1 J/g; 经马尔文纳米粒度分析仪的测定， 正二十焼 /水相变乳液传 热工质的粒径约为 208.4 nm 放电倍率为 2C时， 相对于使用水作为冷却液的电池 组， 以质量分数为 20%的正二十焼 /水相变乳液传热工质作为冷却液时电池组的 最大温差为 2.0°C， 最大温差降低了 1.4°C， 说明正二十焼 /水相变乳液传热工质既 能有效强化电池热管理系统的散热能力， 又能改善电池组的温度一致性， 从而 实现对电池组的温度高效调控， 提高电池性能和可靠性。
[0061] 实施案例 8
[0062] 将质量百分比为 2%的聚乙烯醇 (PVA) 和 2%的聚乙二醇 600 (PEG 600) 加入 质量百分比为 74%的去离子水中， 在 80°C恒温水浴下， 磁力搅拌 500 r/min搅拌均 匀， 得到混合表面活性剂水溶液； 将质量百分比为 20%的正十四醇相变材料恒温 水浴加热到 80°C熔化成液态相变材料， 再将其加入到混合表面活性剂水溶液中， 在功率 800 W条件下超声乳化 10 min, 即得到质量分数为 20%的正十四醇 /水相变 乳液传热工质。
[0063] 上述所得到的正十四醇 /水相变乳液传热工质经 DSC测定， 其相变温度为 36.9°C ， 相变焓为 43.8 J/g; 经马尔文纳米粒度分析仪的测定， 正十四醇 /水相变乳液传 热工质的粒径约为 381.6 nm。 放电倍率为 2C时， 相对于使用水作为冷却液的电池 组， 以质量分数为 20%的正十四醇 /水相变乳液传热工质作为冷却液时电池组的 最大温差为 2.3°C， 最大温差降低了 1.2°C， 说明正十四醇 /水相变乳液传热工质既 能有效强化电池热管理系统的散热能力， 又能改善电池组的温度一致性， 从而 实现对电池组的温度高效调控， 提高电池性能和可靠性。
[0064] 上述实施例只是用于帮助理解本发明的方法及其核心思想， 但本发明的实施方 式并不受上述实施例的限制， 其他的任何未背离本发明的精神实质与原理下所 作的改变、 修饰、 替代、 组合、 简化， 均应为等效的置换方式， 都包含在本发 明的保护范围之内。

Claims

权利要求书
[权利要求 1] 一种电池热管理系统， 其特征在于， 包括由若干电池组成的电池组， 电池单体之间缝隙内设置有冷却管， 所述冷却管内设置有强制对流的 相变乳液传热工质。
[权利要求 2] 根据权利要求 1所述的一种电池热管理系统， 其特征在于， 所述电池 为圆柱形电池、 矩形电池或软包电池。
[权利要求 3] 根据权利要求 1所述一种电池热管理系统， 其特征在于， 所述电池组 为若干电池通过平行或交错排布方式组成的电池组。
[权利要求 4] 根据权利要求 1所述的一种电池热管理系统， 其特征在于， 所述若干 电池的电极通过点焊镍片或母排锁螺丝方式进行连接。
[权利要求 5] 根据权利要求 1所述的一种电池热管理系统， 其特征在于， 所述冷却 管材质包括铜， 氧化铝和不锈钢。
[权利要求 6] 一种用于如权利要求 1至 5中任一项所述的电池热管理系统的相变乳液 传热工质， 其特征在于， 所述相变乳液传热工质以质量百分比计， 包 括：
5~30%的相变材料， 0.5~10%的表面活性齐 ij， 0~5%的成核剂和 55~94. 5%的去离子水。
[权利要求 7] 根据权利要求 6所述的相变乳液传热工质， 其特性在于， 所述相变材 料为相变熔化温度为 25~45°C的脂肪烃或脂肪醇； 和 /或所述相变材料 的相变潜热为 150~260 J/g。
[权利要求 8] 根据权利要求 6所述的相变乳液传热工质， 其特征在于， 所述表面活 性剂包括十二烷基苯磺酸钠、 十二烷基硫酸钠、 十六烷基三甲基溴化 铵、 聚乙二醇山梨糖醇月桂酸酯、 聚氧乙烯脱水山梨醇单硬脂酸酯、 聚氧乙烯山梨糖醇酐单油酸酯、 失水山梨醇单月桂酸酯、 失水山梨醇 硬脂酸酯、 油酸山梨醇酯、 曲拉通 X-100、 聚乙烯醇和聚乙二醇中的 一种或两种以上。
[权利要求 9] 根据权利要求 6所述的相变乳液传热工质， 其特征在于， 所述成核剂 包括纳米石墨粉、 石墨稀、 氧化石墨烯、 碳纳米管、 碳包镍、 纳米铜 、 氧化铝、 二氧化硅、 熔点为 50~80°C的石错、 聚乙烯醇中的一种或 两种以上。
[权利要求 10] —种如权利要求 6至 9中任一项所述的相变乳液传热工质的制备方法， 其特征在于， 包括如下步骤：
将以质量百分比计为 0.5~10%表面活性剂加入 55~94.5%去离子水中， 50°C~70°C恒温水浴加热， 在 200~800 r/min条件下搅拌， 得到第一混 合溶液；
将以质量百分比计为 5~30%相变材料和 0~5%成核剂按一定比例混合 ， 恒温水浴加热至温度高于相变材料熔点但低于 80°C， 在 200~800 r/min条件下搅拌使其充分混合或熔化， 得到第二混合溶液；
50°C~70°C恒温水浴条件下， 将所述第二混合溶液加入到所述第一混 合溶液中， 再在功率 300~1000 W条件下超声乳化 3~30 min， 制得相变 乳液传热工质。
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