WO2025200318A1 - 一种自成型封装材料及其制备方法和应用、灌封电池的方法 - Google Patents

一种自成型封装材料及其制备方法和应用、灌封电池的方法

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Publication number
WO2025200318A1
WO2025200318A1 PCT/CN2024/118242 CN2024118242W WO2025200318A1 WO 2025200318 A1 WO2025200318 A1 WO 2025200318A1 CN 2024118242 W CN2024118242 W CN 2024118242W WO 2025200318 A1 WO2025200318 A1 WO 2025200318A1
Authority
WO
WIPO (PCT)
Prior art keywords
self
packaging material
forming packaging
solution
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/118242
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English (en)
French (fr)
Inventor
凌子夜
卢天正
张正国
方晓明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
South China Institute of Collaborative Innovation
Original Assignee
South China University of Technology SCUT
South China Institute of Collaborative Innovation
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Publication date
Application filed by South China University of Technology SCUT, South China Institute of Collaborative Innovation filed Critical South China University of Technology SCUT
Publication of WO2025200318A1 publication Critical patent/WO2025200318A1/zh
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • H01M10/05—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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/229—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M50/258—Modular batteries; Casings provided with means for assembling
    • H01M50/26—Assemblies sealed to each other in a non-detachable manner
    • 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 application belongs to the technical field of packaged batteries, and specifically relates to a self-forming packaging material, a preparation method and application thereof, and a method for encapsulating batteries.
  • Battery potting technology is a new technology used to address the challenges of battery pack packaging. It involves introducing a mixture of components A and B into the arranged battery pack, allowing the liquid to fill the gaps between the cells and adhere tightly to them. The liquid then solidifies, providing support, fixation, and shock and impact protection. However, the thermal conductivity of battery potting compound is insufficient to effectively control the battery temperature.
  • Battery thermal runaway occurs when a battery's internal temperature rises rapidly during use or charging due to factors such as thermal, electrochemical, or mechanical/electrical factors. This rise cannot be effectively controlled or cooled, ultimately leading to serious safety issues such as overheating, combustion, or explosion.
  • post-runaway protection primarily involves using insulation to slow the spread of heat.
  • existing insulation materials can only slow the spread of heat, leaving the possibility of heat spreading to adjacent battery packs.
  • Battery thermal runaway can be divided into three stages based on reaction kinetics: internal thermal runaway (90°C–200°C), battery bulging (200°C–350°C), and thermal runaway and explosive failure (350°C–850°C). Suppressing the runaway battery pack temperature within the first stage, controlling it within the initial stages of thermal runaway, is undoubtedly the most effective approach.
  • the present application provides a self-forming packaging material, a preparation method and application thereof, and a method for encapsulating batteries.
  • the self-forming packaging material provided in the present application has a two-stage heat absorption capability, which can quickly absorb heat and control the thermal runaway temperature of the battery within 200°C, thereby preventing fire and explosion caused by high temperature.
  • the present application provides a self-forming packaging material, comprising the following raw materials in percentage by weight:
  • the moisturizing material includes lithium chloride and/or calcium chloride.
  • the inorganic hydrated salt includes one or more of sodium acetate trihydrate, disodium hydrogen phosphate dodecahydrate, sodium sulfate decahydrate, calcium chloride hexahydrate, ammonium ferric sulfate dodecahydrate, aluminum sulfate 18hydrate, sodium carbonate decahydrate, potassium aluminum sulfate dodecahydrate, sodium thiosulfate pentahydrate, sodium aluminum silicate nonahydrate, sodium silicate pentahydrate, lithium chloride trihydrate, cobalt chloride hexahydrate, copper sulfate heptahydrate, ferrous sulfate heptahydrate, aluminum nitrate nonahydrate and calcium sulfate dihydrate.
  • the acrylic monomer includes one or more of acrylic acid, sodium acrylate, acrylamide, acrylate, stearic methacrylate, isopropyl acrylamide and hydroxyethyl methacrylate.
  • the polysaccharide monomers include one or more of alginic acid, sodium alginate, chitosan, starch and pectin.
  • the cross-linking agent comprises N,N-methylenebisacrylamide.
  • the initiating material includes one or more of ammonium persulfate, potassium persulfate, hydrogen peroxide, dibenzoyl peroxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate and azobisisobutyronitrile.
  • the present application also provides a method for preparing the self-forming packaging material described in the above technical solution, comprising the following steps:
  • the present application also provides the use of the self-forming packaging material described in the above technical solution or the self-forming packaging material prepared by the preparation method described in the above technical solution in battery potting.
  • the present application also provides a method for encapsulating a battery using the self-forming encapsulation material described in the above technical solution or the self-forming encapsulation material prepared by the preparation method described in the above technical solution, comprising the following steps:
  • the batteries to be packaged are arranged in a battery box, and the battery box is filled with self-forming packaging material, sealed, and cured to obtain a packaged battery pack.
  • the distance between adjacent batteries in the battery box is greater than 0.5 mm.
  • the curing temperature is 20 to 80° C.
  • the curing time is 1 to 40 minutes.
  • the present application provides a self-forming packaging material, comprising the following raw materials in percentage by weight: 60-80% inorganic hydrated salt, 5-15% water, 5-10% acrylic monomer, 0.3-5% crosslinking agent, 0.7-5% polysaccharide monomer, 2-10% moisturizing material, and 1-5% initiating material; the moisturizing material comprises lithium chloride and/or calcium chloride.
  • the self-forming packaging material has two stages of heat absorption capacity, wherein the first stage is before 100°C and the second stage is between 20 and 60°C.
  • the unit heat absorption of the material melting between 100°C and 200°C is greater than 140J/g; the unit heat absorption of the material decomposition between 100°C and 200°C is greater than 980J/g.
  • the heat storage capacity of different temperature ranges can proceed spontaneously after the temperature is reached, forming a continuous heat absorption effect, thereby realizing thermal management and thermal runaway protection of the battery, controlling the runaway battery in the early stage of temperature runaway, and reducing the risk of thermal runaway.
  • FIG1 is a DSC graph of the solid self-forming encapsulating material and disodium hydrogen phosphate dodecahydrate (DHPD) prepared in Example 1;
  • FIG2 is a schematic diagram of the structure of the arrangement of 18650 lithium-ion batteries in a battery box
  • Figure 3 shows the temperature curves of different battery packs at different detection times
  • FIG4 is a temperature variation curve of different positions of the battery pack of Comparative Example 1 at different detection times
  • FIG5 is a temperature variation curve of different positions of the battery pack of Example 1 at different detection times.
  • the present application provides a self-forming packaging material, comprising the following raw materials in percentage by weight:
  • the moisturizing material includes lithium chloride and/or calcium chloride.
  • the raw materials for preparing the self-forming packaging material include 60-80% of inorganic hydrated salts, preferably 65-70%, based on mass percentage.
  • the inorganic hydrated salts preferably include one or more of sodium acetate trihydrate, disodium hydrogen phosphate dodecahydrate (DHPD), sodium sulfate decahydrate, calcium chloride hexahydrate, ammonium ferric sulfate dodecahydrate, aluminum sulfate 18hydrate, sodium carbonate decahydrate, potassium aluminum sulfate dodecahydrate, sodium thiosulfate pentahydrate, sodium aluminum silicate nonahydrate, sodium silicate pentahydrate, lithium chloride trihydrate, cobalt chloride hexahydrate, copper sulfate heptahydrate, ferrous sulfate heptahydrate, magnesium sulfate heptahydrate, aluminum nitrate nonahydrate and calcium sulfate dihydrate, more preferably sodium acetate trihydrate, disodium hydrogen
  • the raw materials for preparing the self-forming packaging material include 5-10% acrylic monomers, preferably 8-10%, by weight percentage.
  • the acrylic monomers preferably include one or more of acrylic acid, sodium acrylate, acrylamide, acrylate, methacrylate stearate, isopropyl acrylamide, and hydroxyethyl methacrylate, more preferably one of acrylic acid, sodium acrylate, acrylamide, acrylate, methacrylate stearate, isopropyl acrylamide, and hydroxyethyl methacrylate, and even more preferably sodium acrylate, acrylamide, or acrylate.
  • the acrylic monomers include two or more of the above-mentioned specific substances, this application has no special requirements for the ratio of the specific substances, and any ratio can be used.
  • the self-forming packaging material has two-stage heat absorption capacity.
  • the heat absorption capacity of the two stages preferably includes the heat absorption capacity of the first stage material melting and the heat absorption capacity of the second stage material decomposition.
  • the melting temperature of the first stage material is preferably 20-60°C, more preferably 26.5-57.6°C;
  • the unit weight heat absorption of melting is preferably >140J/g, more preferably 147.2-171.1J/g;
  • the decomposition temperature of the second stage material is preferably 100-200°C;
  • the unit weight heat absorption of the second stage material decomposition is preferably 100-200°C;
  • the amount is preferably greater than 980 J/g, more preferably 983 to 1565 J/g.
  • the self-forming packaging material provided in the present application will spontaneously melt and decompose after reaching the endothermic temperature, forming a continuous endothermic effect.
  • the present application also provides a method for preparing the self-forming packaging material described in the above technical solution, comprising the following steps:
  • the melting temperature is preferably 10-20°C higher than the melting temperature of the inorganic hydrated salt.
  • the melting is preferably accompanied by stirring. There is no special requirement for stirring in the present application, as long as the melting is complete.
  • an acrylic acid monomer is dissolved in a second portion of water and then mixed with a crosslinker, a polysaccharide monomer, and a moisturizing material for ionic crosslinking to obtain Solution B.
  • the mass percentage of the second portion of water relative to the total mass of water is preferably 10-60%, more preferably 45-50%.
  • the dissolution is preferably performed under stirring, and there are no specific requirements for stirring, as long as complete dissolution is achieved.
  • the mixing is preferably carried out under stirring conditions.
  • the present application has no special requirements for the stirring, as long as the mixing can be uniform.
  • the ionic crosslinking is that the polysaccharide monomers and acrylic monomers will first undergo ionic crosslinking with the metal cations in the moisturizing material.
  • a self-forming encapsulating material prepolymer is obtained through ionic crosslinking.
  • the present application mixes the solution B and solution A to obtain solution Liquid C.
  • the mixing is preferably adding Solution B to Solution A.
  • the temperature of the system during the addition is preferably 5 to 15°C higher than the melting temperature of the inorganic hydrated salt, more preferably 10°C higher than the melting temperature of the inorganic hydrated salt.
  • the addition is preferably accompanied by stirring. There are no special requirements for stirring in the present application, as long as uniform mixing is achieved.
  • the present application preferably continuously stirs the liquid self-forming packaging material to prevent solidification.
  • the present application also provides the use of the self-forming packaging material described in the above technical solution or the self-forming packaging material prepared by the preparation method described in the above technical solution in battery potting.
  • the present application also provides a method for encapsulating a battery using the self-forming packaging material described in the above technical solution or the self-forming packaging material prepared by the preparation method described in the above technical solution, comprising the following steps:
  • the batteries to be packaged are arranged in a battery box, and the battery box is filled with self-forming packaging material, sealed, and cured to obtain a packaged battery pack.
  • the battery to be packaged is preferably a lithium-ion battery.
  • the spacing between adjacent batteries in the battery box is preferably greater than 0.5 mm, and more preferably 1 to 5 mm.
  • This application has no special requirements for the shape and size of the battery box, and it can be designed according to the needs of the battery module.
  • the bottom of the battery box is sealed, and the top of the battery box is open or has a top cover with a hole, which is preferably a vent or a filling port.
  • the flow rate of the self-forming packaging material during the filling process is preferably 0.1 to 2.4 L/min, more preferably 1 to 1.2 L/min.
  • the self-forming packaging material can fill all gaps in the battery box during the filling process.
  • the present application specifically defines the sealant, and conventional methods in the art may be used.
  • the temperature for initiating curing is preferably 20-80°C, and the time for initiating curing is preferably 1-40 minutes.
  • the present application preferably determines the curing initiation method based on the type of initiator.
  • the present application can control the curing time by controlling reaction parameters such as reaction temperature, initiator concentration, and ultraviolet light intensity.
  • Potassium persulfate was dissolved in the remaining deionized water and then added (with stirring) to solution C to obtain a liquid self-forming packaging material with a viscosity of 22 cP.
  • the preparation method of the self-forming packaging material is as follows:
  • the self-forming packaging material includes the following raw materials, calculated by weight percentage: 70% sodium sulfate decahydrate, 12% deionized water, 10% acrylamide, 0.3% N,N-methylbisacrylamide, 0.7% starch, 5% calcium chloride, and 2% ammonium persulfate.
  • the preparation method of the self-forming packaging material is as follows:
  • solution A Sodium sulfate decahydrate was dissolved (with stirring) in a portion of deionized water (accounting for 25% of the total amount of deionized water) at 50° C. to obtain solution A;
  • the self-forming packaging material includes the following raw materials, calculated by weight percentage: 60% magnesium sulfate heptahydrate, 25% deionized water, 7% sodium acrylate, 0.3% N,N-methylbisacrylamide, 0.7% starch, 5% calcium chloride, and 2% ammonium persulfate.
  • the preparation method of the self-forming packaging material is as follows:
  • a liquid self-forming encapsulation material was prepared according to the method of Example 1, except that the self-forming encapsulation material included the following raw materials: 80% disodium hydrogen phosphate dodecahydrate, 5% deionized water, 5% sodium acrylate, 0.3% N,N-methylenebisacrylamide, 0.7% sodium alginate, 7% calcium chloride, and 2% potassium persulfate.
  • the viscosity of the obtained liquid self-forming encapsulation material was 21 cP.
  • the liquid self-forming encapsulating materials prepared in Examples 1 to 5 were cured according to the following method and the melting temperature, heat absorption per unit weight of melting, and heat absorption per unit weight of decomposition of the cured solid materials were measured using DSC. The results are listed in Table 1.
  • the DSC procedure is as follows:
  • the liquid self-forming packaging materials prepared in Examples 1 and 5 were thermally cured at a temperature of 60°C for 3 minutes to obtain a solid self-forming packaging material; the liquid self-forming packaging material prepared in Example 2 was subjected to a curing reaction at 70°C for 40 minutes using ultraviolet light to obtain a solid self-forming packaging material; the liquid self-forming packaging materials prepared in Examples 3 and 4 were subjected to a curing reaction at a constant temperature of 50°C for 40 minutes using ultraviolet light to obtain a solid self-forming packaging material.
  • FIG1 is a thermal analysis curve (DSC) diagram of the solid self-forming packaging material prepared in Example 1 and disodium hydrogen phosphate dodecahydrate (DHPD).
  • DSC thermal analysis curve
  • the thermal management test of the lithium-ion battery pack was carried out according to the following method; 18650 lithium-ion batteries were used as test objects, three in parallel were connected as a group, and three groups were connected in series for a total of nine batteries, arranged in a crisscross pattern in the battery box, with a distance of 1mm between two adjacent batteries.
  • the battery pack without potting material was used as a bare cell; the liquid self-forming packaging material prepared in Example 1 was filled into the battery box at a rate of 1L/min, and then sealed and cured (60°C, 3min) to obtain a battery pack potted with the self-forming packaging material; the battery box was filled with silicone potting glue (purchased from Shanghai Putai New Materials Technology Co., Ltd.) to obtain a battery pack potted with silicone potting glue as comparative example 1.
  • the center battery temperature at a 3C discharge rate was tested using a thermocouple at different times.
  • FIG2 is a schematic structural diagram of the arrangement of batteries in a battery box.
  • Figure 3 is a temperature curve diagram of different battery groups at different detection times.
  • Example 1 shows a stage with a relatively gentle slope. This is due to the continuous heat absorption of the first endothermic peak, which causes the temperature slope to become gentle. This plays a role in temperature control in the test.
  • the maximum temperature drops from 109°C for the bare cell and 92°C for the potting compound to 54°C. The temperature drops significantly, and the temperature control effect of the self-forming packaging material of Example 1 is significant.
  • the battery thermal runaway test of the lithium-ion battery pack is carried out according to the following method: the battery arrangement is the same as that of test example 2, 9 batteries are arranged in a crisscross pattern, the battery spaces are filled with materials, the positive and negative electrodes are connected by iron sheets, and the heat is transferred through the iron sheets when simulating the thermal runaway of the actual battery pack. After the battery is fully charged, the positive electrode faces down and the negative electrode faces up. A new energy battery short-circuit needle puncture and extrusion explosion-proof test box is used to conduct the needle puncture test. A needle puncture machine is used to puncture the battery. Insert the needle into the negative pole of the center battery (No. 5) to a depth of 20mm to induce thermal runaway. Paste a high-temperature thermocouple in the center of each battery to monitor the temperature changes of each battery.
  • FIG4 and FIG5 are temperature change curves of different positions of the battery packs of Comparative Example 1 and Example 1 at different test times, respectively.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Packages (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本申请属于封装电池技术领域，具体涉及一种自成型封装材料及其制备方法和应用、灌封电池的方法。本申请提供的自成型封装材料，包括以下质量百分含量的制备原料：60～80％无机水合盐、5～15％去离子水、5～10％丙烯酸类单体、0.3～5％交联剂、0.7～5％多糖类单体、2～10％保湿材料和1～5％引发材料；所述保湿材料包括氯化锂和/或氯化钙。在本申请中，自成型封装材料具备熔化与分解两段的吸热能力，熔化的温度为20～60℃，熔化吸热＞140J/g，热分解段在100～200℃之间发生化学反应并主动吸收热量，分解吸热＞980J/g，在达到化学反应条件后会自发进行，形成持续吸热的效果，从而实现对电池的热管理和热失控防护。

Description

一种自成型封装材料及其制备方法和应用、灌封电池的方法
本申请要求于2024年03月27日提交中国专利局、申请号为CN202410353898.4、发明名称为“一种自成型封装材料及其制备方法和应用、灌封电池的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于封装电池技术领域，具体涉及一种自成型封装材料及其制备方法和应用、灌封电池的方法。
背景技术
随着新能源汽车的普及，动力电池作为新能源车的核心部件，其技术发展趋势备受关注。电池的能量密度决定了电动汽车的最大行驶里程，也是影响电池性能的关键印刷。然而，更高的能量密度会造成电池组封装难度大、电池控温难度高以及热失控风险增加的问题。
电池灌封技术是为了应对电池组封装难度大所使用到的新技术，通过AB组分混合后的液体导入排列好的电池组内，让液体填充电池缝隙并与电池紧密贴合，随后固化对电池起到支撑固定、防震防撞等作用。然而，电池灌封胶的导热能力并不足以对电池进行有效控温。
电池热失控是指电池在使用或充电时，由于热诱因、电化学诱因或机械电气诱因等因素导致电池内部温度急剧上升，无法有效地控制或冷却，最终可能导致电池过热、燃烧或爆炸的严重安全问题。除了对电池进行热管理将温度控制在正常工作温度范围以防止热失控发生的防护手段外，在热失控发生后的防护措施主要是通过隔热材料延缓热蔓延的发生。然而，现有的隔热材料仅能减缓热蔓延的进程，依然会存在热蔓延至相邻电池组的可能。电池热失控在反应动力学机制下可分为三个阶段——电池内部热失控阶段(90℃～200℃)、电池鼓包阶段(200℃～350℃)、热失控与爆炸失效阶段(350～850℃)。将失控电池组温度抑制在温度200℃以内的第一阶段，将其控制在温度失控初期无疑才是更合理的做法。
发明内容
有鉴于此，本申请提供了一种自成型封装材料及其制备方法和应用、灌封电池的方法，本申请提供的自成型封装材料具备两段的吸热能力，能够快速吸热将电池热失控温控制在200℃以内，防止高温造成的起火和爆炸。
为了解决上述技术问题，本申请提供了一种自成型封装材料，包括以下质量百分含量的制备原料：
所述保湿材料包括氯化锂和/或氯化钙。
优选的，所述无机水合盐包括三水合醋酸钠、十二水合磷酸氢二钠、十水合硫酸钠、六水合氯化钙、十二水合硫酸铁铵、十八水合硫酸铝、十水合碳酸钠、十二水合硫酸铝钾、五水合硫代硫酸钠、九水合铝硅酸钠、五水合硅酸钠、三水合氯化锂、六水合氯化钴、七水合硫酸铜、七水合硫酸亚铁、九水合硝酸铝和二水合硫酸钙中的一种或多种。
优选的，所述丙烯酸类单体包括丙烯酸、丙烯酸钠、丙烯酰胺、丙烯酸酯、甲基丙烯酸硬脂酸酯、异丙基丙烯酰胺和甲基丙烯酸羟乙酯中的一种或多种。
优选的，所述多糖类单体包括海藻酸、海藻酸钠、壳聚糖、淀粉和果胶中的一种或多种。
优选的，所述交联剂包括N,N-亚甲基双丙烯酰胺。
优选的，所述引发材料包括过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、2,4,6-三甲基苯甲酰基苯基膦酸乙酯和偶氮二异丁腈中的一种或多种。
本申请还提供了上述技术方案所述自成型封装材料的制备方法，包括以下步骤：
S1：将无机水合盐和第一部分水混合进行熔融，得到溶液A；
S2：将丙烯酸类单体溶解于第二部分水后和交联剂、多糖类单体、保湿材料混合进行离子交联，得到溶液B；所述保湿材料包括氯化锂和/或氯化钙；
S3：将所述溶液B和溶液A混合，得到溶液C；
S4：将引发材料溶解于剩余水后和溶液C混合，得到所述自成型封装材料。
优选的，所述熔融的温度比无机水合盐的熔化温度高10～20℃。
优选的，将所述溶液B和溶液A的混合为将溶液B加入溶液A中；所述加入过程中体系的温度比无机水合盐的熔化温度高5～15℃。
本申请还提供了上述技术方案所述自成型封装材料或上述技术方案所述的制备方法制备得到的自成型封装材料在电池灌封中的应用。
本申请还提供了利用上述技术方案所述自成型封装材料或上述技术方案所述的制备方法制备得到的自成型封装材料灌封电池的方法，包括以下步骤：
将待封装的电池排列在电池盒内，向电池盒内填充自成型封装材料后密封、引发固化，得到封装电池组。
优选的，所述电池盒内中相邻电池的间距大于0.5mm。
优选的，所述固化的温度为20～80℃，时间为1～40min。
本申请提供了一种自成型封装材料，包括以下质量百分含量的制备原料：60～80％无机水合盐、5～15％水、5～10％丙烯酸类单体、0.3～5％交联剂、0.7～5％多糖类单体、2～10％保湿材料和1～5％引发材料；所述保湿材料包括氯化锂和/或氯化钙。在本申请中，所述自成型封装材料成型前为液体状态，具有低粘度且易于流动，对于各种狭窄电池缝隙均可进行渗透；在引发材料作用下后，可通过对应的引发手段(紫外或高温)对液体材料进行引发，从而使丙烯酸类单体和多糖类单体与交联剂在溶液中形成三维半互穿网络，利用单体中的亲水基团(羧基和/或氨基)对水合无机盐进行限制(通过大量与水分子连接的氢键将水分子限制在络中，离子浓度较高时水分子形成的氢键较多，吸水性能相对也就较强)，引发后材料为固态。在本申请中，所述自成型封装材料具备两段的吸热能力，其中第一段在100℃以前，在20～60℃ 间的材料熔化的单位吸热量大于140J/g；在100℃～200℃之间材料分解的单位吸热量大于980J/g，不同温度段的储热能力在温度达到后就能自发进行，形成持续吸热的效果，从而实现对电池的热管理和热失控防护，控制失控电池在温度失控初期，减少热失控风险。
附图说明
图1为实施例1制备得到的固态自成型封装材料和十二水合磷酸氢二钠(DHPD)的DSC图；
图2为18650锂离子电池在电池盒内排列方式的结构示意图；
图3为不同电池组在不同检测时间的温度曲线；
图4为对比例1的电池组的不同位置在不同检测时间下温度变化曲线；
图5为实施例1的电池组的不同位置在不同检测时间下温度变化曲线。
具体实施方式
本申请提供了一种自成型封装材料，包括以下质量百分含量的制备原料：
所述保湿材料包括氯化锂和/或氯化钙。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括60～80％无机水合盐，优选为65～70％。在本申请中，所述无机水合盐优选包括三水合醋酸钠、十二水合磷酸氢二钠(DHPD)、十水合硫酸钠、六水合氯化钙、十二水合硫酸铁铵、十八水合硫酸铝、十水合碳酸钠、十二水合硫酸铝钾、五水合硫代硫酸钠、九水合铝硅酸钠、五水合硅酸钠、三水合氯化锂、六水合氯化钴、七水合硫酸铜、七水合硫酸亚铁、七水合硫酸镁、九水合硝酸铝和二水合硫酸钙中的一种或多种，更优选为三水合醋酸钠、十二水 合磷酸氢二钠、十水合硫酸钠、六水合氯化钙、十二水合硫酸铁铵、十八水合硫酸铝、十水合碳酸钠、十二水合硫酸铝钾、五水合硫代硫酸钠、九水合铝硅酸钠、五水合硅酸钠、三水合氯化锂、六水合氯化钴、七水合硫酸铜、七水合硫酸亚铁、七水合硫酸镁、九水合硝酸铝和二水合硫酸钙中的一种，更进一步优选为三水合醋酸钠、十二水合磷酸氢二钠、十水合硫酸钠或七水合硫酸镁。在本申请中，当无机水合盐包括两种以上上述具体物质时，本申请对具体物质的配比无特殊要求，采用任意配比即可。在本申请中，所述无机水合盐为吸热材料。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括5～15％水，优选为10～12％。在本申请中，所述水优选为去离子水。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括5～10％丙烯酸类单体，优选为8～10％。在本申请中，所述丙烯酸类单体优选包括丙烯酸、丙烯酸钠、丙烯酰胺、丙烯酸酯、甲基丙烯酸硬脂酸酯、异丙基丙烯酰胺和甲基丙烯酸羟乙酯中的一种或多种，更优选为丙烯酸、丙烯酸钠、丙烯酰胺、丙烯酸酯、甲基丙烯酸硬脂酸酯、异丙基丙烯酰胺和甲基丙烯酸羟乙酯中的一种，更进一步优选为丙烯酸钠、丙烯酰胺或丙烯酸酯。在本申请中，当丙烯酸类单体包括两种以上上述具体物质时，本申请对具体物质的配比无特殊要求，采用任意配比即可。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括0.3～5％交联剂，优选为0.3％。在本申请中，所述交联剂优选包括N,N-亚甲基双丙烯酰胺。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括0.7～5％多糖类单体，优选为0.7％。在本申请中，所述多糖类单体优选包括海藻酸、海藻酸钠、壳聚糖、淀粉和果胶中的一种或多种，更优选为海藻酸、海藻酸钠、壳聚糖、淀粉和果胶中的一种，更进一步优选为壳聚糖或淀粉。在本申请中，当多糖类单体包括两种以上上述具体物质时，本申请对具体物质的配比无特殊要求，采用任意配比即可。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括2～10％保湿材料，优选为5～7％。在本申请中，所述保湿材料包括氯化锂和/ 或氯化钙，优选为氯化锂或氯化钙。在本申请中，当所述保湿材料为氯化锂和氯化钙时，本申请对氯化锂和氯化钙的配比无特殊要求，采用任意配比即可。在本申请中，所述保湿材料能够更好的锁住水分，防止材料中水分的流失，利于保持无机水合盐吸热材料的作用。
以质量百分含量计，在本申请中，制备所述自成型封装材料的原料包括1～5％引发材料，优选为2～4％。在本申请中，所述引发材料优选包括过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、2,4,6-三甲基苯甲酰基苯基膦酸乙酯和偶氮二异丁腈中的一种或多种，更优选为过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、2,4,6-三甲基苯甲酰基苯基膦酸乙酯和偶氮二异丁腈中的一种，更进一步优选为过硫酸铵、过硫酸钾或2,4,6-三甲基苯甲酰基苯基膦酸乙酯。
在本申请中，所述自成型封装材料在固化前的粘度优选为20～3000cp；所述自成型封装材料固化后得到的固态材料的硬度优选为40～400HC，更优选为100～300HC。
在本申请中，无机水合盐吸热进行热管理、热失控，丙烯酸类单体和多糖类单体在交联剂和引发剂的作用下可以在熔融的水合盐内形成三维半互穿网络，在交联后使材料呈现固态，对水合盐进行限制，即使水合盐在高于熔化温度的情况下熔化了，材料依然呈现固态，不会出现流动态。而无机水合盐的控温能力主要体现在结合水，失去了结合水就没有吸热能力，添加保湿材料则是能更好的锁住水分，防止水分的流失，利于保持无机水合盐的控温能力。
在本申请中，所述自成型封装材料的含义为：材料初始形态为液体，以流体的方式可以填充电池之间的间隙，然后通过原位聚合反应后液体固化形成有一定机械强度的凝胶或固体，为电池做支撑的材料。
在本申请中，所述自成型封装材料具备两段的吸热能力。在本申请中，所述两段的吸热能力优选包括第一段材料熔化吸热能力和第二段材料分解吸热能力。在本申请中，第一段材料熔化的温度优选为20～60℃，更优选为26.5～57.6℃；熔化的单位重量吸热量优选＞140J/g，更优选为147.2～171.1J/g；第二段材料分解的温度优选为100～200℃；第二段材料分解的单位重量吸热 量优选＞980J/g，更优选为983～1565J/g。本申请提供的自成型封装材料在到达吸热温度后会自发进行熔化和分解，形成持续吸热的效果。
本申请还提供了上述技术方案所述自成型封装材料的制备方法，包括以下步骤：
S1：将无机水合盐和第一部分水混合进行熔融，得到溶液A；
S2：将丙烯酸类单体溶解于第二部分水后和交联剂、多糖类单体、保湿材料混合进行离子交联，得到溶液B；所述保湿材料包括氯化锂和/或氯化钙；
S3：将所述溶液B和溶液A混合，得到溶液C；
S4：将引发材料溶解于剩余水后和溶液C混合，得到所述自成型封装材料；
所述步骤S1和S2没有时间顺序限制。
本申请将无机水合盐和第一部分水混合进行熔融，得到溶液A。在本申请中，所述第一部分水占水总质量的质量百分含量优选为10～30％，更优选为20～25％。在本申请中，所述第一部分水的作用为加快无机水合盐的熔融过程。
在本申请中，所述熔融的温度优选比无机水合盐的熔化温度高10～20℃。在本申请中，所述熔融优选伴随搅拌。本申请对所述搅拌无特殊要求，只要能够熔融完全即可。
本申请将丙烯酸类单体溶解于第二部分水后和交联剂、多糖类单体、保湿材料混合进行离子交联，得到溶液B。在本申请中，所述第二部分水占水总质量的质量百分含量优选为10～60％，更优选为45～50％。在本申请中，所述溶解优选在搅拌的条件下进行，本申请对所述搅拌无特殊要求，只要能够溶解完全即可。
在本申请中，所述混合优选在搅拌的条件下进行，本申请对所述搅拌无特殊要求，只要能够混合均匀即可。
在本申请中，所述离子交联为多糖类单体、丙烯酸类单体会与保湿材料中的金属阳离子先发生离子交联，本申请经过离子交联得到自成型封装材料预聚体。
得到溶液A和溶液B后，本申请将所述溶液B和溶液A混合，得到溶 液C。在本申请中，所述混合优选为将溶液B加入溶液A中。在本申请中，所述加入过程中体系的温度优选比无机水合盐的熔化温度高5～15℃，更优选比无机水合盐的熔化温度高10℃。在本申请中，所述加入过程中优选伴随搅拌。本申请对所述搅拌无特殊要求，只要能够混合均匀即可。
得到溶液C后，本申请将引发材料溶解于剩余水后和溶液C混合，得到所述自成型封装材料。本申请对所述溶解无特殊要求，只要能够溶解完全即可。在本申请中，溶解得到的引发剂溶液的质量浓度优选大于1％，更有优选为2～4％。在本申请中，所述混合优选在搅拌的条件下进行，本申请对所述搅拌无特殊要求，只要能够混合均匀即可。
本申请优选对液态的自成型封装材料进行持续的搅拌避免发生固化。
本申请还提供了上述技术方案所述自成型封装材料或上述技术方案所述的制备方法制备得到的自成型封装材料在电池灌封中的应用。
本申请还提供了上述技术方案所述自成型封装材料或上述技术方案所述的制备方法制备得到的自成型封装材料灌封电池的方法，包括以下步骤：
将待封装的电池排列在电池盒内，向电池盒内填充自成型封装材料后密封、引发固化，得到封装电池组。
在本申请中，所述待封装的电池优选为锂离子电池。
在本申请中，所述电池盒内中相邻电池的间距优选大于0.5mm，更优选为1～5mm。本申请对所述电池盒的形状和尺寸无特殊要求，根据电池模组的需要设计即可。在本申请中，所述电池盒的底部为密闭的，所述电池盒的顶部是敞开的或者带有孔的顶盖，所述孔优选为排气孔或灌注口。
在本申请中，所述填充过程中自成型封装材料的流速优选为0.1～2.4L/min，更优选为1～1.2L/min。本申请在填充过程中所述自成型封装材料能够填满电池盒内所有缝隙。
本申请对所述密封物特殊限定，采用本领域常规的方式即可。
在本申请中，所述引发固化的温度优选为20～80℃，所述引发固化的时间优选为1～40min。本申请优选根据引发剂的种类确定固化的引发方式，本申请可以通过控制反应参数如反应温度、引发剂浓度、紫外光强等调控固化的时间。
在本申请中，所述固化后的封装材料的硬度优选为40～100HC，拉伸强度优选为10～300kPa，压缩弹性模量优选为300～3000kPa。在本申请中，所述固化后的封装材料能够对电池起到支撑保护作用的同时还能起到热管理的作用。在本申请中，所述封装电池组为能多段电池控温的封装电池组。
为了进一步说明本申请，下面结合实施例对本申请提供的技术方案进行详细地描述，但不能将它们理解为对本申请保护范围的限定。
实施例1
以质量百分含量计，自成型封装材料包括以下原料：70％十二水合磷酸氢二钠、10％去离子水、8％丙烯酸钠、0.3％N,N-亚甲基双丙烯酰胺、0.7％海藻酸钠、7％氯化钙、4％过硫酸钾。
自成型封装材料的制备方法为：
将十二水合磷酸氢二钠于50℃下溶解(伴随搅拌)于部分去离子水(占去离子水总量的25％)，得到溶液A；
将丙烯酸钠在搅拌的条件下溶解于部分去离子水(占去离子水总量的50％)后加入N,N-亚甲基双丙烯酰胺、海藻酸钠和氯化钙，搅拌至完全溶解后进行离子交联，得到溶液B；
在50℃下向溶液B中加入(伴随搅拌)溶液A，混合均匀，得到溶液C；
将过硫酸钾溶解于剩余去离子水后加入(伴随搅拌)溶液C，得到粘度为22cP的液态自成型封装材料。
实施例2
以质量百分含量计，自成型封装材料包括以下原料：65％三水合醋酸钠、15％去离子水、8％丙烯酸酯、0.3％N,N-亚甲基双丙烯酰胺、0.7％壳聚糖、10％氯化锂、1％2,4,6-三甲基苯甲酰基苯基膦酸乙酯(光引发剂)。
自成型封装材料的制备方法为：
将三水合醋酸钠于70℃下溶解(伴随搅拌)于部分去离子水(占去离子水总量的25％)，得到溶液A；
将丙烯酸酯在搅拌的条件下溶解于部分去离子水(占去离子水总量的25％)后加入N,N-亚甲基双丙烯酰胺、海壳聚糖和氯化锂，搅拌至完全溶解后进行离子交联，得到溶液B；
在70℃下向溶液B中加入(伴随搅拌)溶液A，混合均匀，得到溶液C；
将2,4,6-三甲基苯甲酰基苯基膦酸乙酯和剩余去离子水混合后加入(伴随搅拌)溶液C，得到粘度为20cp的液态自成型封装材料。
实施例3
以质量百分含量计，自成型封装材料包括以下原料：70％十水合硫酸钠、12％去离子水、10％丙烯酰胺、0.3％N,N-甲基双丙烯酰胺、0.7％淀粉、5％氯化钙、2％过硫酸铵。
自成型封装材料的制备方法为：
将十水合硫酸钠于50℃下溶解(伴随搅拌)于部分去离子水(占去离子水总量的25％)，得到溶液A；
将丙烯酰胺在搅拌的条件下溶解于部分去离子水(占去离子水总量的50％)后加入N,N-亚甲基双丙烯酰胺、淀粉和氯化钙，搅拌至完全溶解后进行离子交联，得到溶液B；
在50℃下向溶液B中加入(伴随搅拌)溶液A，混合均匀，得到溶液C；
将过硫酸铵溶解于剩余去离子水后加入(伴随搅拌)溶液C，得到粘度为22cp的液态自成型封装材料。
实施例4
以质量百分含量计，自成型封装材料包括以下原料：60％七水合硫酸镁、25％去离子水、7％丙烯酸钠、0.3％N,N-甲基双丙烯酰胺、0.7％淀粉、5％氯化钙、2％过硫酸铵。
自成型封装材料的制备方法为：
将七水合硫酸镁于60℃下溶解(伴随搅拌)于部分去离子水(占去离子水总量的25％)，得到溶液A；
将丙烯酸钠在搅拌的条件下溶解于部分去离子水(占去离子水总量的50％)后加入N,N-亚甲基双丙烯酰胺、海藻酸钠和氯化钙，搅拌至完全溶解后进行离子交联，得到溶液B；
在60℃下向溶液B中加入(伴随搅拌)溶液A，混合均匀，得到溶液C；
将过硫酸铵溶解于剩余去离子水后加入(伴随搅拌)溶液C，得到粘度为23cp的液态自成型封装材料。
实施例5
按照实施例1的方法制备液态自成型封装材料，不同之处在于，自成型封装材料包括以下原料：80％十二水合磷酸氢二钠、5％去离子水、5％丙烯酸钠、0.3％N,N-亚甲基双丙烯酰胺、0.7％海藻酸钠、7％氯化钙、2％过硫酸钾，得到的液态自成型封装材料的粘度为21cP。
测试例1
按照以下方法对实施例1～5制备得到的液态自成型封装材料进行固化并使用DSC测试固化得到的固体材料的熔化温度、熔化单位重量吸热量、分解单位重量吸热量，其结果列于表1中；DSC程序如下：
1. 0℃恒温1min；
2. 1℃/min速率升温至200℃；
3. 200℃恒温1min。
在60℃的温度下对实施例1、5制备得到的液态自成型封装材料进行热固化3min，得到固态自成型封装材料；利用紫外光照在70℃下对实施例2制备得到的液态自成型封装材料引发固化反应40min，得到固态自成型封装材料；在50℃恒温环境下使用紫外光照对实施例3、4制备得到的液态自成型封装材料引发固化反应40min，得到固态自成型封装材料。
表1实施例1～5制备的固态自成型封装材料的性能参数
图1为实施例1制备得到的固态自成型封装材料和十二水合磷酸氢二钠(DHPD)的热分析曲线(DSC)图。
结合表1和图1可以看出实施例1～5制成的固态自成型封装材料在100℃前存在一个吸热峰，具有一定的熔化吸热能力，熔化温度与纯水合盐 相比相差不大，对水合盐本身的熔化温度无太大影响。在100℃后具有一个分解的峰，由于额外的去离子水的加入，分解吸热的降幅比例相较熔化吸热的降幅比例有较大的减少，将分解单位重量吸热量保持在了较高的水平。
测试例2
按照以下方法对锂离子电池组进行热管理测试；以18650锂离子电池作为测试对象，三个并联为一组，三组串联共九个电池，井字排布于电池盒中，相邻两个电池间距为1mm。没有填充灌封材料的电池组作为裸电池；按照1L/min的速率向电池盒内填充实施例1制备得到的液态自成型封装材料后密封、固化(60℃、3min)，得到灌封自成型封装材料的电池组；向电池盒内填充有机硅灌封胶(购自上海普汰新材料科技有限公司)，得到灌封胶的电池组作为对比例1。使用热电偶在不同时间测试在3C放电倍率下中心电池温度。
图2为电池在电池盒内排列方式的结构示意图。
将中心电池最高温度结果列于表2中，图3为不同电池组在不同检测时间的温度曲线图。
表2测试得到的中心电池最高温度
由表2和图3可以看出实施例1的曲线出现了一段坡度较缓的阶段，为第一段吸热峰的持续吸热导致温度坡度变缓，在测试中起到了控温的作用，最高温度从裸电池的109℃、灌封胶92℃降至54℃，温度有较大降幅，实施例1的自成型封装材料控温效果显著。
测试例3
按照以下方法对锂离子电池组进行电池热失控测试：电池排布与测试例2相同，9电池以井字排列，电池间填充材料，正负极通过铁片相连，模拟实际电池组热失控时热量通过铁片传递，电池充满电后，正极朝下，负极朝上，使用新能源电池短路针刺挤压防爆试验箱进行针刺实验，使用针刺机扎 入中心电池(5号)负极处，深度20mm，以引发热失控，在各电池中心粘贴高温热电偶以手机各电池温度变化情况。
将测试结果列于表3中，图4和图5分别为对比例1和实施例1电池组的不同位置在不同检测时间下温度变化曲线。
表3检测得到的中心和周边电池最高温度
由表3和图4、5可以看出在热失控测试中，实施例1失控电池在温度高于100℃后，周边的材料持续吸热，将中心电池的温度抑制在200℃以内，且周边电池最高温度不超过50℃，仍处于电池正常工作温度范围内，具有较好的热失控防护效果。
尽管上述实施例对本申请做出了详尽的描述，但它仅仅是本申请一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本申请保护范围。

Claims (14)

  1. 一种自成型封装材料，其特征在于，包括以下质量百分含量的制备原料：
    所述保湿材料包括氯化锂和/或氯化钙。
  2. 根据权利要求1所述自成型封装材料，其特征在于，所述无机水合盐包括三水合醋酸钠、十二水合磷酸氢二钠、十水合硫酸钠、六水合氯化钙、十二水合硫酸铁铵、十八水合硫酸铝、十水合碳酸钠、十二水合硫酸铝钾、五水合硫代硫酸钠、九水合铝硅酸钠、五水合硅酸钠、三水合氯化锂、六水合氯化钴、七水合硫酸铜、七水合硫酸亚铁、九水合硝酸铝和二水合硫酸钙中的一种或多种。
  3. 根据权利要求1所述自成型封装材料，其特征在于，所述丙烯酸类单体包括丙烯酸、丙烯酸钠、丙烯酰胺、丙烯酸酯、甲基丙烯酸硬脂酸酯、异丙基丙烯酰胺和甲基丙烯酸羟乙酯中的一种或多种。
  4. 根据权利要求1所述自成型封装材料，其特征在于，所述多糖类单体包括海藻酸、海藻酸钠、壳聚糖、淀粉和果胶中的一种或多种。
  5. 根据权利要求1所述自成型封装材料，其特征在于，所述交联剂包括N,N-亚甲基双丙烯酰胺。
  6. 根据权利要求1所述自成型封装材料，其特征在于，所述引发材料包括过硫酸铵、过硫酸钾、过氧化氢、过氧化二苯甲酰、2,4,6-三甲基苯甲酰基苯基膦酸乙酯和偶氮二异丁腈中的一种或多种。
  7. 权利要求1～6任一项所述自成型封装材料的制备方法，包括以下步骤：
    S1：将无机水合盐和第一部分水混合进行熔融，得到溶液A；
    S2：将丙烯酸类单体溶解于第二部分水后和交联剂、多糖类单体、保湿材料混合进行离子交联，得到溶液B；所述保湿材料包括氯化锂和/或氯化钙；
    S3：将所述溶液B和溶液A混合，得到溶液C；
    S4：将引发材料溶解于剩余水后和溶液C混合，得到所述自成型封装材料；
    所述步骤S1和S2没有时间顺序限制。
  8. 根据权利要求7所述制备方法，其特征在于，所述熔融的温度比无机水合盐的熔化温度高10～20℃。
  9. 根据权利要求7所述制备方法，其特征在于，将所述溶液B和溶液A的混合为将溶液B加入溶液A中；所述加入过程中体系的温度比无机水合盐的熔化温度高5～15℃。
  10. 权利要求1～6任一项所述自成型封装材料或权利要求7～9任一项所述的制备方法制备得到的自成型封装材料在电池灌封中的应用。
  11. 利用权利要求1～6任一项所述自成型封装材料或权利要求7～9任一项所述的制备方法制备得到的自成型封装材料灌封电池的方法，包括以下步骤：
    将待封装的电池排列在电池盒内，向电池盒内填充自成型封装材料后密封、引发固化，得到封装电池组。
  12. 根据权利要求11所述的方法，其特征在于，所述电池盒内中相邻电池的间距大于0.5mm。
  13. 根据权利要求11所述的方法，其特征在于，所述填充过程中自成型封装材料的流速为0.1～2.4L/min。
  14. 根据权利要求11所述的方法，其特征在于，所述固化的温度为20～80℃，时间为1～40min。
PCT/CN2024/118242 2024-03-27 2024-09-11 一种自成型封装材料及其制备方法和应用、灌封电池的方法 Pending WO2025200318A1 (zh)

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