CN116622136B - 一种电池包用柔性发泡材料及制备方法 - Google Patents
一种电池包用柔性发泡材料及制备方法 Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
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- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 13
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 10
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
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- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明提供了一种电池包用柔性发泡材料及制备方法与应用，涉及柔性发泡材料技术领域。本发明的柔性发泡材料由丁腈橡胶、氯醋树脂、陶瓷前驱体聚合物、耐火粘土、磷酸酯、氢氧化镁、助熔剂、碳酸氢钠、过氧化二异丙苯、三烯丙基异氰酸酯、润滑剂、防老剂、颜料等原料构成。本发明的柔性发泡材料在常温下具有优异弹性和柔性，且具备均匀细密的微孔发泡结构，能够为材料提供良好的隔热性能和力学性能，在高温或遇火条件下可形成陶瓷化的具有多孔结构的烧结体，具备更高的防火级别，能够在新能源动力电池领域发挥重要作用。
Description
技术领域
本发明涉及柔性发泡材料技术领域，尤其涉及一种电池包用柔性发泡材料及制备方法与应用。
背景技术
发展新能源汽车是我国推动绿色发展的一项重要战略举措。电池包作为新能源汽车的核心动力源，为整车驱动提供电能。电池包内和电芯单元间需要一种具有防火隔热以及缓震抗冲击性能的防护材料。
作为微孔柔性弹性体发泡材料，橡塑发泡材料在新能源电池领域可以提供绝佳的隔热、缓冲减震、阻燃、密封、支撑等功能，并且可在动力电池包的不同区域位置中使用。基于目前技术，橡塑发泡材料虽然可以达到难燃B1级，但相比不燃A级材料，现有产品仍存在防火级别低的缺点，导致其在新能源电池领域应用受限。另外，普通橡塑发泡材料的密度小于95 kg/m3，相比微发泡材料压缩和拉伸撕裂等物理力学性能欠佳。
因此，如何提高橡塑发泡材料的弹性和力学性能并使其在高温或遇火条件下具有优异的烧结特性和防火隔热性与加工性能，使其能够用于新能源电池领域以提高新能源电池包的防火性能和隔热安全性是目前亟须解决的技术问题。
发明内容
为解决上述问题，本发明提供了一种电池包用柔性发泡材料，该柔性发泡材料在常温下具有优异弹性和柔性，且具备均匀细密的微孔发泡结构，能够为材料提供良好的隔热性能和力学性能，在高温或遇火条件下可形成陶瓷化的具有多孔结构的烧结体，进而具备更高的防火级别。
本发明所述电池包用柔性发泡材料具体包括以下重量份的原料：
丁腈橡胶10-25份、氯醋树脂3-10份、陶瓷前驱体聚合物3-10份、耐火粘土15-35份、磷酸酯5-15份、氢氧化镁10-35份、助熔剂1-5、碳酸氢钠6-15份、过氧化二异丙苯（DCP）0.3-1.0份、三烯丙基异氰酸酯（TAIC）0.5-1.5份、润滑剂0.5-1.5份、防老剂0.5-1份、颜料0.1-1份。
进一步地，所述陶瓷前驱体聚合物为聚氮硅烷（PSZ）、聚硅氧烷（PSO）、聚碳硅烷（PCS）、烯丙基聚碳硅烷（AHPCS）或超支化聚碳硅烷（HPCS）。
进一步地，所述耐火粘土为高铝粘土。
进一步地，上述高铝粘土的Al2O3含量≥50wt%。
进一步地，所述磷酸酯为磷酸三异丙基苯酯（IPPP）或磷酸二苯基异癸酯（DPDP）。
进一步地，所述助熔剂为低熔点玻璃粉、氧化硼和硼酸锌中的一种或几种。
进一步地，所述低熔点玻璃粉的熔点为390-780℃。
进一步地，所述碳酸氢钠为超细碳酸氢钠，所述超细碳酸氢钠粒度为3-10 μm，分解温度为130℃-190℃，发气量为100-200 mL/g。
进一步地，所述润滑剂为硬脂酸锌和聚乙二醇中的一种或两种。
进一步地，所述润滑剂由硬脂酸锌和聚乙二醇按重量比为1-2：1的比例构成。
进一步地，所述防老剂为防老剂4020和防老剂A中的一种或两种。
进一步地，所述颜料为耐温颜料。
优选的，所述颜料为色素炭黑、氧化铁黑中的一种或两种。
本发明还提供了所述电池包用柔性发泡材料的制备方法，具体包括以下步骤：
S1、将磷酸酯、碳酸氢钠混合均匀，以便对碳酸氢钠进行预分散包覆处理得到混合物；
S2、向混合物中加入陶瓷前驱体聚合物、助熔剂、DCP、TAIC、润滑剂、防老剂、颜料并混合均匀，得到预分散混合料；
S3、将丁腈橡胶密炼；
S4、将预分散混合料、氯醋树脂、耐火粘土和氢氧化镁与丁腈橡胶进行混炼；
S5、将混炼完成的胶料开炼出条；
S6、将胶条喂入带真空排气的挤出机，经挤出模具定型后进入发泡炉进行连续发泡生产，即得柔性发泡材料。
进一步地，S1中混合时间为5-20 min，转速为100-300 r/min。
进一步地，S2中混合时间为10-40 min，混合转速为100-450 r/min。
进一步地，S3中密炼时间为1-2 min，密炼转速为15-35 r/min。
进一步地，S4中混炼时间为8-15 min，混炼温度为60℃-100℃。
进一步地，S5中所述开炼时间为5-10 min，所述开炼机温度为25℃-40℃。
进一步地，S6中所述发泡炉各区温度分别为一区115-120℃、二区115-120℃、三区120-130℃、四区125-135℃、五区145-160℃、六区165-180℃，各区速度分别为一区0.5-1.0m/min、二区0.5-1.0 m/min、三区1.2-1.6 m/min、四区2.0-3.0 m/min、五区3.5-4.5 m/min、六区5.0-6.0 m/min。
本发明提供所述电池包用柔性发泡材料的应用，具体方法为：作为隔绝材料隔绝新能源电池包内和电芯，提供绝佳的隔热、缓冲减震、阻燃、密封、支撑功能。
阻燃填充能够使本发明的发泡材料在高温或着火时能够吸热、覆盖、中断链反应或释放不燃气体，从而降低材料的可燃性和热释放量，提高阻燃性能；其次是在高温烧结时可形成耐高温相的主要结构。阻燃增塑能够使本发明的发泡材料在高温或着火时能够与塑料分子发生化学反应，形成难燃或不燃的化合物，从而降低塑料的可燃性和热释放量，提高阻燃性能；阻燃补强能够使本发明的发泡材料在高温或着火时能够增强材料的力学性能和结构稳定性，从而延缓材料的分解和熔滴，提高阻燃性能；阻燃助熔能够使本发明的发泡材料在高温或着火时能够迅速融化成液体，并与其他阻燃剂反应形成陶瓷化保护层，从而隔绝空气和热源，提高阻燃性能。
本发明利用阻燃填充、阻燃增塑、阻燃补强以及阻燃助熔多体系之间的协同增效作用，使发泡材料在遇到高温和着火情况下能够迅速形成耐火性能极好的、具有自支撑性的多孔保护层结构，从而阻止火焰和热量向内传播。高温条件下形成的烧结保护层即使在受到持续热攻击下，也能够保证多孔结构的稳定性和另一侧的安全性能。
本发明发泡工艺选用碳酸氢钠不仅具有优异的环保特性，而且经过预混合包覆处理，大大提高了其在体系中的分散性和可发性，使制备的发泡材料泡孔密实且分布均匀，导热系数低，物理力学性能优异。
本发明的发泡材料密度为100-300 kg/m3，导热系数为0.030-0.065 W/（m·k）（25℃），拉伸强度为2.0-15.0 MPa，撕裂强度为5-30 KN/m，压缩永久变形≤3%，在1000℃以上火焰持续燃烧下仍能保证其完整性和隔热性。
本发明的电池包用柔性发泡材料相比较于真空隔热板、玻璃棉和气凝胶隔热材料等常用的电池包内隔绝材料，缓冲抗撕裂等物理力学性能得到大大改善，并且防火隔热性能远优于普通橡塑泡棉，极大地提高了电池的安全性。
与现有技术相比，本发明的有益技术效果：
（1）本发明采用低温混炼胶法，混合效果好，节能高效，采用连续性挤出硫化发泡法制备工艺，生产效率高、质量稳定，密度可控；
（2）本发明的柔性发泡材料具有很好的耐火性能，并且具有柔性好、物理力学性能优异等优点，能够在新能源动力电池领域发挥重要作用。
具体实施方式
以下结合实施例对本发明提供的技术方案进行进一步说明。
实施例1
称取以下重量份的原料：丁腈橡胶11份、氯醋树脂5份、聚氮硅烷6.5份、耐火粘土29份、磷酸酯10份、氢氧化镁25份、低熔点玻璃粉3.5份、碳酸氢钠7.5份、过氧化二异丙苯（DCP）0.5份、三烯丙基异氰酸酯（TAIC）0.7份、润滑剂0.8份、防老剂4020 0.5份、色素炭黑0.5份。
按以下步骤制备一种电池包用柔性发泡材料：
原料预分散：
（a）先将按比例称取的磷酸酯、碳酸氢钠投入到高速混合机中进行混合，目的是对碳酸氢钠进行预分散包覆处理，时间15 min，转速300 r/min；
（b）接着按配比将陶瓷前驱体聚合物、助熔剂、DCP、TAIC、润滑剂、防老剂4020、色素炭黑等投入混合机中，混合时间为30 min，混合转速450 r/min，混合结束后得到预分散混合料；
混炼胶制备：
（a）将丁腈橡胶投入密炼机密炼，时间1 min，密炼转速30 r/min。
（b）将步骤预分散混合料、氯醋树脂、耐火粘土和氢氧化镁投入密炼机一起进行混炼，时间为10 min，温度为85℃；
（c）将混炼完成的胶料投入开炼机进行开炼出条，开炼时间8 min，开炼机温度25℃；
挤出与硫化发泡：
将胶条喂入带真空排气的挤出机，经过挤出模具定型后进入发泡炉进行连续发泡生产，得到柔性发泡材料。
实施例2
同实施例1，区别在于：由以下重量份的原料构成：丁腈橡胶13份、氯醋树脂6份、聚硅氧烷6份、耐火粘土24份、磷酸酯10份、氢氧化镁25份、氧化硼2.5份、碳酸氢钠10份、过氧化二异丙苯（DCP）0.6份、三烯丙基异氰酸酯（TAIC）1.0份、润滑剂1.1份、防老剂A 0.8份、色素炭黑0.8份。
经检测，该实施例值得的产品表面光滑整洁，泡孔均匀致密。
实施例3
同实施例1，区别在于：由以下重量份的原料构成：丁腈橡胶16份、氯醋树脂7份、聚碳硅烷6份、耐火粘土23份、磷酸酯10份、氢氧化镁20份、硼酸锌2份、碳酸氢钠12份、过氧化二异丙苯（DCP）0.5份、三烯丙基异氰酸酯（TAIC）1.3份、润滑剂1.4份、防老剂4020 0.8份、氧化铁黑0.8份。
实施例4
同实施例1，区别在于：由以下重量份的原料构成：
丁腈橡胶10份、氯醋树脂3份、陶瓷前驱体聚合物3份、耐火粘土15份、磷酸酯5份、氢氧化镁10份、助熔剂1、碳酸氢钠6份、DCP 0.3份、TAIC 0.5份、润滑剂0.5份、防老剂A0.5份、色素炭黑0.1份。
实施例5
同实施例1，区别在于：由以下重量份的原料构成：
丁腈橡胶25份、氯醋树脂10份、陶瓷前驱体聚合物10份、耐火粘土35份、磷酸酯15份、氢氧化镁35份、助熔剂5、碳酸氢钠15份、DCP 1.0份、TAIC 1.5份、润滑剂1.5份、防老剂4020 1份、氧化铁黑1份。
对比例1
同实施例2，区别在于：原料中不包括陶瓷前驱体聚合物，氢氧化镁的添加量改为31重量份。
对比例2
同实施例2，区别在于：原料中不包括耐火粘土，氢氧化镁的添加量改为49重量份。
对比例3
同实施例2，区别在于：采用AC发泡剂替代碳酸氢钠。
测试例
对实施例及对比例的柔性发泡材料试样进行性能测试。
其中，耐火测试条件如下：
样品规格为400 mm×400 mm×10 mm，将样品用支架竖向垂直固定，采用火焰喷枪距离样品中心3 cm距离持续点燃10 min；试验结束后，观察测试结果。该测试中采用的火焰喷枪持续点燃3-5 min后，表面温度可达到1000℃以上。
性能测试结果如下：
| 类别 | 参照标准 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 |
| 密度，kg/m3 | GB/T 17794 | 204 | 164 | 113 | 168 | 162 | 95 |
| 导热系数（25℃），W/（m·k） | GB/T 10294 | 0.057 | 0.044 | 0.039 | 0.059 | 0.052 | 0.041 |
| 拉伸强度，MPa | GB/T 6344 | 6.05 | 4.73 | 3.35 | 3.16 | 3.22 | 0.95 |
| 撕裂强度，KN/m | GB/T 10808 | 24.3 | 19.4 | 15.6 | 10.5 | 11.3 | 7.6 |
| 压缩永久变形，23±2℃，22h | GB/T 6669 | 0.88 | 1.35 | 1.64 | 3.44 | 3.37 | 3.87 |
| 阻燃等级 | GB/T 2408 | V0 | V0 | V0 | V1 | V1 | V1 |
| 耐火测试 | 是否完整 | 完整 | 完整 | 完整 | 烧穿 | 烧穿 | 烧穿 |
本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处。综上所述，本说明书内容不应理解为对本发明的限制。
Claims (5)
1.一种电池包用柔性发泡材料，其特征在于，包括以下重量份的原料：
丁腈橡胶10-25份、氯醋树脂3-10份、陶瓷前驱体聚合物3-10份、耐火粘土15-35份、磷酸酯5-15份、氢氧化镁10-35份、助熔剂1-5份、碳酸氢钠6-15份、过氧化二异丙苯0.3-1.0份、三烯丙基异氰酸酯0.5-1.5份、润滑剂0.5-1.5份、防老剂0.5-1份、颜料0.1-1份；
所述陶瓷前驱体聚合物为聚氮硅烷、聚硅氧烷、聚碳硅烷、烯丙基聚碳硅烷或超支化聚碳硅烷；
所述碳酸氢钠为超细碳酸氢钠；
所述耐火粘土为高铝粘土；
所述磷酸酯为磷酸三异丙基苯酯或磷酸二苯基异癸酯；
所述助熔剂为低熔点玻璃粉、氧化硼和硼酸锌中的一种或几种。
2.根据权利要求1所述的一种电池包用柔性发泡材料，其特征在于，所述润滑剂为硬脂酸锌和聚乙二醇中的一种或两种。
3.根据权利要求1所述的一种电池包用柔性发泡材料，其特征在于，所述防老剂为防老剂4020、防老剂A中的一种或两种。
4.权利要求1-3任一项所述电池包用柔性发泡材料的制备方法，其特征在于，包括以下步骤：
S1、将磷酸酯、碳酸氢钠混合均匀，以便对碳酸氢钠进行预分散包覆处理得到混合物；
S2、向混合物中加入陶瓷前驱体聚合物、助熔剂、过氧化二异丙苯、三烯丙基异氰酸酯、润滑剂、防老剂、颜料并混合均匀，得到预分散混合料；
S3、将丁腈橡胶密炼；
S4、将预分散混合料、氯醋树脂、耐火粘土和氢氧化镁与丁腈橡胶进行混炼；
S5、将混炼完成的胶料开炼出条；
S6、将胶条喂入带真空排气的挤出机，经挤出模具定型后进入发泡炉进行连续发泡生产，即得柔性发泡材料。
5.权利要求1-3任一项所述电池包用柔性发泡材料的在新能源电池中的应用，其特征在于，作为隔绝材料应用在新能源电池包中。
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