化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3159-3173.DOI: 10.16085/j.issn.1000-6613.2023-0855
• 材料科学与技术 • 上一篇
收稿日期:
2023-05-24
修回日期:
2023-07-02
出版日期:
2024-06-15
发布日期:
2024-07-02
通讯作者:
方敏
作者简介:
何瑞强(1997—),男,硕士研究生,研究方向为定型复合相变储能材料。E-mail:herq0809@163.com。
基金资助:
HE Ruiqiang1(), FANG Min1(
), ZHOU Jianduo1, FEI Hua1, YANG Kai2
Received:
2023-05-24
Revised:
2023-07-02
Online:
2024-06-15
Published:
2024-07-02
Contact:
FANG Min
摘要:
热塑性弹性体(TPE)因其出色的柔韧性、低成本和强相容性,可作为相变材料(PCM)的载体,将其与相变材料和导热填料复合制备的柔性复合相变材料(FCPCM)在电池热管理(BTM)领域具有广泛的应用前景。本文通过总结国内外关于TPE基柔性复合相变材料在电池热管理领域的研究成果,对常用的TPE材料进行了分类并对其工作原理和制备方法等进行了详细介绍。针对相变材料在电池热管理应用中存在的低导热性、低形状稳定性、不良力学性能等问题,本文重点介绍了TPE基柔性复合相变材料的热物理性能(相变潜热和热导率)、电池热管理效果(最高温度和最大温差)、力学性能和抗振性能等。指出当前电池热管理中柔性复合相变材料存在的局限性并对未来的发展方向进行了展望,寻找潜在的柔性材料、协同的二元柔性载体和二元导热填料,提高柔性复合相变材料的绝缘性、介电性和低温适应性等方面应是未来的主要研究方向,增强柔性复合相变材料在振动条件下对锂电池的温控性也需要进一步探索。该综述对电池热管理中TPE基柔性复合相变材料的进一步研究和开发提供重要参考价值。
中图分类号:
何瑞强, 方敏, 周健夺, 费华, 杨凯. 锂电池热管理用TPE基柔性复合相变材料的研究进展[J]. 化工进展, 2024, 43(6): 3159-3173.
HE Ruiqiang, FANG Min, ZHOU Jianduo, FEI Hua, YANG Kai. Research progress of TPE-based flexible composite phase change materials for thermal management of lithium batteries[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3159-3173.
材料类型 | 种类 | 价格/CNY·kg-1 | 途径 |
---|---|---|---|
TPE | SEBS(美国科腾G1654) | 14.8 | 东莞市晟华塑胶原料有限公司 |
SEPS(YH-4051) | 23 | 岳阳市巴陵佳云石化有限公司 | |
SBS | 11 | 惠州市惠州LCY弹性体有限公司 | |
EVA(美国杜邦EVA 660) | 20 | 东莞市英翔塑胶原料有限公司 | |
POE(A4090S) | 13.8 | 东莞市缘信塑胶原料有限公司 | |
OBC(陶氏9530) | 18.8 | 深圳市万塑源橡塑有限公司 | |
SR(HY系列) | 58 | 深圳红叶硅胶股份科技有限公司 | |
TPC-et(Hytrel 30HS) | 35 | 东莞市塑佳高分子原料有限公司 | |
TPE(陶氏杜邦4000-60A) | 20 | 苏州腾旺国际贸易有限公司 | |
PCM | 切片石蜡(690189610) | 70 | 国药集团化学试剂有限公司 |
石蜡 | 45 | 上海焦耳蜡业有限公司 |
表1 部分TPE和PCM的成本比较
材料类型 | 种类 | 价格/CNY·kg-1 | 途径 |
---|---|---|---|
TPE | SEBS(美国科腾G1654) | 14.8 | 东莞市晟华塑胶原料有限公司 |
SEPS(YH-4051) | 23 | 岳阳市巴陵佳云石化有限公司 | |
SBS | 11 | 惠州市惠州LCY弹性体有限公司 | |
EVA(美国杜邦EVA 660) | 20 | 东莞市英翔塑胶原料有限公司 | |
POE(A4090S) | 13.8 | 东莞市缘信塑胶原料有限公司 | |
OBC(陶氏9530) | 18.8 | 深圳市万塑源橡塑有限公司 | |
SR(HY系列) | 58 | 深圳红叶硅胶股份科技有限公司 | |
TPC-et(Hytrel 30HS) | 35 | 东莞市塑佳高分子原料有限公司 | |
TPE(陶氏杜邦4000-60A) | 20 | 苏州腾旺国际贸易有限公司 | |
PCM | 切片石蜡(690189610) | 70 | 国药集团化学试剂有限公司 |
石蜡 | 45 | 上海焦耳蜡业有限公司 |
柔性载体 | CPCM | 质量分数比/% | 熔点/℃ | 潜热/kJ·kg-1 | 热导率/W·m-1·K-1 | 参考文献 |
---|---|---|---|---|---|---|
SEBS | PA/h-BN/SEBS | 60/20/20 | 41.1 | 127.8 | 2.7 | [ |
SEBS | PA/EG/SEBS | 76.2/4.8/19 | 47.35 | 159.2 | 1.226 | [ |
SEPS | PA/EG/SEPS | (85.5/81/72/63)/ (5/10/20/30)/ (9.5/9/8/7) | 48/49.1/50.2/53.1 | 211.9~155.4 | 2.671/4.495/7.475/10.019 | [ |
SEPS | PA/EG/SEPS | 81/4/15 | 42.5 | 202.78 | 1.581 | [ |
SBS | PA/CNT/SBS | 85/2/13 | 61.56 | 147.63 | 0.39 | [ |
PA/SBS | 85/15 | 64.14 | 140.74 | 0.3 | ||
PA | 61.55 | 200.01 | 0.28 | |||
SBS | PA/AlN/SBS | 35/15/50 | 46.82 | 57.06 | 0.5 | [ |
SBS | PA/EG/SBS | 46/5/50 | 47.7 | 79.8 | 0.87 | [ |
TPS(SBS/SEBS) | PA/EG/TPS | 50/7/43 | 44 | 1.271 | [ |
表2 TPS类部分柔性复合相变材料的热物性参数
柔性载体 | CPCM | 质量分数比/% | 熔点/℃ | 潜热/kJ·kg-1 | 热导率/W·m-1·K-1 | 参考文献 |
---|---|---|---|---|---|---|
SEBS | PA/h-BN/SEBS | 60/20/20 | 41.1 | 127.8 | 2.7 | [ |
SEBS | PA/EG/SEBS | 76.2/4.8/19 | 47.35 | 159.2 | 1.226 | [ |
SEPS | PA/EG/SEPS | (85.5/81/72/63)/ (5/10/20/30)/ (9.5/9/8/7) | 48/49.1/50.2/53.1 | 211.9~155.4 | 2.671/4.495/7.475/10.019 | [ |
SEPS | PA/EG/SEPS | 81/4/15 | 42.5 | 202.78 | 1.581 | [ |
SBS | PA/CNT/SBS | 85/2/13 | 61.56 | 147.63 | 0.39 | [ |
PA/SBS | 85/15 | 64.14 | 140.74 | 0.3 | ||
PA | 61.55 | 200.01 | 0.28 | |||
SBS | PA/AlN/SBS | 35/15/50 | 46.82 | 57.06 | 0.5 | [ |
SBS | PA/EG/SBS | 46/5/50 | 47.7 | 79.8 | 0.87 | [ |
TPS(SBS/SEBS) | PA/EG/TPS | 50/7/43 | 44 | 1.271 | [ |
柔性载体 | CPCM | 质量分数比/% | 熔点/℃ | 潜热/kJ·kg-1 | 热导率/W·m-1·K-1 | 参考文献 |
---|---|---|---|---|---|---|
EVA | PA/EG/EVA | (50/49.5/48.5/47.5)/ (0/1/3/5)/ (50/49.5/48.5/47.5) | 53 | 141/129/123/121 | 0.3/0.4/0.9/1.7 | [ |
EVA | PA/EG/EVA-g-MAH/MA/TPP | 60/3.5/11.5/10/15 | 47.5 | 125.7 | 1.39 | [ |
POE | PA/EG/POE | (27/36/45/54/63)/ (3/4/5/6/7)/ (70/60/50/40/30) | 65.4/63/64.2/65.3 /65.6 | 51.5/67.1/90.5/108.5/126.7 | 0.62/0.78/0.96/1.41/1.43 | [ |
OBC | PA/EG/OBC | 45/10/45 | 约51 | 101 | 1.57 | [ |
OBC | PA/OBC/EG/AlN | 57/20/3/20 | 44.1 | 145.26 | 1.564 | [ |
OBC | PA/EG/OBC | (79.2/76/72)/ (1/5/10)/ (19.8/19/18) | 50.73/49.67/47.42 | 197.7/185.4 /176.7 | 0.62/2.34/5.5 | [ |
OBC | PA/EG/OBC | 72/10/18 | 42.3 | 130 | 3 | [ |
表3 TPO类部分柔性复合相变材料的热物性参数
柔性载体 | CPCM | 质量分数比/% | 熔点/℃ | 潜热/kJ·kg-1 | 热导率/W·m-1·K-1 | 参考文献 |
---|---|---|---|---|---|---|
EVA | PA/EG/EVA | (50/49.5/48.5/47.5)/ (0/1/3/5)/ (50/49.5/48.5/47.5) | 53 | 141/129/123/121 | 0.3/0.4/0.9/1.7 | [ |
EVA | PA/EG/EVA-g-MAH/MA/TPP | 60/3.5/11.5/10/15 | 47.5 | 125.7 | 1.39 | [ |
POE | PA/EG/POE | (27/36/45/54/63)/ (3/4/5/6/7)/ (70/60/50/40/30) | 65.4/63/64.2/65.3 /65.6 | 51.5/67.1/90.5/108.5/126.7 | 0.62/0.78/0.96/1.41/1.43 | [ |
OBC | PA/EG/OBC | 45/10/45 | 约51 | 101 | 1.57 | [ |
OBC | PA/OBC/EG/AlN | 57/20/3/20 | 44.1 | 145.26 | 1.564 | [ |
OBC | PA/EG/OBC | (79.2/76/72)/ (1/5/10)/ (19.8/19/18) | 50.73/49.67/47.42 | 197.7/185.4 /176.7 | 0.62/2.34/5.5 | [ |
OBC | PA/EG/OBC | 72/10/18 | 42.3 | 130 | 3 | [ |
柔性载体 | CPCM | 质量分数比/% | 熔点/℃ | 潜热/kJ·kg-1 | 热导率/W·m-1·K-1 | 参考文献 |
---|---|---|---|---|---|---|
SR | PA/BN/EG/SR | 30/5.6/3.4/61 | 47.3 | 62.7 | 0.95 | [ |
TPC-et | PA/EG/TPC-et | 45/10/45 | 102 | 1.64 | [ | |
TPE | PA/EG/TPE | (27/36/45/54/63)/(3/4/5/6/7)/ (70/60/50/40/30) | 50.4/53/53.8/57.8/59 | 62.3/83.1/103.5/124.6/145.4 | 0.6/0.9/1.4/1.8/2.2 | [ |
TPEE | PA/EG/TPEE | (59.4/58.2/57)/(1/3/5)/(39.6/38.8/38) | 47.4/46.5/46.4 | 111.2/113.2/112.5 | 0.248/0.502/1.267 | [ |
表4 其他类柔性复合相变材料的热物性参数
柔性载体 | CPCM | 质量分数比/% | 熔点/℃ | 潜热/kJ·kg-1 | 热导率/W·m-1·K-1 | 参考文献 |
---|---|---|---|---|---|---|
SR | PA/BN/EG/SR | 30/5.6/3.4/61 | 47.3 | 62.7 | 0.95 | [ |
TPC-et | PA/EG/TPC-et | 45/10/45 | 102 | 1.64 | [ | |
TPE | PA/EG/TPE | (27/36/45/54/63)/(3/4/5/6/7)/ (70/60/50/40/30) | 50.4/53/53.8/57.8/59 | 62.3/83.1/103.5/124.6/145.4 | 0.6/0.9/1.4/1.8/2.2 | [ |
TPEE | PA/EG/TPEE | (59.4/58.2/57)/(1/3/5)/(39.6/38.8/38) | 47.4/46.5/46.4 | 111.2/113.2/112.5 | 0.248/0.502/1.267 | [ |
柔性载体 | CPCM | 质量分数比/% | 环境温度/℃ | 放电倍率 | 最高温度/℃ | 最大温差/℃ | 参考文献 |
---|---|---|---|---|---|---|---|
SEBS | PA/h-BN/SEBS | 60/20/20 | 25 | 1C/2C/3C | 35/40/47 | 1.1/1.2/2.1 | [ |
NC | — | 25 | 1C/2C/3C | 43/58/76.1 | 4.3/5.4/6.7 | ||
SEBS | PA/EG/SEBS | 76.2/4.8/19 | 30 | 1C/2C/3C | 35.8/39.4/42.2 | 1.6/2.5/3.3 | [ |
SEPS | PA/EG/SEPS | 85.5/5/9.5 | — | 2C/3C | 38.6/43.2 | 0.7/1.5 | [ |
PA/EG/SEPS | 72/20/8 | — | 2C/3C | 38.1/42.2 | 0.4/1.0 | ||
SEPS | PA/EG/SEPS | 82/3/15 | — | 1C/2C/3C | 33.73/38.46/42.96 | 0.2/0.5/0.6 | [ |
PA/SEPS | 90/10 | — | 1C/2C/3C | 35.13/40.65/47.35 | 0.4/0.78/1.2 | ||
无PCM | — | — | 1C/2C/3C | 35.15/41.49/51.01 | 0.79/1.68/3.1 | ||
SBS | PA/AlN/SBS | 35/15/50 | — | 1C/2C/3C | 32.5/34/42.5 | 0.9/2/8.9 | [ |
TPS(SBS/SEBS) | PA/EG/TPS | 50/7/43 | 26 | 1C/2C/2.5C | 30.5/33.9/36.2 | 2.9/3.7/4.0 | [ |
NC | — | 26 | 1C/2C/2.5C | 36.4/42.6/47.9 | 4.9/5.7/7.5 |
表5 TPS类柔性复合相变材料的电池热管理参数
柔性载体 | CPCM | 质量分数比/% | 环境温度/℃ | 放电倍率 | 最高温度/℃ | 最大温差/℃ | 参考文献 |
---|---|---|---|---|---|---|---|
SEBS | PA/h-BN/SEBS | 60/20/20 | 25 | 1C/2C/3C | 35/40/47 | 1.1/1.2/2.1 | [ |
NC | — | 25 | 1C/2C/3C | 43/58/76.1 | 4.3/5.4/6.7 | ||
SEBS | PA/EG/SEBS | 76.2/4.8/19 | 30 | 1C/2C/3C | 35.8/39.4/42.2 | 1.6/2.5/3.3 | [ |
SEPS | PA/EG/SEPS | 85.5/5/9.5 | — | 2C/3C | 38.6/43.2 | 0.7/1.5 | [ |
PA/EG/SEPS | 72/20/8 | — | 2C/3C | 38.1/42.2 | 0.4/1.0 | ||
SEPS | PA/EG/SEPS | 82/3/15 | — | 1C/2C/3C | 33.73/38.46/42.96 | 0.2/0.5/0.6 | [ |
PA/SEPS | 90/10 | — | 1C/2C/3C | 35.13/40.65/47.35 | 0.4/0.78/1.2 | ||
无PCM | — | — | 1C/2C/3C | 35.15/41.49/51.01 | 0.79/1.68/3.1 | ||
SBS | PA/AlN/SBS | 35/15/50 | — | 1C/2C/3C | 32.5/34/42.5 | 0.9/2/8.9 | [ |
TPS(SBS/SEBS) | PA/EG/TPS | 50/7/43 | 26 | 1C/2C/2.5C | 30.5/33.9/36.2 | 2.9/3.7/4.0 | [ |
NC | — | 26 | 1C/2C/2.5C | 36.4/42.6/47.9 | 4.9/5.7/7.5 |
柔性载体 | CPCM | 质量分数比/% | 环境温度/℃ | 放电倍率 | 最高温度/℃ | 最大温差/℃ | 参考文献 |
---|---|---|---|---|---|---|---|
EVA | PA/EG/EVA | 47.5/5/47.5 | 30 | 1C/2C/3C/4C | 38/44.3/50/50.3 | 2.8/3.9/4.1/4.5 | [ |
PA/EG/LDPE | 47.5/5/47.5 | 30 | 1C/2C/3C/4C | 40.1/46.3/48/55.8 | 3.5/4.4/4.8/6.1 | ||
EVA | PA/EG/EVA-g-MAH/MA/TPP | 60/3.5/11.5/10/15 | 25 | 1C/2C/3C | 34.3/42.5/44.3 | 1.7/2.6/3 | [ |
OBC | PA/EG/OBC | 76/5/19 | — | 1C/2C/2.5C | 34/42/44 | — | [ |
表6 TPO类部分柔性复合相变材料的电池热管理参数
柔性载体 | CPCM | 质量分数比/% | 环境温度/℃ | 放电倍率 | 最高温度/℃ | 最大温差/℃ | 参考文献 |
---|---|---|---|---|---|---|---|
EVA | PA/EG/EVA | 47.5/5/47.5 | 30 | 1C/2C/3C/4C | 38/44.3/50/50.3 | 2.8/3.9/4.1/4.5 | [ |
PA/EG/LDPE | 47.5/5/47.5 | 30 | 1C/2C/3C/4C | 40.1/46.3/48/55.8 | 3.5/4.4/4.8/6.1 | ||
EVA | PA/EG/EVA-g-MAH/MA/TPP | 60/3.5/11.5/10/15 | 25 | 1C/2C/3C | 34.3/42.5/44.3 | 1.7/2.6/3 | [ |
OBC | PA/EG/OBC | 76/5/19 | — | 1C/2C/2.5C | 34/42/44 | — | [ |
柔性载体 | CPCM | 质量分数比/% | 环境温度/℃ | 放电倍率 | 最高温度/℃ | 最大温差/℃ | 参考文献 |
---|---|---|---|---|---|---|---|
TPC-et | PA/EG/TPC-et | 45/10/45 | 30 | 1C/2C/3C | 33.5/37.2/41.1 | — | [ |
NC | — | 30 | 1C/2C/3C | 34.8/41.6/44.6 | — | ||
TPEE | PA/EG/TPEE | 57/5/38 | 25 | 1C/3C/5C | 32.6/42.3/49.9 | 0.95/1.39/1.95 | [ |
NC | — | — | 1C/3C/5C | 38.1/63.7/82.2 | — | ||
SR | PA/BN/EG/SR | 61.1/5.6/3.3/30 | 25 | 3C/4C | 45.7/53.4 | 1.9/3.7 | [ |
NC | — | 25 | 3C/4C | 60.3/74.3 | 3.3/9.1 |
表7 其他类部分柔性复合相变材料的电池热管理参数
柔性载体 | CPCM | 质量分数比/% | 环境温度/℃ | 放电倍率 | 最高温度/℃ | 最大温差/℃ | 参考文献 |
---|---|---|---|---|---|---|---|
TPC-et | PA/EG/TPC-et | 45/10/45 | 30 | 1C/2C/3C | 33.5/37.2/41.1 | — | [ |
NC | — | 30 | 1C/2C/3C | 34.8/41.6/44.6 | — | ||
TPEE | PA/EG/TPEE | 57/5/38 | 25 | 1C/3C/5C | 32.6/42.3/49.9 | 0.95/1.39/1.95 | [ |
NC | — | — | 1C/3C/5C | 38.1/63.7/82.2 | — | ||
SR | PA/BN/EG/SR | 61.1/5.6/3.3/30 | 25 | 3C/4C | 45.7/53.4 | 1.9/3.7 | [ |
NC | — | 25 | 3C/4C | 60.3/74.3 | 3.3/9.1 |
柔性载体 | CPCM | 质量分数比 /% | 抗压强度 /MPa | 抗拉强度 /MPa | 抗弯强度 /MPa | 最大应力 /MPa | 断裂伸长率 /% | 参考文献 |
---|---|---|---|---|---|---|---|---|
SEBS | PA/h-BN/SEBS | 60/20/20 | — | 0.72 | — | — | — | [ |
SBS | PA/CNT/SBS | (80/85/90)/2/(18/13/8) | — | 0.5~0.75 | — | /1.47/1.78 | 13.79/20.33/2.58 | [ |
SBS | PA/AlN/SBS | 50/15/35 | — | 0.19 | 0.6 | — | — | [ |
EVA | PA/EG/EVA | 47.5/5/47.5 | 8.07 | 0.83 | 0.02 | — | 3.68 | [ |
PA/EG/LDPE | 47.5/5/47.5 | 143.45 | 81.2 | 2.45 | — | 1.98 | ||
OBC | PA/EG/OBC | 45/10/45 | 34.36 | 5.44 | 1.21 | — | 3.62 | [ |
SR | PA/BN/EG/SR | 61.1/5.6/3.4/30 | 0.7 | — | — | — | — | [ |
PW/EG/SR | 0.46 | — | — | — | — | |||
TPC-et | PA/EG/TPC-et | 45/10/45 | 5.02 | 0.88 | 0.14 | — | 5.24 | [ |
TPS(SBS/SEBS) | PA/EG/TPS | 50/7/43 | — | 0.408 | — | — | 41.257 | [ |
TPEE | PA/EG/TPEE | (59.4/58.2/57)/(1/3/5)/(39.6/38.8/38) | — | 4.9/4.6/4.5 | — | — | — | [ |
表8 TPE类部分柔性复合相变材料的力学性能参数
柔性载体 | CPCM | 质量分数比 /% | 抗压强度 /MPa | 抗拉强度 /MPa | 抗弯强度 /MPa | 最大应力 /MPa | 断裂伸长率 /% | 参考文献 |
---|---|---|---|---|---|---|---|---|
SEBS | PA/h-BN/SEBS | 60/20/20 | — | 0.72 | — | — | — | [ |
SBS | PA/CNT/SBS | (80/85/90)/2/(18/13/8) | — | 0.5~0.75 | — | /1.47/1.78 | 13.79/20.33/2.58 | [ |
SBS | PA/AlN/SBS | 50/15/35 | — | 0.19 | 0.6 | — | — | [ |
EVA | PA/EG/EVA | 47.5/5/47.5 | 8.07 | 0.83 | 0.02 | — | 3.68 | [ |
PA/EG/LDPE | 47.5/5/47.5 | 143.45 | 81.2 | 2.45 | — | 1.98 | ||
OBC | PA/EG/OBC | 45/10/45 | 34.36 | 5.44 | 1.21 | — | 3.62 | [ |
SR | PA/BN/EG/SR | 61.1/5.6/3.4/30 | 0.7 | — | — | — | — | [ |
PW/EG/SR | 0.46 | — | — | — | — | |||
TPC-et | PA/EG/TPC-et | 45/10/45 | 5.02 | 0.88 | 0.14 | — | 5.24 | [ |
TPS(SBS/SEBS) | PA/EG/TPS | 50/7/43 | — | 0.408 | — | — | 41.257 | [ |
TPEE | PA/EG/TPEE | (59.4/58.2/57)/(1/3/5)/(39.6/38.8/38) | — | 4.9/4.6/4.5 | — | — | — | [ |
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