CN111430649B - 一种锂离子电池隔膜的制备方法及锂离子电池 - Google Patents
一种锂离子电池隔膜的制备方法及锂离子电池 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 11
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
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- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
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- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 6
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 26
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 18
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于锂离子电池技术领域,具体是一种锂离子电池隔膜的制备方法及锂离子电池,在造孔剂分散液中加入芳香族二元酸酐,再依次逐滴加入第一芳香族二元胺、第二芳香族二元胺和芳香族三元胺交联剂,所述第一芳香族二元胺分子结构不包含醚键或硫醚键,所述第二芳香族二元胺分子结构中包含醚键或硫醚键。本发明利用酸酐和氨基的高反应活性,通过依次加入不同芳香族二元胺的方法,获得类似嵌段共聚物的聚酰胺酸,脱除造孔剂、亚胺化反应后获得具有较高机械强度的锂离子电池隔膜。
Description
技术领域
本发明属于锂离子电池技术领域,涉及一种锂离子电池隔膜的制备方法及锂离子电池。
背景技术
隔膜是锂离子电池的关键组件之一,对电池的充放电性能、安全性能等具有重要的影响。随着对锂离子电池性能要求越来越高,对隔膜的性能也要求越来越高。聚酰亚胺(PI)具有耐高温、耐溶剂性好等特性,聚酰亚胺隔膜正研究的越来越多,但目前聚酰亚胺隔膜的机械强度还有不足。
发明内容
本发明的一个目的在于克服现有技术缺陷,提供一种锂离子电池隔膜的制备方法,二元酸酐依次与第一芳香族二元胺和第二芳香族二元胺进行反应,获得类似嵌段共聚物的聚酰胺酸预聚物,相比现有的一次性加入芳香族二元胺的方法,能提供更高的机械强度。
本发明还有一个目的是提供一种锂离子电池。
本发明的技术方案如下:
一种锂离子电池隔膜的制备方法,包括以下步骤,
S1、按重量份数计,将20~60份造孔剂分散在500~700份有机溶剂中,获得造孔剂分散液;所述有机溶剂选自N,N-二甲基甲酰胺(MDF)、N,N-二甲基乙酰胺(MDAc)和N-甲基吡咯烷酮(NMP)中的一种。所述造孔剂的平均粒径为0.03~0.15μm,更优选的为0.03~0.1μm。
S2、在步骤S1的造孔剂分散液中加入芳香族二元酸酐,置于冰水浴中搅拌均匀,逐滴加入第一芳香族二元胺,滴加完搅拌20~60分钟;继续滴加第二芳香族二元胺,滴加完搅拌20~60分钟;继续滴加芳香族三元胺交联剂,滴加完置于室温中搅拌2~10小时,获得混合溶液;所述第一芳香族二元胺分子结构不包含醚键或硫醚键;所述第二芳香族二元胺分子结构中包含醚键或硫醚键;所述芳香族三元胺交联剂分子结构中不包含醚键;为了更顺利的实现滴加,所述第一芳香族二元胺、第二芳香族二元胺或芳香族三元胺交联剂可以溶解在有机溶剂中,形成溶液。
S3、将步骤S2获得混合溶液涂布在基材上形成厚度为60~150μm的膜,升温至所述造孔剂分解,拉伸,升温进行亚胺化反应,获得所述锂离子电池隔膜。所述拉伸的拉伸比为2~3。所述亚胺化反应的条件为温度升至160~200℃保温1~2小时,升温至250~300℃保温1~2小时,升温至330~350℃保温1~2小时。
优选的,步骤S1中所述造孔剂常压下的分解温度或挥发温度在90~130℃,选自草酸铵、氯化铵和硝酸铵中的至少一种。
优选的,步骤S2中所述造孔剂分散液和芳香族二元酸酐的重量比为100:5~10。
优选的,步骤S2中所述芳香族二元酸酐、第一芳香族二元胺、第二芳香族二元胺和芳香族三元胺交联剂的摩尔比为1:0.6~0.8:0.2~0.4:0.1~0.2。更优选的,所述芳香族二元酸酐的摩尔数与第一芳香族二元胺和第二芳香族二元胺摩尔数之和的比为1:0.9~1.05。
优选的,步骤S2中所述芳香族二元酸酐选自均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、3,3',4,4'-二苯酮四羧酸二酐、2,3,3,4-联苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、2,3,3',4'-联苯四甲酸二酐、2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-二苯醚四甲酸二酐、3,3',4,4'-二苯砜四羧酸二酐和2,2',3,3'-二苯砜四羧酸二酐中的至少一种。
优选的,步骤S2中所述第一芳香族二元胺选自对苯二胺、间苯二胺、邻苯二胺、2,6-二氨基甲苯、1,4-二氨基三氟甲苯、3,5-二氨基三氟甲苯、联苯二胺、4,4'-二氨基二苯甲烷、3,4'-二氨基二苯甲烷、3,3'-二甲基-4,4'-二氨基二苯甲烷、3,3'-二异丙基-4,4'-二氨基二苯甲烷、3,3',5,5'-四甲基-4,4'-二氨基二苯甲烷、3,3',5,5'-四乙基-4,4'-二氨基二苯甲烷和3,3',5,5'-四异丙基-4,4'-二氨基二苯甲烷中的至少一种。
优选的,步骤S2中所述第二芳香族二元胺选自4,4'-双(3-氨基苯氧基)二苯硫醚、4,4'-双(4-氨基苯氧基)二苯硫醚、4,4'-二氨基二苯醚、3,4'-二氨基二苯醚、3,3'-二氨基二苯醚、八氟-4,4-二氨基二苯醚、4,4'-二氨基二苯硫醚和4,4'-二氨基二苯二硫醚中的至少一种。
优选的,步骤S2中所述芳香族三元胺交联剂选自1,3,5-三氨基苯和1,3,5-三(4-氨基苯氧基)苯中的至少一种。
优选的,步骤S3中所述升温至所述造孔剂分解的温度为比常压下造孔剂的分解温度或挥发温度高3~10℃。更优选的,所述升温至造孔剂分解前预先升温至50~80℃保温1~2小时。
一种锂离子电池,包含上述任一实施方案所述的制备方法获得的锂离子电池隔膜。
本发明的有益效果是:本发明采用现有的聚酰亚胺隔膜的各种原料,通过改变加料顺序和反应方式,获得具有较高力学强度的锂离子电池隔膜。芳香族二元酸酐与芳香族二元胺有较高的反应活性,本发明通过芳香族二元酸酐与不含醚键或硫醚键的芳香族二元胺先进行反应,获得硬段预聚物,再与含醚键或硫醚键的芳香族二元胺反应,获得软段部分的聚合物,因此形成硬段-软段预聚物,形成类似嵌段共聚物的聚酰胺酸预聚物,再与芳香族三元胺交联剂进行交联,获得交联聚酰胺酸;交联聚酰胺酸除去造孔剂后进行拉伸,既可以增加硬段的结晶性,又可以提高孔隙率,同时软段亚胺化反应后获得的锂离子电池隔膜具有较高的机械强度和孔隙率。现有技术是采用一次加入芳香族二元酸酐的方法,获得的是无规共聚物。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
如无特别指明,以下实施方案中的份数都为重量份数。
实施例1
将20份造孔剂草酸铵分散在500份DMF中,获得造孔剂分散液;
在上述造孔剂分散液中加入25份均苯四甲酸二酐,置于冰水浴中搅拌均匀,逐滴加入含7.45份对苯二胺的DMF溶液,滴加完搅拌25分钟;继续滴加含13.8份4,4'-双(4-氨基苯氧基)二苯硫醚的DMF溶液,滴加完搅拌30分钟;继续滴加含2.85份1,3,5-三氨基苯的DMF溶液,滴加完置于室温中搅拌3小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为70μm的聚酰胺酸膜,升温至50℃维持1小时,升温至100℃分解草酸铵,拉伸比2.1下进行拉伸,升温至170℃保温2小时、升温至250℃保温2小时、升温至330℃保温2小时,获得锂离子电池隔膜,记为PI-1。
实施例2
将40份造孔剂氯化铵分散在600份NMP中,获得造孔剂分散液;
在上述造孔剂分散液中加入40份3,3',4,4'-联苯四羧酸二酐,置于冰水浴中搅拌均匀,逐滴加入含10.3份间苯二胺的NMP溶液,滴加完搅拌40分钟;继续滴加含19.2份4,4'-双(4-氨基苯氧基)二苯硫醚的NMP溶液,滴加完搅拌40分钟;继续滴加含8.2份1,3,5-三(4-氨基苯氧基)苯的NMP溶液,滴加完置于室温中搅拌6小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为100μm的聚酰胺酸膜,升温至60℃维持1.5小时,升温至106℃挥发氯化铵,拉伸比2.5下进行拉伸,升温至180℃保温1.5小时、升温至280℃保温1.5小时、升温至350℃保温1小时,获得锂离子电池隔膜,记为PI-2。
实施例3
将60份硝酸铵造孔剂分散在700份DMAc中,获得造孔剂分散液;
在上述造孔剂分散液中加入70份2,3,3',4'-联苯四甲酸二酐,置于冰水浴中搅拌均匀,逐滴加入含23.3份2,6-二氨基甲苯的DMAc溶液,滴加完搅拌60分钟;继续滴加含9.55份4,4'-二氨基二苯醚的DMAc溶液,滴加完搅拌60分钟;继续滴加含2.97份1,3,5-三氨基苯的DMAc溶液,滴加完置于室温中搅拌10小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为150μm的聚酰胺酸膜,升温至80℃维持1小时,升温至116℃分解硝酸铵,拉伸比3下进行拉伸,升温至200℃保温1小时、升温至300℃保温1小时、升温至330℃保温1小时,获得锂离子电池隔膜,记为PI-3。
实施例4
将35份草酸铵造孔剂分散在600份DMF中,获得造孔剂分散液;
在上述造孔剂分散液中加入45份3,3',4,4'-联苯四羧酸二酐,置于冰水浴中搅拌均匀,逐滴加入含20份联苯二胺的DMF溶液,滴加完搅拌35分钟;继续滴加含12.4份4,4'-二氨基二苯醚的DMF溶液,滴加完搅拌40分钟;继续滴加含1.9份1,3,5-三氨基苯的DMF溶液,滴加完置于室温中搅拌8小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为90μm的聚酰胺酸膜,升温至50℃维持1小时,升温至102℃分解造孔剂,拉伸比2.4下进行拉伸,升温至180℃保温1小时、升温至280℃保温1小时、升温至330℃保温1小时,获得锂离子电池隔膜,记为PI-4。
实施例5
将40份草酸铵造孔剂分散在600份DMF中,获得造孔剂分散液;
在上述造孔剂分散液中加入50份3,3',4,4'-二苯酮四羧酸二酐,置于冰水浴中搅拌均匀,逐滴加入18.5份含4,4'-二氨基二苯甲烷的DMF溶液中,滴加完搅拌40分钟;继续滴加含11.7份4,4'-二氨基二苯硫醚的DMF溶液中,滴加完搅拌50分钟;继续滴加含6.2份1,3,5-三(4-氨基苯氧基)苯的DMF溶液中,滴加完置于室温中搅拌8小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为120μm的聚酰胺酸膜,升温至50℃维持1小时,升温至102℃分解造孔剂,拉伸比2.4进行拉伸,升温至170℃保温1小时、升温至280℃保温1小时、升温至340℃保温1小时,获得锂离子电池隔膜,记为PI-5。
实施例6
将40份草酸铵造孔剂分散在650份DMAc中,获得造孔剂分散液;
在上述造孔剂分散液中加入60份均苯四甲酸二酐,置于冰水浴中搅拌均匀,逐滴加入含19.5份对苯二胺的DMAc溶液中,滴加完搅拌30分钟;继续滴加含16.5份4,4'-二氨基二苯醚的DMAc溶液中,滴加完搅拌60分钟;继续滴加含3.4份1,3,5-三氨基苯的DMAc溶液中,滴加完置于室温中搅拌10小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为90μm的聚酰胺酸膜,升温至50℃维持1小时,升温至102℃分解造孔剂,拉伸比2.4下进行拉伸,升温至180℃保温1小时、升温至300℃保温1小时、升温至330℃保温1小时,获得锂离子电池隔膜,记为PI-6。
对比例1
将40份草酸铵造孔剂分散在650份DMAc中,获得造孔剂分散液;
在上述造孔剂分散液中加入60份均苯四甲酸二酐,置于冰水浴中搅拌均匀,逐滴加入含33份对苯二胺的DMAc溶液中,滴加完搅拌30分钟;继续滴加含3.4份1,3,5-三氨基苯的DMAc溶液中,滴加完置于室温中搅拌10小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为90μm的聚酰胺酸膜,升温至50℃维持1小时,升温至102℃分解造孔剂,拉伸比2.4下进行拉伸,升温至180℃保温1小时、升温至300℃保温1小时、升温至330℃保温1小时,获得锂离子电池隔膜,记为PI-7。
对比例2
将40份草酸铵造孔剂分散在650份DMAc中,获得造孔剂分散液;
在上述造孔剂分散液中加入60份均苯四甲酸二酐,置于冰水浴中搅拌均匀,滴加含58份4,4'-二氨基二苯醚的DMAc溶液中,滴加完搅拌60分钟;继续滴加含3.4份1,3,5-三氨基苯的DMAc溶液中,滴加完置于室温中搅拌10小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为90μm的聚酰胺酸膜,升温至50℃维持1小时,升温至102℃分解造孔剂,拉伸比2.4下进行拉伸,升温至180℃保温1小时、升温至300℃保温1小时、升温至330℃保温1小时,获得锂离子电池隔膜,记为PI-8。
对比例3
将40份草酸铵造孔剂分散在650份DMAc中,获得造孔剂分散液;
在上述造孔剂分散液中加入60份均苯四甲酸二酐,置于冰水浴中搅拌均匀,逐滴加入含19.5份对苯二胺和16.5份4,4'-二氨基二苯醚的DMAc溶液中,滴加完搅拌50分钟;继续滴加含3.4份1,3,5-三氨基苯的DMAc溶液中,滴加完置于室温中搅拌10小时,获得混合溶液;
将上述混合溶液涂布在基材上形成厚度为90μm的聚酰胺酸膜,升温至50℃维持1小时,升温至102℃分解造孔剂,拉伸比2.4下进行拉伸,升温至180℃保温1小时、升温至300℃保温1小时、升温至330℃保温1小时,获得锂离子电池隔膜,记为PI-9。
上述各实施例和对比例中PI-1~PI-9的机械性能如表1所示。
表1
因此,采用本发明的锂离子电池隔膜的制备方法获得的聚酰亚胺型锂离子电池隔膜,相比单独使用一种芳香族二元胺或两种芳香族二元胺的无规共聚,具有更好的力学性能。
如上所述,显示和描述了本发明的基本原理、主要特征和优点。本领域技术人员应该了解本发明不受上述实施例的限制,上述实施例仅为本发明的较佳实施例而已,不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。
Claims (10)
1.一种锂离子电池隔膜的制备方法,其特征在于,包括以下步骤,
S1、按重量份数计,将20~60份造孔剂分散在500~700份有机溶剂中,获得造孔剂分散液;
S2、在步骤S1的造孔剂分散液中加入芳香族二元酸酐,置于冰水浴中搅拌均匀,逐滴加入第一芳香族二元胺,滴加完搅拌20~60分钟;继续滴加第二芳香族二元胺,滴加完搅拌20~60分钟;继续滴加芳香族三元胺交联剂,滴加完置于室温中搅拌2~10小时,获得混合溶液;所述第一芳香族二元胺分子结构不包含醚键或硫醚键;所述第二芳香族二元胺分子结构中包含醚键或硫醚键;所述芳香族三元胺交联剂分子结构中不包含醚键;
S3、将步骤S2获得混合溶液涂布在基材上形成厚度为60~150μm的膜,升温至所述造孔剂分解,拉伸,升温进行亚胺化反应,获得所述锂离子电池隔膜。
2.根据权利要求1所述的制备方法,其特征在于,步骤S1中所述造孔剂常压下的分解温度或挥发温度在90~130℃,选自草酸铵、氯化铵和硝酸铵中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于,步骤S2中所述造孔剂分散液和芳香族二元酸酐的重量比为100:5~10。
4.根据权利要求1所述的制备方法,其特征在于,步骤S2中所述芳香族二元酸酐、第一芳香族二元胺、第二芳香族二元胺和芳香族三元胺交联剂的摩尔比为1:0.6~0.8:0.2~0.4:0.1~0.2。
5.根据权利要求1所述的制备方法,其特征在于,步骤S2中所述芳香族二元酸酐选自均苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、3,3',4,4'-二苯酮四羧酸二酐、2,3,3,4-联苯四甲酸二酐、3,3',4,4'-联苯四羧酸二酐、2,3,3',4'-联苯四甲酸二酐、2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-二苯醚四甲酸二酐、3,3',4,4'二苯砜四羧酸二酐和2,2',3,3'-二苯砜四羧酸二酐中的至少一种。
6.根据权利要求1所述的制备方法,其特征在于,步骤S2中所述第一芳香族二元胺选自对苯二胺、间苯二胺、邻苯二胺、2,6-二氨基甲苯、1,4-二氨基三氟甲苯、3,5-二氨基三氟甲苯、联苯二胺、4,4'-二氨基二苯甲烷、3,4'-二氨基二苯甲烷、3,3'-二甲基-4,4'-二氨基二苯甲烷、3,3'-二异丙基-4,4'-二氨基二苯甲烷、3,3',5,5'-四甲基-4,4'-二氨基二苯甲烷、3,3',5,5'-四乙基-4,4'-二氨基二苯甲烷和3,3',5,5'-四异丙基-4,4'-二氨基二苯甲烷中的至少一种。
7.根据权利要求1所述的制备方法,其特征在于,步骤S2中所述第二芳香族二元胺选自4,4'-双(3-氨基苯氧基)二苯硫醚、4,4'-双(4-氨基苯氧基)二苯硫醚、4,4'-二氨基二苯醚、3,4'-二氨基二苯醚、3,3'-二氨基二苯醚、八氟-4,4-二氨基二苯醚、4,4'-二氨基二苯硫醚和4,4'-二氨基二苯二硫醚中的至少一种。
8.根据权利要求1所述的制备方法,其特征在于,步骤S2中所述芳香族三元胺交联剂选自1,3,5-三氨基苯和1,3,5-三(4-氨基苯氧基)苯中的至少一种。
9.根据权利要求1所述的制备方法,其特征在于,步骤S3中所述升温至所述造孔剂分解的温度为比常压下造孔剂的分解温度或挥发温度高3~10℃。
10.一种锂离子电池,其特征在于,包含权利要求1-9任一项所述的制备方法获得的锂离子电池隔膜。
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