CN1388597A - 生产电化学元件用电极片的方法 - Google Patents
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Abstract
一种生产电化学元件用电极片的方法,该电极片包含至少一个锂－嵌入(嵌有锂的)电极,该电极由至少两种共聚氟化聚合物的混合物组成,在该电极的聚合物基质中精细地分散着不溶于该聚合物的电化学活性材料,按该法,氟化物聚合物,溶解在溶剂中之后,与电化学活性材料进行混合,如此获得的糊料物质挤出成形为片材,然后与聚烯烃隔膜进行层合,该隔膜备有这两种聚合物的混合物,其中每种情况均采用PVDF－HFP共聚物作为该聚合物而且其HFP的比例小于8wt%。
Description
技术领域
本发明涉及生产电化学元件用电极片的方法，该电极片包含至少一个锂-嵌入电极，该电极由至少两种共聚氟化聚合物的混合物组成，在该电极的聚合物基质中精细地分散着不溶于该聚合物的电化学活性材料。本发明还涉及具有如此生产的电极的电化学元件。
背景技术
电极材料与隔膜以及电极与各自的输出导电片之间的附着对于电化学元件正常工作特别重要。由于电极在电解质中溶胀导致接触的简单破坏或者由于分解产生气体，也可能在电化学意义上丧失接触。层合的电池在此种情况下则具有优势，因为不会由于出气而导致接触的自发丧失，因此该成形因素意味着可以达到高能量密度。由于其生产方法，层合物通常也更抗溶胀。
由聚偏二氟乙烯-六氟丙烯共聚物薄膜与以导电盐形式分布于其中的锂盐组成的聚合物电解质的应用，公开在美国专利5 296 318中。按该专利，共聚物中HFP的比例应介于8～25wt％。
美国专利5 460 904公开一种锂-嵌入电极，其中活性物质分布在由聚偏二氟乙烯-六氟丙烯共聚物组成的基质中。一种由相同材料制成的凝胶隔膜布置在这些电极之间，包含软化剂，特别是邻苯二甲酸二丁酯，它随后还将被溶出。在该凝胶电解质和电极片中，HFP所占比例，每种情况均介于8～25wt％。
该生产电池的方法缺点在于，软化剂必须被溶出。再者，它形成一种非常软的隔膜，生产过程中它非常容易被“层合穿透”，从而导致电池的短路。因此，要求较厚的隔膜层，这势必降低能量密度。另外，隔膜中二氧化硅所占比例，当与锂电极配合使用时，不能长期保持稳定。
发明内容
因此，本发明的目的是规定一种生产本文开头所提到的那种类型电极片的方法，它容易实施，按此法可在隔膜材料与电极材料之间提供良好接触，并且它们又能组装形成高能量密度的电池。
在本文开头所提到的那种类型的方法中，本发明的目的是由权利要求1的优异特征达到的。从属权利要求规定了该方法的改进设计，以及采用此种电极片的电化学元件。
PVDF(聚偏二氟乙烯)-HFP(六氟丙烯)组成中HPF所占的此种小比例，尤其提供正电极对铝输出导电片之间的良好结合，现已发现，仅具有半导电性质的活性材料的氧化颗粒与聚合物中此种少量HFP能实现较好接触。再者，HFP比例的减少改善了加工特性。活性材料的混合以及均匀地挤出成形为片材乃至该片材层合的能力，均得到改善。聚烯烃基隔膜涂以PVDF-HFP共聚物的用法，使得电极材料与隔膜之间很容易实现良好结合。
例如，N-甲基吡咯烷(pyrolidin)-2-酮或丙酮被用作生产电极和涂布聚烯烃隔膜的涂料用的溶剂。HFP在PVDF-HFP共聚物中所占比例，在负电极与正电极之间可以不同。典型的试剂是solef 20615，其HFP占6wt％；以及Kynar Powerflex，HFP占到5～6wt％。
正电极片的电化学活性材料是选自三元(Li-Me1-O)或四元(Li-Me1-Me2-O)锂过渡金属氧化物的材料，其中Me1和Me2选自族Ti、V、Cr、Fe、Mn、Ni、Co，并且要求的话，该化合物另外包含最高15％，按原子量计，镁、铝、氮或氟，以便稳定该结构。
正电极的电化学活性材料的BET表面面积可介于0.1～2m2/g；粒度介于1～50μm。特别是，采用Li/Co比例介于0.98～1.05的LiCoO2作为正电极材料。生产正电极片材的糊料混合物应包含65～98wt％，优选75～95wt％锂过渡金属氧化物。
特别是，负电极片材包含石墨化碳改性物作为其电化学活性材料。生产负电极片材的糊料混合物包含55～95wt％，优选65～85wt％碳材料。
一般而言，生产此种电极片的糊料混合物包含50～75wt％，优选55～65wt％溶剂。初始糊料的粘度规定在1～10帕，优选3～6帕。
具体实施方式
实例
9.9g粘结剂聚合物(Kynar Powerflex)、94g LiCoO2、3.3g导电碳黑(Super P)、3.3g石墨(KS6)和16.5g邻苯二甲酸二丁酯，加入到丙酮中以生产阴极，如此获得的涂料物质借助半自动刮涂膜设备(Simex)涂抹到载体片材上。随后，将所形成的、自由站立的正物质膜层合到金属网(2A16-077F，Delker)上，使网位于中央。
为制备阳极，12.4g粘结剂聚合物(SOLEF 20615)、96.2g球形石墨(MCMB)、2.75g导电碳黑(Super P)和26.1g邻苯二甲酸二丁酯，加入到丙酮中，所获得的涂布物质借助半自动刮涂膜设备(Simex)涂抹到载体片材上。随后，将所形成的、自由站立的负物质膜层合到金属网(2Cu6-077F+A，Delker)上，使网位于中央。
市售供应的聚烯烃隔膜借助气刷喷枪涂以P(VdF-HFP)以及可能地，诸如邻苯二甲酸二丁酯之类软化剂，在丙酮中的溶液，以便在丙酮蒸发后干膜厚度为约1～2μm。
两个层合的阴极组件，两面各涂以隔膜，然后再层合上阳极组件，结果形成对称电池。如此获得的六个电池叠摞起来形成叠层，然后焊接到输出导体上。用有机锂电解质(LP 50，Merck)置换软化剂，随后包装在双面涂布的铝复合片材(Lawson Mardon，USA)之后，这些叠层经过成形，脱气，然后放在室温、1C(电流)条件下循环工作。
附图显示，6-双电池叠层的电容(CB)随放电周期数目n的变化，其中电流在3.0～4.2V(室温)电压下的大小是1C(750mA)(曲线1)。
与此相比，曲线2则显示采用具有11～12wt％HFP的载体聚合物的6-双电池叠层的电容。
采用HFP比例小于8wt％和采用涂以相同聚合物混合物的聚烯烃隔膜的优点是，这将产生一种沿边界表面具有最佳附着力的电池组件。像这样的电池，具有更大的负载能力和改善的周期稳定性。
Claims (12)
1.一种生产电化学元件用电极片的方法，该电极片包含至少一个锂-嵌入电极，该电极由至少两种共聚氟化聚合物的混合物组成，在该电极的聚合物基质中精细地分散着不溶于该聚合物的电化学活性材料，其特征在于，按该法，溶解在溶剂中的氟化物聚合物与电化学活性材料进行混合，如此获得的糊料物质挤出成形为片材，然后与聚烯烃隔膜进行层合，该隔膜备有这两种聚合物的混合物，其中每种情况均采用PVDF-HFP共聚物作为该聚合物而且其HFP的比例小于8wt％。
2.权利要求1的方法，其中N-甲基吡咯烷(pyrolidin)-2-酮(NMP)或丙酮被用作溶剂。
3.权利要求1或2的方法，其中PVDF-HFP在负电极中与在正电极中的比例不同。
4.权利要求1或3中任何一项的方法，其中作为正电极片的电化学活性材料，使用选自三元(Li-Me1-O)或四元(Li-Me1-Me2-O)锂过渡金属氧化物的材料，其中Me1和Me2选自族Ti、V、Cr、Fe、Mn、Ni、Co，并且要求的话，该化合物另外包含最高15％，按原子量计，镁、铝、氮或氟，以便稳定该结构。
5.权利要求1～4之任何一项的方法，其中采用石墨化碳改性物作为负电极片的电化学活性材料。
6.权利要求1～5中一项或多项的方法，其中采用BET表面面积介于0.1～2m2/g且粒度介于1～50μm的材料作为正电极片的活性材料。
7.权利要求1～6中一项或多项的方法，其中LiCoO2，其Li/Co比值等于0.98～1.05，被用作正电极的材料。
8.权利要求1～7中一项或多项的方法，其中负电极片用的糊料混合物包含55～95wt％，优选65～85wt％碳材料。
9.权利要求1～8中一项或多项的方法，其中正电极片用的糊料混合物含有65～98wt％，优选75～95wt％锂过渡金属氧化物。
10.权利要求1～9中一项或多项的方法，其中糊料混合物包含50～75wt％，优选55～65wt％溶剂。
11.权利要求1～10中一项或多项的方法，其中初始糊料的粘度规定在1～10帕，优选3～6帕。
12.一种具有至少一个采用权利要求1～11之一的方法生产的电极片的电化学元件。
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| DE10125616A DE10125616A1 (de) | 2001-05-25 | 2001-05-25 | Verfahren zur Herstellung von Elektrodenfolien für galvanische Elemente |
| DE10125616.7 | 2001-05-25 |
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| EP (1) | EP1261048B1 (zh) |
| JP (1) | JP4426154B2 (zh) |
| KR (1) | KR100865996B1 (zh) |
| CN (1) | CN1331259C (zh) |
| AT (1) | ATE538506T1 (zh) |
| DE (1) | DE10125616A1 (zh) |
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| CN109585934A (zh) * | 2019-01-10 | 2019-04-05 | 南京科技职业学院 | 一种电池制备设备 |
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| US8232007B2 (en) | 2005-10-05 | 2012-07-31 | California Institute Of Technology | Electrochemistry of carbon subfluorides |
| US7794880B2 (en) | 2005-11-16 | 2010-09-14 | California Institute Of Technology | Fluorination of multi-layered carbon nanomaterials |
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| US8658309B2 (en) * | 2006-08-11 | 2014-02-25 | California Institute Of Technology | Dissociating agents, formulations and methods providing enhanced solubility of fluorides |
| US7605030B2 (en) * | 2006-08-31 | 2009-10-20 | Micron Technology, Inc. | Hafnium tantalum oxynitride high-k dielectric and metal gates |
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| DE102010039416A1 (de) | 2010-08-17 | 2012-02-23 | Varta Micro Innovation Gmbh | Flexible Batterieelektroden und ihre Herstellung |
| US9178199B2 (en) * | 2012-02-21 | 2015-11-03 | Samsung Sdi Co., Ltd. | Lithium battery |
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| DE102016221298A1 (de) | 2016-10-28 | 2018-05-03 | Volkswagen Aktiengesellschaft | Neue Bindersysteme für Silicium-haltige Kompositelektroden für Lithium-Ionen-Batterien |
| DE102017211504A1 (de) | 2017-07-06 | 2019-01-10 | Bayerische Motoren Werke Aktiengesellschaft | Elektrochemischer Energiespeicher, Herstellungsverfahren, Energiespeichermodul und Fahrzeug |
| CN108045026A (zh) * | 2017-12-08 | 2018-05-18 | 苏州爱康薄膜新材料有限公司 | 一种高阻水阻燃的锂电池封装用复合膜及其制备方法 |
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- 2001-05-25 DE DE10125616A patent/DE10125616A1/de not_active Withdrawn
-
2002
- 2002-05-02 AT AT02009821T patent/ATE538506T1/de active
- 2002-05-02 EP EP02009821A patent/EP1261048B1/de not_active Expired - Lifetime
- 2002-05-09 KR KR1020020025434A patent/KR100865996B1/ko active IP Right Grant
- 2002-05-22 US US10/154,141 patent/US7157184B2/en not_active Expired - Lifetime
- 2002-05-24 CN CNB021201900A patent/CN1331259C/zh not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107863477A (zh) * | 2017-10-17 | 2018-03-30 | 浙江歌瑞新材料有限公司 | 一种pvdf‑bp微孔聚合物隔膜及制备方法 |
| CN109585934A (zh) * | 2019-01-10 | 2019-04-05 | 南京科技职业学院 | 一种电池制备设备 |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE538506T1 (de) | 2012-01-15 |
| EP1261048B1 (de) | 2011-12-21 |
| KR100865996B1 (ko) | 2008-10-29 |
| CN1331259C (zh) | 2007-08-08 |
| US7157184B2 (en) | 2007-01-02 |
| US20020177041A1 (en) | 2002-11-28 |
| DE10125616A1 (de) | 2002-12-05 |
| EP1261048A3 (de) | 2004-09-22 |
| KR20020090118A (ko) | 2002-11-30 |
| JP2003017041A (ja) | 2003-01-17 |
| EP1261048A2 (de) | 2002-11-27 |
| JP4426154B2 (ja) | 2010-03-03 |
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