CN108779360A - 具有高含量无机材料的含氟聚合物组合物 - Google Patents
具有高含量无机材料的含氟聚合物组合物 Download PDFInfo
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- CN108779360A CN108779360A CN201780017634.XA CN201780017634A CN108779360A CN 108779360 A CN108779360 A CN 108779360A CN 201780017634 A CN201780017634 A CN 201780017634A CN 108779360 A CN108779360 A CN 108779360A
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- 235000017281 sodium acetate Nutrition 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Chemical class 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
本发明提供了一种包含电活性材料的含氟聚合物组合物颗粒,其中所述电活性材料包含石墨和金属化合物以及它们的组合;所述组合物还包含水和沸点介于70℃和200℃之间的有机液体。本发明还提供了制备糊料的方法和制备电极的方法以及用所述糊料制成的电极。
Description
技术领域
本公开涉及具有高含量电活性材料的含水含氟聚合物组合物。本公开还涉及涂覆有所述组合物的制品以及制备此类制品和此类组合物的方法。
背景技术
在一些应用中,含氟聚合物用作无机材料的粘结剂。需要提供具有高含量的实质上无机材料的含氟聚合物组合物。此类组合物可用于(例如)制备能量产生装置(诸如燃料电池或蓄电池)的部件。典型部件包括电极。电子工业有一种生产由较小和较轻的电池供电的较小装置的趋势。锂电池,例如具有包含具有锂离子的锂化合物或含碳材料的负极和包含锂金属氧化物或盐的正极的电池可提供更高的功率和更低的重量。电极通常通过用包含电活性材料、含氟聚合物作为粘结剂和任选的填料的电极形成组合物涂覆多孔或织物样载体材料来制备。使涂层经受热处理以形成电极。
含氟聚合物已用作用于形成电极的粘结剂,因为它们具有优异的耐电-化学品性。聚四氟乙烯(PTFE)已用作如例如美国专利6,156,453中所述的粘结剂。然而,PTFE不溶于水或溶剂中,并且仅通过施加高温而形成光滑膜,这继而可能损坏或降低热敏电极材料的反应性。聚偏二氟乙烯(PVDF)(部分氟化的含氟聚合物)已用作替代或附加粘结剂,因为其可溶解于有机溶剂中。由于其部分氟化单元的高含量,PVDF具有减小的化学惰性和减小的工作温度。有机溶剂的使用从环境角度呈现出问题。有机溶剂必须是可再循环的,废弃或焚烧。在美国专利9,202,638B2中,公开了用于制备锂电池中的电极的水性含氟聚合物组合物,该组合物被报道为具有良好的成膜特性。
发明内容
申请人已发现,持续需要提供适于制备电极的水基组合物。优选地,所述组合物具有足够的粘度以允许涂覆用于电极制备中的多孔和织物样载体材料。有利地,此类组合物允许高载量的电活性材料。
以下提供了一种含氟聚合物组合物,所述含氟聚合物组合物包含
(i)含氟聚合物颗粒,所述含氟聚合物颗粒包含来源于以下的重复单元:至少一种全氟化共聚单体,所述全氟化共聚单体选自四氟乙烯(TFE)、六氟丙烯(HFP)以及它们的组合,和一种或多种非全氟化共聚单体,所述非全氟化共聚单体选自偏二氟乙烯(VDF)、乙烯(E)、丙烯(P)、以及它们的组合;其中基于共聚单体以摩尔为单位的总量计,所述全氟化共聚单体的总量为至少40摩尔%,并且其中所述含氟聚合物为可熔融加工的;
(ii)包含电活性材料的颗粒,其中所述电活性材料选自石墨、金属化合物、以及它们的组合;
(iii)任选地,与石墨不同的含碳颗粒;
(iv)水;以及
(v)沸点介于70℃和200℃之间的有机液体,所述有机液体选自非官能烃和官能烃,所述官能烃包含一种或多种选自腈、氯和含氧官能团的官能团,所述含氧官能团选自醚、醇、羧酸盐、羧酸酯以及它们的组合,
其中所述实质上无机颗粒(ii)按重量计的量大于含氟聚合物颗粒(i)的量,并且其中水按重量计的量大于有机液体的量。
在另一方面,提供一种制备含氟聚合物组合物的方法,所述方法包括制备含水混合物,所述含水混合物包含水和:
a)包含电活性材料的颗粒,所述电活性材料选自石墨、金属化合物以及它们的组合,以及任选地与石墨不同的含碳颗粒;
b)含氟聚合物颗粒;
c)有机液体;
其中所述包含电活性材料的颗粒按重量计的量大于所述含氟聚合物颗粒的量并且其中水按重量计的量大于有机液体的量,并且其中所述含氟聚合物颗粒包含来源于以下的重复单元:至少一种全氟化共聚单体,所述全氟化共聚单体选自四氟乙烯(TFE)、六氟丙烯(HFP)以及它们的组合,以及一种或多种非全氟化共聚单体,所述非全氟化共聚单体选自偏二氟乙烯(VDF)、乙烯(E)、丙烯(P)以及它们的组合;其中基于共聚单体按摩尔计的总量计,所述全氟化共聚单体的总量为至少40摩尔%,并且其中所述含氟聚合物为可熔融加工的,并且其中所述有机液体具有介于70℃和200℃之间的沸点并且选自非官能烃和官能烃,所述官能烃包含一种或多种选自腈、氯和含氧官能团的官能团,所述含氧官能团选自醚、醇、羧酸盐、羧酸酯以及它们的组合。
在另一方面,提供一种制备电极的方法,所述方法包括用包含含氟聚合物组合物的糊料涂覆用于电极的载体材料并使所述糊料经受干燥。
在另一方面,提供一种电极,所述电极包括从含氟聚合物组合物获得的涂层。
具体实施方式
在详细解释本公开内容的任何实施方案之前,应当理解,本公开内容的应用并不限于下面描述中给出的构造与部件布置方式的细节。本发明能够具有其它实施方案并能够以各种方式实施或执行。如本文所用,术语“一个”、“一种”和“所述”可互换使用并且意指一个或多个;并且“和/或”用于指示一种或两种所描述的情况可能发生,例如A和/或B包括(A和B)和(A或B)。而且,在本文中,由端点表述的范围包括该范围内包含的所有数值(例如,1至10包括1.4、1.9、2.33、5.75、9.98等)。而且,在本文,表述“至少一个”包括一个及大于一的所有数字(例如,至少2、至少4、至少6、至少8、至少10、至少25、至少50、至少100等)。而且,应当理解,本文使用的措辞和术语是用于说明目的而不应视为限制性的。与意在具有限制性的“由……组成”的使用相反,使用“包括”、“含有”、“包含”或“具有”以及它们的变型形式意在具有非限制性,并且涵盖之后所列的项目以及附加的项目。
除非另外指明,否则组合物的成分的量可以以重量%(或“%wt”或“wt.-%”或“重量百分比”)指示。除非另外指明,否则所有成分的量给出100重量%。如果用摩尔%标识成分的量,除非另外指明,否则各自成分的量给出100摩尔%。
除非另外指出,否则本公开的所有实施方案可以自由地组合。
在下文中,提供含氟聚合物组合物,所述组合物包含高含量的电活性材料,例如基于所述组合物的重量计量为至少10重量%或至少50重量%的电活性材料。
所述组合物可为可铺展的。它们适用于制备电极。
通常,所述组合物包含含氟聚合物颗粒和包含电活性材料的颗粒。
优选地,电活性材料颗粒适于用作电活性电极材料。此类颗粒包含电活性材料,所述电活性材料包含涉及化学电池的电极反应的化合物。
在一个实施方案中,所述组合物适于制备用于锂电池的电极。
所述组合物为含水(水性),其意指所述组合物的主要液体组分(按重量计)为水。
组合物的固体含量可高于液体组分的量。
术语“液体”是指在环境条件(20℃,101325Pa)下的液体状态。
基于组合物的重量计,固体的量包括但不限于约30重量%至约70重量%。
含氟聚合物颗粒
本公开的含氟聚合物颗粒是可熔融加工的。这意味着含氟聚合物在297℃和5kg负载下具有至少0.1g/10min的熔体流动指数(MFI 297/5),优选至少5g/10min(MFI 297/5)。通常上限为500g/10min,优选至多150g/10min,更优选至多100g/10min。
含氟聚合物颗粒可用作包含电活性材料的颗粒在电极制备中的粘结剂,通常通过将含氟聚合物带到熔体中。含氟聚合物的熔点可为约90℃至约280℃。在一个实施方案中,使用熔点为约100℃至约200℃,优选约105℃至约161℃的含氟聚合物。有利的是,低熔点含氟聚合物可作为粘结剂在相当低的温度下活化,并且还可在电极形成组合物中使用热敏电活性材料。
含氟聚合物可以是全氟化或部分氟化的。全氟化聚合物仅包含来源于全氟化单体的单元。部分氟化聚合物包含至少一种全氟化单体单元和至少一种部分氟化或至少一种非氟化单体单元或两者的组合。优选地,本公开的含氟聚合物中全氟化单体单元的量为至少40摩尔%,或至少45摩尔%,或至少50摩尔%;或大于60摩尔%(添加至多100摩尔%的单体总量)。
全氟化单体的示例包括全氟化的C2-C8烯烃,诸如四氟乙烯(TFE)、六氟丙烯(HFP)、全氟化乙烯基醚(统称为PAVE)和全氟化烯丙基醚(统称为PAAE)。合适的烯丙基醚和乙烯基醚的示例包括对应于以下通式的那些:
CF2=CF-(CF2)n-O-Rf (I)。
在式(I)中,n代表0或1。Rf表示直链或支链的环状或非环状全氟化烷基残基,其任选地可包含一个或多个链中氧原子。Rf可包含最多8个,优选地最多6个碳原子,诸如1个、2个、3个、4个、5个以及6个碳原子。Rf的典型示例包括任选间插有一个或多于一个氧原子的直链或支链烷基残基。在一个具体实施方案中,Rf选自全氟甲基(全氟甲基乙烯基醚(PMVE)或全氟甲基烯丙基醚(PMAE));和全氟丙基(PPVE或PPAE)。Rf的另外的示例包括含有下列一个或多个单元以及它们的组合的残基:
-(CF2O)-、-(CF2CF2-O)-、(–O-CF2)-、–(O-CF2CF2)-、-CF(CF3)-、-CF(CF2CF3)-、-O-CF(CF3)-、-O-CF(CF2CF3)-、-CF(CF3)-O-、-CF(CF2CF3)-O-。
合适的部分氟化单体的示例包括氟化和氯化单体,包括氯三氟乙烯(CTFE)、2-氯五氟丙烯、2,3,3,3-四氟丙烯、1,2,3,3,3-五氟丙烯(1-HPFP)、1,1,3,3,3-五氟丙烯(2-HPFP)、二氯二氟乙烯。部分氟化的单体的其它示例包括乙烯基氟化物(VF)、偏二氟乙烯(VDF)。合适的非氟化单体的示例包括乙烯(E)和丙烯(P)。
合适的非氟化共聚单体包括氯乙烯、偏二氯乙烯和C2-C8烯烃,诸如乙烯(E)和丙烯(P)。非氟化共聚单体(当存在时)的量通常介于0摩尔%和50摩尔%之间,优选介于1摩尔%和40摩尔%之间。
含氟聚合物的具体示例包括,例如,具有如下单体的组合的共聚物(其中全氟化单体的总量按摩尔计为至少40摩尔%,或至少45摩尔%):TFE-P、TFE-HFP-VDF(THV)、TFE-VDF-PAVE、TFE-HFP、E-TFE-HFP(HTE)、TFE-PAVE、TFE-E-PAVE、TFE-E(ETFE)和进一步包括来源于含氯单体如CTFE的单元的任何前述共聚物。在一些实施方案中,全氟化单体的量为至少45摩尔%,或至少65摩尔%,并且非全氟化单体的量为至少8摩尔%。
在一个具体实施方案中,含氟聚合物具有以下组成:TFE:50—88重量%;HFP 0-36重量%;乙烯8-26重量%;PAVE和/或PAAE 0-12重量%;(总组合物加至100重量%)。
在一个实施方案中,含氟聚合物为熔点在90℃-280℃,或100℃至200℃,优选105℃至161℃范围内的THV聚合物。
将含氟聚合物作为颗粒加入。它们可作为干粉(自由流动的颗粒)提供,或可分散或悬浮在另一介质中。优选地,将含氟聚合物作为含水分散体加入。
含氟聚合物的含水分散体通常通过本领域已知的含水乳液聚合来制备。它们产生小的含氟聚合物颗粒,通常在约50nm至500nm的尺寸内。
通过碾磨聚合物粒料获得的聚合物颗粒通常产生更大的颗粒尺寸。
乳液聚合通常涉及使用氟化乳化剂,但出于监管原因,不期望使用氟化乳化剂。优选地,使用含氟聚合物,所述含氟聚合物通过含水乳液聚合而不使用氟化乳化剂制备。此类聚合物可通过使用非氟化乳化剂代替来制备。所得分散体不含添加的氟化乳化剂,并且仅包含少量乳化剂。它们包含比用氟化乳化剂制备然后随后例如通过如本领域已知的相分离或阴离子交换处理以除去氟化乳化剂的分散体更低量的乳化剂。此类处理涉及添加相当高含量的稳定用非氟化乳化剂。
无非氟化乳化剂的含氟聚合物的聚合描述于(例如)WO2007/120348和WO2011/014715中,所述文献以引用方式并入本文。
基于所述组合物的重量计,根据本公开的含水组合物中含氟聚合物的量包括但不限于0.5重量%至10重量%。
包含电活性材料的颗粒
本发明的组合物包含颗粒,所述颗粒包含电活性材料。所述颗粒适于制备电极。所述材料包含电活性材料或由其组成,即,可参与化学电池的电极反应的材料。颗粒可作为固体添加,或分散或悬浮于另一种材料中。通常,颗粒作为干燥固体提供,例如以自由流动粉末的形式提供。
电活性颗粒可具有小于15,000μm,或小于5,000μm的尺寸。一般来讲,平均粒度(数均)为500nm至约2,000μm。所述颗粒可为大致球形的,其包括球形颗粒和细长颗粒,所述细长颗粒可近似为具有至多为第二最长轴的长度的2倍的最长轴的球体。所述颗粒可为纤维形式,例如其中最长轴具有其直径的长度的超过5倍或超过10倍的纤维,或者所述颗粒可具有其它形状。通常,颗粒分散或悬浮于水中,其通常已经包含有机液体,并且任选地包含润湿剂。
电活性材料可包含石墨、金属化合物以及它们的组合。
在一个实施方案中,颗粒由电活性材料组成,所述电活性材料优选由选自石墨和/或金属化合物的颗粒组成。
在另一个实施方案中,颗粒包含电活性材料和一种或多种载体材料。例如,石墨和/或金属化合物可涂覆在载体材料上或与载体材料混合。
所述颗粒可包含显著量的石墨或金属化合物,例如按所述颗粒的重量计至少30%,或按所述颗粒的重量计至少50重量%,或按所述颗粒的重量计至少95重量%。
金属化合物包括金属盐、金属氧化物以及它们的组合。金属化合物的具体示例包括锂和/或过渡金属的氧化物和金属盐(包括但不限于钴、锰、铝、钛、或镍,以及铁磷酸盐、磷酸锰)。还设想了锂的双盐和三倍盐。盐的示例包括但不限于硫化物、氢氧化物、磷酸盐以及它们的组合。具体示例包括锂金属氧化物,诸如锂钴氧化物、锂锰磷酸盐、锂镍氧化物和锂锰氧化物。
优选的电极材料包括但不限于LiCoO2、LiNixCo1-xO2、LiMn2O2、LiNiO2、LiFePO4、LiNixCoyMnzOm、LiNix-MnyAlzOm,其中x+y+z=1并且m是表示在氧化物中的氧原子数以提供电平衡的分子的整数。
含氟聚合物与电活性颗粒的重量比可取决于颗粒类型、聚合物类型和电极设计。通常包含电活性材料的颗粒的量大于含氟聚合物颗粒的量。一般来讲,含氟聚合物与包含电活性材料的颗粒的重量比可为约1:2至约1:100。基于所述组合物的总重量计,包含电活性材料的颗粒的量包括但不限于25重量%至65重量%。
含碳材料:
所述组合物还可包含与石墨不同的含碳材料。含碳材料包括但不限于碳。具体形式的碳包括得自热解或燃烧的碳,诸如煤烟、炭黑、乙炔黑。其它形式包括碳纳米管等。也可使用碳纤维。
含碳材料可掺杂有锂离子或其它离子。
含碳材料可作为固体的组合物,更具体地讲为干燥颗粒的组合物,例如以自由流动粉末的形式提供。
含碳材料可由具有小于15,000μm,或小于5,000μm的颗粒尺寸的颗粒组成。一般来讲,平均粒度(数均)为500nm至约2,000μm。所述颗粒可为大致球形的,其包括球形颗粒和细长颗粒,所述细长颗粒可近似为具有至多为第二最长轴的长度的2倍的最长轴的球体。所述颗粒可为纤维形式,例如其中最长轴具有其直径的长度的超过5倍或超过10倍的纤维,或者所述颗粒可具有其它形状。
含碳材料可与包含上述电活性材料的颗粒共混,然后悬浮或分散在水中,并且作为含水分散体提供。
如果使用含碳材料,则优选添加少量润湿剂以有助于分散含碳颗粒。
含碳材料可用作填料。在导电的材料的情况下,其也可用作支撑电极材料。
基于组合物的重量计,含碳材料的量包括但不限于0重量%至约45重量%,例如0.2重量%至25重量%或1.5重量%至15重量%。
有机液体
本文所公开的组合物包含一种或多种有机液体(即熔点低于20℃的有机液体)。该液体的沸点为约70至至多200℃,优选约80℃至约150℃。
优选地,有机液体选自非官能烃和官能烃,其中官能烃包含一个或多个选自以下的官能团:醇(-OH基);醚(-O-)、氯(-Cl)、腈(-CN)、羧基(-COOH、COOM,其中M为金属离子)、羧酸根(-C(=O)O-R)以及它们的组合。羧酸根基团是羧酸的酯,并且R表示可不包含官能团或可包含一个或多个如上所述的官能团的烃残基。
通常,有机液体包含至少3个至至多12个且包括12个碳原子。优选地,它们是无环的。
在一个优选的实施方案中,有机液体是无环的,并且选自可与水形成共沸物的那些。具体的液体包括但不限于乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、烯丙醇、乙酸乙酯、乙酸丙酯、甲酸、乙酸、丙酸、甲苯、二甲苯、苯、环己烯、碳四氯、二氯乙烷、2-甲氧基乙醇。可容易地从涂覆的组合物移除共沸物,这改善了它们的处理,尤其是在工业规模中。优选地,有机液体与水以其中共沸物形成或原位形成例如在干燥过程期间形成的比率加入,其中在干燥过程期间除去第一过量量的较低沸点组分,使得产生共沸组合物形成比率。
据信有机液体充当润滑剂并有助于形成均匀的膜。
有机液体优选不溶解或软化含氟聚合物,因为此类液体可能难以从涂层中移除。可例如通过向10g聚合物添加100mL液体(具有小于1,000μm颗粒尺寸的聚合物颗粒和在50℃下保持的有机液体中搅拌1小时)来确定液体是否溶解或软化含氟聚合物。通过可见的检测,然后可确定聚合物颗粒是否已溶解或软化。当颗粒变粘或肿胀或两者时,颗粒软化。上清液的粘度增加还指示聚合物已溶解到其中。
优选的有机液体包括具有或不具有附加羟基和/或醚官能团的羧酸酯。其它优选的有机液体包括醚醇。
基于组合物的总重量计,可被使用的量包括但不限于1重量%至14重量%。有机液体按重量计的量通常小于水的量。
润湿剂
本公开的组合物可包含少量润湿剂(例如,乳化剂)。然而,润湿剂可能难以从电极涂层中移除。高残余量的润湿剂可导致电池的内阻增加和循环特性恶化。
本发明的组合物的优点在于它们可仅包含非常少量的润湿剂。事实上,润湿剂的量可低至至多1.0重量%并且包括1.0重量%。在一个实施方案中,所述组合物仅包含至多0.5%的润湿剂,或甚至仅包含至多0.2重量%的润湿剂(基于组合物的总重量计)。优选地,所述组合物包含最多0.1重量%的润湿剂。在一个实施方案中,润湿剂的量为0.03重量%至0.09重量%。
优选地,所述组合物不含或基本上不含氟化乳化剂以满足政府规则要求。如本文所用,“基本上不含”是指小于500ppm,优选小于50ppm(基于组合物的总重量计)的量。氟化乳化剂包括氟化链烷酸,其中链烷链可一次或多于一次地间插有氧原子。通常,使用对应于以下通式:
[Rf-O-L-Z-]X+ (II)
的乳化剂。在式(II)中,L表示直链或支链或环状的部分或完全氟化的亚烷基基团或脂族烃基团,Rf表示直链或支链的部分或完全氟化的脂族基团或可一次或多于一次地间插有氧原子的直链或支链的部分或完全氟化的基团。Z-表示酸阴离子(包括羧酸基团或磺酸基团或硫酸根基团),并且X+表示阳离子。在乳化剂包含部分氟化的脂族基团的情况下,它被称为部分氟化的乳化剂。优选地,乳化剂的阴离子部分的分子量小于1,000克/摩尔,最优选地,乳化剂的分子量小于1,000克/摩尔。优选地,L是直链的。氟化乳化剂的具体示例包括如例如美国专利公开2007/0015937(Hintzer等人)中所述的那些。示例性乳化剂包括但不限于:CF3CF2OCF2CF2OCF2COOH、CHF2(CF2)5COOH、CF3(CF2)6COOH、CF3O(CF2)3OCF(CF3)COOH、CF3CF2CH2OCF2CH2OCF2COOH、CF3O(CF2)3OCHFCF2COOH、CF3O(CF2)3OCF2COOH、CF3(CF2)3(CH2CF2)2CF2CF2CF2COOH、CF3(CF2)2CH2(CF2)2COOH、CF3(CF2)2COOH、CF3(CF2)2(OCF(CF3)CF2)OCF(CF3)COOH、CF3(CF2)2(OCF2CF2)4OCF(CF3)COOH、CF3CF2O(CF2CF2O)3CF2COOH以及它们的盐。
可用的非氟化润湿剂包括但不限于离子和非离子表面活性剂。可用的物质包括但不限于烷基硫酸盐、磺酸盐、磷酸盐、膦酸盐,其中烷基残基可任选地包含醚官能团。非离子乳化剂的示例包括但不限于脂族和芳族聚醚醇、烷基多聚糖苷和山梨醇酐,诸如来自陶氏(Dow)的TRITON或TERGITOL系列(聚醚醇),以及来自科宁(Cognis)的GLUCOPON系列(烷基多聚糖苷)。其它示例包括但不限于硅氧烷乳化剂,例如乙氧基化硅烷,诸如以商品名SILWET得自迈图(Momentive)的那些。也可以使用乳化剂的组合。优选地,乳化剂不是芳族的。
其它成分
本公开的组合物不需要其它成分的存在,尽管可添加其它成分,包括但不限于pH调节剂、触变剂、粘附促进剂和其它成分。基于所述组合物的重量计,其它成分的量可为0重量%至15重量%。在一个实施方案中,附加成分的量按重量计小于1%或甚至为0%。
粘度
所述含水组合物可通过使用液体与固体成分的比率使得所述组合物具有所需粘度来配制。在电极的制备中,电极形成组合物可铺展在多孔支撑结构上。优选地,所述组合物具有足够高的粘度,所述粘度允许组合物铺展在此类支撑结构上。优选地,所述组合物具有至少1,000mPa s的粘度(如通过在20℃,100s-1的剪切速率下的流变仪测定,板-板流变仪)。优选地,在这些条件下组合物的粘度小于1,000,000mPa s-1,因为此类糊料可能过于粘稠并且不再方便地可铺展。优选地,所述组合物在介于800/s和1,000/s之间的剪切速率下具有介于100m Pa s-1和2,000m Pa s-1之间的粘度。
组合物和电极的制备
在一个优选的实施方案中,根据本公开的组合物通过制备包含润湿剂(如果需要)的含水溶液或混合物来制备。如果组合物包含石墨或与石墨不同的含碳材料,则可能需要润湿剂。可将有机液体加入到含水组合物中,但也可将其添加到含氟聚合物组合物中或在组合物制备期间任何时候单独加入到最终组合物中。含水溶液或混合物可构成最终组合物的大部分水相。向该溶液或混合物中,加入如上所述的适于制备电极的材料和如上所述的含碳材料,优选在搅拌下以小份加入。然后在搅拌下加入含氟聚合物颗粒,优选作为含水分散体,并且更优选地滴加或以小份加入。优选地,通过含水乳液聚合而不使用氟化乳化剂来制备含氟聚合物分散体。此类分散体可用非氟化乳化剂制备。乳化剂可为非离子或阴离子乳化剂。所得含氟聚合物分散体可具有此类乳化剂的残基。如果需要,可将预定量的润湿剂加入到分散体中,然而这可能不是必需的,并且优选避免。
为了制备电极,根据本领域已知的方法,诸如通过刷、辊、橡皮扫帚或真空涂覆,将含水组合物施加到载体上的至少一个表面,且优选两个面表面。载体可为导电基板。它通常是薄的。通常它包括导电材料并且为金属(诸如铝、铜、锂、铁、不锈钢、镍、钛或银)的箔、网片或网的形式。然后干燥经过涂覆的载体基板以形成内聚的复合电极层。所述材料可经受一个或多个压延步骤和附加的处理步骤。电极可例如在电池中,例如在诸如锂电池的非含水型电池中使用。
本公开的含水电极组合物在加工中具有优点,在于其可快速且在相当低的温度下干燥,并且在一些实施方案中,在接近含氟聚合物的熔融温度的温度下,例如在熔点为约105℃至161℃的含氟聚合物的实施方案中。作为本发明组合物的另一个优点,有机液体可通过热处理容易地从涂层中移除。由于所使用的有机液体的沸点相当高,并且在优选的实施方案中另外还由于它们与水的混溶性或溶解性,所述组合物可安全处理。具有高沸点的溶剂和软化剂趋于保持在电极膜中的一些延伸,并且可不利地影响电极的性能。具有低沸点的溶剂或软化剂趋于具有高蒸气压和高挥发性,因此可能需要附加的其处理的安全要求以避免暴露于工人。另外难以从电极涂层中除去乳化剂,但是本发明的组合物仅包含可接受的最小量。使用能够与水形成共沸物的有机液体的另一个优点是它们可容易地与水一起移除。这降低了在所得涂层中留下残留物的风险。即使具有比水更高沸点的液体可作为共沸物在较低的温度下被移除。这进一步降低了待处理电极涂层的温度和停用热敏电活性材料,尤其是锂盐的风险。更多的热敏电活性材料可用于电极制备。
本公开的电极可用于通过本领域已知的方法形成电化学装置,诸如蓄电池、电容器、电双层电容器、膜电极组件(MEA)或燃料电池。非含水型蓄电池可通过在分隔体的任一侧上放置负极和正极来形成。分隔体通常为浸渍有电解质溶液的聚合物多孔膜。
实施例
以举例的方式进一步说明本公开,但不旨在将本公开限制于所示出的实施例和具体实施方案。在此之前,描述用于表征材料以及它们的特性的测试方法。
固体含量的测定
根据ISO 12086重量分析确定固体含量。
粒度
使用Malvern 1000 HAS Zetasizer,通过非弹性光散射测量分散体中的含氟聚合物颗粒的颗粒尺寸。将颗粒尺寸报告为D50。固体组合物上的粒度是通过使用得自德国新帕泰克公司(Sympatech GmbH,Germany)的HELOS(氦氖光学系统)[H 1959]+RODOS的激光衍射分析(ISO 13320)测定,并且也报告为D50。应遵循针对设备和程序的制造商建议,针对粒度范围内的具体粒度范围而不是实施例中待测定所述的那些选择合适的设备。将平均颗粒尺寸表示为D50值。
MFI和熔点
熔体流动指数和熔点根据ISO 12086(在2015年使用的版本)来测定。
粘度
使用得自德国安通帕有限公司(Anton Paar Germany GmbH,Germany)的模块化紧凑流变仪MCR 102测定粘度。在20℃(下板保持在20℃)下,在板-板构型下进行测量,板的间隙尺寸为0.4mm。
实施例1(比较例)
将0.2g SILWET L77加入到210.6g蒸馏水中。在使用匀化器(KA T25 digital–Ultra–Turrax)在4,000至9,000rpm下,聚醋酸钠(THV共聚物)的搅拌下向所得溶液中分批加入251.1g磷酸铁和2g炭黑,接着逐滴加入99.0g的含水含氟聚合物分散体(THV共聚物,根据WO 2207/120348无需添加氟化乳化剂制备,固体含量29.5;<0.1重量%的GENAPOL LRO;MFI 13.5g/10min(265℃/5kg);熔点113℃,平均粒度73nm)。所得糊料在100/s剪切速率下具有2-3×105m Pa s和在1000/s的剪切速率下具有3-8×103m Pa s的粘度。标称固体含量为51重量%。该糊料是可铺展的,但在具有500μm开口的金属织物上铺展之后,其具有不均匀且易碎的外观。
实施例2
重复实施例1,不同的是将0.2g的SILWET L77加入到179.0g蒸馏水和31.6g的2-甲氧基乙醇的混合物中。通过温和搅拌匀化混合物。向所述混合物中分批并且在搅拌下使用实施例1的匀化器,以至多10,000rpm的速度持续8分钟,加入251.1g的磷酸铁和11.7g的炭黑。然后使用实施例1的匀化器在搅拌下滴加99.0g实施例1的含氟聚合物分散体。当加入完成时,使混合物在3200rpm下进行搅拌,直至糊料均匀。所得糊料在100/s剪切速率下具有1-2×105m Pa s和在1000/s剪切速率下具有2-6×102m Pa s的粘度。标称固体含量为51重量%。将糊料铺展在用于实施例1纤维网的金属织物上并且保持均匀。
Claims (15)
1.一种含氟聚合物组合物,所述含氟聚合物组合物包含:
(i)含氟聚合物颗粒,所述含氟聚合物颗粒包含(a)来源于至少一种全氟化共聚单体的重复单元,所述全氟化共聚单体选自四氟乙烯、六氟丙烯以及它们的组合;和(b)一种或多种非全氟化共聚单体,所述非全氟化共聚单体选自偏二氟乙烯、乙烯、丙烯以及它们的组合;
其中基于共聚单体以摩尔为单位的总量计,所述全氟化共聚单体的总量为至少40摩尔%,并且其中所述含氟聚合物为可熔融加工的;
(ii)包含电活性材料的颗粒,其中所述电活性材料选自石墨、金属化合物以及它们的组合;
(iii)水;
(iv)沸点介于70℃和200℃之间的有机液体,所述有机液体选自非官能烃和官能烃,所述官能烃包含一种或多种选自腈、氯和含氧官能团的官能团,所述含氧官能团选自醚、醇、羧酸盐、羧酸酯以及它们的组合,
其中所述包含电活性材料的颗粒(ii)按重量计的量大于含氟聚合物颗粒(i)的量,并且其中水按重量计的量大于有机液体的量。
2.根据权利要求1所述的组合物,其中所述有机液体具有3至12个碳原子。
3.根据前述权利要求中任一项所述的组合物,其中所述有机液体为沸点为至少80℃至至多150℃的无环化合物。
4.根据前述权利要求中任一项所述的组合物,其中所述有机液体能够与水形成共沸物。
5.根据前述权利要求中任一项所述的组合物,其中所述含氟聚合物的熔点在90℃和280℃之间。
6.根据前述权利要求中任一项所述的组合物,其中所述含氟聚合物颗粒包含共聚物,所述共聚物包含选自以下的单元:(a)四氟乙烯、六氟丙烯和偏二氟乙烯;(b)四氟乙烯、六氟丙烯和乙烯;(c)四氟乙烯和乙烯;以及(d)四氟乙烯和丙烯。
7.根据前述权利要求中任一项所述的组合物,基于所述组合物的总重量计,所述组合物包含小于1.0重量%的乳化剂。
8.根据前述权利要求中任一项所述的组合物,所述组合物还包含与石墨不同的含碳颗粒,其中所述与石墨不同的含碳颗粒选自碳颗粒、碳纳米管、碳纤维以及它们的组合。
9.根据前述权利要求中任一项所述的组合物,基于所述组合物的总重量计,所述组合物包含5重量%至50重量%的水。
10.根据前述权利要求中任一项所述的组合物,基于所述组合物的总重量计,所述组合物包含约30重量%至约70重量%的所述包含电活性材料的颗粒。
11.根据前述权利要求中任一项所述的组合物,其中所述电活性材料包括选自锂盐、锂氧化物、锂-金属氧化物、锂-金属盐以及它们的组合的金属化合物。
12.根据前述权利要求中任一项所述的组合物,其中所述组合物为糊料并且具有在20℃和50s-1的剪切速率下通过流变仪测定的至少1,000mPa s的粘度。
13.一种制备根据前述权利要求中任一项所述的含氟聚合物组合物的方法,所述方法包括
制备含水混合物,所述含水混合物包含水和
a)包含电活性材料的颗粒,所述电活性材料选自石墨、金属化合物以及它们的组合,以及任选地与石墨不同的含碳颗粒;
b)含氟聚合物颗粒;和
c)有机液体;
其中所述包含电活性材料的颗粒按重量计的量大于所述含氟聚合物颗粒的量,
并且其中水按重量计的量大于有机液体的量,
并且其中所述含氟聚合物颗粒包含来源于以下的重复单元:(i)至少一种全氟化共聚单体,所述全氟化共聚单体选自四氟乙烯、六氟丙烯以及它们的组合,和(ii)一种或多种非全氟化共聚单体,所述非全氟化共聚单体选自偏二氟乙烯、乙烯、丙烯以及它们的组合;
另外,其中基于共聚单体以摩尔为单位的总量计,所述全氟化共聚单体的总量为至少40摩尔%,并且其中所述含氟聚合物为可熔融加工的,
并且其中所述有机液体具有介于70℃和200℃之间的沸点并且选自非官能烃和官能烃,所述官能烃包含一种或多种选自腈、氯和含氧官能团的官能团,所述含氧官能团选自醚、醇、羧酸盐、羧酸酯以及它们的组合。
14.一种制备电极的方法,所述方法包括用根据权利要求1至12中任一项所述的组合物涂覆用于电极的载体材料并使所述组合物经受干燥。
15.一种电极,所述电极包括由根据权利要求1至12中任一项所述的组合物获得的涂层。
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EP3219771B1 (en) | 2016-03-14 | 2019-02-06 | 3M Innovative Properties Company | Fluoropolymer compositions with high content of inorganic material |
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CN103140964A (zh) * | 2010-09-30 | 2013-06-05 | 旭硝子株式会社 | 非水系二次电池用正极合剂、使用其的非水系二次电池用正极及二次电池 |
CN103391951A (zh) * | 2011-02-18 | 2013-11-13 | 旭硝子株式会社 | 含氟共聚物胶乳的制造方法、含氟共聚物胶乳、电极制造用粘结剂、蓄电装置用电极合剂以及蓄电装置用电极 |
CN103650222A (zh) * | 2011-07-29 | 2014-03-19 | 旭硝子株式会社 | 蓄电装置用粘合剂 |
CN104737339A (zh) * | 2012-10-19 | 2015-06-24 | 旭硝子株式会社 | 蓄电装置用粘合剂组合物的制造方法 |
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JP6557426B2 (ja) | 2019-08-07 |
EP3219771B1 (en) | 2019-02-06 |
US10947378B2 (en) | 2021-03-16 |
KR101971414B1 (ko) | 2019-04-22 |
KR20180115332A (ko) | 2018-10-22 |
WO2017160786A1 (en) | 2017-09-21 |
JP2019513285A (ja) | 2019-05-23 |
EP3219771A1 (en) | 2017-09-20 |
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