CN103855350A - 锂电池与其形成方法 - Google Patents
锂电池与其形成方法 Download PDFInfo
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- CN103855350A CN103855350A CN201210574300.1A CN201210574300A CN103855350A CN 103855350 A CN103855350 A CN 103855350A CN 201210574300 A CN201210574300 A CN 201210574300A CN 103855350 A CN103855350 A CN 103855350A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 19
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- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 7
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
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- KMPGLZNWOILKLD-UHFFFAOYSA-N [Co].[Mn].[Li].[Mn].[Ni].[Li] Chemical compound [Co].[Mn].[Li].[Mn].[Ni].[Li] KMPGLZNWOILKLD-UHFFFAOYSA-N 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
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- 229920000642 polymer Polymers 0.000 description 3
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明是锂电池与其形成方法。锂电池,包括:正极板;负极板;聚烯烃隔离膜,置于正极板与负极板之间;有机无机混成膜,置于正极板与聚烯烃隔离膜之间,和/或置于负极板与聚烯烃隔离膜之间,其中有机无机混成膜包括:无机氧化物粒子与氟系高分子粘结剂,且无机氧化物粒子与氟系高分子粘结剂的重量比约介于40:60至80:20之间。
Description
【技术领域】
本发明涉及锂电池,更特别地涉及其应用的有机无机混成膜。
【背景技术】
一般二次电池(例如锂离子二次电池)由正极板、负极板以及置于正负极板之间的隔离膜形成的电极组合所构成。隔离膜主要在于提供正负极板之间电子绝缘能力,除可避免正负极板接触形成短路之外,还吸附及保留电解液的功能,以维持锂离子在极板间的传输路径。然而传统锂电池发生短路时,因短时间释放大量热量而使结构中聚烯烃材质的隔离膜无法耐受高温而熔融收缩。若无法阻隔局部热或中止短路反应,则锂电池中的活性物质及有机电解液将裂解产生高压气体,遇热甚至发生燃烧爆炸等危害。
综上所述,目前亟需新的方式解决锂电池内短路的问题。
【发明内容】
本发明一实施例提供一种锂电池,包括:正极板;负极板;聚烯烃隔离膜,置于正极板与负极板之间;有机无机混成膜,置于正极板与聚烯烃隔离膜之间,和/或置于负极板与聚烯烃隔离膜之间,其中有机无机混成膜包括:无机氧化物粒子与氟系高分子粘结剂,且无机氧化物粒子与氟系高分子粘结剂的重量比约介于40:60至80:20之间。
本发明一实施例提供一种锂电池的形成方法,包括:将无机氧化物粒子、氟系高分子粘结剂、及溶剂混合后成膜,再去除溶剂以形成有机无机混成膜,其中有机无机混成膜包括无机氧化物粒子与氟系高分子粘结剂,且无机氧化物粒子与氟系高分子粘结剂的重量比约介于40:60至80:20之间;将聚烯烃隔离膜置于正极板与负极板之间;以及将有机无机混成膜置于正极板与聚烯烃隔离膜之间,和/或置于负极板与聚烯烃隔离膜之间。
【附图说明】
图1至3为本发明实施例中的锂电池的示意图;
图4为本发明实施例中的锂电池经针刺后的电压/时间与温度/时间的曲线图;以及
图5为本发明一实施例中不同材质的薄膜在不同温度下的尺寸变化曲线。
【主要附图标记说明】
10~锂电池;
11~有机无机混成膜;
13~聚烯烃隔离膜;
15~正极板;
17~负极板。
【具体实施方式】
首先,将无机氧化物粒子、氟系高分子粘结剂与溶剂混合。一般而言,无机氧化物粒子会均匀分散于溶剂中,而氟系高分子粘结剂可溶于溶剂中。在本发明一实施例中,可将氟系高分子粘结剂溶于溶剂形成氟系高分子溶液后,再将无机氧化物粒子分散于氟系高分子溶液中。在本发明另一实施例中,可先将无机氧化物粒子分散于溶剂中形成分散液,并将氟系高分子粘结剂溶于另一溶剂形成氟系高分子溶液,再将两者混合。适用的溶剂可为极性溶剂如二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、其他极性溶剂、或上述的组合。
无机氧化物粒子可为氧化硅、氧化镁、氧化钛、氧化锌、氧化铝、氧化锡、其他无机氧化物粒子、或上述的组合。在本发明一实施例中,无机氧化物粒子的粒径约介于10nm至300nm之间。若无机氧化物粒子过小,则因为无机氧化物比表面积过大,有机粘着剂不易有效将粒子粘合,而有粒子剥离的疑虑;此外无机氧化物粒子过小可能造成颗粒之间紧密堆迭,不利于锂离子的穿透与传输。若无机氧化物粒子过大,则因为无机粒子比表面积过低可能使有机粘着剂含量过剩,导致多余的高分子阻碍锂离子扩散的路径,使得锂电池性能表现不佳。
氟系高分子粘结剂可为聚四氟乙烯(PTFE)、全氟(乙烯丙烯)(FEP)共聚物、聚全氟烷氧基(PFA)树脂、聚三氟氯乙烯(PCTFF)、乙烯-三氟氯乙烯共聚物(ECTFE)、乙烯-四氟乙烯(ETFE)共聚物、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、其他氟系高分子粘结剂、或上述的组合。在本发明一实施例中,氟系高分子粘结剂的重均分子量约介于280,000至1,000,000之间,或约介于300,000至500,000之间。上述无机氧化物粒子与氟系高分子粘结剂的重量比约介于40:60至80:20之间。
接着将无机氧化物粒子、氟系高分子粘结剂、与溶剂的混合物成膜。成膜方式可为常见的旋转涂布法、浸润法、刮刀涂布法、狭缝涂布法、喷涂法、或其他类似的湿式涂布法。接着以真空法、风干法、加热法、或其他类似方法去除膜层中的溶剂,即得有机无机混成膜。在本发明一实施例中,有机无机混成膜的厚度约介于1μm至10μm之间或约介于2μm至5μm之间。
接着如图1所示,将有机无机混成膜11置于锂电池10的聚烯烃隔离膜13与正极板15之间。在本发明另一实施例,有机无机混成膜11置于聚烯烃隔离膜13与负极板17之间,如图2所示。在本发明又一实施例中,有机无机混成膜11置于聚烯烃隔离膜13与正极板15之间,以及置于聚烯烃隔离膜13与负极板17之间,如图3所示。
聚烯烃隔离膜可为聚乙烯(PE)隔离膜,聚丙烯(PP)隔离膜、PE/PP双层聚烯烃隔离膜、PP/PE/PP三层聚烯烃隔离膜、PE/PP/PE三层聚烯烃隔离膜以及其组合而成的多层隔离膜材料。
值得注意的是,本发明并不直接将无机氧化物粒子、氟系高分子粘结剂、与溶剂的混合物成膜于正极板15或负极板17上。这是因为混合物中的无机氧化物粒子会填入正极板15或负极板17的孔洞中,而无法形成平坦的膜层而降低其机械性质(比如挠曲性及耐热性),亦可能造成锂离子不易扩散而使阻抗上升。另一方面,本发明亦不直接将无机氧化物粒子、氟系高分子粘结剂、与溶剂的混合物成膜于聚烯烃隔离膜13上,因为高温去除溶剂的动作会破坏聚烯烃隔离膜13。另外形成有机无机混成膜,再将其置于正极与聚烯烃隔离膜之间和/或置于负极与聚烯烃隔离膜之间的作法,可得挠曲性与耐热性良好的有机无机混成膜,且具有良好的制程弹性。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂,下文特举多个实施例配合所附图示,作详细说明如下:
【实施例】
制备例1(制备中孔氧化铝材料)
将10.23g十六烷基三甲基溴化铵(CTAB)溶于50克去离子水后,加入7.24克异丙醇铝(Aluminium isopropanolate,AIP)并于室温下搅拌30分钟。接着以硝酸(10wt%)将溶液的pH值调到4.5,再老化处理此溶液5小时。接着将溶液置于110℃烘箱15小时进行聚合反应以形成粉末,接着将洗净的粉末置于650℃煅烧5小时,以得到8.6克的中孔(mesoporous)氧化铝粉末材料(孔洞大小为2nm至50nm;经X-光粉末绕射仪(XRD)及穿透式电子显微镜(TEM)确认)。
实施例1(中孔氧化铝与聚偏二氟乙烯的有机无机混成膜)
取4g制备例1的中孔氧化铝材料,以及6克聚偏二氟乙烯(购自Kureha的KF1300,Mw=350,000)混合于90g N,N-二甲基乙酰胺(DMAc)中,于常温下搅拌3小时得到100g分散液(固含量10wt%,且中孔氧化铝与聚偏二氟乙烯的重量比为40:60)。以60μm刮刀将此涂料涂布于基材后以50℃、140℃、及210℃各烘烤5分钟,以得厚度为2-3μm的有机无机混成膜。上述有机无机混成膜具有可挠性且可随意卷曲。
实施例2(13纳米氧化铝与聚偏二氟乙烯的有机无机混成膜)
将4g 13纳米的氧化铝(购自六和的γ-氧化铝(Gamma Aluminum Oxide))以及6g聚偏二氟乙烯(购自Kureha的KF1300)溶于90g DMAc中,于常温下搅拌3小时得到100g分散液(固含量10wt%,且13纳米氧化铝与聚偏二氟乙烯的重量比为40:60)。以60μm刮刀将此涂料涂布于基材后以50℃、140℃、及210℃各烘烤5分钟,以得厚度介于2-3μm的有机无机混成膜。上述有机无机混成膜具有可挠性且可随意卷曲。
实施例3(300纳米氧化铝与聚偏二氟乙烯的有机无机混成膜)
将4g 300纳米的氧化铝(购自LECO的α-氧化铝(Alpha Aluminum Oxide))以及6g聚偏二氟乙烯(购自Kureha的KF1300)溶于90g DMAc中,于常温下搅拌3小时得到100g分散液(固含量10wt%,且300纳米氧化铝与聚偏二氟乙烯的重量比为40:60)。以60μm刮刀将此涂料涂布于基材后以50℃、140℃、及210℃各烘烤5分钟,以得厚度介于2-3μm的有机无机混成膜。上述有机无机混成膜具有可挠性且可随意卷曲。
实施例4(含有机无机混成膜的薄型锂电池)
将实施例1制备的中孔氧化铝与聚偏二氟乙烯的有机无机混成膜置于聚乙烯(polyethylene,PE)隔离膜(购自Asahi的N9620)与超微介相石墨粉负极板(购自中钢碳素的SMGP-A)之间。PE隔离膜的另一侧为锂镍锰钴-锂锰正极板(购自Amita的LNMC-LM)组装成尺寸为50mm×40mm×1.5mm的铝箔袋薄型电池,其中电解液为1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液。组装完成的薄型电池在静置8小时后,利用1kHz交流阻抗计测量其电池阻抗,并以0.1C/0.1C的充放电速率进行电池活化程序,观察电池电性及其不可逆电容量差异,如表1所示。
实施例5(含有机无机混成膜的薄型锂电池)
将实施例2制备的13纳米氧化铝与聚偏二氟乙烯的有机无机混成膜,置于PE隔离膜(购自Asahi的N9620)与超微介相石墨粉负极板(购自中钢碳素的SMGP-A)之间。PE隔离膜的另一侧为锂镍锰钴-锂锰正极板(购自Amita的LNMC-LM)组装成尺寸为50mm×40mm×1.5mm的铝箔袋薄型电池,其中电解液为1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液。组装完成的薄型电池在静置8小时后,利用1kHz交流阻抗计测量其电池阻抗,并以0.1C/0.1C的充放电速率进行电池活化程序,观察电池电性及其不可逆电容量差异,如表1所示。
实施例6(含有机无机混成膜的薄型锂电池)
将实施例3制备的300纳米氧化铝与聚偏二氟乙烯的有机无机混成膜,置于PE隔离膜(购自Asahi的N9620)与超微介相石墨粉负极板(购自中钢碳素的SMGP-A)之间。PE隔离膜的另一侧为锂镍锰钴-锂锰正极板(购自Amita的LNMC-LM)组装成尺寸为50mm×40mm×1.5mm的铝箔袋薄型电池,其中电解液为1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液。组装完成的薄型电池在静置8小时后,利用1kHz交流阻抗计测量其电池阻抗,并以0.1C/0.1C的充放电速率进行电池活化程序,观察电池电性及其不可逆电容量差异,如表1所示。
比较例1(不含有机无机混成膜的薄型锂电池)
PE隔离膜(购自Asahi的N9620)的一侧为超微介相石墨粉负极板(购自中钢碳素的SMGP-A),另一侧为锂镍锰钴-锂锰正极板(购自Amita的LNMC-LM),三者组装成尺寸为50mm×40mm×1.5mm的铝箔袋薄型电池,其中电解液为1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液。组装完成的薄型电池在静置8小时后,利用1kHz交流阻抗计测量其电池阻抗,并以0.1C/0.1C的充放电速率进行电池活化程序,观察电池电性及其不可逆电容量差异,如表1所示。
由表1的比较可知,实施例4-6中含有机无机混成膜的薄型锂电池,与比较例1中不含有机无机混成膜的薄型锂电池的电性差异不大,可知有机无机混成膜在降低锂电池内短路的问题时,不会大幅影响锂电池电性。
表1
实施例7(含有机无机混成膜的卷绕方型电池)
将实施例2制备的13纳米氧化铝与聚偏二氟乙烯的有机无机混成膜,置于PE隔离膜(购自Asahi的N9620)与超微介相石墨粉负极板(购自中钢碳素的SMGP-A)之间。PE隔离膜的另一侧为氧化锂钴正极板(购自LICO的LiCoO2),卷绕组装成尺寸为5×37×59mm的卷绕方型电池,其中电解液为1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液。组装完成的卷绕方型电池在静置8小时后,利用1kHz交流阻抗计测量其电池阻抗,并以0.1C/0.1C的充放电速率进行电池活化程序,观察电池电性及其不可逆电容量差异,如表2所示。电池在充电至电压为4.2V后随即进行电池针刺安全测试,其温度与时间的相对曲线如图4所示。
比较例2(不含有机无机混成膜的卷绕方型电池)
PE隔离膜(购自Asahi的N9620)的一侧为超微介相石墨粉负极板(购自中钢碳素的SMGP-A),另一侧为另一侧为氧化锂钴正极板(购自LICO的LiCoO2),三者组装成尺寸为5×37×59mm的卷绕方型电池,其中电解液为1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液。组装完成的卷绕方型电池在静置8小时后,利用1kHz交流阻抗计测量其电池阻抗,并以0.1C/0.1C的充放电速率进行电池活化程序,观察电池电性及其不可逆电容量差异,如表2所示。电池在充电至电压为4.2V后随即进行电池针刺安全测试,其温度与时间的相对曲线如图4所示。
由图4可知,实施例7与比较例2的电池在针刺测试后的电压均迅速降至0V。实施例7的电池在600秒内的温度由约50℃升至约100℃,而比较例2的电池则在50秒内快速升温至650℃,外观有烧焦毁损痕迹。由上述可知,含有机无机混成膜的卷绕方型电池可有效避免内短路造成的快速升温等问题。
由表2的比较可知,实施例7中含有机无机混成膜的卷绕方型电池,与比较例2中不含有机无机混成膜的卷绕方型电池的电性差异不大,可知有机无机混成膜在降低卷绕方型电池内短路的问题时,不会大幅影响卷绕方型电池的电性。
表2
实施例8(有机无机混成膜的物性测试)
取实施例2的分散液以250μm刮刀将此涂料涂布于基材后,以50℃、140℃、及210℃各烘烤5分钟,以得厚度介于11-13μm的有机无机混成膜。取上述混成膜、20μm的PE膜(购自Asahi的N9620)、及20μm的PVDF膜(制备方法:10g聚偏二氟乙烯(购自Kureha的KF1300)溶于90g DMAc中,于常温下搅拌3小时得到100g聚偏二氟乙烯溶液(固含量10wt%)。以750μm刮刀将此聚偏二氟乙烯溶液涂布于基材后,以50℃、140℃、及210℃各烘烤5分钟,以得厚度20μm的PVDF膜)透过热机械分析仪(TMA)分析上述薄膜于不同温度下的尺寸变化,如图5所示。由图5可知,混成膜在加热至200℃仍不致大幅改变,PE膜在加热至约130℃即收缩,而PVDF膜在加热至约165℃即大幅膨胀。由上述可知,混成膜的耐热性明显优于PE膜与PVDF膜。
取上述混成膜、及上述PE膜置入120℃烘箱1小时后测其尺寸变化,得知混成膜的收缩率小于1%,PE膜的收缩率约为15%。当混成膜搭配PE膜使用时,即使PE膜收缩率达15%,几乎不收缩的混成膜仍能阻隔正负极,降低短路的发生。取上述混成膜与PE膜测试机械强度(QCTECH拉力测试机),得混成膜的杨氏系数为2.345GPa,而PE膜的杨氏系数为0.925GPa。由上述可知,较薄的混成膜的机械强度高于较厚的PE膜。
将上述混成膜浸置于1.1M LiPF6的碳酸丙烯酯/碳酸乙烯酯/碳酸二乙酯(PC/EC/DEC=2:3:5)溶液一个月后取出,未观察到溶解或变形等现象。
另外,市售商品直接将热阻隔材料(具有高含量的无机粒子及低含量的有机高分子粘着剂)涂布于极板或隔离膜表面,除了材料可能易增加电池内阻之外,无机填充物在使用过程中易剥落而失去应有的保护功能。此外,上述热阻隔材料所形成的涂层具脆裂性,极板或隔离膜经卷绕挠曲后其表面的热阻隔材料涂层易产生龟裂与涂层剥落的情况。
将购自Panasonic的18650圆筒型锂电池拆解后,其负极表面涂布有热阻隔材料。此涂布有热阻隔材料的负极经过挠曲后,热阻隔材料龟裂剥落。然而使用实施例的有机无机混成膜夹设于电极与聚烯烃隔离膜之间,混成膜具有良好的挠曲性与耐热性,没有龟裂剥落的问题。
虽然本发明已以多个优选实施例披露如上,然其并非用以限定本发明,任何本发明所属技术领域中的技术人员,在不脱离本发明的精神和范围内,应可作任意更改与润饰。因此,本发明的保护范围应以所附权利要求书限定的范围为准。
Claims (12)
1.一种锂电池,包括:
正极板;
负极板;
聚烯烃隔离膜,置于该正极板与该负极板之间;
有机无机混成膜,置于该正极板与该聚烯烃隔离膜之间,和/或置于该负极板与该聚烯烃隔离膜之间,
其中该有机无机混成膜包括:
无机氧化物粒子和氟系高分子粘结剂,且无机氧化物粒子与氟系高分子粘结剂的重量比为40:60至80:20。
2.如权利要求1所述的锂电池,其中该有机无机混成膜的厚度为1μm至10μm。
3.如权利要求1所述的锂电池,其中该无机氧化物粒子包括氧化硅、氧化镁、氧化钛、氧化锌、氧化铝、氧化锡、或上述的组合。
4.如权利要求1所述的锂电池,其中该无机氧化物粒子的粒径为10nm至300nm。
5.如权利要求1所述的锂电池,其中该氟系高分子粘结剂包括聚四氟乙烯(PTFE)、全氟(乙烯丙烯)(FEP)共聚物、聚全氟烷氧基(PFA)树脂、聚三氟氯乙烯(PCTFF)、乙烯-三氟氯乙烯共聚物(ECTFE)、乙烯-四氟乙烯(ETFE)共聚物、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、或上述的组合。
6.如权利要求1所述的锂电池,其中该氟系高分子粘结剂的重均分子量为280,000至1,000,000。
7.一种锂电池的形成方法,包括:
将无机氧化物粒子、氟系高分子粘结剂、及溶剂混合后成膜,再去除溶剂以形成有机无机混成膜,其中该有机无机混成膜包括无机氧化物粒子与氟系高分子粘结剂,且无机氧化物粒子与氟系高分子粘结剂的重量比为40:60至80:20;
将聚烯烃隔离膜置于正极板与负极板之间;以及
将该有机无机混成膜置于该正极板与该聚烯烃隔离膜之间,和/或置于该负极板与该聚烯烃隔离膜之间。
8.如权利要求7所述的锂电池的形成方法,其中该有机无机混成膜的厚度为1μm至10μm。
9.如权利要求7所述的锂电池的形成方法,其中该无机氧化物粒子包括氧化硅、氧化镁、氧化钛、氧化锌、氧化铝、氧化锡、或上述的组合。
10.如权利要求7所述的锂电池的形成方法,其中该无机氧化物粒子的粒径为10nm至300nm。
11.如权利要求7所述的锂电池的形成方法,其中该氟系高分子粘结剂包括聚四氟乙烯(PTFE)、全氟(乙烯丙烯)(FEP)共聚物、聚全氟烷氧基(PFA)树脂、聚三氟氯乙烯(PCTFF)、乙烯-三氟氯乙烯共聚物(ECTFE)、乙烯-四氟乙烯(ETFE)共聚物、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、或上述的组合。
12.如权利要求7所述的锂电池的形成方法,其中该氟系高分子粘结剂的重均分子量为280,000至1,000,000。
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CN104898541A (zh) * | 2015-04-23 | 2015-09-09 | 河南职业技术学院 | 一种智能plc电器自动化控制台 |
CN105185938A (zh) * | 2015-07-21 | 2015-12-23 | 大连比克动力电池有限公司 | 一种锂离子电池负极及其制得的锂离子电池 |
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TWI555261B (zh) * | 2015-08-10 | 2016-10-21 | 有量科技股份有限公司 | 鋰電池模組 |
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KR101147604B1 (ko) * | 2007-10-12 | 2012-05-23 | 주식회사 엘지화학 | 젤리-롤형 전극조립체의 변형을 억제하기 위한 제조방법 |
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CN1728439A (zh) * | 2004-09-03 | 2006-02-01 | 松下电器产业株式会社 | 锂离子二次电池 |
US20090111026A1 (en) * | 2007-02-05 | 2009-04-30 | Seok-Koo Kim | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
CN101281961A (zh) * | 2007-04-06 | 2008-10-08 | 比亚迪股份有限公司 | 锂离子电池隔膜用的涂层组合物及该隔膜的制造方法 |
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CN104898541A (zh) * | 2015-04-23 | 2015-09-09 | 河南职业技术学院 | 一种智能plc电器自动化控制台 |
CN105185938A (zh) * | 2015-07-21 | 2015-12-23 | 大连比克动力电池有限公司 | 一种锂离子电池负极及其制得的锂离子电池 |
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TWI599087B (zh) | 2017-09-11 |
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