CN102668174B - 层叠膜及非水电解质二次电池 - Google Patents
层叠膜及非水电解质二次电池 Download PDFInfo
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Abstract
本发明提供层叠膜和非水电解质二次电池。该层叠膜为使具有关闭功能的多孔膜、由无机填料和粘结剂构成的耐热多孔层、保护多孔层依次相接并层叠而成的层叠膜。该非水电解质二次电池是具有正极、负极、配置于该正极与该负极之间的隔膜、以及电解质的非水电解质二次电池,该隔膜为前述的层叠膜。
Description
技术领域
本发明涉及层叠膜及非水电解质二次电池。本发明特别涉及作为隔膜有用的层叠膜和使用该膜作为隔膜的非水电解质二次电池。
背景技术
隔膜是具有微孔的膜。隔膜配置于锂离子二次电池、锂聚合物二次电池等非水电解质二次电池的正极与负极之间。非水电解质二次电池是将正极片材、隔膜、负极片材、隔膜依次重叠、卷绕而得到电极组,并将该电极组收纳于电池外壳内,然后将非水电解液注入电池外壳内而进行制造的。
非水电解质二次电池中的隔膜要求在因正极与负极间的短路等原因而在电池内流入异常电流时,具有阻断电流、阻止过大电流流过的功能,即具有关闭功能(shutdown
function)。隔膜在超过电池通常的使用温度时,通过闭塞微孔来进行关闭。关闭后,电池内的温度有时仍旧升高。隔膜还要求即便电池内的温度升高至一定程度的高温,也不会因该温度发生膜破裂、而维持关闭的状态,换而言之还要求耐热性高。
作为以往的隔膜,专利文献1中公开了在具有关闭功能的聚乙烯多孔膜的至少单面上层叠了含无机填料的耐热多孔层的层叠膜。具体地说,将无机填料和作为粘结剂的聚乙烯醇分散于水,将所得分散液涂布于多孔膜的表面,通过干燥将水除去,将耐热多孔层层叠于聚乙烯多孔膜上。
现有技术文献
技术文献
[专利文献1] 日本特开2009−143060号公报。
发明内容
当使用上述层叠膜作为隔膜进行上述卷绕时,由于片材之间的摩擦力大,因而难以使正极片材、隔膜和负极片材密合进行卷绕。结果引起所得电池的放电容量的循环性能等电池特性的降低。本发明的目的在于提供具有关闭功能、耐热性优异、且作为提供电池特性优异的非水电解质二次电池的隔膜极为有用的层叠膜。
本发明提供以下内容。
<1>
一种层叠膜,其为使具有关闭功能的多孔膜、由无机填料和粘结剂构成的耐热多孔层以及保护多孔层依次相接、进行层叠而成的层叠膜。
<2>
<1>所述的层叠膜,其中耐热多孔层以相对于无机填料和粘结剂的总体积为20体积%以上且小于100体积%的比例含有无机填料。
<3>
<1>或<2>所述的层叠膜,其中保护多孔层由颗粒构成。
<4>
<3>所述的层叠膜,其中颗粒的平均粒径为0.01μm以上且3μm以下。
<5>
<1>~<4>任一项所述的层叠膜,其中保护多孔层的孔隙率为30体积%以上且80体积%以下。
<6>
<1>~<5>任一项所述的层叠膜,其中多孔膜的厚度为13μm以上且17μm以下。
<7>
<1>~<6>任一项所述的层叠膜,其中耐热多孔层的厚度为1μm以上且10μm以下。
<8>
<1>~<7>任一项所述的层叠膜,其中保护多孔层的厚度为0.02μm以上且5μm以下。
<9>
<1>~<8>任一项所述的层叠膜,其为隔膜。
<10>
一种非水电解质二次电池,其为具有正极、负极、配置于该正极与该负极之间的隔膜、以及电解质的非水电解质二次电池,其中该隔膜是上述<1>~<8>任一项所述的层叠膜。
<11>
<10>所述的非水电解质二次电池,其中层叠膜的保护多孔层配置于正极侧。
具体实施方式
本发明的层叠膜是使具有关闭功能的多孔膜、由无机填料和粘结剂构成的耐热多孔层、以及保护多孔层依次相接并层叠而成的层叠膜。
<多孔膜>
本发明的多孔膜具有关闭功能。非水电解质二次电池中,为了使多孔膜具有关闭功能,多孔膜的材料优选为在80℃~180℃发生软化的材料。多孔膜的材料优选为聚乙烯、聚丙烯等聚烯烃。从在更低温下使之软化并关闭的观点出发,更优选聚乙烯。作为聚乙烯的具体例,可举出低密度聚乙烯、高密度聚乙烯、线性聚乙烯等聚乙烯,还可举出分子量为100万以上的超高分子量聚乙烯。为了进一步提高多孔膜的穿刺强度,优选多孔膜含有超高分子量聚乙烯。从制造多孔膜的观点出发,有时也优选多孔膜含有由低分子量(重均分子量1万以下)的聚烯烃构成的蜡。
多孔膜具有微孔。该孔的大小(直径)通常为3μm以下、优选为1μm以下。多孔膜的孔隙率通常为30体积%以上且80体积%以下、优选为40体积%以上且70体积%以下。非水电解质二次电池超过通常的使用温度时,多孔膜通过构成其的材料的软化,可以将微孔闭塞。
多孔膜的孔隙率可由下式(1)求得。
Pv1(%)={(Va1−Vt1)/Va1}×100 (1)
Pv1(%):多孔膜的孔隙率(体积%)
Va1:多孔膜的表观体积
Vt1:多孔膜的理论体积
这里,Va1可以由多孔膜的长、宽和厚度的值求得,Vt1可以由多孔膜的重量、构成材料的重量比例和各构成材料的真比重的值求得。
多孔膜的厚度通常为3μm以上且30μm以下、优选为3μm以上且25μm以下、更优选为13μm以上且17μm以下。通过为13μm以上且17μm以下,特别是可以在不损害多孔膜的强度的情况下获得薄膜。
<多孔膜的制造方法>
多孔膜的制造方法并无特别限定。例如可举出如日本特开平7−29563号公报所记载的那样,在热塑性树脂中添加增塑剂进行膜成形后,用适当的溶剂将该增塑剂除去的方法;或如日本特开平7−304110号公报所记载的那样,使用由利用公知方法制造的热塑性树脂构成的膜、将该膜的结构上弱的非晶部分选择性拉伸、形成微孔的方法。
多孔膜在由含超高分子量聚乙烯和重均分子量1万以下的低分子量聚烯烃的聚烯烃系树脂形成时,从制造成本的观点出发,优选利用以下所示的方法制造。即,含有下述工序的方法:
(1)将超高分子量聚乙烯100重量份、重均分子量1万以下的低分子量聚烯烃5~200重量份和无机填充剂100~400重量份混炼,获得聚烯烃系树脂组合物的工序
(2)对前述聚烯烃系树脂组合物进行成形,获得片材的工序
(3)从工序(2)获得的片材中将无机填充剂除去的工序
(4)对工序(3)获得的片材进行拉伸,获得多孔膜的工序;
或者含有下述工序的方法:
(1)将超高分子量聚乙烯100重量份、重均分子量1万以下的低分子量聚烯烃5~200重量份和无机填充剂100~400重量份混炼,获得聚烯烃系树脂组合物的工序
(2)对前述聚烯烃系树脂组合物进行成形,获得片材的工序
(3)对工序(2)获得的片材进行拉伸,获得拉伸片材的工序
(4)从工序(3)获得的拉伸片材中将无机填充剂(C)除去,获得多孔膜。从能够进一步降低层叠膜的关闭温度的观点出发,优选前面的方法,即将片材的无机填充剂除去后进行拉伸,获得多孔膜的方法。
从多孔膜的强度和锂离子透过性的观点出发,无机填充剂优选平均粒径为0.5μm以下、更优选为0.2μm以下。这里,无机填充剂的平均粒径是通过使用了激光衍射式粒度分布测定装置的测定所决定的体积基准的D50的值。
作为无机填充剂的例子,可举出碳酸钙、碳酸镁、碳酸钡、氧化锌、氧化钙、氢氧化铝、氢氧化镁、氢氧化钙、硫酸钙、硅酸、氧化锌、氯化钙、氯化钠、硫酸镁等。这些无机填充剂可以通过与酸或碱溶液接触而被溶解,从而从片材或膜上除去。由于易于获得微细的粒径,因而优选碳酸钙。
上述聚烯烃系树脂组合物的制造方法并无特别限定。例如使用轧辊、班伯里混合机、单轴挤出机、双轴挤出机等混合装置对聚烯烃系树脂或无机填充剂等构成聚烯烃系树脂组合物的材料进行混合,获得聚烯烃系树脂组合物。混合构成材料时,还可根据需要将脂肪酸酯、稳定剂、抗氧化剂、紫外线吸收剂、阻燃剂等添加剂添加至构成材料中。
由上述聚烯烃系树脂组合物构成的片材的制造方法并无特别限定。作为该方法,可举出吹胀加工、压延加工、T模挤出加工、旋削法等片材成形方法。由于可获得膜厚精度更高的片材,因而优选下述方法。
由聚烯烃系树脂组合物构成的片材的优选制造方法是使用一对旋转成形工具、对聚烯烃系树脂组合物进行压延成形的方法,将该工具的表面温度调整至较构成聚烯烃系树脂组合物的聚烯烃系树脂的最高熔点还高的温度。旋转成形工具的表面温度优选为前述熔点+5℃以上。对于表面温度的上限而言,优选为前述熔点+30℃以下、更优选为前述熔点+20℃以下。作为一对的旋转成形工具,可举出轧辊或皮带。一对的旋转成形工具各自的旋转周速度并无必要严格地一样,它们之间的差异只要是±5%以内左右即可。使用通过这种方法获得的片材制造的多孔膜的强度或锂离子透过性、透气性等优异。还可以将多个通过前述方法获得的片材层叠,制造多孔膜。
在利用一对的旋转成形工具对聚烯烃系树脂组合物进行压延成形时,还可将由挤出机排出的线条状的聚烯烃系树脂组合物直接导入至一对的旋转成形工具间,也可导入暂先进行了颗粒化的聚烯烃系树脂组合物。
上述拉伸可以使用拉幅机、轧辊或Autograph等来进行。从多孔膜的透气性的观点出发,拉伸倍率优选为2~12倍、更优选为4~10倍。拉伸温度通常为聚烯烃系树脂组合物的软化点以上且熔点以下的温度、优选为80~115℃。拉伸温度过低时,则拉伸时变得易于发生膜破裂;过高时,则所得膜的透气性或锂离子透过性会降低。拉伸后还可进行热定型。热定型温度优选是低于聚烯烃系树脂的熔点的温度。
<耐热多孔层>
耐热多孔层由无机填料和粘结剂构成。耐热多孔层与多孔膜相接触。非水电解质二次电池中的多孔膜在关闭后,电池内的温度进一步上升,即便电池内温度上升至一定程度的高温,耐热多孔层也不会使多孔膜发生膜破裂、仍可维持关闭的状态。耐热多孔层还可以与多孔膜的单面相接而进行层叠,还可以与两面相接而进行层叠。
作为耐热多孔层中的无机填料,例如可举出氧化铝、二氧化硅、氧化钛、氧化锆、氧化镁、氧化铈、氧化钇、氧化锌、氧化铁等氧化物系陶瓷;氮化硅、氮化钛、氮化硼等氮化物系陶瓷;勃姆石、碳化硅、轻质碳酸钙、重质碳酸钙、硫酸铝、氢氧化铝、钛酸钾、滑石、高岭土粘土、高岭石、埃洛石、叶腊石、蒙脱石、绢云母、云母、镁绿泥石、膨润土、石棉、沸石、硅酸钙、硅酸镁、硅藻土、硅砂等陶瓷;玻璃纤维等。各自的熔点均超过200℃。这些无机填料可单独使用还可混合2种以上使用。无机填料优选为选自氧化铝、二氧化硅、勃姆石、氧化钛、高岭土粘土、轻质碳酸钙和氧化镁中的1种以上的材料。通过使用这种无机填料,可以在维持耐热多孔层的耐热性的同时提高开孔度、进一步提高锂离子的透过性。
无机填料的平均粒径可考虑耐热多孔层形成的容易程度、层厚度控制的容易程度而适宜选择。无机填料的平均粒径优选为0.01μm以上且2μm以下、更优选为0.01μm以上且0.5μm以下。通过将无机填料的平均粒径设定为前述范围,可以以更均一的层厚高效地形成耐热多孔层。这里,无机填料的平均粒径是通过使用了激光衍射式粒度分布测定装置的测定决定的体积基准的D50的值。
耐热多孔层含有粘结剂。粘结剂可以使无机填料粘结在多孔膜上,还可使构成无机填料的颗粒之间粘结。当后述的保护多孔层由颗粒构成时,还可以使保护多孔层粘结在耐热多孔层上。
粘结剂优选不溶于非水电解质二次电池的电解液中。作为优选的粘结剂的例子,可举出苯乙烯−丁二烯共聚物;羧甲基纤维素等纤维素化合物;乙烯−醋酸乙烯基酯共聚物;聚偏氟乙烯(以下也称作PVdF)、聚四氟乙烯等含氟树脂;聚乙烯醇等。
耐热多孔层以相对于无机填料和粘结剂的总体积为优选20体积%以上且小于100体积%的比例、更优选50体积%以上且小于100体积%的比例、进一步优选80体积%以上且小于100体积%的比例含有无机填料。通过使无机填料的体积比例为80体积%以上且小于100体积%,特别是锂离子的透过性更为提高。
耐热多孔层的厚度从耐热性与锂离子透过性的平衡的观点出发,优选为1μm以上且10μm以下、更优选为1μm以上且8μm以下、进一步优选为1μm以上且5μm以下。
耐热多孔层的孔隙率可考虑耐热性、机械强度、锂离子的透过性等而适宜设定,优选为30体积%以上且80体积%以下、更优选为40体积%以上且70体积%以下。耐热多孔层的孔隙率可通过下式(2)计算。
Pv2(%)={(Va2−Vt2)/Va2}×100 (2)
Pv2(%):耐热多孔层的孔隙率(体积%)
Va2:耐热多孔层的表观体积
Vt2:耐热多孔层的理论体积
这里,Va2可以由耐热多孔层的长、宽和厚度的值求得,Vt2可以由耐热多孔层的重量、构成材料的重量比例和各构成材料的真比重的值求得。
<耐热多孔层的形成方法>
耐热多孔层可以通过将无机填料和粘结剂涂布在多孔膜的至少单面上来形成。还可使用无机填料和粘结剂分散或溶解于溶剂中而得的涂布液。使用涂布液时,在多孔膜的至少单面上涂布涂布液后,通过干燥等将溶剂除去,可以获得耐热多孔层。
作为前述涂布液中的溶剂的例子,可举出N−甲基吡咯烷酮(以下也称作NMP)、N,N−二甲基甲酰胺、N,N-二甲基乙酰胺、水、乙醇、甲苯、热二甲苯、己烷等。为了涂布液的分散稳定化或涂布性的提高,还可在涂布液中添加表面活性剂等分散剂;增粘剂;湿润剂;消泡剂;含酸、碱的PH调节剂等添加剂等。添加剂优选在溶剂除去时被除去。添加剂在使用非水电解质二次电池时,只要电化学稳定、不阻碍电池反应、且在200℃左右仍稳定,则可以残存在耐热多孔层内。本发明中,耐热多孔层还可含有涂布时所用溶剂的残存部分或粘结剂所含的添加物等成分。
作为涂布液的制造方法、即将无机填料和粘结剂溶解或分散于溶剂中的方法,例如可举出利用球磨机、珠磨机、行星式球磨机、振动球磨机、砂磨机、胶体磨、磨碎机、辊磨机、高速叶轮分散、分散器、匀浆机、高速冲击磨、超声波分散、搅拌桨叶的机械搅拌等。作为将涂布液涂布在多孔膜上的方法,例如可举出棒涂法、凹版涂布法、小径凹版涂布法、逆转辊涂布法、转送辊涂布法、吻涂法、浸渍涂布法、刮刀涂布法、气刀涂布法、刀片涂布法、棒式涂布法、挤压涂布法、流延涂布法、模涂布法、丝网印刷法、喷雾涂布法等。
在对涂布液进行涂布之前,若对多孔膜表面进行表面处理,则涂布液变得易于涂布、耐热多孔层与多孔膜的粘接性会提高。作为表面处理的方法,例如可举出电晕放电处理法、机械粗糙化法、溶剂处理法、酸处理法、紫外线氧化法等。
作为从通过涂布获得的涂布膜中将溶剂除去的方法,可举出在多孔膜的熔点以下的温度下进行干燥的方法、进行减压干燥的方法等。
<保护多孔层>
保护多孔层与耐热多孔层相接触。保护多孔层起到保护耐热多孔层的作用。保护多孔层通过抑制卷取层叠膜时的卷取辊等装置构件的磨耗、抑制耐热多孔层中的粘结剂所诱发的水分的吸附、抑制耐热多孔层中的无机填料所诱发的灰尘等的附着,可以保护耐热多孔层。
保护多孔层优选由颗粒构成,由此制造电极组时的片材之间的摩擦力进一步降低。这里,颗粒可以并非将耐热多孔层的表面完全覆盖,颗粒之间也可并非紧密相邻。保护多孔层中的颗粒的平均粒径优选为0.01μm以上且3μm以下、更优选为0.01μm以上且0.5μm以下。颗粒具有这种平均粒径,则保护多孔层在起到保护耐热多孔层的作用的同时,还进一步提高锂离子透过性。
保护多孔层优选为电化学上稳定的层。作为构成保护多孔层的材料,可举出将其成形为多孔膜并用作锂离子二次电池的隔膜、即便以4.2~4.5V的充电状态保持该电池数小时也不会变质的材料。作为这种材料,例如可举出聚乙烯、聚丙烯等聚烯烃;聚四氟乙烯、四氟乙烯−六氟丙烯的共聚物等含氟高分子;羧甲基纤维素等水溶性纤维素;乙烯−丙烯共聚物等聚烯烃系共聚物;聚对苯二甲酸乙二醇酯等芳香族聚酯等。其中优选聚烯烃、含氟高分子。
保护多孔层的孔隙率优选为30体积%以上且80体积%以下、更优选为50体积%以上且80体积%以下。通过达到这种孔隙率,保护多孔层在起到保护耐热多孔层的作用的同时,还进一步提高锂离子透过性。予以说明,保护多孔层的孔隙率可由下式(3)求得。
Pv3(%)={(Va3−Vt3)/Va3}×100 (3)
Pv3(%):耐热多孔层的孔隙率(体积%)
Va3:耐热多孔层的表观体积
Vt3:耐热多孔层的理论体积
这里,Va3可以由耐热多孔层的长、宽和厚度的值求得,Vt3可以由耐热多孔层的重量、构成材料的重量比例和各构成材料的真比重的值求得。
保护多孔层的厚度优选为0.02μm以上且5μm以下、更优选为0.02μm以上且3μm以下。通过达到这种厚度,保护多孔层在起到保护耐热多孔层的作用的同时,还进一步提高锂离子透过性。
<保护多孔层的形成方法>
保护多孔层可以通过将构成保护多孔层的颗粒分散于溶剂而成的涂布液涂布在耐热多孔层的表面,然后进行干燥等将溶剂除去来形成。
作为前述涂布液中的溶剂的例子,可举出NMP、N,N−二甲基甲酰胺、N,N−二甲基乙酰胺、水、乙醇、甲苯、热二甲苯、己烷等。为了涂布液的分散稳定化或涂布性的提高,还可在涂布液中添加表面活性剂等分散剂;增粘剂;湿润剂;消泡剂;含酸、碱的PH调节剂等添加剂等。添加剂优选在溶剂除去时被除去。添加剂在使用非水电解质二次电池时,只要是电化学稳定、不阻碍电池反应、且直至200℃左右仍稳定,则可以残存在保护多孔层内。
作为涂布液的制造方法、即将构成保护多孔层的颗粒分散于溶剂中的方法,例如可举出利用球磨机、珠磨机、行星式球磨机、振动球磨机、砂磨机、胶体磨、磨碎机、辊磨机、高速叶轮分散、分散器、匀浆机、高速冲击磨、超声波分散、搅拌翼的机械搅拌等。作为将涂布液涂布在耐热多孔层表面的方法,例如可举出棒涂法、凹版涂布法、小径凹版涂布法、逆转辊涂布法、转送辊涂布法、吻涂法、浸渍涂布法、刮刀涂布法、气刀涂布法、刀片涂布法、棒式涂布法、挤压涂布法、流延涂布法、模涂布法、丝网印刷法、喷雾涂布法等。
作为从通过涂布获得的涂布膜中将溶剂除去的方法,可举出在多孔膜的熔点以下的温度下进行干燥的方法、进行减压干燥的方法等。
<隔膜>
通过本发明,可获得直至200℃左右仍基本上没有强度劣化、直至300℃左右仍保持形状的耐热性优异的膜。非水电解质二次电池中,由于循环容量等电池特性提高,因而作为锂离子二次电池、锂聚合物二次电池等非水电解质二次电池用隔膜特别有用。作为水系电解质二次电池用、非水电解质一次电池用、电容器用的隔膜也可充分地使用。
<非水电解质二次电池>
本发明的非水电解质二次电池是具有正极、负极、配置于该正极与该负极之间的隔膜、和电解质的非水电解质二次电池,该隔膜为上述本发明的层叠膜。接着,以锂离子二次电池为例说明本发明的非水电解质二次电池。
锂离子二次电池例如可如下制造:将正极片材、隔膜、负极片材、隔膜按顺序层叠或者边层叠边卷绕,获得电极组,将该电极组装在电池罐等电池外壳内,向电池外壳内注入电解液,从而制造。这里,作为隔膜使用本发明的层叠膜。在正极片材、隔膜、负极片材、隔膜的层叠时,若按照层叠膜的保护多孔层配置在正极片材侧对它们进行层叠时,则获得层叠膜的保护多孔层配置于正极侧的非水电解质二次电池。通过将保护多孔层配置在正极侧,电池的电化学稳定性进一步提高。
作为前述电极组的形状,例如可举出在与卷绕轴垂直的方向上截断该电极组时的截面呈圆、椭圆、长方形、带棱角的长方形等形状。作为电池的形状,例如可举出纸片型、纽扣型、圆筒型、多边型等形状。
<正极>
作为前述正极片材,通常使用在正极集电体上层叠有含正极活物质、导电剂和粘结剂的正极合剂的电极。正极合剂优选含有可用锂离子掺杂且脱掺杂的材料作为正极活物质、含有碳材料作为导电剂、含有热塑性树脂作为粘结剂。
作为前述正极活物质,可举出可用锂离子掺杂且脱掺杂的材料。作为正极活物质的具体例,可举出含有选自V、Mn、Fe、Co、Ni、Cr和Ti中的至少1种过渡金属元素和Li、Na等碱金属元素的复合金属氧化物。正极活物质优选为以α−NaFeO2型结构为母体的复合金属氧化物,从平均放电电位高的观点出发,更优选为钴酸锂、镍酸锂、镍酸锂的镍的一部分被Mn、Co等其它元素取代了的锂复合金属氧化物。作为正极活物质,还可举出以锂锰尖晶石等尖晶石型结构为母体的复合金属氧化物。
作为前述粘结剂,可举出热塑性树脂。作为热塑性树脂的具体例,可举出聚偏氟乙烯、偏二氟乙烯的共聚物、聚四氟乙烯、四氟乙烯−六氟丙烯的共聚物、四氟乙烯−全氟烷基乙烯基醚的共聚物、乙烯−四氟乙烯的共聚物、偏二氟乙烯−六氟丙烯−四氟乙烯共聚物、热塑性聚酰亚胺、羧甲基纤维素、聚乙烯、聚丙烯等。
作为前述导电剂,可举出碳材料。作为碳材料的具体例,可举出天然石墨、人造石墨、焦炭类、乙炔黑、科琴黑等炭黑等,还可将2种以上混合使用。
作为前述正极集电体,可举出Al、不锈钢等,从轻量、廉价、加工容易的观点出发优选Al。作为在正极集电体上层叠前述正极合剂的方法,可举出利用加压成型的方法,进一步使用溶剂等获得正极合剂糊料、将该糊料涂布在正极集电体上、干燥后压制进行压合的方法等。
<负极>
前述负极片材可以使用在比正极片材更低的电位下、可用锂离子掺杂且脱掺杂的材料。作为负极,可举出在负极集电体上层叠有含负极材料的负极合剂的电极、或者由负极材料单独构成的电极。作为负极材料,可举出为碳材料、硫属元素化合物(氧化物、硫化物等)、氮化物、金属或合金,且在比正极更低的电位下可用锂离子掺杂且脱掺杂的材料。还可将这些负极材料混合使用。
以下例示前述负极材料。作为前述碳材料的例子,具体可举出天然石墨、人造石墨等石墨、焦炭类、炭黑、热分解碳类、碳纤维、高分子烧成体等。作为前述氧化物的例子,具体可举出SiO2、SiO等式SiOx(这里x为正实数)所示的硅的氧化物,TiO2、TiO等式TiOx(这里x为正实数)所示的钛的氧化物,V2O5、VO2等式VOx(这里x为正实数)所示的钒的氧化物,Fe3O4、Fe2O3、FeO等式FeOx(这里x为正实数)所示的铁的氧化物,SnO2、SnO等式SnOx(这里x为正实数)所示的锡的氧化物,WO3、WO2等通式WOx(这里x为正实数)所示的钨的氧化物,Li4Ti5O12、LiVO2(包括Li1.1V0.9O2)等含锂及钛和/或钒的复合金属氧化物等。作为前述硫化物的例子,具体可举出Ti2S3、TiS2、TiS等式TiSx(这里x为正实数)所示的钛的硫化物,V3S4、VS2 、VS等式VSx(这里x为正实数)所示的钒的硫化物,Fe3S4、FeS2、FeS等式FeSx(这里x为正实数)所示的铁的硫化物,Mo2S3、MoS2等式MoSx(这里x为正实数)所示的钼的硫化物,SnS2 、SnS等式SnSx(这里x为正实数)所示的锡的硫化物,WS2等式WSx(这里x为正实数)所示的钨的硫化物,Sb2S3等式SbSx(这里x为正实数)所示的锑的硫化物,Se5S3、SeS2、SeS等式SeSx(这里x为正实数)所示的硒的硫化物等。作为前述氮化物的例子,具体可举出Li3N、Li3 − xAxN(这里A为Ni和/或Co,0<x<3。)等含锂的氮化物。这些碳材料、氧化物、硫化物、氮化物还可组合2种以上使用。它们可以是结晶质或非晶质的任一种。这些碳材料、氧化物、硫化物、氮化物主要层叠在负极集电体上作为电极使用。
作为前述金属的例子,具体可举出锂金属、硅金属、锡金属。作为前述合金的例子,可举出Li−Al、Li−Ni、Li−Si等锂合金、Si−Zn等硅合金、Sn−Mn、Sn−Co、Sn−Ni、Sn−Cu、Sn−La等锡合金、Cu2Sb、La3Ni2Sn7等合金。这些金属、合金主要单独作为电极使用(例如以片材状使用)。
从所得二次电池的电位平坦性高、平均放电电位低、循环特性良好等观点出发,上述负极材料优选为以天然石墨、人造石墨等石墨为主成分的碳材料。作为碳材料的形状,例如可举出如天然石墨的薄片状、如中间相碳微球的球状、如石墨化碳纤维的纤维状或微粉末的凝集体等。
前述的负极合剂还可根据需要含有粘结剂。作为粘结剂可举出热塑性树脂。作为热塑性树脂,具体可举出PVdF、热塑性聚酰亚胺、羧甲基纤维素、聚乙烯、聚丙烯等。
作为前述负极集电体,可举出Cu、Ni、不锈钢等,从难以与锂制成合金、易于加工成薄膜的观点出发,优选Cu。作为在负极集电体上层叠负极合剂的方法,与正极的情况同样,可举出利用加压成型的方法,进一步使用溶剂等获得负极合剂糊料、将该糊料涂布在负极集电体上干燥后压制、进行压合的方法等。
<电解液>
电解液通常含有电解质和有机溶剂。作为电解质的例子,可举出LiClO4、LiPF6、LiAsF6、LiSbF6、LiBF4、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2CF3)(COCF3)、Li(C4F9SO3)、LiC(SO2CF3)3、Li2B10Cl10、LiBOB(这里BOB是指双乙二酸硼酸盐(bis(oxalato)borate))、低级脂肪族羧酸锂盐、LiAlCl4等锂盐,可以混合2种以上的电解质使用。其中,通常使用选自LiPF6、LiAsF6、LiSbF6、LiBF4、LiCF3SO3、LiN(SO2CF3)2和LiC(SO2CF3)3中的1种以上的含氟锂盐。
在前述电解液中,作为有机溶剂例如可举出碳酸亚丙酯、碳酸亚乙酯(以下有时称作EC)、碳酸二甲酯(以下有时称作DMC)、碳酸二乙酯、碳酸甲乙酯(以下有时称作EMC)、4−三氟甲基−1,3−二氧杂环戊烷−2−酮、1,2−二(甲氧基羰基氧基)乙烷等碳酸酯类;1,2−二甲氧基乙烷、1,3−二甲氧基丙烷、五氟丙基甲基醚、2,2,3,3−四氟丙基二氟甲基醚、四氢呋喃、2−甲基四氢呋喃等醚类;甲酸甲酯、乙酸甲酯、γ−丁内酯等酯类;乙腈、丁腈等腈类;N,N−二甲基甲酰胺、N,N−二甲基乙酰胺等酰胺类;3−甲基−2−噁唑烷酮等氨基甲酸酯类;环丁砜、二甲基亚砜、1,3−丙烷磺内酯等含硫化合物,另外可以使用在上述有机溶剂中进一步引入了氟取代基的溶剂。通常使用混合有其中二种以上有机溶剂的混合溶剂。其中,优选含碳酸酯类的混合溶剂,更优选环状碳酸酯和非环状碳酸酯的混合溶剂、或环状碳酸酯和醚类的混合溶剂。作为环状碳酸酯和非环状碳酸酯的混合溶剂,从工作温度范围大、负荷特性优异,且即便使用天然石墨、人造石墨等石墨材料作为负极的活性物质时也为难分解性的观点出发,优选含EC、DMC和EMC的混合溶剂。特别是从获得优异的安全性提高效果的观点出发,优选使用含有LiPF6等含氟锂盐和具有氟取代基的有机溶剂的电解液。含有五氟丙基甲基醚、2,2,3,3−四氟丙基二氟甲基醚等具有氟取代基的醚类和DMC的混合溶剂的大电流放电特性也优异,更加优选。
实施例
接着,通过实施例进一步具体地说明本发明。本发明并非限定于这些实施例。
制造例1(正极片材的制作)
作为正极活物质,使用LiCoO2所示的锂复合金属氧化物。使用乙炔黑作为导电剂。使用聚四氟乙烯及羧甲基纤维素作为粘结剂。使用水作为溶剂。使用Al箔作为集电体(正极集电体)。将正极活物质、导电剂、粘结剂和溶剂混合,获得正极合剂糊料。正极合剂糊料中的正极活物质∶导电剂∶粘结剂∶溶剂的重量比为92∶3∶5∶45。粘结剂中的聚四氟乙烯∶羧甲基纤维素的重量比为9∶1。
将该正极合剂糊料涂布于Al箔的两面、进行干燥而获得干燥片材,用辊压机对该片材进行压制后,熔接铝制引线,获得正极片材。
制造例2(负极片材的制作)
使用天然石墨作为负极材料。使用羧甲基纤维素作为粘结剂。使用水作为溶剂。使用铜箔作为集电体(负极集电体)。将负极材料、粘结剂和溶剂混合,获得负极合剂糊料。负极合剂糊料中的负极材料∶粘结剂∶溶剂的重量比为98∶2∶110。
将该负极合剂糊料涂布于铜箔的两面、进行干燥,获得干燥片材,用辊压机对该片材进行压制后,熔接铜制引线,获得负极片材。
制造例3(电解液的制作)
电解液是在以体积比16∶10∶74混合有EC、DMC和EMC的混合溶剂中溶解作为电解质的LiPF6,使其浓度达到1.3摩尔/升,从而制备。
制造例4(非水电解质二次电池的制作和评价)
将制造例1的正极片材、隔膜、制造例2的负极片材、隔膜依次层叠、进行卷绕获得电极组,将所得电极组收纳于电池盒中后,向盒内注入制造例3的电解液,制造锂离子二次电池。在以下条件下进行二次电池的充放电试验和循环试验。
<充放电试验>
试验温度20℃
充电最大电压4.2V、充电时间4小时、充电电流1mA/cm2
放电最小电压3.0V、恒电流放电、放电电流1mA/cm2
<循环试验>
试验温度20℃
充电最大电压4.2V、充电时间4小时、充电电流15mA/cm2
放电最小电压3.0V、恒电流放电、放电电流10mA/cm2
循环数50次
放电容量维持率(%)=第50个循环的放电容量/第1个循环的放电容量×100。
比较例1
使用聚乙烯制的多孔膜(厚度15μm、孔隙率50%)作为具有关闭功能的多孔膜。使用α−氧化铝(平均粒径0.3μm)作为无机填料。使用聚偏氟乙烯作为粘结剂。使用NMP作为溶剂。将无机填料、粘结剂和溶剂混合制作涂布液(1)。该涂布液(1)中的无机填料∶粘结剂∶溶剂的重量比为30∶1∶99。将该涂布液(1)涂布在多孔膜的单面,在70℃下干燥,形成耐热多孔层,获得比较膜1。作为涂布装置使用棒涂机。比较膜1的耐热多孔层的厚度为3.0μm、孔隙率为65体积%。相对于耐热多孔层中无机填料和粘结剂的总体积的无机填料的体积比例为93体积%。
使用比较膜1作为隔膜,根据制造例4制作比较二次电池。这里,以使比较膜1的耐热多孔层位于正极片材侧的方式进行配置。进行比较二次电池的充放电试验。将所得放电容量作为100。进行比较二次电池的循环试验。使所得放电容量维持率为100。进行循环试验后,将电池分解,目视确认电极组的卷绕状况,结果确认到松弛。
实施例1
使用聚乙烯制的多孔膜(厚度15μm、孔隙率50%)作为具有关闭功能的多孔膜。使用α−氧化铝(平均粒径0.3μm)作为无机填料。使用聚偏氟乙烯作为粘结剂。使用NMP作为溶剂。将无机填料、粘结剂和溶剂混合,制作涂布液(1)。该涂布液(1)中的无机填料∶粘结剂∶溶剂的重量比为30∶1∶99。将该涂布液(1)涂布在多孔膜的单面,在70℃下干燥,形成耐热多孔层。作为涂布装置使用棒涂机。耐热多孔层的厚度为3.1μm、孔隙率为66体积%。相对于耐热多孔层中无机填料和粘结剂的总体积的无机填料的体积比例为93体积%。
使用聚四氟乙烯的颗粒(平均粒径0.3μm)作为构成保护多孔层的颗粒。使用水作为溶剂(分散介质)。将前述聚四氟乙烯的颗粒和溶剂混合并分散,制作涂布液(2)。该涂布液(2)中的颗粒∶溶剂的重量比为5∶95。将该涂布液(2)涂布在耐热多孔层的单面,在70℃下干燥,形成保护多孔层,获得层叠膜1。作为涂布装置使用棒涂机。保护多孔层的厚度为1μm、孔隙率为70体积%。
使用层叠膜1作为隔膜,根据制造例4制作锂离子二次电池1。这里,以使层叠膜1的保护多孔层位于正极片材侧的方式进行配置。进行锂离子二次电池1的充放电试验。所得放电容量的比例相对于比较二次电池的放电容量的100基本为100,未见容量的差异。进行锂离子二次电池1的循环试验。所得放电容量维持率相对于比较二次电池的放电容量维持率的100为103,确认到放电容量维持率的提高。进行循环试验后,将电池分解,目视确认电极组的卷绕状况,结果确认到松弛。
实施例2
除了使用聚乙烯的颗粒(平均粒径0.6μm)作为构成保护多孔层的颗粒以外,与实施例1同样地获得层叠膜2。保护多孔层的厚度为1.2μm、孔隙率为68体积%。
使用层叠膜2作为隔膜,根据制造例4制作锂离子二次电池2。这里,以使层叠膜2的保护多孔层位于正极片材侧的方式进行配置。进行锂离子二次电池2的充放电试验。所得放电容量的比例相对于比较二次电池的放电容量的100基本为100,未见容量的差异。进行锂离子二次电池2的循环试验。所得放电容量维持率相对于比较二次电池的放电容量维持率的100为104,确认到放电容量维持率的提高。进行循环试验后,将电池分解,目视确认电极组的卷绕状况,确认到松弛。
产业实用性
使用本发明的层叠膜作为非水电解质二次电池的隔膜时,可以降低将正极片材、隔膜、负极片材、隔膜依次重叠、进行卷绕制造电极组时的片材之间的摩擦力,可以获得正极片材、隔膜和负极片材更加密合的电极组。结果可获得循环性也优异的二次电池。具有本发明的层叠膜作为隔膜的非水电解质二次电池具有关闭功能、耐热性优异、循环性等电池特性也优异。在本发明的层叠膜制造中的卷取之际,由于卷取辊等装置构件难以被磨耗,因而可以抑制金属粉、树脂粉等的产生或它们混入到层叠膜中。另外,由于本发明的层叠膜难以吸附水分,因而可以抑制吸湿所导致的电绝缘性的降低。而且,由于本发明的层叠膜也难以带电,因此也可抑制大气中的异物等的吸附。本发明的层叠膜的处理也极为优异,本发明极富有实用性。
Claims (8)
1.一种层叠膜,其为使具有关闭功能的多孔膜、由无机填料和粘结剂构成的耐热多孔层、以及保护多孔层依次相接、进行层叠而成的层叠膜,所述多孔膜的材料为聚烯烃,所述保护多孔层的材料为含氟高分子,耐热多孔层以相对于无机填料和粘结剂的总体积为20体积%以上且小于100体积%的比例含有无机填料。
2.根据权利要求1所述的层叠膜,其中保护多孔层的孔隙率为30体积%以上且80体积%以下。
3.根据权利要求1或2所述的层叠膜,其中多孔膜的厚度为13μm以上且17μm以下。
4.根据权利要求1或2所述的层叠膜,其中耐热多孔层的厚度为1μm以上且10μm以下。
5.根据权利要求1或2所述的层叠膜,其中保护多孔层的厚度为0.02μm以上且5μm以下。
6.根据权利要求1或2所述的层叠膜,其为隔膜。
7.一种非水电解质二次电池,其为具有正极、负极、配置于该正极与该负极之间的隔膜、以及电解质的非水电解质二次电池,其中该隔膜是权利要求1或2所述的层叠膜。
8.根据权利要求7所述的非水电解质二次电池,其中层叠膜的保护多孔层配置于正极侧。
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KR101858426B1 (ko) | 2018-05-15 |
CN102668174A (zh) | 2012-09-12 |
EP2498319A1 (en) | 2012-09-12 |
KR20120091271A (ko) | 2012-08-17 |
TW201133991A (en) | 2011-10-01 |
KR20170138586A (ko) | 2017-12-15 |
KR101807887B1 (ko) | 2017-12-11 |
US20120251868A1 (en) | 2012-10-04 |
JP2011100635A (ja) | 2011-05-19 |
EP2498319A4 (en) | 2013-05-01 |
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