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CN102306778B - 一种非水性电化学电池及其制备方法 - Google Patents

一种非水性电化学电池及其制备方法 Download PDF

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CN102306778B
CN102306778B CN2011102581176A CN201110258117A CN102306778B CN 102306778 B CN102306778 B CN 102306778B CN 2011102581176 A CN2011102581176 A CN 2011102581176A CN 201110258117 A CN201110258117 A CN 201110258117A CN 102306778 B CN102306778 B CN 102306778B
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lithium
negative pole
anodal
electrochemical battery
capacity
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CN102306778A (zh
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何献文
劳忠奋
潘文硕
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Huizhou Desay Battery Technology Co., Ltd.
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Huizhou Huiderui Lithium Electrode Technology Co Ltd
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Priority to EP11871789.1A priority patent/EP2752924A4/en
Priority to US13/818,299 priority patent/US20130302699A1/en
Priority to PCT/CN2011/079487 priority patent/WO2013029282A1/zh
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Abstract

本发明属于化学电池领域，它公开了一种非水性电化学电池及其制备方法，该电化学电池包括具有正极涂层且整体作为正极的正极集流体、负极、电解液和隔膜，所述的集流体和负极上均设有极耳，正负所述负极是金属锂或锂铝合金；正极单位面积的容量与负极单位面积的容量之比值小于1.0；正极理论总容量与负极理论总容量之比值大于1.0。在制备方法中，所述的正极、负极隔膜叠放时，正极的起始端与负极的起始端是错位叠放。该工艺减少了制程短路率，在保障大电流放电能力的前提下，使电池的安全性能大大提高。

Description

一种非水性电化学电池及其制备方法
技术领域
本发明涉及一种化学电池领域，尤其涉及一种非水性电化学电池及其制备方法。 
背景技术
目前电子器件的多样化、小型化的飞速更新换代，促使了电池的进步，要求电池比能量、比功率高、寿命长、价格适宜、使用方便。小型电器的飞速发展使小型民用电池市场定单数量要求成倍增加,而且要求品种多、搁置寿命长、一次容量高、体积小。锂-二硫化铁电池很好地适应了这一发展趋势。作为锂-二硫化铁电池，要在好的大电流放电能力和好的安全性能之间找到平衡。如果电池中，负极活性物质多于正极活性物质，在反应后电池内存在较多剩余负极活性物质，由于锂是高能量物质，存在一定安全隐患；又由于锂电池正极极耳一般使用钢带或镍带，较为尖锐，在极端情况容易刺穿隔膜，引发电池内部短路造成恶性事故，因此需要采用一定措施保护。在大电流放电时，电池可反应的只有面对面的部分，而锂带太少，会在放电后期断裂，从而导致电池无法放出理论上的容量。CN1659729涉及一种非水型电池，它包含锂金属箔阳极和阴极涂层，此涂层包含作为活性材料的二硫化铁，其中涂层至少加在金属基底的一个表面，此金属基底起阴极电流收集器的作用，但该发明仍存在短路率高和安全隐患的问题。 
发明内容
针对上述技术问题，本发明需要解决的技术问题是减少了制程短路率，在保障大电流放电能力的前提下，使电池的安全性能有了明显改善。即在电池的大电流放电能力和电池的安全性之间取得平衡。 
本发明要解决的技术问题是通过以下技术方案实现的：一种非水性电化学电池，包括具有正极涂层且整体作为正极的正极集流体、负极、电解液和隔膜，所述的集流体和负极上均设有极耳，所述负极是金属锂或锂铝合金；所述正极涂层的各成份的重量比是黄铁矿∶导电碳黑∶石墨∶添加剂∶粘接剂(80－90)∶(0.5－4)∶(1－4)∶(0－4) ∶（1-4）；    正极单位面积的容量与负极单位面积的容量之比值小于1.0；正极理论总容量与负极理论总容量之比值大于1.0。 
进一步：在上述的非水性电化学电池中，所述的添加剂是MnO2、TiO2、LiCoO2、LiMnO2、LiNiO2、Li2TiO3、Li4Ti5O12中的一种或几种混合物。所述粘接剂是聚乙烯醇PVA、聚偏二氟乙烯PVDF、聚四氟乙烯PTFE、羧甲基纤维素钠CMC、丁苯橡胶乳液SBR、N-甲基吡咯烷酮NMP中的一种或两种的混合物。所述羧甲基纤维素钠CMC与丁苯橡胶乳液SBR的混合物占黄铁矿重量的1－4%，或者聚偏二氟乙烯PVDF与N-甲基吡咯烷酮NMP的混合物占黄铁矿重量的1－4%。所述黄铁矿FeS2纯度在90%以上，粒径小于44μm；石墨的平均颗粒5.0－18.0μm，BET比表面积11.0－14.0 m2/g，灰分占黄铁矿重量小于0.1%。 
所述电解液是有机溶剂和无机锂盐溶质的混合物，所述有机溶剂是N-甲基吡咯烷酮NMP、1,2-丙二醇碳酸酯PC、乙二醇二甲醚 DME、1,3-二氧戊环DOL、二甲基乙烯脲DMI、四氢呋喃THF、二甲基亚砜DMSO、环丁砜SFL中至少两种的混合物，所述无机锂盐溶质是高氯酸锂LiClO4、三氟甲基磺酸锂LiCF3SO3、六氟磷酸锂LiPF6、双草酸硼酸锂LiBOB、碘化锂LiI中至少一种或两种的混合物。优选的：所述无机锂盐溶质是高氯酸锂LiClO4或高氯酸锂LiClO4和双草酸硼酸锂LiBOB的混合物或单独使用碘化锂LiI。 
所述的隔膜是PP和或PE和或PP的聚乙烯树脂。所述的隔膜隔膜的最大有效孔径为0.08－0.12μm、孔隙率为40－50%、阻抗为30－50ｍΩ/mm2。 
所述正极集流体为铝箔，所述极耳为不锈钢带或镍带，其中铝箔厚度为10－25μｍ，不锈钢带或镍带厚度为0.05-0.1ｍｍ。 
本发明还提供了上述非水性电化学电池的制备方法，步骤为：正极的制备，包括将黄铁矿、石墨、乙炔黑、添加剂按配比混合，然后加入水性粘接剂混合均匀成浆料后涂覆在正极集流体上，烘干、碾压到一定预定厚度后裁切成合适尺寸，点焊正极极耳，正极极片烘干后，在相对湿度低于1％的环境下，将电池负极、隔膜卷绕后，装入钢壳，加入电解液后，滚槽、封口；所述的正极、负极隔膜叠放时，正极的起始端与负极的起始端是错位叠放，优选的错位位置尺寸是20-25mm。 
与现有技术相比，本发明所述正极涂层的各成份的重量比是黄铁矿∶导电碳黑∶石墨∶添加剂∶粘接剂等于 (80－90)∶(0.5－4)∶(1－4)∶(0－4) ∶（1-4）；正极单位面积的容量与负极单位面积的容量之比值小于1.0；正极理论总容量与负极理论总容量之比值大于1.0。本发明通过调节正极涂层的配方以及正负极的容量，正负极征错位放置位置的变化，该种电化学电池及其制备方法大大减少了制程短路率，在保证一定大电流放电能力的同时，使电池的安全性能得到大提高。 
具体实施方式
    本发明的主旨是调节正极涂层的配方以及正负极的容量，使非水性电化学电池具有大电流放电能力和电池的安全性之间取得平衡，即保障了大电流的放电，安全性能又高。下面结合实施例对本发明的内容作进一步详述，实施例中所提及的内容并非对本发明的限定，材料中各个原材料的选择可因地制宜而对结果并无实质性影响。 
实施例1
根据本发明，标准型号为AA的锂-二硫化铁电池的生产工艺如下：
使用电池级的黄铁矿粉，其主要成分FeS2（纯度为96%以上），石墨KS-15，乙炔黑，粘结剂用CMC及SBR。将以上物质按比例加入水中，使用高速搅拌机进行混合，充分湿润及混合，使用泊立菲粘度计测试，得到粘度在5000～8000厘泊的泥状浆料。
将该泥状浆料，使用转移式涂布设备，涂覆在0.018mm厚度的铝箔基带表面上，。调整转移式涂布设备，将泥状浆料间歇式的涂覆在铝箔基带表面，每涂覆280mm长，空余10mm不涂覆浆料，同时调整转移式涂布设备，使得涂覆在铝箔基带每一个表面上的泥状浆料，在完全烘干的状态下达到20.02mg/cm2的单位面密度。将铝箔基带两面均涂覆好泥状浆料并烘干后，进行压制，压制后厚度控制在约0.18mm。再将压制好的涂料裁切成长275mm宽39mm的单片，其中275mm长包括270mm的涂覆有泥状浆料的长度及5mm未涂覆泥状浆料的空白长度。在5mm未涂覆泥状浆料的部位，使用超声波焊接设备，焊接一条55mm长2mm宽0.1mm厚度的镍金属带，即作为正极片。 
用0.15mm厚38mm宽，纯度99.9%以上的锂金属箔带作为负极，将一条36mm长4mm宽0.2mm厚度的不锈钢金属带压粘在一条270mm长锂金属箔带的一端，即作为负极片。 
使用从UBE购买的0.025mm厚的UPE3085聚乙烯树脂膜作为隔膜。 
使用卷绕设备将上述正极片、负极片与隔膜卷在一起，使它们变成一个圆柱形电芯。在卷绕电芯时，先将隔膜缠绕在卷绕针上卷绕一小段隔膜，约5mm距离，再加入正极片，将正极片卷绕一小段后，约25mm，再加入负极片，完成将三者卷绕成圆柱形电芯的过程，最后切断隔膜包裹住电芯，使用胶纸粘贴成一个单体电芯。 
将做好的电芯一端伸出的负极耳以90°折向电芯端面，加入绝缘垫片后装入外壳，外壳是外径13.9mm的镀镍钢外壳，将负极耳通过焊接设备与外壳底部焊接在一起。 
正极单位面积的容量与负极单位面积的容量之比由下面的计算给出： 
正极单位面积的容量=［（正极敷料量，4.14g）╳（FeS2干重百分比，0.90）╳（FeS2纯度百分比，0.96）╳（FeS2能量密度893.58mAh/g）］/［（正极敷料长度，270mm）╳（正极敷料宽度，39mm）］=0.3034mAh/mm2；
负极单位面积的容量=［（负极重量，0.82g）╳（Li纯度百分比，0.999）╳（Li能量密度3861.7mAh/g）］/［（负极长度，270mm）╳（负极宽度，38mm）］=0.3083mAh/mm2；
正极单位面积的容量与负极单位面积的容量之比值=正极单位面积的容量/负极单位面积的容量=0.3034/0.3083=0.9843。
正极理论总容量与负极理论总容量之比值由下面的计算得到： 
正极理论总容量=（正极敷料量，4.14g）╳（FeS2干重百分比，0.90）╳（FeS2纯度百分比,0.96）╳（FeS2能量密度893.58mAh/g）=3196.3mAh；
负极理论总容量=（负极重量，0.82g）╳（Li纯度百分比，0.999）╳（Li能量密度3861.7mAh/g）=3163.4mAh；
正极理论总容量与负极理论总容量之比值=正极理论总容量/负极理论总容量=3196.3/3163.4=1.0104。
每个电池加入2.2g电解液，电解液含有体积比3:1的1,3-二氧戊环与乙二醇二甲醚，以及1mol/L的高氯酸锂。再将电芯另一端伸出的正极耳与正极盖焊接起来，采用常规的电池组装和封口方法将电池完工，再对电池进行预放电。 
实施例2
用作比较的AA的锂-二硫化铁电池，采用与方案1同样的生产工艺制造，但涂覆在铝箔基带每一个表面上的泥状浆料，在完全烘干的状态下仅需达到约24.23mg/cm2的单位面密度。
实施例3
用作比较的AA的锂-二硫化铁电池，采用与方案1同样的生产工艺制造，但涂覆在铝箔基带每一个表面上的泥状浆料，在完全烘干的状态下仅需达到约16.66mg/cm2的单位面密度。
实施例4
用作比较的AA的锂-二硫化铁电池，采用与方案1同样的生产工艺制造，但使用一条275mm长锂金属箔带制成负极片，在卷绕电芯时，正极片仅卷入约20mm后，再加入负极片，完成卷绕电芯的操作。
实施例5
用作比较的AA的锂-二硫化铁电池，采用与方案1同样的生产工艺制造，但使用一条280mm长锂金属箔带制成负极片，在卷绕电芯时，正极片仅卷入约15mm后，再加入负极片，完成卷绕电芯的操作。
实施例6
用作比较的AA的锂-二硫化铁电池，采用与方案1同样的生产工艺制造，但使用一条285mm长锂金属箔带制成负极片，在卷绕电芯时，正极片仅卷入约10mm后，再加入负极片，完成卷绕电芯的操作。
实施例7
用作比较的AA的锂-二硫化铁电池，采用与方案1同样的生产工艺制造，但使用一条290mm长锂金属箔带制成负极片，在卷绕电芯时，正极片仅卷入约5mm后，再加入负极片，完成卷绕电芯的操作。
不同正极单位面积的容量与负极单位面积的容量之比值下， 
电池初始放电性能对比见表1：
表1  不同正极单位面积电池放电容量对比（单位：mAh，型号：FR6）
编号 正、负极单位面积容量比 1000mA连续放电至0.8V容量 200mA连续放电至1.0V容量
实施例1 0.98 2492.6 2566.6
实施例2 1.19 2537.8 2600.2
实施例3 0.82 2036.6 2176.6
电池进行80%放电（以1000mA连续放电）后，60℃搁置20天，用来模拟电池部分放电后贮存后的使用性能。电池内阻变化趋势，见表2:
表2  电池内阻变化趋势(单位：mΩ，型号：FR6)
编号 正、负极单位面积容量比 60℃5天 60℃10天 60℃15天 60℃20天
实施例1 0.98 518.5 638 672 688
实施例2 1.19 856 1100 1413 >2000
实施例3 0.82 329 390 386 395
备注：内阻为从60℃取出后再常温搁置24小时后的测试值。
这里用到的正极单位面积的容量与负极单位面积的容量之比值，可以从下面的计算得到： 
正极单位面积的容量=［（正极敷料量）╳（FeS2干重百分比）╳（FeS2纯度百分比）╳（FeS2能量密度893.58mAh/g）］/［（正极敷料长度）╳（正极敷料宽度）］；
负极单位面积的容量=［（负极重量）╳（Li纯度百分比）╳（Li能量密度3861.7mAh/g）］/［（负极长度）╳（负极宽度）］；
正极单位面积的容量与负极单位面积的容量之比值=正极单位面积的容量/负极单位面积的容量。
为了避免在极端情况下(如大电流放电、部分放电后T6测试)，极耳刺穿隔膜，发生电池起火、爆炸等事故；正、负极在卷绕时放置错位，错位5mm以上；卷绕前隔膜覆盖长度、锂带放置位置及朝向、正极片放置位置及朝向如图示1。而该错位会导致电池的正极理论总容量与负极理论总容量之比值大于1.0。 
不同错位情况下，电池制作过程中，卷绕后短路率的数据如下,见表3： 
表3  卷绕短路率对比（型号：FR6）
编号 错位位置尺寸/mm 正、负极理论总容量之比值 卷绕电池数/个 短路数/个 短路率
实施例1 25 1.0104 4932 22 0.45%
实施例4 20 0.9932 4955 26 0.52%
实施例5 15 0.9751 4968 25 0.50%
实施例6 10 0.9587 5005 38 0.76%
实施例7 5 0.9423 4877 56 1.15%
备注：短路数的确定，在9V电压下绝缘电阻小于60MΩ的电芯数量。
   电池放电50%（以200mA电流放电）后，进行T6测试，测试情况见附表4： 
表4  T6测试对比（型号：FR6）
Figure 2011102581176100002DEST_PATH_IMAGE001
不同正极理论总容量与负极理论总容量之比值下，电池完全放电后，进行UL1642，CRUSH测试的情况如下,见表5：
表5  CRUSH测试对比（型号：FR6）
Figure 2011102581176100002DEST_PATH_IMAGE002
 这里用到的正极理论总容量与负极理论总容量之比值，可以从下面的计算得到：
正极理论总容量=（正极敷料量）╳（FeS2干重百分比）╳（FeS2纯度百分比）╳（FeS2能量密度893.58mAh/g）；
负极理论总容量=（负极重量）╳（Li纯度百分比）╳（Li能量密度3861.7mAh/g）；
正极理论总容量与负极理论总容量之比值=正极理论总容量/负极理论总容量。
通过上述的实施例对比发现，正极单位面积的容量与负极单位面积的容量之比值小于1.0；正极理论总容量与负极理论总容量之比值大于1.0。本发明通过调节正极涂层的配方以及正负极的容量，正负极片错位放置位置的变化，优选的错位位置尺寸是20-25mm，减少了制程短路率，在保证一定大电流放电能力的同时，使电池的安全性能得到大提高。 

Claims (8)

1.一种非水性电化学电池，包括具有正极涂层且整体作为正极的正极集流体、负极、电解液和隔膜，所述的正极集流体和负极上均设有极耳，所述负极是金属锂或锂铝合金；其特征在于：所述正极涂层的各成份的重量比是黄铁矿∶导电碳黑∶石墨∶添加剂∶粘接剂等于(80－90)∶(0.5－4)∶(1－4)∶(0－4) ∶（1-4）；
正极单位面积的容量与负极单位面积的容量之比值小于1.0；
正极理论总容量与负极理论总容量之比值大于1.0；
所述粘接剂是羧甲基纤维素钠CMC与丁苯橡胶乳液SBR的混合物，它们占黄铁矿重量的1－4%，或者粘接剂是聚偏二氟乙烯PVDF与N-甲基吡咯烷酮NMP的混合物，它们占黄铁矿重量的1－4%；
所述的正极的起始端与负极的起始端是错位叠放，错位位置尺寸大于等于5mm。
2.根据权利要求1所述的非水性电化学电池，其特征在于：所述的添加剂是MnO2、TiO2、LiCoO2、LiMnO2、LiNiO2、Li2TiO3、Li4Ti5O12中的一种或几种的混合物。
3.根据权利要求2所述的非水性电化学电池，其特征在于：所述黄铁矿FeS2纯度在90%以上，粒径小于44μm；石墨的平均颗粒5.0－18.0μm，BET比表面积11.0－14.0 m2/g，灰分占黄铁矿重量小于0.1%。
4.根据权利要求1所述的非水性电化学电池，其特征在于：所述电解液是有机溶剂和无机锂盐溶质的混合物，所述有机溶剂是N-甲基吡咯烷酮NMP、1,2-丙二醇碳酸酯PC、乙二醇二甲醚 DME、1,3-二氧戊环DOL、二甲基乙烯脲DMI、四氢呋喃THF、二甲基亚砜DMSO、环丁砜SFL中至少两种的混合物，所述无机锂盐溶质是高氯酸锂LiClO4、三氟甲基磺酸锂LiCF3SO3、六氟磷酸锂LiPF6、双草酸硼酸锂LiBOB、碘化锂LiI中至少一种。
5.根据权利要求1所述的非水性电化学电池，其特征在于：所述的隔膜是PP聚丙烯树脂和/或PE聚乙烯树脂。
6.根据权利要求5所述的非水性电化学电池，其特征在于：所述的隔膜的最大有效孔径为0.08－0.12μm、孔隙率为40－50%、阻抗为30－50ｍΩ/mm2。
7.根据权利要求1所述的非水性电化学电池，其特征在于：所述正极集流体为铝箔，所述极耳为不锈钢带或镍带，其中铝箔厚度为10－25μｍ，不锈钢带或镍带厚度为0.05-0.1ｍｍ。
8.一种根据权利要求1-7中任意一项所述非水性电化学电池的制备方法，步骤为：
正极的制备，包括将黄铁矿、石墨、乙炔黑、添加剂按配比混合，然后加入粘接剂混合均匀成浆料后涂覆在正极集流体上，烘干、碾压、切割成正极极片，点焊正极极耳，正极极片烘干后，在相对湿度低于1％的环境下，将电池负极片、隔膜卷绕后，装入钢壳，加入电解液后，滚槽、封口；
所述的正极片、负极片隔膜叠放时，正极的起始端与负极的起始端是错位叠放，错位位置尺寸是20-25mm。
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