CN101373845A - 利用含水电解液的锂电池 - Google Patents
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Abstract
本发明涉及一种包含电池单元的锂电池,包括:正极,负极,以及由锂盐水溶液构成的电解液,其特征在于所述电解液的pH为至少14,所述正极的嵌锂电位高于3.4V,而所述负极的嵌锂电位低于2.2V。
Description
技术领域
本发明涉及一种包括基于锂离子的含水(水性)电解液的锂电池。
因此本发明的电池避免了涉及使用有机电解液的严重局限并且显著增强了动力性能(电源性能,power performance)。
这些电池可在许多领域中应用,尤其是将动力供给到诸如信用卡和智能标签的薄嵌入式系统、移动电话以及电动车辆中。
背景技术
锂电池是基于其正负电极中同时的锂嵌入/脱嵌(或插入/脱出)的原理运行的。
更准确地,产生电流的电化学反应经由传导锂离子的电解液进行来自负极的锂阳离子(其嵌入到正极的受体阵列中)的转移,锂离子在运送中穿过传导锂离子的电解液。
负极通常基于碳材料如石墨并且是充电过程中锂嵌入反应的位置(场所)。
正极基于含锂的过渡金属氧化物(该金属例如可以是钴、镍或锰)并且是充电过程中锂脱嵌反应的位置(场所)。
隔膜(隔板,separator)在负极和正极之间提供物理隔离。传统地,它包括例如聚烯烃如聚乙烯或聚丙烯的微孔膜,其厚度可在20μm至50μm的范围,并且其被液体电解液浸透。
液体电解液必须在充电过程中将锂离子从正极传导到负极,并且在放电过程中反之亦然(即在运行中)。该电解液传统地采取溶解在有机溶剂中的锂盐的形式,通常是碳酸盐类。
这种类型的电解液对于水是高度敏感的。因此,包含它们的可充电电池必须在严格控制的条件下进行组装,必须严格控制环境的相对湿度,通常在清洁室(绝尘室)条件下进行。
而且,基于有机溶剂的电解液具有非常有限的导电性(为10-2S/cm级),因而有必要使用非常好的微孔膜作为支持物(支撑物,support),以限制该可充电电池的电解液电阻,其与膜厚度以及导电率倒数的乘积成比例。
因此,利用基于有机溶剂的锂可充电电池具有相对有限的动力性能。
为了克服与使用基于有机溶剂的电解液相关的缺陷,一些人考虑用水代替有机溶剂。得到的电解液使用pH范围为6至10的水溶液。在这种现有技术的电解液中遭遇到了以下缺陷:
-由于这些pH值,过度释放氢,
-必需使用高电位负极,因而在电池单元输出(cell output)处为低的产生电压。
因此,对于使用含水电解液的锂电池存在实际需要,其中具有有限的严重释放氢的危险并且可以使用比传统使用的负极更低电位的负极,以在电池单元输出处增大产生的电压。
发明内容
因此,本发明涉及一种包括电解槽的锂电池,包括:
-正极,
-负极,以及
-电解液,由设置在所述正极和所述负极之间的锂盐水溶液构成,
其特征在于电解液的pH为至少14,正极的嵌锂电位(lithiumintercalation potential)高于3.4V,以及负极的嵌锂电位低于2.2V。
在上文和下文中,电位(电势)相对于参考电对Li+/Li表示。相对于标准氢电极(NHE),该电对的氧化还原电位为-3.02V。
在进行更详细描述之前,给出以下定义。
正极是指在电池放电时捕获电子并产生阳离子(本文的Li+阳离子)的电极。
负极是指在电池放电时产生电子并捕获阳离子(本文的Li+阳离子)的电极。
嵌锂电位是指包含50%锂的物质(材料,material)(本文的构成负极或正极的物质)的平衡热力学电位。这个值是从作为表示x(x表示物质中的嵌锂比率(lithium intercalation ratio))的函数的电位V(以伏特表示)的参考曲线加以确定的,并且该嵌入电位对应于曲线上x=50%的电位值。图1示出了这种类型的曲线,其中嵌入电位在该曲线上用符号pi标出。
pH是利用商购的校准溶液校准的pH计以传统方式进行测量的。
通过同时控制电解液的pH和电极的特性,本发明的发明人已经获得了具有以下优点的电池:
-使用中较少的释放氢,这限制了释放较多氢的电池发生爆炸的内在危险,
-由于相伴使用具有高嵌锂电位的正极和具有较低嵌锂电位的负极,使得在每个电池单元输出处递送出更高的电压(至少1.2V)。
根据本发明,正极有利地包含选自具有橄榄石结构且通式为LiMPO4的锂氧化物的物质,其中M选自Fe、Mn、Ni和Co以及它们的混合物。
特别地,正极可包含LiFePO4,在这种情况下,嵌锂电位为3.45V(数量)级。一部分铁原子可用选自过渡金属,如Mn、Ni或Co的元素M’代替,在这种情况下,正极包含LiFeM’PO4类型的物质。
根据本发明,负极有利地包含选自钛酸锂、氧化钛TiO2以及它们的混合物的物质。
特别地,负极可包含Li4Ti5O12,它的嵌锂电位为1.55V级。
除了上面提到的构成正极和负极的物质之外,这些电极可进一步包含炭黑、纤维和粘结剂(纤维素聚合物、弹性体)。
正极和负极还可包含集流体,例如镍集流体,通常采用其上沉积有电极的膜形式。
因此,本发明的电池在每一个电池单元(电解槽,cell)中可包含:
-包含LiFePO4的正极和包含Li4Ti5O12的负极,由此在电池单元输出处产生1.9V的电压,或者
-包含LiFePO4的正极和包含TiO2的负极,由此在电池单元输出处产生1.85V的电压。
根据本发明,电解液的pH为至少14,优选大于15,并且是将锂盐如LiOH溶解在水中的结果。
除了溶解的锂盐,电解液可同样有利地由溶解强碱如NaOH和/或KOH而制得的,因此,电解液进一步包含苛性钠和/或苛性钾溶液。添加这种类型的强碱使得更容易获得至少等于14,优选大于15的pH值。
相对于在范围6至10的pH值下运行(分别产生2.686V和2.55V的氢释放电位值),在这样的pH值下运行显著降低了氢释放电位(对于pH值为14,估值为2.214V)。因此,更少地释放氢,大大降低了这种气体释放的内在危险。
同样由于降低了的氢释放电位,所以可以使用具有比现有技术更低的嵌入电位的负极,因而可以在电池单元输出处产生更高的电压。
液体电解液有利地通过聚合物膜支持(支撑),尤其是通过聚烯烃膜如聚乙烯或聚丙烯膜支持。
本发明的锂电池可通过包括以下步骤的方法以传统方式进行制备:
-制备包括正极、隔膜和负极的叠层,该正极和负极符合上文给出的定义,
-用如上所定义的电解液浸透所述隔膜。
接下来本发明将结合以下举例说明性和非限制性实施例进行描述。
附图说明
图1示出了一种表示作为物质中嵌锂比率x(%)的函数的所述物质的电位V(伏特)的典型曲线,点Pi表示所述物质中的嵌锂电位(对于x=50%)。
图2示出了使得以下实施例中制备的可充电电池充电的最初两个循环的恒定电流(1mA)充电曲线。
具体实施方式
实施例
这个实施例举例说明了一种锂电池的制备,该锂电池包括:
-包含LiFePO4的正极,
-包含Li4Ti5O12的负极,
-由4M的LiOH水溶液构成的液体电解液。
上面提到的制备包括:
a)制备电极,
b)制备液体电解液,
c)制备叠层以生成一个正极/电解液/负极叠层(结构)。
a)制备电极
用于制备电极的试剂是:
-用于正极的LiFePO4粉末和用于负极的Li4Ti5O12粉末,
-上等P炭黑粉末(来自Timcal),
-纤维(来自Toho Tenax GmbH),
-2%的CMC溶液(羧甲基纤维素,来自Aldrich),
-41%的NBR溶液(丁腈橡胶,来自PolymerLatex GmbH),
所述这些试剂以以下各个按质量计的比例存在:92%,2%,2%,2%和2%。
方案如下并且对于正极和负极是一样的:
-称重这些粉末和纤维,接着利用刮铲混合该组合物,
-称重并添加2%的CMC溶液,用刮铲混合,接着借助于扩散器搅拌大约20至30分钟,
-称重并添加41%的NBR溶液,接着借助于扩散器搅拌1至2分钟,
-用所得混合物涂覆微孔镍膜。
b)制备电解液
制备的溶液是4M锂盐碱性溶液(lithine solution)。
在量瓶中,将167.84g的LiOH溶解在1L的蒸馏水中,通过磁搅拌促进溶解。
该溶液的pH大于14。
c)制备叠层
可充电电池通过堆叠正极、隔膜和负极制得,隔膜是基于聚丙烯纤维的(来自Freudenberg)。
然后用之前制备的电解液真空浸渍所得组件。
该可充电电池在Arbin型循环工作台上进行电测试。
图2示出了对于以恒定电流(1mA)充电该可充电电池的最初两个循环的曲线,终止电压为2.4V。
在第二个循环结束时,充电容量为5mAh,相当于比该可充电电池的理论额定容量高60%。
Claims (10)
1.包括电池单元的锂电池,包括:
正极,
负极,以及
由锂盐水溶液构成的电解液,
其特征在于所述电解液的pH为至少14,所述正极的锂嵌入电位高于3.4V,并且所述负极的锂嵌入电位低于2.2V。
2.根据权利要求1所述的电池,其中,所述正极包含选自具有橄榄石结构且通式为LiMPO4的锂氧化物的物质,其中M是选自Fe、Mn、Ni和Co以及它们的混合物。
3.根据权利要求2所述的电池,其中,所述正极包含LiFePO4。
4.根据权利要求1至3中任一项所述的电池,其中,所述负极包含选自钛酸锂、氧化锂TiO2以及它们的混合物的物质。
5.根据权利要求4所述的电池,其中,所述负极包含Li4Ti5O12。
6.根据前述权利要求中任一项所述的电池,包括:
包含LiFePO4的正极和包含Li4Ti5O12的负极,或者
包含LiFePO4的正极和包含TiO2的负极。
7.根据前述权利要求中任一项所述的电池,其中,所述锂盐是LiOH。
8.根据前述权利要求中任一项所述的电池,其中,所述电解液进一步包含苛性钠和/或苛性钾水溶液。
9.根据前述权利要求中任一项所述的电池,其中,所述电解液由聚合物膜支持。
10.根据权利要求9所述的电池,其中,所述聚合物膜是聚烯烃。
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FR0757169A FR2920255B1 (fr) | 2007-08-24 | 2007-08-24 | Generateur electrochimique au lithium fonctionnant avec un electrolyte aqueux. |
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CN103311581B (zh) * | 2012-03-13 | 2017-09-05 | 三星Sdi株式会社 | 锂二次电池 |
CN105591104A (zh) * | 2016-01-21 | 2016-05-18 | 河南师范大学 | 一种用于碱性二次电池负极的磷酸铁锂电极及其制备方法 |
CN105591104B (zh) * | 2016-01-21 | 2019-10-18 | 河南师范大学 | 一种用于碱性二次电池负极的磷酸铁锂电极及其制备方法 |
CN107204468A (zh) * | 2016-03-16 | 2017-09-26 | 株式会社东芝 | 二次电池、电池包及车辆 |
CN107204455A (zh) * | 2016-03-16 | 2017-09-26 | 株式会社东芝 | 二次电池、电池包及车辆 |
CN107204455B (zh) * | 2016-03-16 | 2021-08-27 | 株式会社东芝 | 二次电池、电池包及车辆 |
CN109428126A (zh) * | 2017-08-30 | 2019-03-05 | 丰田自动车株式会社 | 水系电解液和水系锂离子二次电池 |
CN109509922A (zh) * | 2017-09-15 | 2019-03-22 | 丰田自动车株式会社 | 水系锂离子二次电池 |
CN109509921A (zh) * | 2017-09-15 | 2019-03-22 | 丰田自动车株式会社 | 水系锂离子二次电池 |
CN108808128A (zh) * | 2018-06-19 | 2018-11-13 | 湖南格兰博智能科技有限责任公司 | 水系锂离子电池及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
ATE528810T1 (de) | 2011-10-15 |
JP2009110931A (ja) | 2009-05-21 |
PL2034543T3 (pl) | 2012-02-29 |
EP2034543A1 (fr) | 2009-03-11 |
US20090087742A1 (en) | 2009-04-02 |
ES2373931T3 (es) | 2012-02-10 |
KR20090021096A (ko) | 2009-02-27 |
FR2920255B1 (fr) | 2009-11-13 |
JP5385565B2 (ja) | 2014-01-08 |
US8597828B2 (en) | 2013-12-03 |
EP2034543B1 (fr) | 2011-10-12 |
FR2920255A1 (fr) | 2009-02-27 |
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