CN1328818C - 混合型水系锂离子电池 - Google Patents

混合型水系锂离子电池 Download PDF

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CN1328818C
CN1328818C CNB2005100252696A CN200510025269A CN1328818C CN 1328818 C CN1328818 C CN 1328818C CN B2005100252696 A CNB2005100252696 A CN B2005100252696A CN 200510025269 A CN200510025269 A CN 200510025269A CN 1328818 C CN1328818 C CN 1328818C
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夏永姚
王永刚
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Beijing Enli Power Technology Co ltd
Enpower Energy Technology Co ltd
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Fudan University
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Abstract

本发明涉及一种新型高性能的混合型水系锂离子电池。本发明将锂离子嵌入-脱嵌机制与电化学超电容器由离子吸附产生的双电层机制协调组合于一个储能器件中。本发明中，正极采用含有锂离子嵌入化合物电极材料，负极采用高比表面的活性炭、介孔碳或碳纳米管等电极材料，电解液采用含锂离子的水系电解质。本发明具有非常长的循环寿命，是普通二次电池的十倍以上，并且具有大功率、安全、低成本和无环境污染的特点，特别适合于作为电动汽车的理想动力电池。

Description

混合型水系锂离子电池
技术领域
本发明属电池和电容器技术领域，具体涉及一种新型的高性能混合型水系锂离子电池。
背景技术
随着经济不断发展，必然引起石油、煤炭等自然资源枯竭、环境污染及地球温室效应的加重。人类必须把握经济增长、环境保护和能源供给这三位一体的“三E”之间的平衡关系。现在世界上能源每年的消费量折算成石油约为80亿吨，其中90％为化石燃料。按现在的消费速度，大约在100年至200年后便会枯竭。新能源、节能技术及环保技术的综合高效开发和利用，已成为十分紧迫的课题。发展电动汽车势在必行，世界各国积极开发电动汽车，现在作为电动汽车的动力电源主要有二次电池、电化学超电容器和燃料电池等，其中二次电池包括铅酸蓄电池、镍氢电池和锂离子电池。但从成本、安全性、电池性能及环境影响等综合面来衡量，上述电源中没有一种电源能满足电动汽车动力电源的要求。铅酸蓄电池、镍氢、锂离子等二次电池虽有较大的能量密度，但循环寿命较短，大电流充放电性能较差；并且铅酸电池比能量低，铅有毒性；现有锂离子电池由于使用有机电解液存在安全性问题。现有电化学双层电容器虽有长寿命，高输出功率，但能量密度偏小。燃料电池成本高而且输出功率(W/Kg)较小，不能满足起动、加速和爬坡的要求等问题。为解决现有电源的上述问题，加拿大Moli Energy公司(国际专利号W095/21470)提出了水系锂离子电池，基本概念与现有的有机体系锂离子电池相似，规定正负极均采用锂离子嵌入化合物，如LiMn2O4、VO2、LiV3O8、FeOOH等。但在水溶液中，当锂离子嵌入脱嵌过程中达到一定电位时会发生析氢、析氧反应，很难找到只发生锂离子嵌入脱嵌而不发生析氢、析氧的电极对材料。而且专利中提到的负极材料循环性能较差，即水系锂离子电池的循环性很差，往往不能超过几十次。
发明内容
本发明的目的在于提出一种循环寿命长、功率大、成本低，而且无环境污染的混合型水系锂离子电池。
本发明提出的水系锂离子电池，由正极膜、负极膜、介于正极膜和负极膜之间的隔膜以及含有阴阳离子并具有离子电导性的电解质组成。其中，所述正极膜采用锂离子可以嵌入和脱嵌的材料，例如可采用过渡金属的氧化物、硫化物、磷化物或氯化物等嵌入化合物。所述负极膜采用含有离子可以吸附和脱附的材料，例如可采用具有大比表面的活性炭、介孔碳或碳纳米管等多孔结构材料，也可采用上述具有多孔结构的材料和其它有准电容性能的材料的混合材料，其它有准电容性能的材料包括金属氧化物、锂离子的嵌入化合物、有机导电高分子材料或含有自由基的材料等。所述含有阴阳离子的电解质为含锂离子的水溶液。
本发明中，电解质形态可以是溶液、凝胶状。电解液为含有上述阳离子的硫酸盐、硝酸盐、磷酸盐、醋酸盐、氯化物或氢氧化物等的一种或几种的混合水溶液。其为浓度为2摩尔/升-10摩尔/升，并且，电解液的pH值≥7。
本发明中能提供离子传递的含有阴阳离子、且具有离子电导性能的电解质溶液，具体可以是Li2SO4、LiCl、LiNO3、LiOH等。为提高离子电导率和离子传递速度，还可加入适量支持电解质，如KCl、K2SO4等。电解质中还可加入适量填充剂(如多孔SiO2等)，制成凝胶状的电解质。
本发明中，电解质中的阳离子包括碱金属中的锂离子，或者锂离子和其他碱金属、碱土金属、稀土金属、铝或锌的一种或几种离子的混合物。
本发明中，正极膜、负极膜的集电体材料可以是金属镍、铝、不锈钢、钛等的多孔、网状或薄膜材料。
本发明中，考虑到水溶液的析氧问题，用作正极膜的所述嵌入化合物可采用锰、镍、钴、铁或钒的氧化物、硫化物、磷化物或氯化物，例如，LiMn2O4、LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiNiO2、LiFePO4、以及上述嵌入化合物的其他金属元素M掺杂的材料，掺杂元素M为Li、Mg、Cr、Al、Co、Ni、Mn、Al、Zn、Cu、La的一种或几种，其掺杂量相对于本体金属元素的摩尔比小于等于50％。考虑到成本和安全性，采用LiMn2O4及其他金属元素M掺杂的LiMxMn2-xO4(M为上述元素中的一种或几种，摩尔比X通常≤0.5)较为适合。所述正极膜材料中还可加入适量(重量≤50％)的电子导电剂(如石墨，碳黑、乙炔黑等)和粘结剂(重量≤20％，如聚四乙烯、水溶性橡胶，纤维素等)。上述混合材料可制成一定黏度的浆料。把该浆料涂在电极集电体上，得到正极电极膜。
本发明中，负极膜采用活性炭、介孔碳或纳米碳管等，比表面可在1000m2/g以上。为提高电极的电子导电性，也可加入适量上述的电子导电剂。将上述混合材料(炭材料、电子导电剂和粘结剂)，制成浆料，涂在电极集电体上，得到负极电极膜。考虑到负极采用单一的高比表面的活性炭、介孔碳或纳米碳管材料，电极的比能量密度较低，在负极中也可加入适量(≤50％)具有准电容性能的材料，例如：LiMn2O4、VO2、LiV3O8、FeOOH或聚苯胺等，这些材料的电位一般在2.5～3V之间。
本发明中，正、负电极之间的隔膜可采用现有水系二次电池用的多孔隔膜，如铅酸蓄电池用的玻璃纤维隔膜，镍氢电池用的多孔聚苯烯隔膜。
本发明电池的形状可以做成圆筒型、方型和钮扣型等。其外壳可以采用有机塑料、金属材料或金属有机材料的复合材料等。
本发明提出的锂离子电池的基本工作原理如图1所示：对装成的电池，首先必须进行充电。充电过程中，锂离子从正极脱出，通过电解液，锂离子吸附在活性碳等材料做成的负极。放电过程中，锂离子从负极上脱附，通过电解液，锂离子嵌入正极。充放电过程，只涉及锂离子在两电极间的转移。因此称本发明电池为混合型水系锂离子电池。混合型水系锂离子电池不同于混合型电化学超电容器，如C/NiOOH，Li4Ti5O12/C等体系，这些体系在电容器充放过程中，涉及到阴阳离子同时在电极上反应，往往造成电解液的贫乏。
本发明采用活性炭等材料作负极，负极主要是利用锂离子在电极上的静电吸附机制，而非嵌入反应，一方面可以通过简单调节正负极活性材料的比，调节负极的电位，使得电池在充放电过程不发生析氢、析氧反应；另一方面锂离子在负极上的吸附、脱附可逆性好，循环性能非常好。混合型水系锂离子电池平均工作电压为1.3V，并且具有非常长的循环寿命，是普通二次电池的十倍以上，克服了以往专利中水系锂离子电池的循环性差的问题。新型混合型水系锂离子电池具有长循环寿命，大功率，安全、低成本和无环境污染的特点。特别适合于作为电动汽车的动力电源。
本发明的混合型水系锂离子放电池是二次电池(包括铅酸蓄电池，镍氢电池和锂离子电池)和电化学超电容器的两者技术的有机结合，因此适用于二次电池和电化学超电容器的制备技术均适用于混合型水系锂离子电池的制备，包括电极的制备工艺(涂膜、压膜、拉浆等)，电极的形状(卷绕式、层叠式和螺旋式等)，以及灌液和封口等工艺。
附图说明
图1为混合型水系锂离子电池的基本工作原理图。
图2采用的圆筒型电池的结构。
图3圆筒混合型水系锂离子电池的充放电曲线。
具体实施方式
下通过实施例对本发明作进一步的说明。
实施例1：
正极材料采用商业锂离子电池用尖晶石型LiMn2O4。正极组成按LiMn2O4∶碳黑∶粘结剂＝80∶10∶10的重量比例混合浆料，均匀涂覆于镍网集流体上，烘干后压制成电极。负极材料采用商用活性炭，浆料配比按照活性炭∶导电剂∶粘结剂＝85∶5∶10混浆，然后均匀涂于镍网集流体上，烘干后压制成电极。该实施例中，正极材料实际容量为80mAh/g，负极为40mAh/g，正极的单面涂布量为5mg/cm2，负极为10mh/cm2。然后将两种电极按照规格裁切，配对组装成2#电池(直径为14mm*高为50mm)，所采用的隔膜为商用镍氢电池的隔膜，电解液为2M的Li2SO4溶液，电池的结构如图2所示。放电曲线如图3所示，在0V-1.8V工作区间，放电电流为1C容量为200mAh，平均工作电压为1.3V，10C充放容量维持在190mAh，经过10000次循环后，容量保持率可有90％(详见表1)。
实施例2：
正极材料采用商业锂离子电池用LiCoO2，其余同实施例1，按照实施例1中的步骤和条件进行混浆、涂布电极和电池制备。正极材料实际容量为120mAh/g，负极为40mAh/g，正极的单面涂布量为3.4mg/cm2，负极为10mg/cm2。在0V-1.8V工作区间，放电电流为2C容量为250mAh，平均工作电压为1.2V，10C充放容量维持在240mAh经过10000次循环后，容量保持率可有87％(详见表1)。
实施例3：
正极材料采用商业锂离子电池用LiCo1/3Ni1/3Mn1/3O2，其余同实施例1，按照实施例1中的步骤和条件进行混浆、涂布电极和电池制备。正极材料实际容量为100mAh/g，负极为40mAh/g，正极的单面涂布量为4mg/cm2，负极为10mg/cm2。在0V-1.8V工作区间，放电电流为1C容量为230mAh，平均工作电压为1.0V，10C充放容量维持在210mAh，经过10000次循环后，容量保持率可有92％(详见表1)。
实施例4：
正极材料采用商业锂离子电池掺杂尖晶石型LiMg0.2Mn1.8O4，其余同实施例1，按照实施例1中的步骤和条件进行混浆、涂布电极和电池制备。正极材料实际容量为78mAh/g，负极为40mAh/g，正极的单面涂布量为5.5mg/cm2，负极为10mg/cm2。在0V-1.8V工作区间，放电电流为1C容量为190mAh，平均工作电压为1.3V，10C充放容量维持在185mAh，经过10000次循环后，容量保持率可有91％(详见表1)。
实施例5：
正极材料采用商业锂离子电池用LiMn2O4。负极采用的是商用活性炭与LiV3O8的混合材料(两者质量比为2∶1)，按照实施例1中的步骤和条件进行混浆、涂布电极和电池制备。正极材料实际容量为80mAh/g，负极为80mAh/g，正极的单面涂布量为10mg/cm2，负极为10mg/cm2。在0V-1.8V工作区间，放电电流为2C容量为300mAh，，平均工作电压为1.2V，20C充放容量维持在250mAh，经过10000次循环后，容量保持率可有80％(详见表1)。
实施例6：
正极材料均采用商业用活性炭，按照实施例1中的步骤和条件进行混浆、涂布电极和电池制备。正极材料实际容量为40mAh/g，负极为40mAh/g，正极的单面涂布量为10mg/cm2，负极为10mg/cm2。在0V-1.8V工作区间，放电电流为1C容量为100mAh，平均工作电压为0.5V，10C充放容量维持在100mAh，经过10000次循环后，容量保持率可有95％(详见表1)。
表1.采用不同正负极材料制备的混合型水系锂离子电池的性能比较。
平均工作电压V     容量mAh(1C) 容量mAh(10C) 容量保持率(10000次后)
 实施例1C/LiMn2O4 1.3 200 190 90％
 实施例2C/LiCoO2 1.2 250 240 87％
 实施例3C/LiCo1/3Ni1/3Mn1/3O2 1.0 230 210 92％
 实施例4C/LiMg0.2Mn1.8O4 1.3 190 185 91％
 实施例5(AC+LiV3O8)/LiMn2O4 1.2 300 250 80％
 实施例6AC/AC 0.5 100 100 95％

Claims (9)

1、一种混合型水系锂离子电池，由正极膜、负极膜、介于两者之间的隔膜及含有阴阳离子并具有离子导电性的电解质组成，其特征在于所述正极膜采用锂离子嵌入化合物，该锂离子嵌入化合物为过渡金属的氧化物、硫化物、磷化物或氯化物；所述负极膜采用多孔结构材料活性炭、介孔碳或碳纳米管，电解质为含锂离子的水溶液。
2、根据权利要求1所述的电池，其特征在于所述电解质为硫酸盐、硝酸盐、磷酸盐、醋酸盐、氯化物或氢氧化物的一种或几种的混合水溶液，其浓度为2摩尔/升-10摩尔/升。
3、根据权利要求1所述的电池，其特征在于所述电解质，其阳离子包括碱金属中的锂离子，或者该锂离子和碱土金属、稀土金属、铝或锌的一种或几种离子的混合物。
4、根据权利要求1所述的电池，其特征在于所述过渡金属为锰、镍、钴、铁或钒。
5、根据权利要求1所述的电池，其特征在于所述嵌入化合物为LiMn2O4、LiCoO2、LiCo1/3Ni1/3Mn1/3O2、LiNiO2或LiFePO4，以及上述嵌入化合物中掺杂与该嵌入化合物所含金属元素不同的其他金属元素M的材料，该掺杂元素M为Li、Mg、Cr、Al、Co、Ni、Mn、Al、Zn、Cu、La的一种或几种。
6、根据权利要求1所述的电池，其特征在于所述正极膜还加入有适量导电剂和粘结剂。
7、根据权利要求1所述的电池，其特征在于所述负极膜还加入有适量导电剂和粘结剂。
8、根据权利要求1所述的电池，其特征在于所述负极膜还加入有适量准电容性能材料：LiMn2O4、VO2、LiV3O8、FeOOH或聚苯胺。
9、根据权利要求1所述的电池，其特征在于所述电解质为Li2SO4、LiCl、LiNO3、LiOH的水溶液。
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