CN1210832C - 锂聚合物二次电池 - Google Patents
锂聚合物二次电池 Download PDFInfo
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- CN1210832C CN1210832C CNB018163920A CN01816392A CN1210832C CN 1210832 C CN1210832 C CN 1210832C CN B018163920 A CNB018163920 A CN B018163920A CN 01816392 A CN01816392 A CN 01816392A CN 1210832 C CN1210832 C CN 1210832C
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- secondary battery
- polymer secondary
- active material
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- H—ELECTRICITY
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Abstract
提供具有将含可电化学嵌入/脱嵌锂的碳材料作为活性物质的负极,将含有锂的硫族化物作为活性物质的正极、及分别与正极和负极形成一体的二个聚合物电解质层的锂二次电池。聚合物电解质层含有保持非水电解液的离子传导性高分子基质,是通过将离子传导性高分子的前体单体与非水电解液的混合液,在负极与正极上使用不同的聚合引发剂进行交联聚合而制得。
Description
技术领域
本发明涉及使用离子传导性高分子的锂二次电池,更详言之,涉及具有将含可电化学嵌入/脱嵌锂的碳材料作为活性物质的负极、将含锂的硫族化物作为活性物质的正极、及配置于正极与负极之间并将非水电解液保持于离子传导性高分子基质中的聚合物电解质层的锂聚合物二次电池。
背景技术
因为锂二次电池的理论能量密度与其他电池相比非常高,且可小型轻量化,所以作为便携式电子设备等的电源进行了积极的研究、开发。特别是关于最近的便携式电子设备,随功能急剧的提升,电力消耗同时也急剧的增加,随此便对电源要求即便是高负荷也具有优越的放电特性。回应这些要求,有在维持习知采用非水电解液的电池(称锂离子蓄电池)的电池形态下,朝使用同时具有非水电解液与习知高分子隔板功能的聚合物电解质的电池方向进行研究。采用聚合物电解质的锂二次电池,具有可小型轻量化、薄型化,且电解液不泄漏等较大优点,颇受瞩目。
聚合物电解质是在离子传导性高分子的基质中保持非水电解液的电解质,是通过将离子传导性高分子的前体单体在非水电解液中施行交联聚合而制得。聚合是施行热聚合或光聚合,必须含有用于产生聚合引发物质的引发剂。但是,已知引发剂若在聚合后尚残留于聚合物电解质中的话,在重复充放电时将产生化学反应,对电池的负荷放电容量及循环特性等性能造成不良影响。
但是,由于为获得具有满足机械强度的凝胶状聚合物电解质而需要一定量的引发剂,所以在聚合后引发剂残留于聚合物电解质中实际上无法避免。
在日本特开平10-15848中,公开了将残留引发剂等利用加热或超音波而予以分解,以降低其浓度。但是,即便利用此方式,残留的引发剂实际上也不可能完全分解,如前所述的因引发剂而对电池性能不良影响的问题依然存在。
在日本特开平8-287890中,公开了当电池封口部、或正极端子与负极端子的绝缘部采用光硬化性树脂时,通过使用氧化膦系引发剂作为树脂的聚合引发剂,而提高封口部强度或正极与负极的绝缘性。但是,此方案与聚合物电解质性能的改善无关。
因此,本发明的目的在于回避或减轻残留引发剂对电池性能的不良影响。
发明的公开
本发明涉及锂聚合物二次电池,具有将可电化学嵌入/脱嵌锂的碳材料作为活性物质的负极、将含锂的硫族化物作为活性物质的正极、及分别与正极和负极形成一体的两个聚合物电解质层,其特征在于,该二个聚合物电解质层是非水电解液被保持在离子传导性高分子基质中,该基质通过在负极侧和正极侧使用不同的引发剂,进行交联聚合而成。
具体而言,在电池内,负极侧的引发剂优选耐还原性优良的化合物,而正极侧的引发剂则优选耐氧化性优良的化合物。这样就防止因为残留在负极侧的引发剂在初期充电时消耗锂离子,造成负极活性物质的锂取用不足之故,而无法获得高能量密度的情形发生。
再者,因为负极与正极的工作电位范围不同,所以在各自的电极工作电位范围中,最好在各电极侧采用可获得接近原本容量维持率的容量维持率的引发剂。由此便可避免或缓和引发剂对电池循环特性的不良影响。
附图的简单说明
图1是实施例1与2之本发明电池的循环特性与比较例1的电池的循环特性进行比较的图。
图2是实施例3与4之本发明电池的循环特性与比较例2和3的电池的循环特性进行比较的图。
实施本发明的最佳方式
本发明的电池可通过在预先准备的负极及正极上分别形成聚合物电解质层,并将二者重叠而制成,但并不仅限于此。
正极、负极基本上是将正极、负极活性质分别利用粘合剂予以固定化的活性物质层,形成于将成为集电体的金属箔上。作为将成为该集电体的金属箔材料,有如铝、不锈钢、钛、铜、镍等,但考虑电化学稳定性、延展性及经济性时,正极主要采用铝箔,而负极则主要采用铜箔。
另外,在本发明中,正极、负极集电体的形态虽主要表示为金属箔,但集电体的形态除金属箔之外,还可例举在网、多孔金属网、板条体、多孔体或树脂薄膜上被覆有电子导电材料的等,但并不仅限于此。
负极活性物质是可电化学嵌入/脱嵌锂的碳材料。其典型例子,有粒状(鳞片状、块状、纤维状、须状、球状、粉碎粒子状等)天然或人造石墨。也可采用将中间相碳微球、中间相沥青粉末、各向同性沥青粉末等进行石墨化所获得的人造石墨。
关于本发明的负极活性物质,如上述,更优选的碳材料可举例如表面上附着有非晶质碳的石墨粒子。此附着方法可通过将石墨粒子浸渍于焦油、沥青等煤系重质油、或重油等石油系重质油中,然后拉起,并加热至碳化温度以上的温度分解重质油,并且按照需要粉碎该碳材料而进行。通过此类处理,因为有效抑制在充电时的负极上发生的非水电解液与锂盐的分解反应,所以可改善充放电循环寿命,且可防止随此分解反应产生气体。
再者,本发明的碳材料中,影响BET法所测比表面积的细孔,将因源自重质油等的碳附着而被阻塞,比表面积为5m2/g以下(优选在1~5m2/g范围内)。比表面积若过大的话,因为与离子传导性高分子间的接触面积将增大,而容易引发副反应,所以不优选。
本发明中,当负极活性物质采用碳质材料时,作为正极所采用的正极活性物质,优选由Lia(A)b(B)cO2(其中,A为过渡金属元素的一种或二种以上的元素。B为由周期表IIIB、IVB及VB族非金属元素及半金属元素、碱土金属、Zn、Cu、Ti等金属元素中选择的一种或二种以上元素。a,b,c分别为0<a≤1.15、0.85≤b+c≤1.30、0<c)所示层状构造的复合氧化物、或含尖晶石构造的复合氧化物中至少选择其中一种。
有代表性的复合氧化物,可举例如LiCoO2、LiNiO2、LiCoxNi1-xO2(0<X<1)等。若采用这些的话,当负极活性物质采用碳质材料时,即便随碳质材料本身的充电、放电而产生电压变化(约1Vvs.Li/Li+),也可显示足够的实用工作电压,以及当负极活性物质采用碳质材料时,具有电池充电、放电反应所必需的Li离子从组装电池前,便已经以如LiCoO2、LiNiO2等形式含有的优点。
在制作正极、负极时,如果需要,将石墨、碳黑、乙炔碳黑、凯金碳黑(ケツチエンブラツク)、碳纤维、导电性金属氧化物等化学稳定的导电材料与活性物质组合使用,可增强电子传导。
粘合剂从具有化学稳定性且溶解于适当溶剂中,但不受非水电解液侵袭的热塑性树脂中选择。这样的热塑性树脂有多种已为众所周知,但最好采用如选择性地溶解于N-甲基-2-吡咯烷酮(NMP)中的聚偏氟乙烯(PVDF)。
其他可使用的热塑性树脂的具体例包括丙烯腈、甲基丙烯腈、氟化乙烯、氯丁二烯、乙烯基吡啶及其衍生物、偏二氯乙烯、乙烯、丙烯、环二烯(如环戊二烯、1,3-环己二烯等)等的聚合物及共聚物。代替溶液,也可改用粘合剂树脂的分散液。
电极是通过将活性物质与必要时的导电材料,利用粘合剂树脂溶液进行混练,而制成糊剂,并采用适当的涂布机将其在金属箔上涂布均匀厚度,干燥后经冲压而制成。活性物质层的粘合剂比例,应为必要的最低限,一般在1~15重量%左右便足够。当使用时,导电材料的量一般为活性物质层的2~15重量%。
这样所制得的各电极与活性物质层形成一体,并形成各自的聚合物电解质层。这些层是在离子传导性高分子基质中浸渍或保持含有锂盐的非水电解液。这样的层在宏观上为固体状态,但在微观上则属盐溶液形成连续相,并且比未采用溶剂的高分子固体电解质具有更高的离子传导率。此层是通过将基质高分子的单体以与含有锂盐的非水电解液的混合物的形式,经热聚合、光聚合等进行聚合而制得。
为此而可使用的单体成分,必须含有聚醚片段,且为使聚合物形成三维交联的凝胶结构,在相关聚合部位必需为多官能团。典型的此类单体是将聚醚多醇的末端羟基利用丙烯酸或甲基丙烯酸(总称为(甲基)丙烯酸)进行酯化后的单体。众所周知的,聚醚多醇是以乙二醇、丙三醇、三羟甲基丙烷等多元醇为起始物,将其单独与环氧乙烷(EO)、或与EO及环氧丙烷(PO)加聚而得到。也可单独将多官能聚醚多醇聚(甲基)丙烯酸酯,或与单官能团聚醚多醇(甲基)丙烯酸酯一起进行共聚。典型的多官能团及单官能团单体,可以用下面通式表示。
(R1为氢原子或甲基;A1,A2,A3为至少具有3个或3个以上环氧乙烷单位(EO),且选择性地含有环氧丙烷单位(PO)聚氧化烯链;PO与EO的数量为PO/EO在0~5范围内,且EO+PO≥35)。
(R2、R3为氢原子或甲基;A4为至少具有3个或3个以上环氧乙烷单位(EO),且选择性地含有环氧丙烷单位(PO)的聚氧化烯链;PO与EO的数量为PO/EO在0~5范围内,且EO+PO≥10)。
(R4为低级烷基;R5为氢原子或甲基;A5为至少具有3个或3个以上环氧乙烷单位(EO),且选择性地含有环氧丙烷单位(PO)聚氧化烯链;PO与EO的数量是PO/EO在0~5范围内,且EO+PO≥3)。
非水电解液是在非质子性的极性有机溶剂中溶解有锂盐的溶液。作为溶质的锂盐,可举例如LiClO4、LiBF4、LiAsF6、LiPF6、LiI、LiBr、LiCF3SO3、LiCF3CO2、LiNC(SO2CF3)2、LiN(COCF3)2、LiC(SO2CF3)3、LiSCN及它们的组合,但并不仅限于此。
上述有机溶剂的非限定例如:碳酸乙烯酯(EC)、碳酸丙烯酯(PC)等环状碳酸酯类;碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)等链状碳酸酯类;γ-丁内酯(GBL)等内酯类;丙酸甲酯、丙酸乙酯等酯类;四氢呋喃及其衍生物、1,3-二氧六环、1,2-二甲氧基乙烷、甲基二甘醇二甲醚等醚类;乙腈、苯甲腈等腈类;间二氧丙酸及衍生物;环丁砜及其衍生物;及它们的混合物。
为抑制在电极,特别是在将石墨系碳材料作为活性物质的负极上所形成的聚合物电解质的非水电解液中与石墨系碳材料间的副反应,适合此目的的有机溶剂优选是以EC为主体,并在其中混合选自PC、GBL、EMC、DEC及DMC中的其他溶剂的混合溶剂体系。譬如在EC为2~50重量%的上述混合溶剂中溶解了锂盐3~35重量%的非水电解液,即便低温下也可获得足够的离子传导度,所以优选。
单体与含有锂盐的非水电解液的配合比率,对于聚合后混合物形成交联凝胶状聚合物电解质层,且在其中非水电解液形成连续相是足够的,但随时间变化,无电解液分离并渗出程度的过剩现象。这一般可通过将单体/电解液的比设定在30/70~2/98范围,优选设定在20/80~2/98范围内而实现。
聚合物电解质层中可使用多孔基材作为支撑材料。此类基材有如聚丙烯、聚乙烯、聚酯等在非水电解液中呈现化学稳定的高分子微多孔膜,或这些高分子纤维的薄片(纸、无纺布等)。这些基材的透气度为1~500秒/cm3,且将聚合物电解质保持在基材:聚合物电解质的重量比为91∶9~50∶50的比率,可获得机械强度与离子传导度的适当平衡,故属优选情况。
当不使用基材便形成与电极一体化的聚合物电解质时,在正负极的各活性物质层上流延含有单体的非水电解液,使聚合后的聚合物电解质位于内侧,再将正极与负极予以贴合便可。
当采用基材时,在任一电极上重叠基材,然后流延含有单体的非水电解液,并施行聚合,而形成基材与电极一体化的聚合物电解质层。按照上述相同方法将其与形成有一体化聚合物电解质层的另一电极相互贴合后,便可作成电池。此方法不仅便利,且可靠形成电极与所用基材形成一体化的聚合物电解质,故属优选情况。
离子传导性高分子前体(单体)单体与含有锂盐的非水电解液的混合液,当根据聚合方法而施行热聚合时,含有过氧化系或偶氮系引发剂,而当施行光聚合(紫外线硬化)时,含有光聚合引发剂譬如苯乙酮系、二苯甲酮系、膦系等引发剂。聚合引发剂的量可在100~1000ppm范围内,基于上述的理由,最好不要添加超过必要量以上的过多量。
本发明中,用于形成聚合物电解质而所使用的引发剂,根据在负极侧与正极侧于各自电极中所发生的电化学反应及工作电位范围,而选择不同的种类。
光聚合(紫外线聚合)可在常温下短时间内完成硬化且可连续式硬化,因此选取光聚合引发剂的例子,可依下述基准进行选择。
如前述,若考虑在负极与正极上所发生的电化学反应,优选负极选择耐还原性佳,而正极则选择耐氧化性佳的引发剂。特定的引发剂到底是耐还原性或耐氧化性,只要观其化学结构便可推敲得知。譬如属氧化膦的双(2,4,6-三甲基苯甲酰基)苯基氧化膦,因为容易还原为相对应的膦,所以并不适用于负极,可推测适用于正极。
此外,所提供的引发剂到底适用于哪一电极,可经由实验确认。具体地,使用实际的正极与负极,并使用适当的参比电极作为各电极的对电极,代替聚合物电解质改用非水电解液组装电池,向电解液添加1000ppm左右的引发剂,利用循环伏安法(CV)测定,测定氧化还原电流的流动电位,当使用于负极时,负极的工作电位范围在0~1.2V范围内,而当使用于正极时,因活性物质而变动,但选择譬如在2.5~4.2V范围内流动的氧化还原电流少的化合物。在CV测定中,因为通过其电极有效面积的变动等定量电流值较为困难,所以仅能进行相对比较。因此必须进行多次实验。
更简单的方法,是代替CV测量,进行采用上述实验用电池的单电极试验,然后再与未含引发剂的体系比较循环特性。在此试验中,在各电极的工作电位范围内,重复进行如100次循环的充放电,此时的容量维持率只要表现为未含引发剂体系的80%以上,优选90%以上,更优选95%以上,便可判断此引发剂对电池性能几乎无不良影响。
本发明者施行此种单电极试验,确认如双(2,4,6-三甲基苯甲酰基)苯基氧化膦或双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦等氧化膦系引发剂系适用于正极,而2,2-二甲氧基-2-苯基苯乙酮等苯乙酮系引发剂则适用于负极。
氧化膦系聚合引发剂的光吸收波长区域比其他引发剂横跨更广范围,利用高波长吸收带可将电解质聚合物或凝胶表面层予以硬化,利用低波长吸收带可将其深部予以硬化。所以,当将离子传导性高分子的前体在电极和/或隔板基材上施行硬化时,不仅渗透入表面层的前体,而且渗透入多孔电极材料及隔板基材细孔内部的前体,也将有效硬化。因此可将电极或隔板内所残留的前体单体或残留引发剂的水平,降低至对电池性能无实质不良影响的程度。
实际上,因为引发剂绝少会残留1000ppm高水平,因此在含过剩引发剂的体系中,若容量维持率显示出未含引发剂体系的容量维持率的80%以上的话,即便实际的电池也可获得足够的循环特性。
显示出足够循环特性的其他负极引发剂,可举例如苯偶姻异丙醚(ベンヅイソブロピルエ-テル)等苯偶姻系引发剂、2,2-二乙氧基-2-苯基苯乙酮、1-羟基环己基苯基酮、二苯甲酮、二乙氧基二苯甲酮等苯基酮系引发剂。
其他已知有芳基重氮鎓盐、二芳基碘鎓盐、三芳基锍盐等光聚合引发剂,利用上述单电极试验便可轻易的确认其适合性。另外,即便不依赖上述CV测定或单电极试验,也可适当的选择适用于各电极的引发剂。
实施例
以下实施例乃以验证为目的,并无限定之意。
实施例1
1)负极的制作
将人造石墨(d002=0.336、平均粒径12μm、R值=0.15、比表面积4m2/g)100重量份装入乳钵中,并添加将粘合剂聚偏氟乙烯(PVDF)9重量份溶解于适量N-甲基-2-吡咯烷酮(NMP)中的溶液,进行混练分散而获得糊剂。将此糊剂涂布于厚度20μm的铜箔上,经干燥后冲压。电极尺寸为3.5×3cm(涂布部分3×3cm),在无涂布部分熔接镍箔(50μm)的导线,制成厚度85μm的负极。
2)负极侧聚合物电解质层的形成
在碳酸乙烯酯(EC)与碳酸甲乙酯(EMC)体积比为1∶1的混合溶剂中,将LiPF6溶解成1mol/l浓度,调制成非水电解液。
在90重量份此非水电解液中,混合下式:
(A1,A2,A3是分别含3个或3个以上EO单位与1个或1个以上PO单位,PO/EO=0.25的聚氧化烯链)所示的分子量为7500~9000三官能团聚醚多醇聚丙烯酸酯单体10重量份,而获得单体的非水电解液溶液。在负极侧溶液中,添加2,2-二甲氧基-2-苯基苯乙酮(DMPA)1000ppm作为引发剂。
其次,将上述获得的负极,与当作电解质层支撑基材用的聚酯无纺布(厚度25μm、透气度380秒/cc),分别浸渍上述非水电解液中的单体溶液。
然后,在各经单体溶液浸渍过的负极上叠层基材,并照射波长365nm、强度30mW/cm2的紫外线3分钟,而形成与负极一体化的凝胶状聚合物电解质层。
3)正极的制作
将平均粒径7μm的LiCoO2100重量份,与作为导电材料的乙炔碳黑5重量份装入乳钵中,并添加将粘合剂PVDF5重量份溶解于适量NMP中的溶液,进行混练分散而获得糊剂。将此糊剂涂布于厚度20μm的铝箔上,经干燥后冲压。电极尺寸为3.5×3cm(涂布部分3×3cm),在无涂布部分熔接铝箔(50μm)的导线,制成厚度80μm的正极。
4)正极侧聚合物电解质层的形成
在正极侧,采用在负极侧所使用的单体/非水电解液混合液中添加作为引发剂的双(2,4,6-三甲基苯甲酰基)苯基氧化膦(BTBPPO)500ppm的溶液。将此溶液浸渍于上述所获得的正极中,并从其上面照射波长365nm、强度30mW/cm2的紫外线3分钟,而形成与正极一体化的凝胶状聚合物电解质层。
5)电池的组装
将上述获得的与聚合物电解质层一体化的负极与正极以聚合物电解质层为内侧相互贴合后,完成电池。
6)用于调查引发剂影响的单电极试验
对依上述方法所制作的负极,采用锂金属作为对电极(参比电极),并将在未含前体单体的上述非水电解液中添加有1000ppm DMPA的溶液作为电解液,进行负极的单电极试验。电流值设定为30mA/g,利用电位范围1.5~0.02V,测定重复100次循环恒定电流充放电时的容量维持率。经数值为相同条件下未含引发剂体系的容量维持率的90%以上。
对正极也采用锂金属作为对电极(参比电极),并将在未含前体单体的上述非水电解液中添加有1000ppm BTBPPO的溶液作为电解液,进行正极的单电极试验。电流值设定为27.4A/g,利用电位范围4.2~2.75V,测定重复100次循环恒定电流充放电时的容量维持率。结果是,此数值为相同条件下未含引发剂体系的容量维持率的90%以上。
比较例1
对于正极侧聚合物电解质的形成,除使用与添加有DMPA1000ppm的负极侧相同的单体/非水电解液之外,其余均同实施例1,制作了电池。在正极单电极试验中,与无添加引发剂的体系相比,容量维持率为80%以下。
由实施例1与比较例1的结果得知,通过在正极侧的聚合引发剂中采用氧化膦系引发剂BTBPPO,可提高正极内部的前体单体硬化率,降低残留单体及残留引发剂的水平,减少电池的循环恶化。
实施例2
除代替DMPA 1000ppm而改用1-羟基环己基苯基酮(HCPK)500ppm作为负极侧的引发剂之外,其余均同实施例1,制作了电池。在负极单电极试验中,与无添加引发剂的体系相比,容量维持率为90%以上。
实施例3
除采用在石墨粒子表面上附着有非晶碳的比表面积2m2/g、粒径15μm的碳材料作为负极活性物质之外,其余均同实施例2,制作了电池。在负极单电极试验中,与实施例2的负极同样与无添加引发剂的体系进行比较,容量维持率为90%以上。
实施例4
除采用利用中间相碳微球的石墨化而获得的比表面积1.8m2/g、粒径15μm的人造石墨作为负极活性物质之外,其余同实施例2,制作了电池。在负极单电极试验中,同实施例2的负极一样与无添加引发剂的体系进行比较,容量维持率为90%以上。
实施例5
除在正极侧聚合物电解质的形成中添加双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦1000ppm之外,其余同实施例1,制作了电池。在正极单电极试验中,显示出无添加引发剂的体系的容量维持率的90%以上的数值。
由实施例5与比较例1的结果得知,通过使用实施例5所使用的氧化膦系引发剂作为正极侧的聚合引发剂,可提高正极内部的前体单体硬化率,降低残留单体及残留引发剂的水平,减少电池的循环恶化。
比较例2
除采用比表面积10m2/g、粒径15μm的人造石墨作为负极活性物质之外,其余同比较例1(正极侧与负极侧的引发剂均为DMPA1000ppm),制作了电池。在单电极试验中,与无添加引发剂的体系比较,正极容量维持率为90%以上,但负极容量维持率为85%以下。
比较例3
除将正极活性物质的组成变更为相对于LiCoO2100重量份,乙炔碳黑为15重量份、PVDF为10重量份之外,其余同比较例2,制作了电池。在单电极试验中,与无添加引发剂的体系比较,正极与负极容量维持率均为85%以下。
电池性能评价
将在实施例与比较例中所获得的电池以恒定电流4.0mA充电至电池电压为4.1V为止,在到达4.1V后,利用恒定电流充电10小时。然后,以恒定电流4.0mA放电至电池电压为2.75V为止,重复该充放电,测定初期3个循环,及之后每20个循环的放电容量,算出以初期容量为1时的容量维持率。实施例1,2与比较例1的电池的结果如图1所示,实施例3,4与比较例2,3的电池的结果如图2所示。
如图1与图2所示,通过在正极侧与负极侧中分别选择适当的不同引发剂,可改善与初期容量相比的容量维持率。
Claims (8)
1.一种锂聚合物二次电池,具有:具有可电化学嵌入/脱嵌锂的碳材料的活性物质层的负极;具有含有锂的硫族化物的活性物质层的正极;及分别与正极和负极形成一体的二个聚合物电解质层,其特征在于,该二个聚合物电解质层是非水电解液被保持在离子传导性高分子基质中,该基质通过在负极侧和正极侧使用不同的引发剂,进行交联聚合而成。
2.如权利要求1所述的锂聚合物二次电池,其中正极侧的引发剂为氧化膦化合物。
3.如权利要求1所述的锂聚合物二次电池,其中不同的引发剂都是光聚合引发剂。
4.如权利要求1所述的锂聚合物二次电池,其中在循环伏安法中,负极侧的引发剂在0~1.2V的电位范围内不显示氧化还原电流。
5.如权利要求1所述的锂聚合物二次电池,其中在循环伏安法中,正极侧的引发剂在2.5~4.2V的电位范围内不显示氧化还原电流。
6.如权利要求1所述的锂聚合物二次电池,其中离子传导性高分子基质的前体单体,是在高分子链中含有环氧乙烷单位与任意环氧丙烷单位的多官能团聚醚多醇的聚丙烯酸酯或聚甲基丙烯酸酯单体、或该多官能团单体与对应的单官能团单体的混合物。
7.如权利要求1~2的任一项所述的锂聚合物二次电池,其中负极活性物质是比表面积为5m2/g以下的碳材料。
8.如权利要求1所述的锂聚合物二次电池,其中负极活性物质是表面上附着有低结晶性碳材料的石墨。
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WO2002029921A1 (en) | 2002-04-11 |
JPWO2002029921A1 (ja) | 2004-02-19 |
KR100772564B1 (ko) | 2007-11-02 |
US20040043296A1 (en) | 2004-03-04 |
KR20030051672A (ko) | 2003-06-25 |
CN1466799A (zh) | 2004-01-07 |
TW518787B (en) | 2003-01-21 |
JP4431938B2 (ja) | 2010-03-17 |
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