CN111971844A - 非水电解质二次电池 - Google Patents
非水电解质二次电池 Download PDFInfo
- Publication number
- CN111971844A CN111971844A CN201980025446.0A CN201980025446A CN111971844A CN 111971844 A CN111971844 A CN 111971844A CN 201980025446 A CN201980025446 A CN 201980025446A CN 111971844 A CN111971844 A CN 111971844A
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- CN
- China
- Prior art keywords
- nonaqueous electrolyte
- negative electrode
- graphite
- secondary battery
- electrolyte secondary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 84
- -1 cyclic carboxylic acid anhydride Chemical class 0.000 claims abstract description 27
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 55
- 239000010439 graphite Substances 0.000 claims description 55
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical group O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007770 graphite material Substances 0.000 abstract description 4
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- 239000010410 layer Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
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- 239000007773 negative electrode material Substances 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 13
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- 238000000576 coating method Methods 0.000 description 11
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Abstract
本发明的一个方式的非水电解质二次电池具备正极、负极和非水电解质,所述负极含有BET比表面积为2m2/g以下的石墨,所述非水电解质含有下述式(1)或式(2)所示的环状羧酸酐。式(1)中,n表示0、1或2,R1~R4分别独立地表示氢原子、烷基、烯基或芳基。式(2)中,R5~R8分别独立地表示氢原子、烷基、烯基或芳基。
Description
技术领域
本发明涉及非水电解质二次电池。
背景技术
近年来,作为高输出、高能量密度的二次电池,广泛使用了具备正极、负极和非水电解质并使锂离子在正极与负极之间移动而进行充放电的非水电解质二次电池。
例如,专利文献1中公开了一种石墨颗粒以及含有该石墨颗粒的锂二次电池用负极,石墨颗粒的比表面积为1.0~3.0m2/g,其通过制造混合物颗粒并将其焙烧/石墨化来制造,上述混合物颗粒是含有可石墨化的骨料或石墨、以及可石墨化的粘结剂的混合物的粉末且被施加了焙烧/石墨化工序中彼此不融合的处理。
现有技术文献
专利文献
专利文献1:日本特开2013-182807号公报
发明内容
发明要解决的问题
专利文献1中记载了,通过在负极使用比表面积低的石墨,从而充放电循环特性得以改善。但是,与使用以往石墨的情况相比,使用比表面积低的石墨的电池存在内部电阻的上升变大的问题。
本发明的课题在于,提供一种可以改善充放电循环特性并抑制内部电阻的上升的非水电解质二次电池。
用于解决问题的方案
本发明的一个方式的非水电解质二次电池具备正极、负极和非水电解质,负极含有BET比表面积为2m2/g以下的石墨,非水电解质含有下述式(1)或式(2)所示的环状羧酸酐,
(式(1)中,n表示0、1或2,R1~R4分别独立地表示氢原子、烷基、烯基或芳基。)
(式(2)中,R5~R8分别独立地表示氢原子、烷基、烯基或芳基。)。
发明的效果
根据本发明的一个方式的非水电解质二次电池,能够改善充放电循环特性并抑制内部电阻的上升。
具体实施方式
对于以往使用比表面积低的石墨作为负极活性物质的非水电解质二次电池的充放电循环特性的改善原因,可认为如下,即由于石墨的比表面积低,随着锂离子的嵌入脱嵌,石墨膨胀收缩的面积变小,因此石墨与非水电解质的副反应得到抑制。但是,使用比表面积低的石墨时,由于石墨表面的每单位面积的锂离子的嵌入脱嵌量增加,负极上形成的覆膜(SEI覆膜)变得更厚。其结果,与使用以往石墨的情况相比,使用比表面积低的石墨的电池中有时内部电阻的上升会变大。
因此,本发明人等进行了深入研究,结果发现,在负极含有BET比表面积为2m2/g以下的石墨的非水电解质二次电池中,通过向非水电解质中添加下述式(1)或式(2)所示的环状羧酸酐,从而改善充放电循环特性并抑制内部电阻的上升。
(式(1)中,n表示0、1或2,R1~R4分别独立地表示氢原子、烷基、烯基或芳基。)
(式(2)中,R5~R8分别独立地表示氢原子、烷基、烯基或芳基。)
通过向非水电解质中添加环状羧酸酐从而在维持充放电循环特性的同时抑制内部电阻的上升的机制尚不完全明确,但例如可以进行以下的推定。即,认为具备包含环状羧酸酐的非水电解质的非水电解质二次电池中,在充放电时,负极上会形成源自非水电解质所含的成分的覆膜(SEI覆膜)。认为该覆膜通过含有源自环状羧酸酐的开环聚合的构成成分而形成牢固的覆膜,抑制充放电时非水电解质的分解。另外,由于源自环状羧酸酐的羰基,覆膜的锂离子传导性变高,因而锂离子的嵌入脱嵌所伴随的非水电解质的分解可得到抑制。其结果,可以推测:因石墨的膨胀收缩而导致的覆膜破坏以及再形成得到抑制的比表面积低的石墨会抑制负极的电阻值伴随非水电解质二次电池的充放电而上升。
以下,对本发明的一个方式涉及的非水电解质二次电池的实施方式进行说明。以下说明的实施方式为一个例子,不用于限定本发明。
作为实施方式的一个例子的非水电解质二次电池具备正极、负极、非水电解质、分隔件和电池壳体。具体而言,具有将卷绕型的电极体及非水电解质收纳于电池壳体中的结构,所述卷绕型的电极体是夹着分隔件卷绕正极和负极而成的。电极体不限定于卷绕型的电极体,也可应用夹着分隔件层叠正极和负极而成的层叠型的电极体等其它形态的电极体。
作为收纳电极体以非水电解质的电池壳体,可以示例出:圆筒形、方形、硬币形、纽扣形等金属制壳体;用树脂片层压金属箔而成形为片所得的树脂制壳体(层压型电池)等。
以下,对作为实施方式的一个例子的非水电解质二次电池中使用的正极、负极、非水电解质、分隔件进行详细说明。
[正极]
正极例如由金属箔等正极集电体、以及形成于正极集电体上的正极活性物质层构成。正极集电体可以使用铝等在正极的电位范围内稳定的金属的箔、将该金属配置于表层的薄膜等。正极活性物质层例如包含正极活性物质、粘结材料、导电材料等。
正极例如可以通过如下方式得到:在正极集电体上涂布包含正极活性物质、导电材料、粘结材料等的正极复合材料浆料并进行干燥,从而在正极集电体上形成正极活性物质层,对该正极活性物质层进行压延。正极集电体的厚度没有特别限制,但例如为10μm以上且100μm以下左右。
正极活性物质层包含由锂过渡金属氧化物构成的正极活性物质。作为锂过渡金属氧化物,可例示出:含有锂(Li)、以及钴(Co)、锰(Mn)和镍(Ni)等过渡金属元素的锂过渡金属氧化物。锂过渡金属氧化物也可以包含除Co、Mn和Ni以外的其它添加元素,例如可举出铝(Al)、锆(Zr)、硼(B)、镁(Mg)、钪(Sc)、钇(Y)、钛(Ti)、铁(Fe)、铜(Cu)、锌(Zn)、铬(Cr)、铅(Pb)、锡(Sn)、钠(Na)、钾(K)、钡(Ba)、锶(Sr)、钙(Ca)、钨(W)、钼(Mo)、铌(Nb)以及硅(Si)等。
作为锂过渡金属氧化物的具体例,例如可举出:LixCoO2、LixNiO2、LixMnO2、LixCoyNi1-yO2、LixCoyM1-yOz、LixNi1-yMyOz、LixMn2O4、LixMn2-yMyO4、LiMPO4、Li2MPO4F(各化学式中,M为Na、Mg、Sc、Y、Mn、Fe、Co、Ni、Cu、Zn、Al、Cr、Pb、Sb和B中的至少1种,0<x≤1.2、0<y≤0.9、2.0≤z≤2.3)。锂过渡金属氧化物可以单独使用1种,也可以多种混合使用。
作为导电材料,可以使用提高正极复合材料层的导电性的公知的导电材料,例如可举出炭黑、乙炔黑、科琴黑、石墨等碳材料等。它们可以是单独1种,也可以组合使用2种以上。
作为粘结材料,可以使用维持正极活性物质、导电材料的良好接触状态并提高正极活性物质等对正极集电体表面的粘结性的公知的粘结材料,例如可举出氟系高分子、橡胶系高分子等。作为氟系高分子,例如可举出聚四氟乙烯(PTFE)、聚偏氟乙烯(PVdF)或它们的改性物等;作为橡胶系高分子,例如可举出乙烯-丙烯-异戊二烯共聚物、乙烯-丙烯-丁二烯共聚物等。它们可以是单独1种,也可以组合使用2种以上。另外,粘结材料也可以同时使用羧甲基纤维素(CMC)、聚氧化乙烯(PEO)等增稠剂。
[负极]
负极由例如金属箔等负极集电体、以及形成于负极集电体上的负极活性物质层构成。负极集电体可以使用铜等在负极的电位范围内稳定的金属的箔、将该金属配置于表层的薄膜等。负极活性物质层例如包含负极活性物质、粘结材料和增稠剂等。
负极例如可以通过如下方式制作:在负极集电体上涂布包含负极活性物质、粘结材料和增稠剂等的负极复合材料浆料,对涂膜进行干燥后进行压延而在集电体的两面形成负极活性物质层。从集电性、机械强度等观点出发,负极集电体的厚度优选为5μm以上且40μm以下、更优选为10μm以上且20μm以下。
本发明的负极活性物质层具备BET比表面积为2m2/g以下的石墨作为吸留、释放锂离子的负极活性物质。可认为,通过像这样使用BET比表面积为2m2/g以下的石墨作为负极活性物质,与非水电解质的副反应得以抑制,非水电解质二次电池的充放电循环特性得以改善。石墨的BET比表面积优选为1.8m2/g以下、更优选为1.5m2/g以下。BET比表面积的下限没有特别限制,但从锂离子的接受性的观点出发,可以为0.1m2/g以上、优选为0.4m2/g以上。需要说明的是,石墨的BET比表面积利用公知的方法测定即可,例如使用比表面积测定装置(株式会社Mountech制,Macsorb(注册商标)HM型号-1201)并基于BET法进行测定。
作为BET比表面积为2m2/g以下的石墨,可使用以往用作非水电解质二次电池的负极活性物质的石墨类材料,例如块状石墨、土状石墨等天然石墨;以及块状人造石墨、石墨化中间相碳微珠等人造石墨。
BET比表面积为2m2/g以下的石墨例如可通过抑制石墨晶体的边缘面的露出以制备比表面积降低的石墨而得到。作为用于抑制石墨晶体的边缘面的露出的方法,例如可列举出对经石墨化处理的石墨化物施加冲击或施加剪切力的方法,作为具体的方法,可列举出将石墨化物在非活性气氛下进行粉碎的方法。作为粉碎方法,可以使用锤磨机、针磨机、喷磨机等。另外,可举出:利用煤类或石油类的沥青涂覆石墨的表面,进一步进行热处理,利用沥青的碳化物覆盖露出的边缘面的方法。另外,在石墨的制造工序中,通过在进行作为原料的碳材料等的热处理(石墨化处理)之前进行粉碎处理,制备成规定的粒径分布后实施热处理,从而可以抑制石墨晶体的边缘面的露出。热处理的温度在以往的石墨化处理的温度范围内即可,例如可为1800℃~3000℃。另外,不仅可以使用这些人造石墨,还可以使用比表面积在本发明范围内的天然石墨。
BET比表面积为2m2/g以下的石墨的体积平均粒径例如为5μm以上且30μm以下、优选为10μm以上且25μm以下。体积平均粒径指的是用激光衍射散射法测定的负极活性物质的体积平均粒径,表示在粒径分布中体积累积值达到50%的粒径。负极活性物质的体积平均粒径例如可使用激光衍射散射式粒径分布测定装置(MicroTrack Bell株式会社制)来测定。
负极复合材料层也可以含有除BET比表面积为2m2/g以下的石墨以外的材料作为负极活性物质,例如可以含有金属锂、锂-铝合金、锂-铅合金、锂-硅合金、锂-锡合金等锂合金;BET比表面积大于2m2/g的石墨、焦炭、有机物焙烧物等碳材料;SnO2、SnO、TiO2等金属氧化物等。从抑制充放电循环时的负极复合材料层的膨胀和收缩、防止形成于负极活性物质上的覆膜的破坏的观点出发,BET比表面积为2m2/g以下的石墨优选为负极活性物质的总量的50质量%以上、更优选为75质量%以上。
作为粘结材料,例如与正极的情况相同地,可使用氟系高分子、橡胶系高分子等,另外,也可使用苯乙烯-丁二烯共聚物(SBR)或其改性物等。
作为增稠剂,例如可举出羧甲基纤维素(CMC)、聚氧化乙烯(PEO)等。它们可以是单独1种,也可以组合使用2种以上。
[非水电解质]
非水电解质包含非水溶剂以及溶解于非水溶剂的电解质盐,还包含后述式(1)或式(2)所示的环状羧酸酐。作为非水电解质中使用的非水溶剂,例如可以使用酯类、醚类、腈类、二甲基甲酰胺等酰胺类、以及它们的2种以上的混合溶剂等,另外,也可以使用将这些溶剂的至少一部分氢用氟等卤素原子取代而成的卤素取代体。它们可以是单独1种,也可以组合使用2种以上。另外,非水电解质不限定于液体电解质(非水电解液),还可以是使用了凝胶状聚合物等的固体电解质。
作为非水电解质中所含的酯类,可以例示出环状碳酸酯类、链状碳酸酯类、羧酸酯类。作为环状碳酸酯类,例如可举出碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯等。作为链状碳酸酯类,例如可举出碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸甲丙酯、碳酸乙丙酯、碳酸甲异丙酯等。
作为羧酸酯类,例如可举出乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯(MP)、丙酸乙酯、γ-丁内酯(GBL)、γ-戊内酯(GVL)等。
作为非水电解质中所含的环状醚类,例如可举出1,3-二氧戊环、4-甲基-1,3-二氧戊环、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、1,2-环氧丁烷、1,3-二噁烷、1,4-二噁烷、1,3,5-三噁烷、呋喃、2-甲基呋喃、1,8-桉树脑、冠醚等。
作为非水电解质中所含的链状醚类,例如可举出1,2-二甲氧基乙烷、二乙醚、二丙醚、二异丙醚、二丁醚、二己醚、乙基乙烯基醚、丁基乙烯基醚、甲基苯基醚、乙基苯基醚、丁基苯基醚、戊基苯基醚、甲氧基甲苯、苄基乙基醚、二苯醚、二苄醚、邻二甲氧基苯、1,2-二乙氧基乙烷、1,2-二丁氧基乙烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚、1,1-二甲氧基甲烷、1,1-二乙氧基乙烷、三乙二醇二甲醚、四乙二醇二甲醚等。
作为非水电解质中所含的腈类,例如可举出乙腈、丙腈、丁腈、戊腈、正庚腈、丁二腈、戊二腈、己二腈、庚二腈、1,2,3-丙烷三甲腈、1,3,5-戊烷三甲腈等。
作为非水电解质中所含的卤素取代体,例如可举出4-氟代碳酸亚乙酯(FEC)等氟代环状碳酸酯、氟代链状碳酸酯、3,3,3-三氟丙酸甲酯(FMP)等氟代链状羧酸酯等。
非水电解质中所含的电解质盐优选为锂盐。锂盐可以是以往非水电解质二次电池中通常使用的支持盐等。作为锂盐的例子,可举出:LiBF4、LiClO4、LiPF6、LiAsF6、LiSbF6、LiAlCl4、LiSCN、LiCF3SO3、LiC(C2F5SO2)、LiCF3CO2、Li(P(C2O4)F4)、Li(P(C2O4)F2)、LiPF6-x(CnF2n+1)x(1≤x≤6、n为1或2)、LiB10Cl10、LiCl、LiBr、LiI、氯硼烷锂、低级脂肪族羧酸锂、Li2B4O7、Li[B(C2O4)2][双乙二酸硼酸锂(LiBOB)]、Li[B(C2O4)F2]等硼酸盐类、Li[P(C2O4)F4]、Li[P(C2O4)2F2]、LiN(FSO2)2、LiN(ClF2l+1SO2)(CmF2m+1SO2){l、m为0以上的整数}等亚胺盐类等。锂盐可以仅使用1种,也可以混合使用2种以上。
对于非水电解质中所含的环状羧酸酐,只要为式(1)或式(2)所示的物质就没有特别限制。式(1)中,n表示0、1或2,R1~R4分别独立地表示氢原子、烷基、烯基或芳基;式(2)中,R5~R8分别独立地表示氢原子、烷基、烯基或芳基。
式(1)中的n优选为0或1。需要说明的是,n为0时,表示具有R1及R2的碳原子与具有R3及R4的碳原子直接键合形成5元环。
R1~R8所示的烷基例如为甲基、乙基等碳数1~5的烷基;R1~R8所示的烯基例如为乙烯基、丙烯基、烯丙基等碳数2~5的烯基;R1~R8所示的芳基例如为苯基、苄基等碳数6~10的芳基。R1~R8优选选自由氢原子、碳数1~3的烷基、碳数2~3的烯基和苯基组成的组;更优选选自由氢原子、甲基、乙基和乙烯基组成的组。
作为式(1)或式(2)所示的环状羧酸酐的具体例子,例如可举出琥珀酸酐、甲基琥珀酸酐、二甲基琥珀酸酐、乙基甲基琥珀酸酐、戊二酸酐、甲基戊二酸酐、己二酸酐、苯基琥珀酸酐、苯基戊二酸酐、以及二甘醇酸酐、甲基二甘醇酸酐、二甲基二甘醇酸酐、乙基二甘醇酸酐、乙烯基二甘醇酸酐、烯丙基二甘醇酸酐、二乙烯基二甘醇酸酐等。它们可以是单独1种,也可以组合2种以上。作为环状羧酸酐,从可以进一步抑制非水电解质二次电池的内部电阻的上升等观点来看,优选二甘醇酸酐、琥珀酸酐、戊二酸酐,更优选二甘醇酸酐。
对于非水电解质中的环状羧酸酐的含量,从可以进一步抑制非水电解质二次电池的内部电阻的上升且不会阻碍活性物质的锂离子的吸留释放来看,优选为0.1质量%以上且2.5质量%以下的范围、更优选为0.2质量%以上且1.5质量%以下的范围。
[分隔件]
分隔件例如可使用具有离子透过性和绝缘性的多孔片等。作为多孔片的具体例子,可举出微多孔薄膜、织布、无纺布等。作为分隔件的材质,聚乙烯、聚丙烯等烯烃系树脂、纤维素等是适宜的。分隔件可以是具有纤维素纤维层和烯烃系树脂等热塑性树脂纤维层的层叠体。另外,可以是包含聚乙烯层和聚丙烯层的多层分隔件,还可以使用在分隔件的表面涂布了芳纶系树脂、陶瓷等材料的分隔件。
实施例
以下通过实施例对本发明进行进一步说明,但本发明不限定于以下的实施例。
<实施例1>
[正极的制作]
作为正极活性物质,使用通式LiNi0.8Co0.15Al0.05O2所示的锂复合氧化物。以该正极活性物质为100质量%、作为导电材料的乙炔黑为1质量%、作为粘结材料的聚偏氟乙烯为0.9质量%的方式进行混合,加入N-甲基-2-吡咯烷酮(NMP)而制备正极复合材料浆料。接着,利用刮刀法将正极复合材料浆料涂布于厚度15μm的铝制正极集电体的两面,将涂膜压延,从而在正极集电体的两面形成厚度70μm的正极活性物质层。将其作为正极。
[负极的制作]
将焦炭与沥青粘结剂粉碎混合后,在1000℃下焙烧,然后在3000℃下进行石墨化处理。通过在N2气氛下用球磨机将其粉碎,并对得到的粉末进行分级,从而得到石墨a1。使用比表面积测定装置(株式会社Mountech制,Macsorb(注册商标)HM型号-1201)以及激光衍射散射式粒径分布测定装置(MicroTrack Bell株式会社制,MT3000)进行测定,结果是,石墨a1的BET比表面积为1.0m2/g,石墨a1的体积平均粒径为16.1μm。以石墨a1 100质量份、作为增稠剂的羧甲基纤维素(CMC)1质量份、作为粘结材料的苯乙烯-丁二烯共聚物(SBR)1质量份的比率混合,加入水而制备负极复合材料浆料。利用刮刀法将负极复合材料浆料涂布于厚度10μm的铜制负极集电体的两面,将涂膜压延,从而在负极集电体的两面形成厚度80μm的负极活性物质层。将其作为负极。
[非水电解质的制备]
将碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)和碳酸二甲酯(DMC)以30:30:40的体积比(室温)混合。在该混合溶剂中,以制备后的非水电解质中浓度达到1.3摩尔/L的量溶解LiPF6,并以制备后的非水电解质中浓度达到0.3质量%的量溶解二甘醇酸酐,从而制备非水电解质。
[非水电解质二次电池的制作]
将上述正极和负极分别裁切成规定的尺寸,然后分别在上述正极安装铝引线、在上述负极安装镍引线,并夹着聚乙烯制分隔件卷绕正极和负极,从而制作卷绕型的电极体。将该电极体收纳于外径18mm、高度65mm的有底圆筒形状的电池壳体主体并注入上述非水电解液,然后用垫片和封口体将电池壳体主体的开口部封口,从而制作18650型圆筒形非水电解质二次电池A1。
<比较例1>
将通过实施例1的石墨化处理得到的石墨化物在大气气氛下利用辊磨机进行粉碎,将得到的粉末分级,从而得到石墨b1。与石墨a1同样地进行测定,结果是,石墨b1的BET比表面积为3.9m2/g,石墨b1的体积平均粒径为22μm。在负极的制作中,除了使用石墨b1代替石墨a1以外,与实施例1同样地制作负极。另外,在非水电解质的制备中,除了不添加二甘醇酸酐以外,与实施例1同样地制备非水电解质。接着,除了使用该负极和该非水电解质以外,与实施例1同样地制作圆筒形非水电解质二次电池B1。
<比较例2>
在负极的制作中,除了使用石墨b1代替石墨a1以外,与实施例1相同地制作负极。接着,除了使用该负极以外,与实施例1同样地制作圆筒形非水电解质二次电池B2。
<比较例3>
在非水电解质的制备中,除了不添加二甘醇酸酐以外,与实施例1相同地制备非水电解质。接着,除了使用该非水电解质以外,与实施例1相同地制作圆筒形非水电解质二次电池B3。
[内部电阻(直流电阻)的测定]
对实施例和比较例的各电池,按照下述顺序进行直流电阻的测定。在25℃的温度环境下,对各电池以0.3It的恒定电流进行充电直至电池电压达到4.1V,然后继续以恒定电压进行充电直至电流值达到0.05It。接着以0.3It的恒定电流放电1小时40分钟,使SOC为50%。获得对该SOC50%的各电池施加0A、0.1A、0.5A、1.0A的放电电流10秒时的电压数据。将相对于所施加的放电电流值的10秒后的电压值利用最小二乘法进行线性近似,基于此时的斜率的绝对值,算出直流电阻值。需要说明的是,1It是将电池容量用1小时放电的电流值。
接着,在45℃的环境温度下,对各实施例和比较例的各非水电解质二次电池以0.5It的恒定电流进行恒定电流充电直至电压达到4.1V,然后以0.5It的恒定电流进行恒定电流放电直至电压达到3.0V。进行该充放电100次循环。然后,与上述同样地使各电池的SOC为50%,获得对SOC50%的各电池施加0A、0.1A、0.5A、1.0A的放电电流10秒时的电压数据,算出各电池的直流电阻值。针对各电池,算出100次循环后的直流电阻值相对于初次充放电循环后的直流电阻值的比率(百分比)作为各电池的充放电循环后的电阻上升率。
[充放电循环试验]
针对实施例和比较例的各非水电解质二次电池,进行与上述内部电阻的测定相同的充放电循环100次循环。然后,通过下式求出容量维持率。该值越高,表示充放电循环特性的降低越得到抑制。
容量维持率=(第100次循环的放电容量/第1次循环的放电容量)×100
表1中针对实施例和比较例1~3的各非水电解质二次电池示出用作负极活性物质的石墨的BET比表面积、二甘醇酸酐相对于非水电解质的含量、初始直流电阻值、100次循环后的电阻上升率、以及100次循环后的容量维持率的结果。需要说明的是,实施例和比较例1~3的各非水电解质二次电池的初始直流电阻值表示相对于比较例1的非水电解质二次电池的初始直流电阻值的比率(百分比)。
[表1]
DGA:二甘醇酸酐
如表1所示,使用BET比表面积为2m2/g以下的石墨a1的实施例1和比较例3的非水电解质二次电池与使用BET比表面积大于2m2/g的石墨b1的比较例1和2的非水电解质二次电池相比,充放电循环试验后的容量维持率示出更高的值。并且,使用包含式(1)或式(2)所示的环状羧酸酐的非水电解质的实施例1的非水电解质二次电池中,由于负极上的覆膜包含源自环状羧酸酐的构成成分,因此覆膜的厚度增加得以抑制,与使用不含该环状羧酸酐的非水电解质的比较例3的非水电解质二次电池相比,初始和充放电循环试验后的内部电阻值示出更低的值。
与之相对,比较例2的非水电解质二次电池中,包含源自环状羧酸酐的构成成分的覆膜由于石墨的膨胀收缩而容易被破坏,覆膜的再形成量增加。其结果,与不含环状羧酸酐的比较例1相比,充放电循环试验后的内部电阻值示出高的值。由此,作为BET比表面积为2m2/g以下的石墨材料与环状羧酸酐的组合而形成的特异性覆膜所带来的协同效果,可以降低初始阶段和充放电循环试验后电池的内部电阻值。
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