CN116601785A - 非水电解质二次电池用正极活性物质和非水电解质二次电池 - Google Patents
非水电解质二次电池用正极活性物质和非水电解质二次电池 Download PDFInfo
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- CN116601785A CN116601785A CN202180084672.3A CN202180084672A CN116601785A CN 116601785 A CN116601785 A CN 116601785A CN 202180084672 A CN202180084672 A CN 202180084672A CN 116601785 A CN116601785 A CN 116601785A
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- Prior art keywords
- positive electrode
- nonaqueous electrolyte
- active material
- secondary battery
- electrolyte secondary
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- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 1
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- 239000011572 manganese Substances 0.000 description 1
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Classifications
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/362—Composites
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Abstract
本发明提供一种有助于兼顾充电容量和放电电压的非水电解质二次电池用正极活性物质。该正极活性物质包含由通式xLiyMO2‑(1‑x)LizMO2(0<x<0.4、1.5≤y≤2.5、0.9≤z≤1.5,M为选自由过渡金属、以及Al、Si、Sn、Ge、Sb、Bi、Mg、Ca和Sr组成的组中的1种以上的元素)表示的锂金属复合氧化物,锂金属复合氧化物具有层状结构,在一个二次颗粒内具有配位于氧的四面***置的Li元素、和配位于氧的八面***置的Li元素。
Description
技术领域
本发明涉及非水电解质二次电池用正极活性物质和非水电解质二次电池。
背景技术
一直以来,使Li离子等在正极和负极之间移动来进行充放电的非水电解质二次电池已被广泛利用,近年来,要求电池特性的日益的改善。在专利文献1中,公开了一种二次电池,其通过在正极中包含Li2NiO2,在充电时向负极供给足够量的Li离子,从而对过放电特性显示效果,且抑制了电池容量的降低。
现有技术文献
专利文献
专利文献1:日本特表2005-521220号公报
发明内容
发明要解决的问题
但是,充电容量(电池容量)变高时,有时放电电压降低。Li2NiO2对于Li离子的吸收/释放缺乏可逆性,专利文献1所公开的技术通过在正极中包含Li2NiO2,有时电池的充电容量反而降低,充电容量和放电电压的兼顾还有改善的余地。
因此,本发明的目的在于提供一种有助于兼顾充电容量和放电电压的非水电解质二次电池用正极活性物质。
用于解决问题的方案
作为本发明的一个方式的非水电解质二次电池用正极活性物质,其特征在于,包含由通式xLiyMO2-(1-x)LizMO2(0<x<0.4、1.5≤y≤2.5、0.9≤z≤1.5,M为选自由过渡金属、以及Al、Si、Sn、Ge、Sb、Bi、Mg、Ca和Sr组成的组中的1种以上的元素)表示的锂金属复合氧化物,锂金属复合氧化物具有层状结构,在一个二次颗粒内具有配位于氧的四面***置的Li元素、和配位于氧的八面***置的Li元素。
作为本发明的一个方式的非水电解质二次电池,其特征在于,具备:包含上述非水电解质二次电池用正极活性物质的正极、负极、和非水电解质,负极包含负极活性物质,负极活性物质以3%以上含有选自由Si、SiC、SiOα(0<α<2)、LiβSiOγ(1<β≤4、1<γ≤4)、Sn、SnO2、Sb和Ge组成的组中的一种或两种以上的混合物。
发明的效果
根据作为本发明的一个方式的非水电解质二次电池用正极活性物质,能够改善电池的充电容量,且改善放电电压。
附图说明
图1是作为实施方式的一例的非水电解质二次电池的截面图。
具体实施方式
非水电解质二次电池通过使Li离子等在正极和负极之间移动来进行充放电。在非水电解质二次电池的充放电时,充电时从正极移动至负极的Li离子的一部分在被负极活性物质吸收的状态下在放电时不从负极释放,可以看到电池的容量维持率降低的现象。该现象在使用一般的石墨等碳系材料的情况下也能看到,在使用Si系材料等不可逆性的材料的情况下特别显著。因此,为了抑制充放电的容量维持率的降低,正在研究通过在正极中包含Li2NiO2作为Li填补剂而在充电时向负极供给足够量的Li离子的方法。但是,Li2NiO2对于Li离子的吸收/释放缺乏可逆性,通过在正极中包含Li2NiO2,有时电池的充电容量反而降低。另外,充电容量变高时,放电电压降低,难以兼顾充电容量和放电电压。
因此,本发明人等为了解决上述课题而进行了深入研究,结果发现,通过使用具有规定的组成、且特定了Li元素的配位位置的锂金属复合氧化物作为正极活性物质,能够特异性地兼顾电池的充电容量和放电电压。推测,锂金属复合氧化物由通式xLiyMO2-(1-x)LizMO2表示、且0<x<0.4范围时,可以使配位于氧的四面***置的Li元素与配位于氧的八面***置的Li元素的比率为优选的范围,因此兼顾充电容量和放电电压。
以下,对本发明的非水电解质二次电池的实施方式的一例进行详细说明。以下,例示卷绕型的电极体收纳于圆筒形的外壳体中的圆筒形电池,但电极体并不限定于卷绕型,也可以为多个正极和多个负极隔着分隔件交替地1张1张地层叠而成的层叠型。另外,外壳体并不限定于圆筒形,例如也可以为方形、硬币形等,还可以为由包含金属层及树脂层的层压片构成的电池壳体。
图1是作为实施方式的一例的非水电解质二次电池10的截面图。如图1所示,非水电解质二次电池10具备:电极体14、非水电解质(未图示)、和用于收纳电极体14及非水电解质的电池壳体15。电极体14具有正极11和负极12隔着分隔件13卷绕而成的卷绕结构。电池壳体15由有底圆筒形状的外壳罐16、和阻塞外壳罐16的开口部的封口体17构成。
电极体14由长条状的正极11、长条状的负极12、长条状的2片分隔件13、接合于正极11的正极极耳20、接合于负极12的负极极耳21构成。负极12以比正极11还大一圈的尺寸形成以防止锂的析出。即,负极12比正极11在长度方向和宽度方向(宽方向)上还长地形成。2片分隔件13以至少比正极11大一圈的尺寸形成,例如以夹持正极11的方式配置。
非水电解质二次电池10具备分别配置于电极体14的上下的绝缘板18、19。图1所示的例子中,安装于正极11上的正极极耳20通过绝缘板18的贯通孔而向封口体17侧延伸,安装于负极12上的负极极耳21通过绝缘板19的外侧而向外壳罐16的底部侧延伸。正极极耳20通过焊接等与封口体17的底板23的下表面连接,与底板23电连接的封口体17的盖27成为正极端子。负极极耳21通过焊接等与外壳罐16的底部内表面连接,外壳罐16成为负极端子。
外壳罐16例如为有底圆筒形状的金属制容器。在外壳罐16与封口体17之间设有垫片28,电池壳体15的内部空间被密闭。外壳罐16例如具有从外部加压侧面部而形成的、用于支撑封口体17的沟槽部22。沟槽部22优选沿外壳罐16的圆周方向以环状形成,以其上表面支撑封口体17。
封口体17具有从电极体14侧起依次层叠有底板23、下阀体24、绝缘构件25、上阀体26、和盖27的结构。构成封口体17的各构件例如具有圆板形状或环形状,除绝缘构件25之外的各构件彼此被电连接。下阀体24与上阀体26在各自的中央部彼此被连接,绝缘构件25夹设于各自的周缘部之间。电池的内压因异常发热而上升时,下阀体24以将上阀体26推入盖27侧的方式变形而断裂,下阀体24与上阀体26之间的电流通路被阻断。内压进一步上升时,上阀体26断裂,气体从盖27的开口部排出。
以下,对构成非水电解质二次电池10的正极11、负极12、分隔件13、和非水电解质、特别是对构成正极11的正极合剂层31中所含的正极活性物质进行详细说明。
[正极]
正极11具有:正极集电体30、和在正极集电体30的两面形成的正极合剂层31。正极集电体30可以使用铝、铝合金等在正极11的电位范围内稳定的金属的箔、将该金属配置在表层的薄膜等。正极合剂层31可以包含正极活性物质、导电剂和粘结剂。正极11例如可以通过在正极集电体30的表面涂布包含正极活性物质、导电剂和粘结剂等的正极合剂浆料,使涂膜干燥后,压缩而在正极集电体30的两面形成正极合剂层31来制作。
作为正极合剂层31中所含的导电剂,可以例示炭黑、乙炔黑、科琴黑、石墨等碳系材料。作为正极合剂层31中所含的粘结剂,可以例示聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVdF)等氟树脂、聚丙烯腈(PAN)、聚酰亚胺、丙烯酸类树脂、聚烯烃等。这些树脂可以与羧甲基纤维素(CMC)或其盐、聚环氧乙烷(PEO)等并用。
正极合剂层31中所含的正极活性物质包含由通式xLiyMO2-(1-x)LizMO2(0<x<0.4、1.5≤y≤2.5、0.9≤z≤1.5,M为选自由过渡金属、以及Al、Si、Sn、Ge、Sb、Bi、Mg、Ca和Sr组成的组中的1种以上的元素)表示的锂金属复合氧化物(Y)。需要说明的是,在不损害本发明目的的范围内,正极活性物质也可以包含除锂金属复合氧化物(Y)之外的锂金属复合氧化物、或其他化合物。
锂金属复合氧化物(Y)例如是多个一次颗粒聚集而成的二次颗粒。构成二次颗粒的一次颗粒的粒径例如为0.05~1μm。一次颗粒的粒径作为由扫描型电子显微镜(SEM)观察到的颗粒图像中的外切圆的直径而测定。
锂金属复合氧化物(Y)的二次颗粒的粒径为体积基准的中值粒径(D50),例如为3μm~30μm。D50是指:在体积基准的粒度分布中频率的累积从粒径小者起成为50%的粒径,也被称为中位径。锂金属复合氧化物(Y)的粒度分布可以使用激光衍射式的粒度分布测定装置(例如,MicrotracBEL Corp.制、MT3000II),将水作为分散介质进行测定。
在表示锂金属复合氧化物(Y)的通式xLiyMO2-(1-x)LizMO2中,M优选为选自由Ni、Co、Mn、Fe和Al组成的组中的1种以上的元素。
锂金属复合氧化物(Y)具有层状结构,在一个二次颗粒内具有配位于氧的四面***置的Li元素、和配位于氧的八面***置的Li元素。锂金属复合氧化物(Y)的层状结构例如包含过渡金属层、Li层和氧层。Li层是Li可逆地进出的层。
锂金属复合氧化物(Y)以空间群R3-m为主体,也可以具有空间群P3-m1的区域作为层叠缺陷。通过以空间群R3-m为主体,充电容量改善,晶体结构具有稳定性。通过具有空间群P3-m1的区域作为层叠缺陷,放电电压改善。在表示锂金属复合氧化物(Y)的通式xLiyMO2-(1-x)LizMO2中,x和(1-x)各自表示空间群P3-m1的区域和空间群R3-m的区域的比率。
锂金属复合氧化物(Y)在CuKα的XRD测定中,分别在17.1°以上且不足18.1°和18.1°以上且不足19.1°时具有峰值,17.1°以上且不足18.1°的积分强度S1与18.1°以上且不足19.1°的积分强度S2可以满足0<S1/(S1+S2)<0.4。S1/(S1+S2)表示空间群P3-m1的区域的比率。
XRD测定例如可以使用粉末X射线衍射装置(Rigaku Co.,Ltd.制、商品名“RINT-TTR”、射线源Cu-Kα),在以下的条件下进行。
测定范围:15-120°
扫描速度:4°/分钟
解析范围:30-120°
背景:B-样条
曲线函数:分割型拟合Voigt函数
ICSD No.:98-009-4814
在放电至1.5V的状态下,锂金属复合氧化物(Y)可以具有由通式xLiyMO2-(1-x)LizMO2(0<x<0.4、1.5≤y≤2.5、0.9≤z≤1.5,M为上述M)表示的组成。锂金属复合氧化物(Y)的组成根据电池的充放电而变化,但通过放电至1.5V而回复至上述组成。
正极活性物质中所含的锂金属复合氧化物(Y)例如将具有空间群R3-m的锂金属复合氧化物(X)和Li金属浸渍于在2-甲基四氢呋喃(2-MeTHF)中溶解有二苯甲酮的二苯甲酮2Me-THF溶液中,在室温下搅拌1~24小时后,过滤即可制作。通过上述工序,在具有空间群R3-m的锂金属复合氧化物(X)中作为层叠缺陷导入空间群P3-m1。导入空间群P3-m1的比例例如可以通过温度、2-MeTHF中的二苯甲酮的浓度、搅拌时间等来调整。
具有空间群R3-m的锂金属复合氧化物(X)例如可以通过在不含Li的金属复合化合物中添加Li源并混合,在200℃~1050℃下烧成来合成。作为金属复合化合物,可以例示含有Ni、Mn等的氧化物、氢氧化物、碳酸化合物等。作为Li源,可以例示LiOH等。
[负极]
负极12具有:负极集电体40、和在负极集电体40的两面形成的负极合剂层41。负极集电体40可以使用铜、铜合金等在负极12的电位范围内稳定的金属的箔、将该金属配置在表层的薄膜等。负极合剂层41可以包含负极活性物质和粘结剂。负极12例如可以通过在负极集电体40的表面涂布包含负极活性物质、粘结剂等的负极合剂浆料,使涂膜干燥后,进行压延,在负极集电体40的两面形成负极合剂层41来制作。需要说明的是,在充电状态下,也可以在负极12析出锂金属。
作为负极合剂层41中所含的负极活性物质,只要能够可逆地吸储、释放锂离子就没有特别限定,通常使用石墨等碳系材料。石墨可以为鳞片状石墨、块状石墨、土状石墨等天然石墨、块状人造石墨、石墨化中间相碳微珠等人造石墨中的任意者。另外,作为负极活性物质,可以使用:Si、Sn等与Li合金化的金属、包含Si、Sn等的金属化合物、锂钛复合氧化物等。另外,也可以使用在它们上设置了碳覆膜者。对于负极活性物质,优选以3%以上含有选自由Si、SiC、SiOα(0<α<2)、LiβSiOγ(1<β≤4、1<γ≤4)、Sn、SnO2、Sb和Ge组成的组中的一种或两种以上的混合物。
负极合剂层41中所含的粘结剂中,与正极11的情况同样地,可以使用PTFE、PVdF等含氟树脂、PAN、聚酰亚胺、丙烯酸类树脂、聚烯烃等,但优选使用苯乙烯-丁二烯橡胶(SBR)。另外,负极合剂层41中也可以包含CMC或其盐、聚丙烯酸(PAA)或其盐、聚乙烯醇(PVA)等。
[分隔件]
分隔件13中例如使用具有离子透过性和绝缘性的多孔性片。作为多孔性片的具体例,可以举出微多孔薄膜、机织布、无纺布等。作为分隔件的材质,聚乙烯、聚丙烯等聚烯烃、纤维素等是理想的。分隔件13可以为单层结构,也可以具有层叠结构。另外,也可以在分隔件13的表面设置芳族聚酰胺树脂等耐热性高的树脂层、包含无机化合物的填料的填料层。
[非水电解质]
非水电解质例如包含:非水溶剂、和溶解于非水溶剂中的电解质盐。非水溶剂可以使用例如酯类、醚类、乙腈等腈类、二甲基甲酰胺等酰胺类、和它们的2种以上的混合溶剂等。非水溶剂可以包含将这些溶剂的氢的至少一部分用氟等卤素原子取代而成的卤素取代物。作为卤素取代物,可以举出氟代碳酸亚乙酯(FEC)等氟化环状碳酸酯、氟化链状碳酸酯、氟代丙酸甲酯(FMP)等氟化链状羧酸酯等。
作为上述酯类的例子,可以举出碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯等环状碳酸酯、碳酸二甲酯(DMC)、碳酸乙基甲酯(EMC)、碳酸二乙酯(DEC)、碳酸甲基丙酯、碳酸乙基丙酯、碳酸甲基异丙酯等链状碳酸酯、γ-丁内酯(GBL)、γ-戊内酯(GVL)等环状羧酸酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯(MP)、丙酸乙酯(EP)等链状羧酸酯等。
作为上述醚类的例子,可以举出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、1,3-二氧杂环己烷、1,4-二氧杂环己烷、1,3,5-三氧杂环己烷、呋喃、2-甲基呋喃、1,8-桉油醇、冠醚等环状醚、1,2-二甲氧基乙烷、***、二丙醚、二异丙醚、二丁醚、二己醚、乙基乙烯醚、丁基乙烯醚、甲基苯醚、乙基苯醚、丁基苯醚、戊基苯醚、甲氧基甲苯、苄基***、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***、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、四乙二醇二甲醚等链状醚等。
电解质盐优选为锂盐。作为锂盐的例子,可以举出LiBF4、LiClO4、LiPF6、LiAsF6、LiSbF6、LiAlCl4、LiSCN、LiCF3SO3、LiCF3CO2、Li(P(C2O4)F4)、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)F2)等硼酸盐类、LiN(SO2CF3)2、LiN(C1F2l+1SO2)(CmF2m+1SO2){l、m为0以上的整数}等酰亚胺盐类等。这些锂盐可以单独使用1种,也可以混合多种而使用。其中,从离子传导性、电化学稳定性等的观点出发,优选使用LiPF6。锂盐的浓度例如为每1L非水溶剂为0.8摩尔~1.8摩尔。另外,还可以添加碳酸亚乙烯酯、丙磺酸内酯系添加剂。
实施例
以下,根据实施例和比较例,对本发明进一步进行说明,但本发明不限定于以下的实施例。
<实施例>
[正极活性物质的制作]
将通过共沉得到的组成为Ni0.8Mn0.2(OH)2的镍锰复合氢氧化物在500℃下进行热处理,得到镍锰复合氧化物。接着,以使Ni、Mn的总量与Li的摩尔比为1.02:1的方式,将镍锰复合氧化物与LiOH混合。将该混合物在900℃下烧成10小时后,进行粉碎,得到具有R3-m的锂金属复合氧化物(X)。
将锂金属复合氧化物(X)和Li金属浸渍于1摩尔/L的二苯甲酮2Me-THF溶液中,在室温下搅拌12小时后进行过滤,制作锂金属复合氧化物(Y),将其作为正极活性物质。作为XRD测定的结果,该锂金属复合氧化物(Y)的S1/(S1+S2)为0.21。
[正极的制作]
将该正极活性物质、乙炔黑与聚偏二氟乙烯(PVdF)以96.3:2.5:1.2的固体成分质量比混合,加入适量的N-甲基-2-吡咯烷酮(NMP)后,将其混炼,制备正极合剂浆料。将该正极合剂浆料涂布于由铝箔构成的正极芯体的两面,使涂膜干燥后,使用辊压延涂膜,切断为规定的电极尺寸,得到在正极芯体的两面形成有正极合剂层的正极。
[非水电解质的制备]
将氟代碳酸亚乙酯(FEC)、碳酸亚乙酯(EC)与碳酸乙基甲酯(EMC)以1:1:6的体积比混合,得到非水溶剂。通过在该非水溶剂中以1.0摩尔/L的浓度溶解LiPF6,得到非水电解质。
[试验电池单元的制作]
在上述正极和Li金属制的对电极上分别安装引线,通过聚烯烃制的分隔件将正极和对电极相对配置,由此制作电极体。将该电极体和上述非水电解质封入由铝层压薄膜构成的外壳体内,制作试验电池单元。
[充电容量和平均放电电压的测定]
在25℃的温度环境下,以0.2C的恒定电流进行恒定电流充电直至电池单元电压为4.5V,以4.5V进行恒定电压充电直至电流值为0.02C。之后,以0.2C的恒定电流进行恒定电流放电直至电池单元电压为2.5V。测定此时的充电容量和平均放电电压。
<比较例1>
在正极活性物质的制作中,除将二苯甲酮2Me-THF溶液中的锂金属复合氧化物(X)的搅拌时间设定为24小时之外,与实施例1同样地制作试验电池单元,进行评价。
<比较例2>
在正极活性物质的制作中,除将二苯甲酮2Me-THF溶液中的锂金属复合氧化物(X)的搅拌条件设定为在45℃下24小时之外,与实施例1同样地制作试验电池单元,进行评价。
<比较例3>
在正极活性物质的制作中,不将锂金属复合氧化物(X)浸渍在二苯甲酮2Me-THF溶液中,而将锂金属复合氧化物(X)作为正极活性物质使用,除此之外,与实施例1同样地制作试验电池单元,进行评价。
<比较例4>
在正极活性物质的制作中,除将二苯甲酮2Me-THF溶液中的锂金属复合氧化物(X)的搅拌条件设定为在45℃下48小时之外,与实施例1同样地制作试验电池单元,进行评价。
实施例和比较例的充电容量和平均放电电压如表1所示。另外,表1示出由XRD测定算出的各正极活性物质的S1/(S1+S2)的值。
[表1]
如表1所示,实施例的试验电池单元与比较例1~4的试验电池单元相比,充电容量与平均放电电压的平衡优异,能够改善充电容量,且改善放电电压。
附图标记说明
10非水电解质二次电池、11正极、12负极、13分隔件、14电极体、15电池壳体、16外壳罐、17封口体、18、19绝缘板、20正极极耳、21负极极耳、22沟槽部、23底板、24下阀体、25绝缘构件、26上阀体、27盖、28垫片、30正极集电体、31正极合剂层、40负极集电体、41负极合剂层。
Claims (7)
1.一种非水电解质二次电池用正极活性物质,其中,该正极活性物质包含由通式xLiyMO2-(1-x)LizMO2表示的锂金属复合氧化物,该通式中,0<x<0.4、1.5≤y≤2.5、0.9≤z≤1.5,M为选自由过渡金属、以及Al、Si、Sn、Ge、Sb、Bi、Mg、Ca和Sr组成的组中的1种以上的元素,
所述锂金属复合氧化物具有层状结构,在一个二次颗粒内具有配位于氧的四面***置的Li元素、和配位于氧的八面***置的Li元素。
2.根据权利要求1所述的非水电解质二次电池用正极活性物质,其中,所述锂金属复合氧化物以空间群R3-m为主体,作为层叠缺陷具有空间群P3-m1的区域。
3.根据权利要求1或2所述的非水电解质二次电池用正极活性物质,其中,所述锂金属复合氧化物在CuKα的XRD测定中,分别在17.1°以上且不足18.1°、和18.1°以上且不足19.1°具有峰值,17.1°以上且不足18.1°的积分强度S1与18.1°以上且不足19.1°的积分强度S2满足0<S1/(S1+S2)<0.4。
4.根据权利要求1~3中任一项所述的非水电解质二次电池用正极活性物质,其中,所述M是选自由Ni、Co、Mn、Fe和Al组成的组中的1种以上的元素。
5.一种非水电解质二次电池,其中,该二次电池具备:包含权利要求1~4中任一项所述的非水电解质二次电池用正极活性物质的正极、负极、和非水电解质,
所述负极包含负极活性物质,
所述负极活性物质以3%以上含有选自由Si、SiC、SiOα、LiβSiOγ、Sn、SnO2、Sb和Ge组成的组中的一种或两种以上的混合物,其中,0<α<2、1<β≤4、1<γ≤4。
6.根据权利要求5所述的非水电解质二次电池,其中,在充电状态下,在所述负极析出锂金属。
7.根据权利要求5或6所述的非水电解质二次电池,其中,在放电至1.5V的状态下,所述锂金属复合氧化物具有由通式xLiyMO2-(1-x)LizMO2表示的组成,该通式中,0<x<0.4、1.5≤y≤2.5、0.9≤z≤1.5,M为前述M。
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