CN116583483A - 非水电解质二次电池用的复合颗粒和非水电解质二次电池 - Google Patents
非水电解质二次电池用的复合颗粒和非水电解质二次电池 Download PDFInfo
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- CN116583483A CN116583483A CN202180082133.6A CN202180082133A CN116583483A CN 116583483 A CN116583483 A CN 116583483A CN 202180082133 A CN202180082133 A CN 202180082133A CN 116583483 A CN116583483 A CN 116583483A
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Abstract
非水电解质二次电池用的复合颗粒包含:锂锆酸盐相、和分散于锂锆酸盐相内的硅相。复合颗粒中,相对于氧以外的全部元素,锆的含有比率MZr例如为14.6质量%以上且54.6质量%以下,且相对于氧以外的全部元素,锂的含有比率MLi例如为0.9质量%以上且10.4质量%以下。
Description
技术领域
本公开主要涉及能作为非水电解质二次电池的电极活性物质使用的复合颗粒。
背景技术
非水电解质二次电池、特别是锂离子二次电池具有高电压且高能量密度,因此,期待作为小型民用用途、电力储藏装置和电动汽车的电源。在要求电池的高能量密度化的过程中,作为理论容量密度高的负极活性物质,期待利用包含与锂合金化的硅(Silicon)的材料。
专利文献1中,提出了一种负极活性物质,其具备:Li2zSiO2+z(0<z<2)所示的锂硅酸盐相和分散于锂硅酸盐相内的硅颗粒(以下,也称为LSX)。
现有技术文献
专利文献
专利文献1:国际公开第2016/35290号小册子
发明内容
LSX与SiO2相内分散有硅颗粒的SiOx相比,不可逆容量小,初始的充放电效率增大。
然而,LSX中的锂硅酸盐相有时产生与非水电解质的副反应,要求减少保存电池时的气体产生量。
鉴于以上,本公开的一方案涉及一种非水电解质二次电池用的复合颗粒,其包含:锂锆酸盐相、和分散于前述锂锆酸盐相内的硅相。
本公开的另一方案涉及一种非水电解质二次电池,其具备:正极、负极和非水电解质,前述负极包含上述复合颗粒。
根据本公开,可以减少保存非水电解质二次电池时的气体产生量。
附图说明
图1为示出本公开的一实施方式的复合颗粒的XRD谱图的例子的图。
图2为示意性示出本公开的一实施方式的复合颗粒的剖视图。
图3为切去了本公开的一实施方式的非水电解质二次电池的一部分的立体简图。
具体实施方式
[非水电解质二次电池用负极活性物质]
本公开的实施方式的非水电解质二次电池用的复合颗粒包含:锂锆酸盐相、和分散于锂锆酸盐相内的硅相。复合颗粒(以下,也称为LZX颗粒。)例如可以作为非水电解质二次电池的负极中所含的高容量的负极活性物质使用。
LZX颗粒中的锂锆酸盐相与锂硅酸盐相内分散有硅相的LSX颗粒中的锂硅酸盐相相比,耐酸性和耐碱性优异。由此,LZX颗粒中,与由副反应生成、非水电解质中所含的酸成分或碱成分的副反应比LSX颗粒还被抑制。其结果,伴有保存电池时的副反应的气体产生被抑制。
LZX颗粒实质上可以不含锂硅酸盐和SiO2。总计了LZX颗粒中的锂硅酸盐和SiO2的含量例如可以为3质量%以下。
LZX颗粒中,相对于氧以外的全部元素,锆的含有比率MZr可以为14.6质量%以上且54.6质量%以下,且相对于氧以外的全部元素,锂的含有比率MLi可以为0.9质量%以上且10.4质量%以下。锆的含有比率MZr和锂的含有比率MLi为上述范围内的情况下,容易得到稳定性和离子传导性优异的锆酸盐相。需要说明的是,上述稳定性包含化学稳定性(耐酸性和耐碱性)和热稳定性这两者。锆的含有比率MZr更优选29.0质量%以上且54.6质量%以下。
另外,从容易得到稳定性和离子传导性优异的锂锆酸盐相的观点出发,将锆的含有比率MZr设为100时,锂的含有比率MLi相对于锆的含有比率MZr之比(即,MLi/MZr)可以为4.7以上且23.2以下。锂的含有比率MLi在MLi/MZr满足上述数值范围的基础上,更优选1.8质量%以上且9.7质量%以下。
从兼顾高容量化和循环特性改善的观点出发,LZX颗粒中,相对于氧以外的全部元素,硅的含有比率MSi例如优选40质量%以上且90质量%以下,更优选42质量%以上且82质量%以下。上述硅的含有比率MSi是LZX颗粒中的构成硅相的Si的量。
复合颗粒的由X射线衍射(XRD)测定得到的复合颗粒的XRD谱图中,可以在2θ=x°附近观测到源自锂锆酸盐相的峰。x°为选自由18.6°、26.5°和36.5°组成的组中的至少1者。XRD测定的X射线中使用Cu的Kα射线。需要说明的是,本说明书中,为x°附近是指例如为x±1°的范围内。
ZrO2可以相分散于锂锆酸盐相内。结晶性高的微细的ZrO2相能以岛状分布于锆酸盐相的基质中。ZrO2相的硬度高,因此,伴有硅相的膨胀收缩的锆酸盐相的膨胀、裂缝容易被抑制。另外,ZrO2相的稳定性高,因此,保存电池时的副反应容易被抑制,气体产生量容易减少。由X射线衍射测定得到的复合颗粒的X射线衍射谱图中,在2θ=30.7°附近可以观测到源自ZrO2相的峰。LZX颗粒中的ZrO2相的含量例如为0质量%以上且10质量%以下。
此处,图1示出本公开的一实施方式的复合颗粒(后述的实施例4(LZX4))的XRD谱图的例子。
在LZX的2θ=28°附近观察到源自硅相的Si(111)面的峰。另外,在2θ=30.7°附近观察到源自ZrO2相的峰。
在2θ=18.6°附近、2θ=26.5°附近和2θ=36.5°附近观察到源自锂锆酸盐相的Li6Zr2O7、Li2ZrO3和Li5.52Zr2.62O8的峰(图1中的(i)、(ii)和(iii)的峰)。
复合颗粒具有作为海部的锂锆酸盐相内分散有作为岛部的微细的硅相的海岛结构。锂锆酸盐相具有良好的离子传导性,借助锂锆酸盐相基于硅相的锂离子的吸储和释放顺利地进行。通过控制分散于锂锆酸盐相的硅相的量,从而可以实现高容量化。由锂锆酸盐相来缓和硅相的膨胀收缩。由此,能容易实现兼顾电池的高容量化与循环特性的改善。从硅相的膨胀收缩的缓和的观点出发,锂锆酸盐相可以为非晶态。
复合颗粒中,包含锂锆酸盐相和硅相的多个一次颗粒结合,构成二次颗粒。复合颗粒(二次颗粒)的平均粒径例如为1μm以上且25μm以下,可以为4μm以上且15μm以下。在上述粒径范围内,容易缓和基于伴有充放电的复合颗粒的体积变化的应力,变得容易得到良好的循环特性。复合颗粒的表面积也成为适度的大小,基于与非水电解质的副反应的容量降低也被进一步抑制。复合颗粒的平均粒径是指,由激光衍射散射法测定的粒度分布中,体积累积值成为50%的粒径(体积平均粒径)。测定装置中可以使用例如株式会社堀场制作所(HORIBA)制“LA-750”。复合颗粒的表面由导电层覆盖的情况下,导电层的厚度实质上小至不对复合颗粒的平均粒径造成影响的程度,因此,可以将具有导电层的复合颗粒的平均粒径视为复合颗粒的平均粒径。
复合颗粒可以通过以下的方法从电池取出。首先,将完全放电状态的电池解体,取出包含复合颗粒的电极(例如负极),将该电极用碳酸酐甲乙酯或碳酸二甲酯清洗,将非水电解质成分去除。如后述,电极具备集电体和负载于其表面的电极合剂层。因此,从集电体剥离电极合剂层,用乳钵粉碎,得到试样粉。接着,将试样粉在干燥气氛中干燥1小时,浸渍在较弱地煮沸的6M盐酸中10分钟,去除源自复合颗粒以外的元素。接着,用离子交换水清洗试样粉,滤除并以200℃干燥1小时。之后,在氧气气氛中加热至900℃,去除导电层,从而可以仅将复合颗粒离析。需要说明的是,完全放电状态是指放电深度(DOD)为90%以上(充电状态(SOC)为10%以下)的状态。
(锂锆酸盐相)
锂锆酸盐包含锂(Li)、锆(Zr)和氧(O)。锂锆酸盐中的O相对于Zr的原子比(即,O/Zr)例如为2.0以上且6.0以下。O/Zr的原子比为上述范围内的情况下,在锂锆酸盐相的稳定性和离子传导性的方面是有利的。
锂锆酸盐相优选包含选自由Li6Zr2O7、Li2ZrO3和Li5.52Zr2.62O8组成的组中的至少1种作为主成分。此处,“主成分”是指占锂锆酸盐相整体的质量的50质量%以上的成分,也可以占70质量%以上的成分。
锂锆酸盐相除Li、Zr和O之外,可以进一步包含其他元素M。元素M例如可以为选自由钠(Na)、钾(K)、钙(Ca)、镁(Mg)、硼(B)、磷(P)和镧(La)组成的组中的至少1种。锂锆酸盐相通过包含元素M,从而锂锆酸盐相的稳定性和离子传导性进一步改善。另外,基于锂锆酸盐相与非水电解质的接触的副反应被抑制。从对于非水电解质的耐性和锂锆酸盐相的结构稳定性的观点出发,元素M优选包含选自由P和B组成的组中的至少1种。
元素M可以形成化合物。作为该化合物,根据元素M的种类,例如可以为元素M的氧化物,也可以为元素M的锆酸盐。锂锆酸盐相中,元素M的含量相对于氧以外的全部元素,例如为0.3摩尔%以上且3摩尔%以下。
锂锆酸盐相可以进一步包含微量的铬(Cr)、镍(Ni)、锰(Mn)、铜(Cu)、钼(Mo)等元素。
锂锆酸盐相中的Li、Zr、元素M的含量例如可以通过分析电极合剂层的截面而测定。
首先,将完全放电状态的电池分解,取出电极,将电极用无水碳酸甲乙酯或碳酸二甲酯清洗,将非水电解质成分去除并干燥后,用截面抛光机(CP)得到电极合剂层的截面。接着,用扫描型电子显微镜(SEM)观察电极合剂层的截面。
然后,根据以下的任意方法,可以求出各元素的含量。另外,由各元素的含量算出锂锆酸盐相的组成。
<EDX>
从电极合剂层的反射电子图像的截面图像,随机选出颗粒的最大直径为5μm以上的复合颗粒10个,对于各自,进行基于能量色散型X射线(EDX)的元素的映射分析。用图像解析软件算出成为对象的元素的含有面积。观察倍率理想的是2000~20000倍。将颗粒10个中所含的规定元素的含有面积的测定值进行平均。由得到的平均值算出成为对象的元素的含量。
以下,示出理想的截面SEM-EDX分析的测定条件。
<SEM-EDX测定条件>
加工装置:JEOL制、SM-09010(Cross Section Polisher)
加工条件:加速电压6kV
电流值:140μA
真空度:1×10-3~2×10-3Pa
测定装置:电子显微镜HITACHI制SU-70
分析时加速电压:10kV
字段:自由模式
探针电流模式:中
探针电流范围:高
阳极Ap.:3
OBJ Ap.:2
分析区域:1μm见方
分析软件:EDAX Genesis
CPS:20500
Lsec:50
时间常数:3.2
<AES>
从电极合剂层的反射电子图像的截面图像随机选出颗粒的最大直径为5μm以上的复合颗粒10个,对于各自,用俄歇电子能谱(AES)分析装置(例如日本电子株式会社制、JAMP-9510F)进行元素的定性定量分析。测定条件例如可以设为加速电压10kV、射束电流10nA、分析区域将颗粒10个中所含的规定元素的含量进行平均算出含量。
需要说明的是,EDX分析、AES分析对距离复合颗粒的截面的周端缘1μm以上内侧的范围进行。
<ICP>
将复合颗粒的试样全溶解于加热后的酸溶液(氢氟酸、硝酸和硫酸的混酸)中,将溶液残渣的碳过滤并去除。之后,将得到的滤液用电感耦合等离子体发射分光光度分析法(ICP)进行分析,测定各元素的光谱强度。然后,使用市售的元素的标准溶液制成标准曲线,算出复合颗粒中所含的各元素的含量。
此外,各元素的定量也可以使用电子探针显微分析仪(EPMA)、激光消融ICP质谱(LA-ICP-MS)、X射线光电子能谱(XPS)等而进行。
另外,复合颗粒中所含的B、Na、K和Al的含量可以依据JIS R3105(1995)(硼硅酸玻璃的分析方法)而进行定量分析。
复合颗粒中所含的Ca的含量可以依据JIS R3101(1995)(钠石灰玻璃的分析方法)而进行定量分析。
可以使用碳·硫分析装置(例如株式会社堀场制作所制的EMIA-520型)测定复合颗粒中所含的碳含量。在磁性板上量取试样,加入助燃剂,插入到加热至1350℃的燃烧炉(载气:氧气),根据红外线吸收检测燃烧时产生的二氧化碳气体量。标准曲线例如使用Bureau of Analysed Samples.Ltd制的碳钢(碳含量0.49%)而制成,算出试样的碳含量(高频感应加热炉燃烧-红外线吸收法)。
可以使用氧/氮/氢分析装置(例如株式会社堀场制作所制的EGMA-830型)测定复合颗粒中所含的氧含量。在Ni胶囊中放入试样,与成为助溶剂的Sn粒料和Ni粒料一起投入到以电力5.75kW加热的碳坩埚,检测释放的一氧化碳气体。标准曲线使用标准试样Y2O3而制成,算出试样的氧含量(非活性气体熔解-非分散型红外线吸收法)。
构成复合颗粒中的硅相的Si量可以使用Si-NMR而定量。
以下,示出理想的Si-NMR的测定条件。
<Si-NMR测定条件>
测定装置:Varian公司制、固体核磁共振光谱测定装置(INOVA-400)
探针:Varian 7mm CPMAS-2
MAS:4.2kHz
MAS速度:4kHz
脉冲:DD(45°脉冲+信号收集时间1H去耦)
重复时间:1200秒~3000秒
观测幅度:100kHz
观测中心:-100ppm附近
信号收集时间:0.05秒
累积次数:560
试样量:207.6mg
(硅相)
硅相为硅(Si)单质的相,伴有电池的充放电而重复锂离子的吸储和释放。由硅相参与的法拉第反应体现容量。硅相的容量大,因此,伴有充放电的膨胀与收缩的程度也大。但是,硅相分散于锂锆酸盐相内,因此,基于硅相的膨胀和收缩的应力得到缓和。
硅相可以由多个微晶构成。硅相的微晶尺寸优选30nm以下。硅相的微晶尺寸为30nm以下的情况下,可以减小基于伴有充放电的硅相的膨胀收缩的体积变化量,循环特性进一步提高。例如,基于硅相收缩时在硅相的周围形成孔隙的硅相的孤立被抑制,充放电效率的降低被抑制。硅相的微晶尺寸的下限值没有特别限定,例如为1nm以上。
硅相的微晶尺寸更优选10nm以上且30nm以下,进一步优选15nm以上且25nm以下。硅相的微晶尺寸为10nm以上的情况下,可以较小地抑制硅相的表面积,因此,不易产生伴有不可逆容量的生成的硅相的劣化。硅颗粒的微晶尺寸为30nm以下的情况下,容易使硅相的膨胀收缩均匀化,复合颗粒中产生的应力容易得到缓和,可以改善循环特性。硅相的微晶尺寸由X射线衍射谱图的归属于硅相(单质Si)的(111)面的衍射峰的半值宽度、根据谢勒公式算出。
初次充电前的电池中所含的复合颗粒的硅相例如为颗粒状。颗粒状的硅相的平均粒径优选500nm以下、更优选200nm以下、进一步优选50nm以下。初次充电后,硅相的平均粒径优选400nm以下、更优选100nm以下。通过使硅相微细化,从而充放电时的复合颗粒的体积变化变小,复合颗粒的结构稳定性进一步改善。硅相的平均粒径用由SEM得到的复合颗粒的截面图像而测定。具体而言,硅相的平均粒径通过将任意的100个硅相的最大直径进行平均而求出。
从高容量化的观点出发,复合颗粒中的硅相的含量优选30质量%以上、更优选35质量%以上、进一步优选55质量%以上。该情况下,锂离子的扩散性良好,得到优异的负荷特性。另一方面,从循环特性改善的观点出发,复合颗粒中的硅相的含量优选95质量%以下、更优选75质量%以下、进一步优选70质量%以下。该情况下,未由硅酸盐相覆盖而露出的硅相的表面减少,非水电解质与硅相的副反应容易被抑制。
(导电层)
在复合颗粒(二次颗粒)的表面的至少一部分可以形成包含导电性材料的导电层。由此,复合颗粒的导电性改善。导电层的厚度优选实质上薄至不对复合颗粒的平均粒径造成影响的程度。对于导电层的厚度,如果考虑导电性的确保和锂离子的扩散性,则优选1~200nm、更优选5~100nm。导电层的厚度可以通过使用SEM或TEM的复合颗粒的截面观察而测量。
导电性材料优选导电性碳材料。作为导电性碳材料,可以使用无定形碳、石墨、易石墨化碳(软碳)、难石墨化碳(硬碳)等。其中,在容易形成覆盖复合颗粒的表面的薄的导电层的方面,优选无定形碳。作为无定形,可以举出炭黑、沥青的烧成物、焦炭、活性炭等。作为石墨,可以举出天然石墨、人造石墨、石墨化中间相碳等。
[复合颗粒的制造方法]
复合颗粒例如通过包括以下的第1工序至第4工序的制造方法而制造。
(第1工序)得到作为原料的锂锆酸盐(以下,也称为原料锆酸盐)的工序。
(第2工序)将原料锆酸盐与原料硅复合化,使硅相分散于锆酸盐相内,得到复合中间体的工序。
(第3工序)对复合中间体实施热处理,得到包含锆酸盐相和分散于锆酸盐相内的硅相的烧结体的工序。
(第4工序)将烧结体粉碎,得到包含锆酸盐相和分散于锆酸盐相内的硅相的复合颗粒的工序。
(第1工序)
第1工序例如包括如下工序:将锆化合物与锂化合物与根据需要的包含元素M的化合物混合,得到混合物的工序1a;和,将混合物烧成,得到原料锆酸盐的工序1b。工序1b的烧成例如在氧化气氛中进行。工序1b的烧成温度优选400℃以上且1200℃以下,更优选800℃以上且1100℃以下。
作为锆化合物,可以举出氧化锆(ZrO2)、氢氧化锆、碳酸锆等。锆化合物可以单独使用1种,也可以组合2种以上而使用。
作为锂化合物,可以举出碳酸锂、氧化锂、氢氧化锂、氢化锂等。锂化合物可以单独使用1种,也可以组合2种以上而使用。
作为包含元素M的化合物,可以使用元素M的氧化物、氢氧化物、氢化物、卤化物、碳酸盐、草酸盐、硝酸盐、硫酸盐等。包含元素M的化合物可以单独使用1种,也可以组合2种以上而使用。
第1工序中,原料锆酸盐的制作过程中不与锂化合物反应的锆化合物可能残留在原料锆酸盐中。对锂化合物,锆化合物的用量大的情况下,锆化合物容易残留。原料锆酸盐中残留的锆化合物为ZrO2的情况下,最终得到的复合颗粒中,可以形成分散于锂锆酸盐相内的ZrO2相。
(第2工序)
第2工序例如具有如下工序:边对原料锆酸盐与原料硅的混合物赋予剪切力边将混合物粉碎并微粒化,得到复合中间体。此处,例如,可以将原料锆酸盐与原料硅以规定的质量比混合,使用球磨机那样的粉碎装置,边将混合物搅拌边进行微粒化。
原料硅中可以使用平均粒径为几μm~几十μm左右的硅的粗颗粒。最终得到的硅颗粒优选以由X射线衍射谱图的归属于Si(111)面的衍射峰的半值宽度、根据谢勒公式算出的微晶尺寸成为10nm以上的方式进行控制。
需要说明的是,第2工序不限定于上述。例如,可以不使用粉碎装置,合成硅纳米颗粒和原料锆酸盐的纳米颗粒,并将它们混合。
(第3工序)
第3工序例如具有如下工序:边利用热压等对微粒化后的复合中间体施加压力边将复合中间体烧成得到烧结体。复合中间体的烧成例如在非活性气氛(例如氩气、氮气等气氛)中进行。烧成温度优选450℃以上且1000℃以下。为上述温度范围的情况下,容易使微小的硅颗粒分散于结晶性低的锆酸盐相内。原料锆酸盐在上述温度范围内是稳定的,基本不与硅反应。烧成温度优选550℃以上且900℃以下,更优选650℃以上且850℃以下。烧成时间例如为1小时以上且10小时以下。
(第4工序)
第4工序是将烧结体以具有期望的粒度分布的方式进行粉碎,得到包含锆酸盐相和分散于锆酸盐相内的硅相的复合颗粒的工序。复合颗粒例如以平均粒径成为1~25μm的方式进行粉碎。
(第5工序)
进而,复合颗粒的制造方法可以包括如下第5工序:将复合颗粒的表面的至少一部分由导电性材料覆盖而形成导电层。导电性材料优选在电化学上稳定,优选导电性碳材料。作为由导电性碳材料覆盖复合颗粒的表面的方法,可以示例原料中使用乙炔、甲烷等烃气体的CVD法;将煤炭沥青、石油沥青、酚醛树脂等与复合颗粒混合并加热、炭化的方法等。另外,也可以使炭黑附着在复合颗粒的表面。第5工序中,例如,将复合颗粒与导电性碳材料的混合物例如在非活性气氛(例如氩气、氮气等气氛)中以700℃以上且950℃以下进行加热,从而也可以在复合颗粒的表面形成导电层。
此处,图2为示意性示出本公开的一实施方式的负极活性物质(复合颗粒)的剖视图。
复合颗粒20具备由多个一次颗粒24聚集而成的二次颗粒构成的母颗粒23。母颗粒23(一次颗粒24)具备锂锆酸盐相21、和分散于锂锆酸盐相21内的硅相22。母颗粒23具有锂锆酸盐相21的基质中分散有微细的硅相的海岛结构。
进而,微细的ZrO2相28可以分散于锂锆酸盐相21内。母颗粒23的表面的至少一部分可以由导电层26覆盖。锂锆酸盐相21可以包含元素M。伴有充放电的重复,彼此相邻的颗粒状的硅相22彼此连接,可以形成网络状的硅相。
[非水电解质二次电池]
本公开的实施方式的非水电解质二次电池具备:正极、负极和非水电解质,负极包含上述复合颗粒。
以下,对非水电解质二次电池详细进行说明。
[负极]
负极可以具备负极集电体、和负载于负极集电体的表面的负极合剂层。负极合剂层可以通过将分散介质中分散有负极合剂的负极浆料涂布于负极集电体的表面并干燥而形成。可以将干燥后的涂膜根据需要进行压延。负极合剂层可以形成于负极集电体的一个表面,也可以形成于两者的表面。
负极合剂包含负极活性物质作为必须成分,可以包含粘结剂、导电剂、增稠剂等作为任意成分。负极活性物质至少包含上述复合颗粒。
负极活性物质优选还包含电化学上吸储和释放锂离子的碳材料。复合颗粒伴有充放电而体积发生膨胀收缩,因此,在负极活性物质中其所占的比率如果变大,则容易产生伴有充放电而负极活性物质与负极集电体的接触不良。另一方面,通过并用复合颗粒与碳材料,从而可以边对负极赋予硅颗粒的高容量,边实现优异的循环特性。从高容量化和循环特性改善的观点出发,碳材料在复合颗粒与碳材料的总计中所占的比率优选98质量%以下,更优选70质量%以上且98质量%以下,进一步优选75质量%以上且95质量%以下。
作为碳材料,例如可以示例石墨、易石墨化碳(软碳)、难石墨化碳(硬碳)等。其中,优选充放电的稳定性优异、不可逆容量也少的石墨。石墨是指,具有石墨型晶体结构的材料,例如包含天然石墨、人造石墨、石墨化中间相碳颗粒等。碳材料可以单独使用1种,也可以组合2种以上而使用。
作为负极集电体,使用无孔的导电性基板(金属箔等)、多孔性的导电性基板(筛体、网体、冲孔板等)。作为负极集电体的材质,可以示例不锈钢、镍、镍合金、铜、铜合金等。负极集电体的厚度没有特别限定,从负极的强度与轻量化的均衡性的观点出发,优选1~50μm,5~20μm更理想。
作为粘结剂,可以示例树脂材料、例如聚四氟乙烯、聚偏二氟乙烯(PVDF)等氟树脂;聚乙烯、聚丙烯等聚烯烃树脂;芳族聚酰胺树脂等聚酰胺树脂;聚酰亚胺、聚酰胺酰亚胺等聚酰亚胺树脂;聚丙烯酸、聚丙烯酸甲酯、乙烯-丙烯酸共聚物等丙烯酸类树脂;聚丙烯腈、聚乙酸乙烯酯等乙烯基树脂;聚乙烯基吡咯烷酮;聚醚砜;丁苯共聚橡胶(SBR)等橡胶状材料等。粘结剂可以单独使用1种,也可以组合2种以上而使用。
作为导电剂,例如可以示例乙炔黑等碳类;碳纤维、金属纤维等导电性纤维类;氟化碳;铝等的金属粉末类;氧化锌、钛酸钾等导电性晶须类;氧化钛等导电性金属氧化物;亚苯基衍生物等有机导电性材料等。导电剂可以单独使用1种,也可以组合2种以上而使用。
作为增稠剂,例如可以举出羧甲基纤维素(CMC)和其改性体(也包含Na盐等盐)、甲基纤维素等纤维素衍生物(纤维素醚等);聚乙烯醇等具有乙酸乙烯酯单元的聚合物的皂化物;聚醚(聚环氧乙烷等聚环氧烷等)等。增稠剂可以单独使用1种,也可以组合2种以上而使用。
作为分散介质,无特别限制,例如可以示例水、乙醇等醇、四氢呋喃等醚、二甲基甲酰胺等酰胺、N-甲基-2-吡咯烷酮(NMP)、或它们的混合溶剂等。
[正极]
正极可以具备正极集电体、和负载于正极集电体的表面的正极合剂层。正极合剂层可以通过将分散介质中分散有正极合剂的正极浆料涂布于正极集电体的表面并干燥而形成。可以将干燥后的涂膜根据需要进行压延。正极合剂层可以形成于正极集电体的一个表面,也可以形成于两者的表面。正极合剂包含正极活性物质作为必须成分,可以包含粘结剂、导电剂等作为任意成分。作为正极浆料的分散介质,使用NMP等。
作为正极活性物质,例如可以使用含锂的复合氧化物。例如可以举出LiaCoO2、LiaNiO2、LiaMnO2、LiaCobNi1-bO2、LiaCobMe1-bOc、LiaNi1-bMebOc、LiaMn2O4、LiaMn2-bMebO4、LiMePO4、Li2MePO4F(Me为选自由Na、Mg、Sc、Y、Mn、Fe、Co、Ni、Cu、Zn、Al、Cr、Pb、Sb、B组成的组中的至少1种)。此处,a=0~1.2、b=0~0.9、c=2.0~2.3。需要说明的是,表示锂的摩尔比的a值根据充放电而增减。
其中,优选LiaNibMe1-bO2(Me为选自由Mn、Co和Al组成的组中的至少1种,0<a≤1.2,0.3≤b≤1)所示的锂镍复合氧化物。从高容量化的观点出发,更优选满足0.85≤b<1。从晶体结构的稳定性的观点出发,进一步优选包含Co和Al作为Me的LiaNibCocAldO2(0<a≤1.2、0.85≤b<1、0<c<0.15、0<d≤0.1、b+c+d=1)。
作为粘结剂和导电剂,可以使用与对于负极示例者同样的物质。作为导电剂,可以使用天然石墨、人造石墨等石墨。
正极集电体的形状和厚度可以从符合负极集电体的形状和范围分别选择。作为正极集电体的材质,例如可以示例不锈钢、铝、铝合金、钛等。
[非水电解质]
非水电解质包含非水溶剂、和溶解于非水溶剂的锂盐。非水电解质中的锂盐的浓度例如优选0.5mol/L以上且2mol/L以下。通过使锂盐浓度为上述范围,从而可以得到离子传导性优异、具有适度粘性的非水电解质。但是,锂盐浓度不限定于上述。
作为非水溶剂,例如使用环状碳酸酯、链状碳酸酯、环状羧酸酯、链状羧酸酯等。作为环状碳酸酯,可以举出碳酸亚丙酯(PC)、碳酸亚乙酯(EC)等。作为链状碳酸酯,可以举出碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸二甲酯(DMC)等。作为环状羧酸酯,可以举出γ-丁内酯(GBL)、γ-戊内酯(GVL)等。作为链状羧酸酯,可以举出甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯等。非水溶剂可以单独使用1种,也可以组合2种以上而使用。
作为锂盐,例如可以举出LiClO4、LiBF4、LiPF6、LiAlCl4、LiSbF6、LiSCN、LiCF3SO3、LiCF3CO2、LiAsF6、LiB10Cl10、低级脂肪族羧酸锂、LiCl、LiBr、LiI、硼酸盐类、酰亚胺盐类等。作为硼酸盐类,可以举出双(1,2-苯二醇根合(2-)-O,O’)硼酸锂、双(2,3-萘二醇根合(2-)-O,O’)硼酸锂、双(2,2’-联苯二醇根合(2-)-O,O’)硼酸锂、双(5-氟-2-醇根合-1-苯磺酸-O,O’)硼酸锂等。作为酰亚胺盐类,可以举出双氟磺酰亚胺锂(LiN(FSO2)2)、双三氟甲烷磺酰亚胺锂(LiN(CF3SO2)2)、三氟甲烷磺酸九氟丁磺酰亚胺锂(LiN(CF3SO2)(C4F9SO2))、双五氟乙磺酰亚胺锂(LiN(C2F5SO2)2)等。其中,优选LiPF6。锂盐可以单独使用1种,也可以组合2种以上而使用。
[分隔件]
通常理想的是使分隔件夹设在正极与负极之间。分隔件的离子透过度高,具备适度的机械强度和绝缘性。作为分隔件,可以使用微多孔薄膜、机织布、无纺布等。作为分隔件的材质,优选聚丙烯、聚乙烯等聚烯烃。
作为非水电解质二次电池的结构的一例,可以举出正极和负极隔着分隔件卷绕而成的电极组与非水电解质一起收纳于外壳体而得到的结构。但是,不限定于此,也可以应用其他形态的电极组。例如,也可以为正极与负极隔着分隔件层叠而得到的层叠型的电极组。非水电解质二次电池的形态也无限定,例如只要为圆筒型、方型、硬币型、纽扣型、层压型等即可。
以下,边参照图3边对作为本公开的非水电解质二次电池的一例的方型的非水电解质二次电池的结构进行说明。
电池具备有底方型的电池外壳4、收纳于电池外壳4内的电极组1和非水电解质。电极组1具有长尺寸带状的负极、长尺寸带状的正极和夹设于它们之间的分隔件。负极的负极集电体借助负极引线3与设于封口板5的负极端子6电连接。负极端子6由树脂制垫片7自封口板5绝缘。正极的正极集电体借助正极引线2电连接于封口板5的背面。即,正极与兼具正极端子的电池外壳4电连接。封口板5的周缘嵌合于电池外壳4的开口端部,嵌合部被激光焊接。封口板5上有非水电解质的注入孔,注液后由密封塞8阻塞。
以下,基于实施例和比较例,对本公开具体进行说明,但本发明不限定于以下的实施例。
<实施例1~6>
[复合颗粒(LZX颗粒)的制备]
(第1工序)
将ZrO2与Li2CO3混合,在空气中将混合物以950℃烧成10小时,得到原料锂锆酸盐(LZX颗粒)A1~A6。混合物中,ZrO2与Li2CO3的摩尔比设为使得将锆的含有比率MZr设为100时的MLi与MZr的质量比(MLi/MZr)成为表1所示的值。原料锂锆酸盐以平均粒径成为10μm的方式进行粉碎。
(第2工序)
接着,将原料锂锆酸盐(平均粒径10μm)与原料硅(3N、平均粒径10μm)混合。混合物中,原料锂锆酸盐与原料硅的质量比设为使得Zr与Si的质量比成为表1所示的值。
将混合物填充至行星式球磨机(Fritsch公司制、P-5)的罐(SUS制、容积:500mL),在罐中放入SUS制球(直径20mm)24个,关闭盖子,在非活性气氛中、以200rpm对混合物进行50小时粉碎处理。
(第3工序)
接着,在非活性气氛中取出粉末状的混合物,在非活性气氛中、用热压机边施加压力边以800℃烧成4小时,得到混合物的烧结体。
(第4工序)
将得到的烧结体粉碎,通过40μm的筛子,得到复合颗粒。
(第5工序)
将复合颗粒与煤炭沥青(JFE Chemical公司制、MCP250)混合。将混合物在非活性气氛中、以800℃烧成5小时,在复合颗粒的表面形成包含导电性碳材料的导电层。导电层的覆盖量相对于复合颗粒与导电层的总质量设为5质量%。之后,用筛子,得到具有导电层的平均粒径5μm的复合颗粒(锂锆酸盐相内分散有硅相的LZX颗粒)。
图1为LZX4的XRD谱图。实施例1~6的LZX颗粒1~6(以下也称为LZX1~6)的由XRD测定得到的XRD谱图中,分别确认到硅相、锂锆酸盐相和源自ZrO2相的峰。由所述的方法求出的LZX颗粒中的硅相的微晶尺寸为15nm。
通过所述的方法,求出LZX颗粒中的Li含有比率MLi、Si含有比率MSi和Zr含有比率MZr。将各含有比率的值示于表1。
[负极的制作]
将具有导电层的复合颗粒与石墨以5:95的质量比混合,作为负极活性物质使用。在以97.5:1:1.5的质量比包含负极活性物质与CMC的Na盐与SBR的负极合剂中,添加水并搅拌,制备负极浆料。接着,在铜箔的表面涂布负极浆料,使涂膜干燥后进行压延,制作在铜箔的两面形成有密度1.5g/cm3的负极合剂层的负极。
[正极的制作]
在以95:2.5:2.5的质量比包含钴酸锂与乙炔黑与PVDF的正极合剂中,添加NMP并搅拌,制备正极浆料。接着,在铝箔的表面涂布正极浆料,使涂膜干燥后进行压延,制作在铝箔的两面形成有密度3.6g/cm3的正极合剂层的正极。
[非水电解质的制备]
使LiPF6以1.0mol/L浓度溶解于以3:7的体积比包含EC与DEC的混合溶剂,制备非水电解质。
[非水电解质二次电池的制作]
将分别装有极耳的正极与负极隔着分隔件卷绕,制作极耳位于最外周部的电极组。将电极组插入到铝层压薄膜制的外壳体内,以105℃进行2小时真空干燥后,注入非水电解质,封固外壳体的开口部,得到对应于实施例1~6的LZX1~6的电池A1~A6。
<比较例1>
第2工序中,使用锂硅酸盐代替原料锂锆酸盐,将锂硅酸盐(平均粒径10μm)与原料硅(3N、平均粒径10μm)以50:50的质量比混合。锂硅酸盐如下得到:将SiO2与Li2CO3以SiO2:Li2CO3=70:30的摩尔比混合,在空气中、将混合物以950℃烧成10小时,从而得到。原料硅酸盐以平均粒径成为10μm的方式进行粉碎。
上述以外,通过与实施例1同样的方法,得到具有导电层的复合颗粒(锂硅酸盐相内分散有硅相的LSX颗粒)。
由XRD测定得到的LSX颗粒的XRD谱图中,确认到源自锂硅酸盐相(Li2Si2O5和Li2SiO3)和硅相的峰。LSX颗粒中的硅相的微晶尺寸为15nm。
使用具有导电层的LSX颗粒代替具有导电层的LZX颗粒,除此之外,通过与实施例1同样的方法,制作电池B1。
<比较例2>
第2工序中,使用ZrO2代替原料锆酸盐,将ZrO2(平均粒径10μm)与原料硅(3N、平均粒径10μm)设为Zr与Si的质量比成为表1所示的值。接下来的工序中想要得到复合颗粒,但无法使硅相分散于氧化锆,无法合成复合颗粒。
<比较例3>
第1工序中,以Li与Zr的质量比成为表1所示的值的方式,将ZrO2与Li2CO3混合,想要合成锂锆酸盐(LZX7),但锂锆酸盐的生成不充分,生成复相混合物。接下来的工序中,想要使用LZX颗粒7得到复合颗粒,但难以造粒。
对于上述中得到的电池A1~A6、B1,根据以下的方法进行初次充放电,之后,进行充电。
[初次充放电效率]
<充电>
在25℃下,以1It(800mA)的电流进行恒定电流充电直至电压成为4.2V后,以4.2V的电压进行恒定电压充电直至电流成为1/20It(40mA)。
<放电>
停顿10分钟后,在25℃下,以1It(800mA)的电流进行恒定电流放电直至电压成为2.75V。
在80℃下保存充电状态的各电池3天,根据阿基米德法测定电池内产生的气体量。具体而言,测定由于气体产生而增大的电池的体积增加量。将比较例1的电池B1中得到的气体产生量的值设为100,用相对值表示各电池的气体产生量的值。将评价结果示于表1。
[表1]
氧化物相 | Si(质量%) | Li(质量%) | Zr(质量%) | MLi/MZr | 气体产生量 | |
B1 | LSX | 96.0 | 4.0 | 0 | - | 100 |
B2 | ZrO2 | 62.3 | 0 | 37.7 | 0 | - |
B3 | LZX7 | 65.7 | 85 | 25.7 | 33.2 | - |
A1 | LZX1 | 42.9 | 2.9 | 54.3 | 5.3 | 81 |
A2 | LZX2 | 44.8 | 9.7 | 45.5 | 21.3 | 81 |
A3 | LZX3 | 63.0 | 1.8 | 35.1 | 5.3 | 87 |
A4 | LZX4 | 64.8 | 6.2 | 29.0 | 21.3 | 87 |
A5 | LZX5 | 80.7 | 1.0 | 18.3 | 5.3 | 93 |
A6 | LZX6 | 81.9 | 3.2 | 14.9 | 21.3 | 93 |
使用了LZX颗粒的电池A1~A6中,与使用了LZX颗粒的电池B1相比,气体产生量减少。特别是,电池A1~A4中,气体产生量少。
产业上的可利用性
本公开的非水电解质二次电池对移动体通信设备、便携式电子设备等的主电源是有用的。
附图标记说明
1 电极组
2 正极引线
3 负极引线
4 电池外壳
5 封口板
6 负极端子
7垫片
8密封塞
20复合颗粒
21锂锆酸盐相
22硅相
23母颗粒
24一次颗粒
26导电层
28ZrO2相。
Claims (9)
1.一种非水电解质二次电池用的复合颗粒,其包含:锂锆酸盐相、和分散于所述锂锆酸盐相内的硅相。
2.根据权利要求1所述的复合颗粒,其中,所述复合颗粒中,
相对于氧以外的全部元素,锆的含有比率MZr为14.6质量%以上且54.6质量%以下,且
相对于氧以外的全部元素,锂的含有比率MLi为0.9质量%以上且10.4质量%以下。
3.根据权利要求2所述的复合颗粒,其中,将所述锆的含有比率MZr设为100时,所述锂的含有比率MLi相对于所述锆的含有比率MZr之比为4.7以上且23.2以下。
4.根据权利要求1~3中任一项所述的复合颗粒,其中,所述锂锆酸盐相包含选自由Li6Zr2O7、Li2ZrO3和Li5.52Zr2.62O8组成的组中的至少1种。
5.根据权利要求1~4中任一项所述的复合颗粒,其中,由X射线衍射测定得到的所述复合颗粒的X射线衍射谱图中,
源自所述锂锆酸盐相的峰出现在2θ=x°附近,
所述x°为选自由18.6°、26.5°和36.5°组成的组中的至少1者。
6.根据权利要求1~5中任一项所述的复合颗粒,其中,ZrO2相分散于所述锂锆酸盐相内。
7.根据权利要求6所述的复合颗粒,其中,由X射线衍射测定得到的所述复合颗粒的X射线衍射谱图中,源自所述ZrO2相的峰出现在2θ=30.7°附近。
8.根据权利要求1~7中任一项所述的复合颗粒,其中,所述锂锆酸盐相包含选自由钠、钾、钙、镁、硼、磷和镧组成的组中的至少1种元素。
9.一种非水电解质二次电池,其具备:正极、负极和非水电解质,
所述负极包含权利要求1~8中任一项所述的复合颗粒。
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