CN114466822A - 氧化物、固体电解质、及全固态锂离子二次电池 - Google Patents
氧化物、固体电解质、及全固态锂离子二次电池 Download PDFInfo
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- CN114466822A CN114466822A CN202080067464.8A CN202080067464A CN114466822A CN 114466822 A CN114466822 A CN 114466822A CN 202080067464 A CN202080067464 A CN 202080067464A CN 114466822 A CN114466822 A CN 114466822A
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- oxide
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- substitution
- lithium ion
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 25
- 238000006467 substitution reaction Methods 0.000 claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000000470 constituent Substances 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 18
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- 239000007787 solid Substances 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 description 39
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 2
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明的实施方式的LLZ系氧化物是将Li、La、Zr及O作为主要构成元素的石榴石型氧化物,除主要构成元素之外,还包含Zn等置换元素。置换元素除Zn之外,还可以包含Bi、Nb、Hf等。LLZ系氧化物例如用作全固态锂离子二次电池的固体电解质。全固态锂离子二次电池具备正极、负极、及设置于正极与负极之间的固体电解质层。
Description
技术领域
本发明涉及氧化物、以及包含该氧化物的固体电解质及全固态锂离子二次电池。
背景技术
作为手机、笔记本电脑的电源,锂离子二次电池正在普及。现状是:锂离子二次电池中广泛使用液态的电解质(电解液),但为了扩大向车载用等的用途,作为安全性高、更高容量高输出的二次电池,正在进行使用固体电解质的全固态二次电池等的开发。
作为全固态锂离子二次电池的固体电解质的候补,属于石榴石型氧化物的Li7La3Zr2O12(LLZ)受到关注。石榴石型氧化物通常由A3B2C3O12的组成式表示,具有立方晶的结构。对于LLZ,La3+占据A位点(12面体配位),Zr4+占据B位点(6面体配位),Li+占据C位点(4面体配位)及晶格间位置(8面体配位),与通常的石榴石型结构相比,包含过量的Li,具有特异的晶体结构,成为在固体状态下显示高的锂离子传导性的一个原因。
进而,报告了在LLZ中导入有各种各样添加元素的LLZ系氧化物。例如,专利文献1中报告了:除作为LLZ的基本元素的Li、La、Zr之外,还添加Al作为置换元素,由此致密性、锂离子电导率提高。专利文献2中报告了:通过添加Nb和/或Ta作为置换元素,从而锂离子电导率进一步提高。
现有技术文献
专利文献
专利文献1:日本特开2011-51800号公报
专利文献2:日本特开2011-73962号公报
发明内容
发明要解决的问题
作为固体电解质材料,从更高的离子传导性、锂离子稳定性等的观点出发,要求新的材料的开发。
用于解决问题的方案
LLZ系氧化物是将Li、La、Zr及O作为主要构成元素的石榴石型氧化物,除主要构成元素之外,还包含Zn等置换元素。
LLZ系氧化物的置换元素除Zn以外,还可以包含Bi,例如,可以具有Li(7-2j)ZnjLa(3-k)BikZr2O(12-δ)(0<j<3.5、0<k<3、0≤δ<1)所示的组成。
LLZ系氧化物的置换元素除Zn之外,还可以包含选自由Nb及Hf组成的组中的1种以上的元素,例如,可以具有Li(7-4x+z)HfxLa(3-2y/3)ZnyZr(2-z)NbzO(12-δ)(0<x<1.75、0≤y<3、0≤z<2、0≤δ<1,其中,y及z中的至少任一者不为0)所示的组成。
发明的效果
上述的LLZ系氧化物可以用作全固态锂离子二次电池的固体电解质。
附图说明
图1为实施例的氧化物烧结体的截面SEM图像。
图2为实施例的氧化物烧结体的截面SEM图像。
图3为实施例的氧化物烧结体的X射线衍射图。
图4为实施例的氧化物烧结体的X射线衍射图。
图5为实施例的氧化物烧结体的X射线衍射图。
图6为实施例的氧化物烧结体的X射线衍射图。
具体实施方式
[氧化物]
本发明的一个实施方式是将Li、La、Zr及O作为主要构成元素的石榴石型氧化物。石榴石型的晶体结构为立方晶系,但组成式Li7La3Zr2O12±δ所示的石榴石型氧化物(LLZ)具有立方晶相及正方晶相。另外,已知立方晶相中因形成条件、热历程等而存在低温立方晶相和高温立方晶相。因此,LLZ、及将LLZ的金属元素的一部分用其它金属元素置换而成的氧化物(LLZ系氧化物)的晶体结构除通常的石榴石型的晶体结构之外,还可具有石榴石型类似的晶体结构。本说明书中,也包括具有石榴石型类似的晶体结构的情况在内,记载为“石榴石型氧化物”。石榴石型氧化物可以为单相,也可以为2相以上的混合相。
LLZ可以具有氧缺陷。组成式Li7La3Zr2O12-δ中,δ表示氧缺陷量。Δ可以为0。严格地测定氧缺陷量δ是困难的,通常δ不足1。具有置换元素的LLZ系氧化物也可以具有氧缺陷。
本发明的LLZ系氧化物除作为主要构成元素的Li、La、Zr及O之外,还至少包含Zn作为置换元素。认为作为置换元素的Zn被导入至LLZ的Li位点和/或Zr位点。通过导入作为置换元素的Zn,从而有氧化物的离子电导率提高的倾向。
LLZ系氧化物可以包含除Zn以外的置换元素。作为除Zn以外的置换元素,可举出Bi、Nb、Ta、Na、K、Rb、Mg、Ca、Ba、Sr、Ce、B、Al、Ti、V、Cr、Fe、Ni、Sn、Ga、Ge、In、Sc、Y、Lu、Hf、Pr、Nd、Pm、Sm、Eu、W、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu等。
本发明的LLZ系氧化物的第一实施方式中,包含Bi作为除Zn以外的置换元素。认为作为置换元素的Bi被导入至La位点。包含Zn和Bi作为置换元素的情况下,认为Zn被优先导入至Li位点。因此,包含Zn和Bi作为置换元素的第一实施方式的LLZ系氧化物可以由组成式Li(7-2j)ZnjLa(3-k)BikZr2O(12-δ)表示。此处,0<j<3.5、0<k<3。δ为氧缺陷量,如前所述,通常不足1。
从提高基于Zn的置换效果的观点出发,Zn的置换量j优选0.05以上、更优选0.08以上、进一步优选0.1以上、可以为0.12以上或0.15以上。另一方面,若基于Zn的置换量过大,则有时随着氧化物中的Li量的减少,离子电导率降低。因此,j优选1以下、更优选0.7以下、进一步优选0.5以下、可以为0.4以下、0.3以下或0.2以下。
8配位的Bi3+(离子半径:)与8配位的La3+(离子半径:)的离子半径大致相等,因此即使Bi的置换量k变化,LLZ系氧化物的晶体结构也不会产生大的差异。因此,Bi的置换量k可以为不足3的任意范围。k可以为0.05以上、0.075以上、0.1以上或0.12以上,可以为1以下、0.75以下、0.5以下、0.3以下或0.2以下。
本发明的LLZ系氧化物的第二实施方式中,作为除Zn以外的置换元素,包含Nb和/或Hf。认为作为置换元素的Nb被导入至Zr位点。认为作为置换元素的Hf被导入至Li位点。包含Zn且包含Nb和/或Hf作为置换元素的情况下,认为Zn被优先导入至La位点。因此,除Zn以外还包含Nb和/或Hf作为置换元素的第二实施方式的LLZ系氧化物可以由组成式Li(7-4x+z)HfxLa(3-2y/3)ZnyZr(2-z)NbzO(12-δ)表示。此处,0<x<1.75、0≤y<3、0≤z<2。其中,y及z中的至少任一者不为0。包含Hf作为置换元素时x>0,包含Nb作为置换元素时z>0。δ为氧缺陷量,如前所述,通常不足1。
从提高基于Zn的置换效果的观点出发,Zn的置换量y优选0.05以上、更优选0.08以上、进一步优选0.1以上、可以为0.12以上或0.15以上。另一方面,若基于Zn的置换量过大,则有时随着氧化物中的Li量的减少,离子电导率降低。因此,y优选1以下、更优选0.7以下、进一步优选0.5以下、可以为0.4以下、0.3以下或0.2以下。
Hf比Li的离子半径小,因此认为若Hf的置换量x变大,则有晶格间距变小的倾向,锂离子的扩散路径变窄。另外,若Hf的置换量x变大,则有时随着氧化物中的Li量的减少,离子电导率降低。因此,x优选1以下、更优选0.7以下、进一步优选0.5以下、可以为0.4以下、0.3以下或0.2以下。从得到基于Hf的置换效果的观点出发,Hf的置换量x可以为0.01以上、0.05以上、0.08以上或0.1以上。
若Nb的置换量z变大,则有时随着氧化物中的Li量的增加,离子电导率提高。另一方面,认为若Nb的置换量z变大,则有晶格间距变小的倾向,锂离子的扩散路径变窄。Nb的置换量z可以为0.01以上、0.05以上、0.1以上、0.2以上、0.3以上或0.4以上,可以为1以下、0.8以下、0.7以下或0.6以下。
如上所述,认为通过使LLZ系氧化物包含Zn、Bi、Hf、Nb等作为置换元素,从而晶体结构(晶相、晶格常数)变化、Li离子的含量变化成为使LLZ系氧化物的离子电导率变化的主要因素。优选LLZ系氧化物为立方晶。立方晶的LLZ系氧化物有显示高的离子电导率的倾向,特别是晶体为单相时,有离子电导率变高的倾向。
另外,通过包含置换元素,从而有时抑制烧结体中的孔隙、异常晶粒生长等缺陷的产生。即,Zn等置换元素具有烧结助剂、晶粒生长抑制剂等的作用,认为LLZ系氧化物的烧结体的密度上升也有助于离子电导率的提高。
LLZ系氧化物的密度优选为3.5g/cm3以上,可以为3.8g/cm3以上、4.0g/cm3以上、4.2g/cm3以上、或4.4g/cm3以上。氧化物的密度可以基于粒料的质量和体积来算出。例如圆柱状的粒料的情况下,用测微器(micrometer)对粒料的直径进行多个部位测量并采用平均值,厚度也同样地用测微器进行多个部位测定并采用平均值,根据它们的数值算出体积即可。
LLZ系氧化物的锂离子电导率优选5.0×10-5S/cm以上、更优选1.0×10-4S/cm以上、进一步优选3.0×10-4S/cm以上。锂离子电导率可以通过交流阻抗法来测定。需要说明的是,通过交流阻抗法测定氧化物烧结体的离子电导率时,有时检测到多个电阻成分。例如,晶界的电阻大的情况下,检测到表示晶粒部分的电阻的体电阻(bulk resistance)和表示晶界部分的电阻的晶界电阻。该情况下,可以将体电阻(通常显示相对较低的电阻)作为氧化物的电阻成分来算出离子电导率。
[氧化物的制造方法]
上述的LLZ系氧化物通过将作为主要构成元素源的Li化合物、La化合物及Zr化合物、以及包含Zn等置换元素的化合物混合并进行焙烧来得到。作为一例,对通过将原料混合、预焙烧后成形并进行正式焙烧(烧结)来制造氧化物的烧结体的方法进行说明。
首先,以成为目标氧化物的组成式的化学计量比的方式称量包含各元素的起始物质。作为起始原料,可以使用各元素的氧化物、氢氧化物、氯化物、碳酸盐、硫酸盐、硝酸盐、草酸盐等。对于混合方法,可以以干式进行混合粉碎,也可以添加溶剂以湿式进行混合粉碎。混合中可以使用行星磨、磨碎机、球磨机等。作为以湿式进行混合粉碎时的溶剂,优选Li不易溶解的溶剂,例如可以使用乙醇等有机溶剂。
混合粉末的预焙烧优选设为起始原料发生状态变化(例如气体的产生、相变)的温度以上、并且低于烧结时温度。具体而言,预焙烧温度优选800~1200℃左右。预焙烧通常在空气气氛下(氧化气氛下)进行。
将通过预焙烧得到的材料成形为规定的形状。可以在成形之前进行预焙烧后的材料的粉碎混合。作为成形方法,可举出在粉末中添加粘结剂并进行模具成形的方法、冷等静压成形(CIP)、热等静压成形(HIP)、热压等。烧结可以在大气气氛下实施,也可以在氮气、氩气等非活性气体气氛下实施。根据需要可以在还原气氛下进行焙烧。烧结温度只要为比预焙烧温度高的温度即可,具体而言优选1100℃以上、更优选1150℃以上。
上述的方法为一例,也可以通过其它方法得到LLZ系氧化物。例如,也可以将原料粉末和助熔剂(flux)混合,通过机械化学法制造具有期望组成的LLZ系氧化物。
[氧化物的用途]
上述的LLZ系氧化物可以作为全固态电池的固体电解质利用,特别优选用作全固态锂离子二次电池的固体电解质。全固态电池具备正极、负极、及固体电解质,作为固体电解质,包含上述的氧化物。固体电解质除了包含在配置于正极与负极之间的隔膜中以外,还可以包含在正极和/或负极中。
正极及负极包含活性物质。关于活性物质,作为全固态电池的活性物质而公知的物质均可以使用。例如,作为锂全固态电池的活性物质,可举出LiCoO2;LiNixCo1-xO2(0<x<1);LiNi1/3Co1/3Mn1/3O2;LiMnO2;异种元素置换Li-Mn尖晶石;钛酸锂;磷酸金属锂;过渡金属氧化物;TiS2v石墨、硬碳等碳材料;LiCoN;SiO2;Li2SiO3;Li4SiO4;金属锂;LiSn、LiSi、LiAl、LiGe、LiSb、LiP等锂合金;Mg2Sn、Mg2Ge、Mg2Sb、Cu3Sb等锂贮藏性金属间化合物。锂全固态电池中,可以选择吸藏/放出锂离子的电位(充放电电位)不同的2种物质,将显示高电位的物质作为正极活性物质、将显示低电位的物质作为负极活性物质。
构成正极及负极的电极合剂除活性物质之外,还可以包含固体电解质、导电助剂、粘结剂等。作为电极合剂中包含的固体电解质,可以使用上述LLZ系氧化物。另外,也可以使用上述以外的LLZ系氧化物、硫化物系固体电解质。作为导电助剂,例如,除了气相沉淀碳纤维、乙炔黑、科琴黑、碳纳米管、碳纳米纤维等碳材料以外,还可使用可耐受全固态电池的使用时的环境的金属材料。作为粘结剂的例子,可举出丙烯腈丁二烯橡胶、丁二烯橡胶、聚偏氟乙烯、苯乙烯丁二烯橡胶等橡胶系聚合物。
正极及负极分别具备集电体。作为集电体,优选Cu、Ni、Al、V、Au、Pt、Mg、Fe、Ti、Co、Cr、Zn、Ge、In等金属或包含它们中的2种以上的元素的合金材料。集电体的形状没有特别限定,可以为箔状或网状。正极及负极例如可以通过将浆料状的电极合剂组合物涂布于集电体的表面后进行干燥来形成。也可以通过对电极合剂和集电体进行干式成形来制作正极及负极。
如上所述,全固态电池中,正极及负极中可以包含固体电解质。另外,全固态电池具备作为正极与负极之间的隔膜的固体电解质层。优选该固体电解质层中也包含上述LLZ系氧化物。另外,固体电解质层中可以包含粘结剂。固体电解质层可以通过湿式法及干式法中的任意方法来制作。
实施例
以下,示出实施例更具体地对本发明进行说明,但本发明不限定于下述的实施例。
[试样的制备]
作为原料成分,将氧化锂、氧化镧、氧化锆、氧化锌、氧化铪、氧化铌及氧化铋以表1所示的投料量配混。利用转动球磨机将原料混合粉碎后,使用模具压制成形为圆柱的粒料状。将粒料放入氧化铝坩埚,出于抑制焙烧时的Li挥发的目的,用正方晶Li7La3Zr2O12(LLZ)的粉末覆盖粒料。在流通干燥氮气的气氛下以1100℃进行12小时焙烧。
将焙烧后的粒料在乳钵中破碎混合,使用模具再次压制成形为圆柱的粒料状。将成形体放入氧化铝坩埚中,与焙烧时同样地用正方晶LLZ的粉末覆盖粒料,在流通干燥氮气的气氛下以1230℃保持20小时,得到烧结体(试样1~13)。
[评价]
<烧结体的截面观察>
利用扫描型电子显微镜(SEM)对试样1~11观察截面。将试样1~7的SEM图像示于图1、将试样8~11的SEM图像示于图2。
<X射线衍射>
对试样1~11进行以CuKα为射线源的X射线衍射测定。将试样1~7的X射线衍射图示于图3及图4,将试样8~11的X射线衍射图示于图5及图6。图3及图5为2θ=10~60°的范围的X射线衍射图,图4及图6为2θ=30~40°的范围的X射线衍射图。
<锂离子电导率>
通过Au溅射在试样1~13的两面形成直径8mm的电极,制作离子电导率测定用试样。将该试样在氩气气氛的手套箱内安装于全固态电池评价单元中(宝泉株式会社制),与恒电位仪/恒电流仪(potentiostat/galvanostat)连接,通过交流阻抗测定进行离子电导率的评价。交流阻抗测定的条件设为:频率0.01Hz~1MHz、电压50mV。测定时观测到2个电阻成分(体电阻和晶界电阻)的情况下,采用体电阻的离子电导率σBulk。
将试样1~13的原料投料量及投料组成、以及锂离子电导率σBulk示于表1。
[表1]
试样1~13均显示10-5S/cm级或10-4S/cm级的锂离子电导率,通过置换元素的导入,与无置换的LLZ(锂离子电导率:10-6S/cm~10-7S/cm)相比,传导率提高。
包含Zn、Hf及Nb作为置换元素的试样1~7中,试样1显示最高的锂离子电导率。可知对于相较于试样1增加了基于Hf的置换量的试样2、3,与试样1相比,传导率降低。根据图1可知,试样2、3与试样1相比,空隙变大。对于图4的X射线衍射图,可知试样2、3与试样1相比,衍射峰向高角侧(晶格常数变小)偏移。认为这是由于Li被离子半径相对较小的Hf置换所引起的。对于试样2、3,认为随着基于Hf的置换量的增加,晶格常数变小、锂离子的扩散路径变窄,Li含量减少,从而与试样1相比,传导率变小。
对于相较于试样1增加了基于Zn的置换量的试样4、5,与试样1相比,传导率也降低。图4的X射线衍射图中,认为试样4、5与试样1相比,衍射峰向高角侧偏移、锂离子的扩散路径变窄成为与试样1相比传导率变小的一个原因。
对于相较于试样1增加了基于Nb的置换量的试样6、7,与试样1相比,观察到传导率略有降低。Zr被置换为Nb的情况下,为了补充电荷的差,期待Li的含量增加、传导率增加,但没有观察到这样的现象。图4的X射线衍射图中,试样6、7与试样1相比,衍射峰稍微向高角侧偏移。尽管6配位的Zr4+和6配位的Nb3+的离子半径没有差异,但作为在Nb置换量大的试样6、7中观察到高角偏移的主要因素,推测是因为:作为置换元素而导入的Nb的一部分或全部被导入至La位点、和/或Nb以Nb5+的形式被导入至Zr位点。认为由于8配位的Nb5+比8配位的La3+的离子半径小、6配位的Nb5+比6配位的Zr4+的离子半径小,因此Nb5+被导入至La位点和/或Zr位点时,晶格常数变小。另外,通过Nb以Nb5+的形式被导入,从而Li的含量减少,这也有可能成为离子电导率降低的主要因素。
根据试样1~7的X射线衍射图(图3、4),表明任意试样均为立方晶,但试样1为单相,而试样2~7中确认了多个相。推测试样1中维持了LLZ的石榴石型结构与高离子电导率有关联。
包含Zn及Bi作为置换元素的试样8~13中,试样8显示最高的离子电导率。对于相较于试样8增加了基于Zn的置换量的试样9、及减少了基于Zn的置换量的试样12、13,与试样8相比,传导率降低。认为试样12、13中基于Zn的置换元素导入效果小。图6的X射线衍射图中,认为试样9与试样8相比衍射峰向高角侧偏移,晶格常数变小、Li离子的扩散路径变窄成为传导率降低的一个原因。
对于相较于试样8增加了基于Bi的置换量的试样10、11,观察到随着Bi置换量的增加,衍射峰向高角侧偏移的倾向。另外,试样8为单相,而试样9~11中确认到多个相。推测试样8中维持了LLZ的石榴石型结构也与高离子电导率有关联。
如上述的试样1~13的评价结果所示,包含Zn作为置换元素的LLZ系氧化物具有优异的锂离子电导率。另外,通过调整Zn的置换量、除Zn以外的置换元素的种类及量,有能够进一步提高锂传导率的可能性。
Claims (7)
1.一种氧化物,其是将Li、La、Zr及O作为主要构成元素的石榴石型氧化物,
所述氧化物包含所述主要构成元素和置换元素,所述置换元素至少包含Zn。
2.根据权利要求1所述的氧化物,其中,所述置换元素还包含Bi。
3.根据权利要求2所述的氧化物,其具有Li(7-2j)ZnjLa(3-k)BikZr2O(12-δ)所示的组成,其中,0<j<3.5、0<k<3、0≤δ<1。
4.根据权利要求1所述的氧化物,其中,所述置换元素还包含选自由Nb及Hf组成的组中的1种以上的元素。
5.根据权利要求4所述的氧化物,其具有Li(7-4x+z)HfxLa(3-2y/3)ZnyZr(2-z)NbzO(12-δ)所示的组成,0<x<1.75、0≤y<3、0≤z<2、0≤δ<1,其中,y及z中的至少任一者不为0。
6.一种固体电解质,其包含权利要求1~5中任一项所述的氧化物。
7.一种全固态锂离子二次电池,其具备:正极、负极、及配置于所述正极与负极之间的固体电解质层,
所述固体电解质层包含权利要求1~5中任一项所述的氧化物。
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