CN111048772A - 混合导体、电极、电化学装置及制备混合导体的方法 - Google Patents
混合导体、电极、电化学装置及制备混合导体的方法 Download PDFInfo
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- CN111048772A CN111048772A CN201910962039.4A CN201910962039A CN111048772A CN 111048772 A CN111048772 A CN 111048772A CN 201910962039 A CN201910962039 A CN 201910962039A CN 111048772 A CN111048772 A CN 111048772A
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- 238000004458 analytical method Methods 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
- C01G27/006—Compounds containing, besides hafnium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/02—Arsenates; Arsenites
- C01G28/023—Arsenates; Arsenites of ammonium, alkali or alkaline-earth metals or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/02—Arsenates; Arsenites
- C01G28/026—Arsenates; Arsenites containing at least two metals
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Abstract
本发明涉及混合导体、电极、电化学装置及制备混合导体的方法。由式1表示的混合导体,其中,在式1中,A为单价阳离子,G为单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr,其中0<x<2,0.3<y<5,0<z<5,和0<δ≤3。式1A4±xTi5‑yGzO12‑δ 。
Description
对相关申请的交叉引用
本申请要求于2018年10月11日在美国专利商标局提交的临时美国专利申请No.62/744,618和于2018年10月12日在韩国知识产权局提交的韩国专利申请No.10-2018-0122039的权益、以及由其产生的全部权益,将其全部内容通过引用引入本文中。
技术领域
本公开内容涉及混合导体(即,具有电子传导性和离子传导性二者的材料)、包括所述混合导体的电化学装置、以及制备所述混合导体的方法。
背景技术
在电化学装置如电池中,离子和电子在正极和负极之间通过单独的传输通道迁移,并且当离子和电子在电极处合并时发生电化学反应。
电极包括用于离子传输的离子导体和用于电子传输的电子导体二者。例如,在电极中,有机液体电解质可用作离子导体,且碳质导电剂可用作电子导体。有机液体电解质和碳质导电剂可被在电化学反应期间产生的自由基而容易地分解,使电池的性能劣化。电极中的碳质导电剂阻碍离子传输/扩散,并且液体电解质阻碍电子传输,从而增加电池的内阻。
因此,需要对电化学反应的副产物具有改善的稳定性并且同时传输离子和电子的导体。
发明内容
提供化学稳定的并且同时传输离子和电子的混合导体。
提供包括所述混合导体的电化学装置。
提供制备所述混合导体的方法。
另外的方面将部分地在随后的描述中阐明,并且部分地将从所述描述明晰,或者可通过所呈现的实施方式的实践而获知。
根据一种实施方式的方面,混合导体可由式1表示:
式1
A4±xTi5-yGzO12-δ
其中,在式1中,
A为单价阳离子,
G为单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr,以及
其中0<x<2,0.3<y<5,0<z<5,和0<δ≤3。
公开了包括所述混合导体的电极。
根据另一实施方式的方面,电化学装置包括:正极;包括所述电极的负极;以及在所述正极和所述负极之间的隔板。
根据又一实施方式的方面,制备混合导体的方法包括:提供包括元素A前体、钛前体和元素G前体的混合物,其中所述元素A前体提供单价阳离子,且所述元素G前体提供单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr;以及热处理所述混合物以制备混合导体。
附图说明
由结合附图考虑的实施方式的以下描述,这些和/或其它方面将变得明晰和更容易领会,其中:
图1为强度(任意单位)对衍射角(度,2θ)的图,其说明实施例1-3和对比例1中制备的混合导体的X射线衍射(XRD)分析的结果;
图2A为态密度(DOS)对能量(电子伏特,eV)的图并且显示Li4Ti5O12的总的态密度;
图2B为态密度(DOS)对能量(电子伏特,eV)的图并且显示Li4.5Ti4.5Nb0.5O12的总的DOS;
图2C为态密度(DOS)对能量(电子伏特,eV)的图并且显示Li3.5Ti4NbO12的总的DOS;
图2D为态密度(DOS)对能量(电子伏特,eV)的图并且显示Li3.5Ti4TaO12的总的DOS;
图2E为态密度(DOS)对能量(电子伏特,eV)的图并且显示Li4Ti5O11.5的总的DOS;
图3为说明Li4Ti5O12的尖晶石型晶体结构的示意图;以及
图4为说明锂空气电池的实施方式的示意图。
具体实施方式
现在将详细介绍实施方式,其实例示于附图中,其中相同的附图标记始终表示相同的元件。在这方面,本实施方式可具有不同的形式并且不应解释为限于本文中阐述的描述。因此,以下仅通过参照附图描述实施方式以说明方面。如本文中所使用的,术语“和/或”包括相关所列项目的一个或多个的任意和全部组合。
由于本发明构思允许多种改变和许多实施方式,故而将在图中示出并且在书面描述中详细描述具体实施方式。然而,这不意图将本发明构思限于具体的实践方式,并且将理解,不背离本发明构思的精神和技术范围的所有变化、等同物和替代物均包括在本发明构思中。
本说明书中使用的术语仅用于描述具体实施方式,且不意图为限制性的。以单数使用的表述包括复数的表述,除非其在上下文中具有明显不同的含义。如本文中使用的,单数形式“一个(种)(a,an)”和“所述(该)”意图包括复数形式,包括“至少一个(种)”,除非内容清楚地另外指明。在本说明书中,将理解术语如“包括”、“具有”等意图表示存在说明书中公开的特征、数量、步骤、动作、组分、部件、成分、材料或其组合,且不意图排除可存在或可添加一种或多种其它的特征、数量、步骤、动作、组分、部件、成分、材料或其组合的可能性。如本文中使用的,取决于上下文,“/”可解释为是指“和”或者“或”。“至少一个(种)”不解释为限制“一个(种)”。“或”意味着“和/或”。如本文中使用的,术语“和/或”包括相关所列项目的一个或多个的任意和全部组合。将进一步理解,当用在本说明书中时,术语“包含”和/或“包括”表示存在所述的特征、区域、整体、步骤、操作、元件和/或组分,但不排除存在或添加一种或多种其它的特征、区域、整体、步骤、操作、元件、组分和/或其集合。
如本文中使用的“约”包括所陈述的值且意味着在如由本领域普通技术人员考虑到所讨论的测量和与具体量的测量有关的误差(即,测量系统的限制)而确定的对于具体值的可接受的偏差范围内。例如,“约”可意味着在所陈述的值的一种或多种标准偏差内,或在所陈述的值的±30%、20%、10%或5%内。
在图中,为了清楚,放大或缩小层和区域的厚度。在图和说明书中,相同的附图标记表示相同的元件。在本说明书中,将理解,当一个元件如层、膜、区域或基板被称作“在”另外的元件“上”或“上方”时,其可直接在所述另外的元件上或者还可存在中间元件。尽管术语诸如“第一”、“第二”等可用来描述多种组分,但这样的组分不必限于以上术语。以上术语仅用来使一种组分区别于另外的组分。
如本文中使用的,术语“混合导体”是指同时提供离子传导性和电子传导性二者的导体。例如,所述混合导体同时提供与Li4Ti5O12相比改善的离子传导性和电子传导性二者。
如固态科学中技术人员将理解的并且如本文中使用的,“尖晶石结构”或“尖晶石型”结构是指该化合物与尖晶石即MgAl2O4是同构的。
在下文中,根据实例实施方式,将进一步详述混合导体、包括所述混合导体的电化学装置、以及制备所述混合导体的方法。
根据实施方式的混合导体可由式1表示:
式1
A4±xTi5-yGzO12-δ
其中,在式1中,A可为单价阳离子,G可为单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr,以及其中0<x<2,0.3<y<5,0<z<5,和0<δ≤3。δ表示氧空位的含量。当δ大于0时,所述混合导体含有氧空位。
以上述组成包括如下和氧空位的混合导体提供预料不到的离子传导性和电子传导性的组合:元素A,其为单价阳离子;Ti元素;和元素G,其为单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种。尽管不希望受理论束缚,但理解,离子传导性和电子传导性是由包括所述阳离子元素和氧空位含量引起的。而且,所述混合导体提供预料不到的对自由基等的化学稳定性,所述自由基等理解为在电化学反应期间产生的。尽管不希望受理论束缚,但理解,改善的稳定性是因为与有机化合物相反,所述混合导体是无机氧化物。
在一个方面,式1中的A可为单价碱金属阳离子。式1中的A可为例如Li、Na、或K的至少一种。在一个方面,A为Li。
在一个方面,G可为二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr。式1中的G可包括例如如下的至少一种:Mg、Ca、Sr、Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Zr、Hf、V、Nb、Ta、Mo、W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Ge、Sn、Pb、Sb、Bi、Po、As、Se、或Te。在一个方面,G为如下的至少一种:第5族元素、第7族元素、第9族元素、第11族元素、第13族元素或镧系元素。提及其中G为如下的至少一种的方面:Nb、Ta、Gd、In、Co、Mn、或Cu。在一个方面,G为Nb、Ta、Gd、In、Co、Mn、或Cu。在一个方面,G是Nb、Ta、Gd、或In。
在式1中,x可为0<x<2,0.1<x<1.9,0<x<1.8,0.2<x<1.7,0.3<x<1.6,或0.5<x<1.5。在一个方面,0.1≤x≤1.9,0.1≤x≤1.8,0.2≤x≤1.7,0.3≤x≤1.6,或0.5≤x≤1.5。在一个方面,x为0.5或1。
在式1中,y可为0.3<y<5,0.4<y<4.5,0.5<y<4,0.6<y<3.5,0.7<y<3,0.8<y<2.5,或0.9<y<2。在一个方面,0.35≤y≤4.5,0.4≤y≤4.5,0.5≤y≤4,0.6≤y≤3.5,0.7≤y≤3,0.8≤y≤2.5,或0.9≤y≤2。在一个方面,y为0.5或1。
在式1中,z可为0<z<5,0.1<z<4.5,0.2<z<4,0.3<z<3.5,0.4<z<3,0.5<z<2.5,或0.6<z<2。在一个方面,0.1≤z≤4.5,0.2≤z≤4,0.3≤z≤3.5,0.4≤z≤3,0.5≤z≤2.5,或0.6≤z≤2。在一个方面,z为0.5或1。
如上指出,δ可表示氧空位的含量。δ可为0<δ≤3,0.1<δ≤2,0.2<δ≤1.5,0.3<δ≤1,或0.4<δ≤0.5。在一个方面,δ可为0<δ≤3,0<δ≤2,0<δ≤1.5,0<δ≤1,0<δ≤0.5,或0<δ≤0.3。
所述混合导体可包括例如选自如下的至少一种:Li4±xTi5-yMgzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yCazO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-ySrzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-ySczO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yYzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yLazO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5- yCezO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yPrzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yNdzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-ySmzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yEuzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yGdzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yTbzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5- yDyzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yHozO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yErzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yTmzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yYbzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yLuzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yZrzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5- yHfzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yVzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yNbzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yTazO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yMozO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yWzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yMnzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yTczO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yRezO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yFezO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4± xTi5-yRuzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yOszO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yCozO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yRhzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yIrzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yNizO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yPdzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5- yPtzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yCuzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yAgzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yAuzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yZnzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yCdzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yHgzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5- yAlzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yGazO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yInzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yTlzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yGezO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-ySnzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yPbzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5- ySbzO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yBizO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yPozO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-yAszO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、Li4±xTi5-ySezO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)、或Li4±xTi5-yTezO12-δ(其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ)。在上述混合导体中,例如,0<δ≤3,0<δ≤2,0<δ≤1.5,0<δ≤1,0<δ≤0.5,或0<δ≤0.3。
例如,所述混合导体可具有大于所述混合导体的离子传导率的电子传导率。所述混合导体同时提供离子导电性和电子导电性二者,并且所述混合导体的电子传导率可大于离子传导率。在室温下,例如在25℃下,所述混合导体的电子传导率可例如比所述混合导体的离子传导率大10至106倍、50至106倍、1×102至106倍、5×102至106倍、或1×103至106倍。而且,在室温下,例如在25℃下,所述混合导体的电子传导率可例如比Li4Ti5O12的电子传导率大1×103至106倍、5×103至106倍、或1×104至106倍。
在室温下,例如在25℃下,所述混合导体的电子传导率可为例如1.0×10-6S/cm至1.0S/cm、5.0×10-6S/cm至1.0S/cm、1.0×10-5S/cm至1.0S/cm、5.0×10-5S/cm至1.0S/cm、1.0×10-4S/cm至1.0S/cm、5.0×10-4S/cm至1.0S/cm、或1.0×10-3S/cm至1.0×10-1S/cm。由于所述混合导体具有这样高的电子传导率,故而包括所述混合导体的电化学装置可具有降低的内阻。电子传导率可通过涡流法或开尔文电桥法测定。电子传导率可根据ASTM B-193,“Standard Test Method for Resistivity of Electrical Conductor Materials”,例如在25℃下,或者根据ASTM E-1004,“Standard Test Method for Determining ElectricalConductivity Using the Electromagnetic(Eddy-Current)Method”,例如在25℃下测定。另外的细节可由本领域技术人员在无需过度实验的情况下确定。
在室温下,例如在25℃下,所述混合导体的离子传导率可为例如1.0×10-7S/cm至1.0×10-1S/cm、5.0×10-7S/cm至1.0×10-1S/cm、1.0×10-6S/cm至1.0×10-1S/cm、5.0×10- 6S/cm至1.0×10-1S/cm、或1.0×10-5S/cm至1.0×10-2S/cm。在室温下,例如在25℃下,所述混合导体的离子传导率可为例如1.0×10-7S/cm至10-4S/cm、5.0×10-7S/cm至10-4S/cm、1.0×10-6S/cm至10-4S/cm、5.0×10-6S/cm至10-4S/cm、或1.0×10-5S/cm至10-4S/cm。因为所述混合导体具有这样高的离子传导率,故而包括所述混合导体的电化学装置可具有降低的内阻。离子传导率可通过复合阻抗法在25℃下测定,其进一步的细节可在J.-M.Winand等,“Measurement of Ionic Conductivity in Solid Electrolytes”,EurophysicsLetters,第8卷,第5号,第447-452页,1989中找到。
所述混合导体可包括例如具有尖晶石型晶体结构的相。尽管不希望受理论束缚,但理解所述尖晶石型结构对所述混合导体的改善的电化学稳定性做贡献。
例如,在所述混合导体的X射线衍射(XRD)光谱中,在18°±2.5°的衍射角2θ处的对应于晶面(111)的峰强度(Ia)对在23.5°±2.5°的衍射角2θ处的峰强度(Ib)的峰强度比(Ia/Ib)可为0.001至1、0.001至0.9、0.001至0.8、0.001至0.7、0.001至0.6、0.001至0.5、或0.001至0.4。尽管不希望受理论束缚,但理解,当所述混合导体具有这样的峰强度比时,电子传导性和离子传导性得到改善。
所述混合导体可具有不同于具有尖晶石型晶体结构的相的另外的相。例如,所述混合导体可包括具有尖晶石型晶体结构的相,其属于具有立方对称性、例如具有立方面心布拉维晶格对称性的空间群,例如,Fd-3m空间群,即空间群227,并且除了所述相之外,所述混合导体可包括不同于具有尖晶石型晶体结构的相的另外的相,例如Li2TiO3、Gd2Ti2O7、GdTiO3、LiNbO3、或Nb2O5的至少一种。尽管不希望受理论束缚,但理解,所述混合导体的改善的电子传导性和离子传导性是因为所述混合导体具有包括如下的多晶结构:多个不同的相,例如具有不同的结构类型、不同的布拉维晶格对称性、不同的组成、或不同的空间群的相。
所述混合导体的价带和导带之间的带隙可小于Li4Ti5O12的价带和导带之间的带隙。例如,所述混合导体的价带和所述混合导体的导带之间的带隙可为0.001电子伏特(eV)至2.0eV、0.001eV至1.8eV、0.001eV至1.6eV、0.001eV至1.4eV、或0.001eV至1.2eV。由于所述混合导体具有这样低的在价带和导带之间的带隙的值,故而可使从价带到导带的电子传输容易,从而改善所述混合导体的电子传导性。
在所述混合导体中,例如,Ti可具有在3和4之间的氧化数、例如氧化态或形式氧化态。例如,因为所述混合导体中的Ti具有拥有至少两种不同的氧化数的混合价态,故而可在费米能(Ef)附近观察到新的态密度函数,并且可减小在价带和导带之间的带隙。尽管不希望受理论束缚,但理解,所述混合导体包括在费米能附近的态密度函数,并且该态密度函数对所述混合导体的改善的电子传导性做贡献。
在式1中,所述混合导体中的G可具有例如不同于Ti的氧化数的氧化数。例如,由于在所述混合导体中另外包括具有不同于Ti的氧化数的氧化数的式1中的G,故而可在费米能(Ef)附近观察到另外的新的态密度函数,并且可减小在价带和导带之间的带隙。尽管不希望受理论束缚,但理解改善的电子传导性是由减小的带隙引起的。
通过包括氧空位,所述混合导体可提供进一步改善的离子传导性。例如,由于在所述混合导体中包括氧空位,态密度函数的位置可更靠近于费米能(Ef)移动,并且可减小在价带和导带之间的带隙。最后,所述混合导体可具有进一步改善的离子传导性。尽管不希望受理论束缚,但理解所公开的混合导体包括如下的在价带和导带之间的带隙:其小于具有相同的A、Ti和G含量且没有氧空位的材料的带隙。
在所述混合导体中,例如,参照图3,A可位于尖晶石型晶体结构中的四面体8a位点350、八面体16c位点360和部分地八面体16d位点370的至少一个上。参照图3,当A是锂时,所述混合导体的从四面体8a位点经由八面体16c位点到另外的四面体8a位点的锂过渡(transition)的活化能(Ea,8a->16c->8a)小于Li4Ti5O12的锂过渡的活化能(Ea,8a->16c->8a)。因为所述混合导体在锂过渡时具有比Li4Ti5O12的活化能小的活化能,故而在所述混合导体中可使锂离子的传输和/或扩散容易。所述混合导体中的降低的活化能被理解为导致比Li4Ti5O12的离子传导率大的离子传导率。
电极包括所述混合导体。
根据实施方式的电化学装置可包括所述混合导体。所述电化学装置可包括:正极;包括所述电极的负极;以及在所述正极和所述负极之间的隔板。由于所述电化学装置包括提供改善的化学稳定性并且同时传输离子和电子的所述混合导体,故而可防止所述电化学装置的劣化。
例如,所述电化学装置可为如下的至少一种:电池、蓄电池、超级电容器、燃料电池、传感器和电致变色装置。然而,实施方式不限于此。可使用本领域中可用的任何合适的电化学装置。
所述电池可为例如一次电池或二次电池。所述电池可为例如锂电池、钠电池等。然而,实施方式不限于此。可使用本领域中可用的任何合适的电池。所述锂电池可为例如锂离子电池、锂-空气电池等。然而,实施方式不限于此。可使用本领域中可用的任何合适的锂电池。电致变色装置的实例包括电化学镜、窗、屏幕、立面(表面)等。然而,实施方式不限于此。可使用本领域中可用的任何合适的电致变色装置。
包括所述混合导体的所述电化学装置可为例如锂-空气电池。
所述锂空气电池可包括正极。所述正极可为空气电极。在一个方面,所述正极可在正极集流体上。
所述正极可包括传导性材料(导电材料)。所述传导性材料可为例如多孔的。因为所述传导性材料是多孔的,故而可使空气渗透到所述传导性材料中容易。所述传导性材料可为多孔和/或电传导性的材料。可使用本领域中可用的任何合适的传导性材料。例如,所述传导性材料可为多孔碳质材料。所述碳质材料的实例可包括炭黑、石墨、石墨烯、活性炭、碳纤维等。可使用本领域中可用的任何合适的碳质材料。所述传导性材料可为例如金属材料。所述金属材料可为例如金属纤维、金属网、金属粉末等。所述金属粉末可为例如铜、银、镍、铝等。所述传导性材料可为例如电传导性有机材料。所述电传导性有机材料的实例包括聚亚苯基衍生物或聚噻吩衍生物。所述传导性材料可例如单独地或以组合使用。所述正极可包括混合导体作为所述传导性材料。除了所述混合导体之外,所述正极可进一步包括任意以上列出的传导性材料。
所述正极可进一步包括例如用于氧的氧化/还原的催化剂。所述催化剂可为例如基于金属的催化剂如铂、金、银、钯、钌、铑和锇;基于氧化物的催化剂如锰氧化物、铁氧化物、钴氧化物、镍氧化物;或有机金属催化剂如酞菁钴。然而,实施方式不限于此。可使用本领域中可用的任何合适的用于氧的氧化/还原的催化剂。
例如,所述催化剂可负载在催化剂载体上。所述催化剂载体可为例如氧化物催化剂载体、沸石催化剂载体、基于粘土的矿物催化剂载体、碳催化剂载体等。所述氧化物催化剂载体可为例如包括如下的至少一种金属/准金属的金属氧化物催化剂载体:Al、Si、Zr、Ti、Ce、Pr、Sm、Eu、Tb、Tm、Yb、Sb、Bi、V、Cr、Mn、Fe、Co、Ni、Cu、Nb、Mo、或W。所述氧化物催化剂载体可包括例如氧化铝、二氧化硅、氧化锆、二氧化钛等。所述碳催化剂载体可为炭黑如科琴黑、乙炔黑、槽黑或灯黑;石墨如天然石墨、人造石墨、或可膨胀石墨;活性炭;和碳纤维。然而,实施方式不限于此。可使用本领域中可用的任何合适的催化剂载体。
例如,所述正极可进一步包括粘合剂。所述粘合剂可包括例如热塑性树脂或可热固化树脂。所述粘合剂的非限制性实例包括聚乙烯、聚丙烯、聚四氟乙烯(PTFE)、聚偏氟乙烯(PVdF)、苯乙烯-丁二烯橡胶、四氟乙烯-全氟烷基乙烯基醚共聚物、偏氟乙烯-六氟丙烯共聚物、偏氟乙烯-三氟氯乙烯共聚物、乙烯-四氟乙烯共聚物、聚三氟氯乙烯、偏氟乙烯-五氟丙烯共聚物、丙烯-四氟乙烯共聚物、乙烯-三氟氯乙烯共聚物、偏氟乙烯-六氟丙烯-四氟乙烯共聚物、偏氟乙烯-全氟甲基乙烯基醚-四氟乙烯共聚物、或乙烯-丙烯酸共聚物,其可单独地或以任何合适的组合使用。可使用本领域中可用的任何合适的粘合剂。
例如,可通过如下制造所述正极:将传导性材料、用于氧的氧化/还原的催化剂和粘合剂混合在一起,并且将溶剂添加到所得混合物以制备正极浆料,将所述正极浆料涂覆在基底的表面上,干燥涂覆的正极浆料,并且将所述正极浆料对着所述基底压制成型以改善电极的密度。所述基底可为例如正极集流体、隔板或固体电解质膜。所述正极集流体可为例如气体扩散层。所述传导性材料可包括混合导体。取决于所述正极的类型,可省略所述用于氧的氧化/还原的催化剂和粘合剂。
所述锂-空气电池包括负极。所述负极可包括锂。
所述负极可为例如锂金属薄膜或基于锂金属的合金薄膜。例如,所述基于锂金属的合金可为锂与例如铝、锡、镁、铟、钙、钛或钒的合金。
所述锂-空气电池可包括在所述正极和所述负极之间的电解质膜。
所述电解质膜可包括液体电解质、凝胶电解质和固体电解质的至少一种电解质。所述液体电解质、凝胶电解质和固体电解质没有特别限制,且可为本领域中可用的任何合适的电解质。
所述固体电解质可包括如下的至少一种:包括离子传导性无机材料的固体电解质、包括聚合物离子液体(PIL)和锂盐的固体电解质、包括离子传导性聚合物和锂盐的固体电解质。然而,实施方式不限于此。可使用本领域中可用作固体电解质的任何合适的材料。
所述离子传导性无机材料可包括如下的至少一种:玻璃或无定形金属离子导体、陶瓷活性金属离子导体、和玻璃-陶瓷活性金属离子导体。然而,实施方式不限于此。可使用本领域中可用的任何合适的离子传导性无机材料。所述离子传导性无机材料可为例如离子传导性无机颗粒或片的模塑产物。
例如,所述离子传导性无机材料可为如下的至少一种:BaTiO3、其中0≤a≤1的Pb(Zr1-aTia)O3("PZT")、Pb1-xLaxZr1-yTiyO3("PLZT")(其中0≤x<1和0≤y<1)、Pb(Mg1/3Nb2/3)O3-PbTiO3("PMN-PT")、HfO2、SrTiO3、SnO2、CeO2、Na2O、MgO、NiO、CaO、BaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2、SiO2、SiC、磷酸锂(Li3PO4)、锂钛磷酸盐(LixTiy(PO4)3,其中0<x<2,和0<y<3)、锂铝钛磷酸盐(LixAlyTiz(PO4)3,其中0<x<2,0<y<1,和0<z<3)、Li1+x+y(AlaGa1-a)x(TibGe1-b)2-xSiyP3- yO12(其中0≤a≤1,0≤b≤1,0≤x≤1,和0≤y≤1)、锂镧钛酸盐(LixLayTiO3,其中0<x<2和0<y<3)、锂锗硫代磷酸盐(LixGeyPzSw,其中0<x<4,0<y<1,0<z<1,和0<w<5)、氮化锂(LixNy,其中0<x<4和0<y<2)、SiS2型玻璃(LixSiySz,其中0<x<3,0<y<2,和0<z<4)、P2S5型玻璃(LixPySz,其中0<x<3,0<y<3,和0<z<7)、Li2O、LiF、LiOH、Li2CO3、LiAlO2、基于Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2的陶瓷、基于石榴石的陶瓷、Li3+xLa3M2O12(其中M=Te、Nb、或Zr)或其组合。
所述聚合物离子液体(PIL)可包括例如包含如下的重复单元:i)如下的至少一种阳离子:基于铵的阳离子、基于吡咯烷的阳离子、基于吡啶的阳离子、基于嘧啶的阳离子、基于咪唑的阳离子、基于哌啶的阳离子、基于吡唑的阳离子、基于唑的阳离子、基于哒嗪的阳离子、基于的阳离子、基于锍的阳离子、或基于三唑的阳离子;以及ii)如下的至少一种阴离子:BF4 -、PF6 -、AsF6 -、SbF6 -、AlCl4 -、HSO4 -、ClO4 -、CH3SO3 -、CF3CO2 -、(CF3SO2)2N-、Cl-、Br-、I-、SO4 2-、CF3SO3 -、(C2F5SO2)2N-、(C2F5SO2)(CF3SO2)N-、NO3 -、Al2Cl7 -、CH3COO-、(CF3SO2)3C-、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、SF5CF2SO3 -、SF5CHFCF2SO3 -、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、或(O(CF3)2C2(CF3)2O)2PO-。例如,所述PIL可为聚(TFSI)(二烯丙基二甲基铵)、聚(双(三氟甲磺酰)亚胺1-烯丙基-3-甲基咪唑)、或聚(双(三氟甲磺酰)亚胺N-甲基-N-丙基哌啶)。
所述离子传导性聚合物可包括例如至少一种得自基于醚的单体、基于丙烯酰基的单体、基于甲基丙烯酰基的单体或基于硅氧烷的单体的离子传导性重复单元。
所述离子传导性聚合物可包括例如聚环氧乙烷(PEO)、聚乙烯醇(PVA)、聚乙烯基吡咯烷酮(PVP)、聚砜、聚环氧丙烷(PPO)、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚二甲基硅氧烷、聚丙烯酸、聚甲基丙烯酸、聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯酸2-乙基己酯、聚甲基丙烯酸丁酯、聚甲基丙烯酸2-乙基己酯、聚丙烯酸癸酯、聚乙烯乙酸乙烯酯、磷酸酯聚合物、聚酯硫化物、聚偏氟乙烯(PVdF)、Li取代的Nafion等。然而,实施方式不限于此。可使用本领域中可用作离子传导性聚合物的任何合适的材料。
所述电子传导性聚合物可为例如聚亚苯基衍生物、聚噻吩衍生物等。然而,实施方式不限于此。可使用本领域中可用的任何合适的电子传导性聚合物。
例如,所述凝胶电解质可通过如下获得:向所述正极和所述负极之间的固体电解质添加低分子量溶剂。例如,所述凝胶电解质可通过如下获得:将溶剂如低分子量有机化合物、低聚物等添加至聚合物中。例如,所述凝胶电解质可通过如下获得:将溶剂如低分子量有机化合物、低聚物等添加至上述聚合物电解质中。
例如,所述液体电解质可包括溶剂和锂盐。
所述溶剂可包括有机溶剂、离子液体和低聚物的至少一种。然而,实施方式不限于此。可使用本领域中可用的且在室温(例如25℃)下为液体形式的任何合适的溶剂。
所述有机溶剂可包括例如如下的至少一种:基于醚的溶剂、基于碳酸酯的溶剂、基于酯的溶剂或基于酮的溶剂。例如,所述有机溶剂可包括如下的至少一种:碳酸亚丙酯、碳酸亚乙酯、碳酸氟代亚乙酯、碳酸乙烯基亚乙酯、碳酸亚丁酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、碳酸甲基异丙基酯、碳酸二丙酯、碳酸二丁酯、苄腈、乙腈、γ-丁内酯、二氧戊环、4-甲基二氧戊环、二甲基乙酰胺、二甲亚砜、二烷、1,2-二甲氧基乙烷、环丁砜、二氯乙烷、氯苯、硝基苯、丁二腈、二甘醇二甲醚(DEGDME)、四甘醇二甲醚(TEGDME)、聚乙二醇二甲醚(PEGDME,Mn=约500道尔顿)、二甲醚、二乙醚、二丁醚、二甲氧基乙烷、2-甲基四氢呋喃或四氢呋喃。然而,实施方式不限于此。可使用在室温下本领域中可用的液体形式的任何合适的有机溶剂。
所述离子液体(IL)可包括例如:i)如下的至少一种阳离子:基于铵的阳离子、基于吡咯烷的阳离子、基于吡啶的阳离子、基于嘧啶的阳离子、基于咪唑的阳离子、基于哌啶的阳离子、基于吡唑的阳离子、基于唑的阳离子、基于哒嗪的阳离子、基于的阳离子、基于锍的阳离子、基于三唑的阳离子、及其混合物;以及ii)如下的至少一种阴离子:BF4 -、PF6 -、AsF6 -、SbF6 -、AlCl4 -、HSO4 -、ClO4 -、CH3SO3 -、CF3CO2 -、(CF3SO2)2N-、Cl-、Br-、I-、SO4 2-、CF3SO3 -、(C2F5SO2)2N-、(C2F5SO2)(CF3SO2)N-、NO3 -、Al2Cl7 -、CH3COO-、(CF3SO2)3C-、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、SF5CF2SO3 -、SF5CHFCF2SO3 -、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、(SF5)3C-、或(O(CF3)2C2(CF3)2O)2PO-。
所述锂盐可包括例如如下的至少一种:双(三氟甲磺酰)亚胺锂(LiTFSI,LiN(SO2CF3)2),LiPF6、LiBF4、LiAsF6、LiClO4、LiNO3、双(草酸)硼酸锂(LiBOB)、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO3CF3)2、LiC4F9SO3、LiAlCl4、或三氟甲磺酸锂(LiTfO,LiCF3SO3)。然而,实施方式在本领域中没有限制。可使用本领域中可用作锂盐的任何合适的材料。所述锂盐的浓度可为例如0.01M至5.0M。
在实施方式中,所述锂-空气电池可进一步包括例如在所述正极和所述负极之间的隔板。所述隔板可为具有在锂-空气电池的使用环境下具有合适的耐久性的组成的任何合适的隔板。例如,所述隔板可为聚合物非织造织物如聚丙烯非织造织物或聚苯硫醚非织造织物;基于烯烃的树脂如聚乙烯或聚丙烯的多孔膜;玻璃纤维;或这些材料的至少两种的组合。
例如,所述电解质膜可具有包括浸渍有固体聚合物电解质或液体电解质的隔板的结构。包括浸渍有固体聚合物电解质的隔板的电解质膜可通过如下制备:将固体聚合物电解质膜布置在所述隔板的一个或两个表面上,同时对其进行辊压。在一些实施方式中,包括浸渍有液体电解质的隔板的电解质膜可通过如下制备:将包括锂盐的液体电解质注入所述隔板中。
在将所述负极安装在壳的内侧上之后,可将所述电解质膜布置在所述负极上,随后将所述正极布置在所述电解质膜上,将多孔正极集流体布置在所述正极上,以及布置允许空气传输到空气电极即正极中的压制构件,并且利用所述压制构件推动所述多孔正极集流体以固定单元电池,从而完成所述锂空气电池的制造。所述壳可分成分别与所述负极和所述空气电极接触的上部部分和下部部分。绝缘树脂可在所述上部部分和所述下部部分之间以使所述正极和所述负极彼此电绝缘。
在实施方式中,所述锂-空气电池可用作锂一次电池或锂二次电池。所述锂空气电池可具有多种形状的任一种,不限于特定形状,例如,诸如硬币、钮扣、片、堆、圆柱、平面或喇叭的形状。所述锂空气电池可在用于电动车的电池中使用。
图4是根据实施方式的锂空气电池500的示意图。参照图4,锂空气电池500可包括邻近于第一集流体210并且使用氧气作为活性材料的正极200、邻近于第二集流体310并且包括锂的负极300、以及在正极200和负极300之间的第一电解质膜400。第一电解质膜400可为浸渍有液体电解质的隔板。第二电解质膜450可在正极200和第一电解质膜400之间。第二电解质膜450可为锂离子传导性固体电解质膜。多孔的第一集流体210可充当气体扩散层。而且,允许空气到达正极200的压制构件220可在第一集流体210上。由绝缘树脂形成的壳320可使正极200和负极300彼此电绝缘。空气可通过空气入口230a供应并且通过空气出口230b排出。锂-空气电池500可容纳在不锈钢(SUS)容器中。
如本文中使用的,关于锂-空气电池的术语“空气”不限于大气空气,并且可指包括氧气的气体的组合、或纯氧气。“空气”的该广义定义也适用于包括“空气电池”和“空气电极”在内的其它术语。
根据实施方式的制备混合导体的方法包括:将元素A前体、钛前体和元素G前体混合以制备混合物;以及热处理所述混合物以制备混合导体。通过使用固相法制造混合导体,可简化所述混合导体的批量生产。
所述混合物的制备可例如通过如下进行:将所述元素A前体、所述钛前体和所述元素G前体在有机溶剂和/或水溶液中进行球磨。所述有机溶剂可包括醇如2-丙醇,并且可包括本领域中可用的任何合适的溶剂。所述热处理可在没有溶剂的情况下进行。
所制备的混合导体可例如由式1表示:
式1
A4±xTi5-yGzO12-δ
其中,在式1中,A为单价阳离子,G为单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr,以及其中0<x<2,0.3<y<5,0<z<5,和0<δ≤3。δ表示氧空位的含量。
例如,所述元素A前体可为A的盐或A的氧化物。例如,所述钛前体可为钛盐或钛氧化物。例如,所述元素G前体可为G的盐或G的氧化物。
所述元素A前体可为例如锂前体。所述锂前体可为例如Li2CO3、LiNO3、LiNO2、LiOH、氢氧化锂的水合物如LiOH·H2O、LiH、LiF、LiCl、LiBr、LiI、CH3OOLi、Li2O、Li2SO4、羧酸锂、柠檬酸锂、脂肪酸锂、或烷基锂化合物如丁基锂。然而,实施方式不限于此。可使用本领域中可用的任何合适的锂前体。
所述Ti前体可为例如TiO2、TiCl4、Ti(SO4)2、Ti2O3、或TiO。然而,实施方式不限于此。可使用本领域中可用的任何合适的钛前体。
所述元素G前体可为例如包括如下的至少一种的金属/准金属/非金属前体:Mg、Ca、Sr、Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Zr、Hf、V、Nb、Ta、Mo、W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Ge、Sn、Pb、Sb、Bi、Po、As、Se、或Te。例如,所述元素G前体可为Nb前体、Ta前体、Gd前体或In前体。所述Nb前体可为例如NbO2、Nb2O5、NbF4、NbF5、Nb(OCH2CH3)5、或NbCl5。然而,实施方式不限于此。可使用本领域中可用的任何合适的Nb前体。所述Ta前体可为例如Ta2O5、TaF5、或Ta(OCH2CH2CH2CH3)5。然而,实施方式不限于此。可使用本领域中可用的任何合适的Ta前体。所述Gd前体可为例如GdCl3、GdF3、Gd(NO3)3、Gd2(SO4)3、或Gd2O3。然而,实施方式不限于此。可使用本领域中可用的任何合适的Gd前体。所述In前体可为例如InCl2、InCl、InF3、In(NO3)3、In2(SO4)3、In2O3、或InCl3。然而,实施方式不限于此。可使用本领域中可用的任何合适的In前体。
在制备混合导体的方法中,通过使混合物在固相中反应而制备混合导体可包括:干燥所述混合物;并且在氧化性气氛下对所述混合物进行一次热处理以制备一次热处理产物;粉碎一次热处理产物,将经粉碎的一次热处理产物压制以制备片(粒料,pellet);以及在a)还原性气氛、b)氧化性气氛或c)氧化性气氛和还原性气氛下对所述片进行二次热处理。
在所述二次热处理中,取决于包括在所需混合导体中的金属的氧化数,可独立地选择a)还原性气氛、b)氧化性气氛或c)氧化性气氛和还原性气氛。
所述还原性气氛可为包括还原性气体的气氛。所述还原性气体的实例包括氢气(H2)。然而,实施方式不限于此。可使用本领域中可用的任何合适的还原性气体。所述还原性气氛可为还原性气体和惰性气体的混合物。所述惰性气体的实例包括氮气和氩气。然而,实施方式不限于此。可使用本领域中可用的任何合适的惰性气体。在所述还原性气氛中,所述还原性气体的量可为例如约1体积百分比(体积%)至约99体积%、约2体积%至约50体积%、或约5体积%至约20体积%。当在还原性气氛下进行热处理时,所述混合导体可引入有氧空位。
所述氧化性气氛可为包括氧化性气体的气氛。所述氧化性气体的实例包括氧气或空气。然而,实施方式不限于此。可使用本领域中可用的任何合适的氧化性气体。所述氧化性气氛可为氧化性气体和惰性气体的混合物。所述惰性气体可为氮气、氩气或氦气的至少一种,并且可与在所述还原性气氛中使用的惰性气体相同。
在氧化性气氛和还原性气氛下的二次热处理可通过如下进行:在氧化性气氛下的热处理和然后在还原性气氛下的热处理。氧化性气氛和还原性气氛可分别与所述氧化性气氛和所述还原性气氛相同。
所述一次热处理可例如在约600℃至约1,000℃、约700℃至约900℃、约600℃至约800℃、或约750℃至约850℃范围内的温度下进行。所述一次热处理可进行约2小时至约10小时、约3小时至约9小时、约4小时至约8小时、或约4小时至约6小时。所述二次热处理可例如在约700℃至约1,400℃、约800℃至约1300℃、约900℃至约1200℃、或约900℃至约1100℃范围内的温度下进行。所述二次热处理可进行约6小时至约48小时、约10小时至约40小时、约15小时至约35小时、或约20小时至约30小时。当在这样的条件下进行一次和二次热处理时,所制备的混合导体可具有进一步改善的电化学稳定性。
在下文中,将参照实施例和对比例详细描述实例实施方式。这些实施例仅出于说明性目的提供且不意图限制本发明构思的范围。
实施例
混合导体的制备
实施例1:Li4.5Ti4.5Nb0.5O12-δ
将作为锂前体的Li2CO3、作为钛前体的TiO2和作为铌前体的Nb2O5以化学计量比混合在一起,随后与乙醇混合。将混合物使用包括氧化锆球的球磨机以280转/分钟(rpm)粉碎并且混合4小时,从而获得混合物。将获得的混合物在90℃的温度下干燥6小时,然后在空气气氛下在700℃的温度下经受一次热处理5小时。将一次热处理的产物使用球磨机粉碎,并且在等静压下进行压制以制备片。将所制备的片在950℃的温度下在还原性气氛下经受二次热处理24小时,从而制备混合导体。还原性气氛包括5%氢气和95%氩气。所制备的混合导体具有Li4.5Ti4.5Nb0.5O12-δ(其中0<δ≤3)的组成。
实施例2:Li3.5Ti4.0Nb1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:改变锂前体、钛前体和铌前体的化学计量比以对应于Li3.5Ti4.0Nb1.0O12-δ。
所制备的混合导体具有Li3.5Ti4.0Nb1.0O12-δ(其中0<δ≤3)的组成。
实施例3:Li3.5Ti4.0Ta1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用钽前体Ta2O5代替铌前体,并且改变锂前体、钛前体和钽前体的化学计量比以对应于Li3.5Ti4.0Ta1.0O12-δ。
所制备的混合导体具有Li3.5Ti4.0Ta1.0O12-δ(其中0<δ≤3)的组成。
实施例4:Li4.5Ti4.5Gd0.5O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用钆前体Gd2O3代替铌前体。
所制备的混合导体具有Li4.5Ti4.5Gd0.5O12-δ(其中0<δ≤3)的组成。
实施例5:Li5.0Ti4.0Gd1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用钆前体Gd2O3代替铌前体,并且改变锂前体、钛前体和钆前体的化学计量比以对应于Li5.0Ti4.0Gd1.0O12-δ。
所制备的混合导体具有Li5.0Ti4.0Gd1.0O12-δ(其中0<δ≤3)的组成。
实施例6:Li4.5Ti4.5In0.5O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用铟前体In2O3代替铌前体。
所制备的混合导体具有Li4.5Ti4.5In0.5O12-δ(其中0<δ≤3)的组成。
实施例7:Li5.0Ti4.0In1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用铟前体In2O3代替铌前体,并且改变锂前体、钛前体和铟前体的化学计量比以对应于Li5.0Ti4.0In1.0O12-δ。
所制备的混合导体具有Li5.0Ti4.0In1.0O12-δ(其中0<δ≤3)的组成。
实施例8:Li5.0Ti4.0Mn1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用锰前体Mn2O3代替铌前体,并且改变锂前体、钛前体和锰前体的化学计量比以对应于Li5.0Ti4.0Mn1.0O12-δ。
所制备的混合导体具有Li5.0Ti4.0Mn1.0O12-δ(其中0<δ≤3)的组成。
实施例9:Li5.0Ti4.0Co1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用钴前体Co2O3代替铌前体,并且改变锂前体、钛前体和钴前体的化学计量比以对应于Li5.0Ti4.0Co1.0O12-δ。
所制备的混合导体具有Li5.0Ti4.0Co1.0O12-δ(其中0<δ≤3)的组成。
实施例10:Li5.0Ti4.5Cu0.5O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用铜前体CuO代替铌前体,并且改变锂前体、钛前体和铜前体的化学计量比以对应于Li5.0Ti4.5Cu0.5O12-δ。
所制备的混合导体具有Li5.0Ti4.5Cu0.5O12-δ(其中0<δ≤3)的组成。
实施例11:Li5.0Ti4.0Sb1.0O12-δ
以与实施例1中基本上相同的方式制备混合导体,除了如下之外:使用锑前体Sb2O3代替铌前体,并且改变锂前体、钛前体和锑前体的化学计量比以对应于Li5.0Ti4.0Sb1.0O12-δ。
所制备的混合导体具有Li5.0Ti4.0Sb1.0O12-δ(其中0<δ≤3)的组成。
对比例1:Li4Ti5O12
将可商购的Li4Ti5O12粉末如实施例1中一样在等静压下压制以制备片。
评价实施例1:电子传导率的评价
将实施例1至11和对比例1中制备的混合导体的粒料经受与金的溅射,从而完成离子阻塞电池(单元)(ion blocking cell)。
在室温下,例如在25℃下,通过使用直流DC极化方法测量其电子传导率。测量依赖于时间的电流,其是在向完整的对称性电池施加100毫伏(mV)的恒定电压30分钟时获得的。由测量的电流计算混合导体的电子电阻,并且由电子电阻计算电子传导率。测量的电子传导率的部分结果示于表1中。
评价实施例2:离子传导率的评价
将各自浸渍有液体电解质(在碳酸亚丙酯(PC)中的1摩尔浓度(M)的LiTFSI)的隔板层设置在混合导体的片的两侧上以形成实施例1至11和对比例1中的电解质膜,并且将SUS集流体设置在电解质膜上,从而完成电子阻塞电池(单元)的制造。在室温下,例如在25℃下,使用直流DC极化方法测量其离子传导率。
测量依赖于时间的电流,其是在向完整的对称性电池施加100mV的恒定电压30分钟时获得的。由测量的电流计算电池的离子电阻,且从电池的离子电阻减去固体电解质膜的离子电阻以计算混合导体的离子电阻。由混合导体的离子电阻计算离子传导率。测量的离子传导率的部分结果示于表1中。
表1
参照表1,发现与对比例1相比,实施例1至7中制备的混合导体具有显著改善的电子传导性和离子传导性。
混合导体的电子传导率大于混合导体的离子传导率。
当Li4Ti5O12通过引入氧空位而变为Li4Ti5O12-δ时,其离子传导率小于先前已经报导的关于Li4Ti5O12的离子传导率,1.2·10-8S/cm。
另一方面,尽管实施例1至7的混合导体各自包括氧空位,但是其离子传导率相比于Li4Ti5O12显著改善。
评价实施例3:XRD光谱的评价
测量实施例1至3和对比例1的混合导体的XRD光谱。其结果示于图1中。在各XRD光谱测量中,使用Cu Kα辐射。
如图1中所示,实施例1至3中制备的混合导体显示与具有尖晶石晶体结构的对比例1的Li4Ti5O12的光谱类似的光谱。因此,发现实施例1至3的混合导体具有尖晶石型晶体结构。
而且,如图1中所示,在实施例1至3的混合导体的情况下,在23.5°±2.5°的衍射角(2θ)处观察到新的峰,并且该新峰的强度(Ib)大于对应于尖晶石晶体结构的晶面(111)的峰的强度(Ia)。也就是说,在实施例1至3的混合导体中,在23.5°±2.5°的衍射角(2θ)处的峰强度(Ib)对在18°±2.5°的衍射角(2θ)处的对应于晶面(111)的峰强度(Ia)的峰强度比(Ia/Ib)为1或更小。
尽管未在图中示出,但在实施例7的混合导体的XRD光谱中,发现,混合导体除了具有尖晶石型晶体结构的相之外还包括具有Li2TiO3的组成的相。在实施例7的混合导体的XRD光谱中具有尖晶石型晶体结构的相属于Fd-3m空间群。
尽管未在图中示出,但在实施例5的混合导体的XRD光谱中,发现,混合导体除了具有尖晶石型晶体结构的相之外还包括具有Gd2Ti2O7的组成的相。
评价实施例4:电子能带结构的评价
计算对比例1的Li4Ti5O12、引入有Nb(其为参照实施例1的添加元素)的Li4.5Ti4.5Nb0.5O12、引入有Nb(其为参照实施例2的添加元素)的Li3.5Ti4NbO12、引入有Ta(其为参照实施例3的添加元素)的Li3.5Ti4TaO12、以及参照实施例4的引入有氧空位的Li4Ti5O11.5的电子能带结构。由计算的结果评价带隙。
基于密度泛函理论(DFT)的框架使用Vienna Ab-initio模拟包(simulationpackage)(VASP)计算电子结构。计算结果示于图2A至2E和表2中。
表2
组成 | 带隙[eV] | |
对比例1 | Li<sub>4</sub>Ti<sub>5</sub>O<sub>12</sub> | 2.5 |
参照实施例1 | Li<sub>4.5</sub>Ti<sub>4.5</sub>Nb<sub>0.5</sub>O<sub>12</sub> | 0.9 |
参照实施例2 | Li<sub>3.5</sub>Ti<sub>4</sub>NbO<sub>12</sub> | 0.1 |
参照实施例3 | Li<sub>3.5</sub>Ti<sub>4</sub>TaO<sub>12</sub> | 1.1 |
参照实施例4 | Li<sub>4</sub>Ti<sub>5</sub>O<sub>11.5</sub> | 0.1 |
如表2和图2A中所示,Li4Ti5O12的带隙为约2.5eV。另一方面,如表2和图2B至2E中所示,Li4.5Ti4.5Nb0.5O12、Li3.5Ti4NbO12、Li3.5Ti4TaO12、和Li4Ti5O11.5的带隙各自为2.0eV或更小。
如图2B至2E中所示,Ti具有3和4的氧化数,且作为添加元素的Nb和Ta各自具有5的氧化数。
而且,如评价实施例1的表1中所示,发现其中引入氧空位和具有不同氧化数的其它添加元素的实施例1的混合导体(Li4.5Ti4.5Nb0.5O12-δ)和实施例2的混合导体(Li3.5Ti4NbO12-δ)、以及实施例3的混合导体(Li3.5Ti4TaO12-δ)与对比例1的Li4Ti5O12相比提供改善的电子传导性。因此,Li4Ti5O12被引入有氧空位和与Ti异价的添加元素,故而具有混合价态。从而,其带隙减小,并且因此,混合导体的电子传导性得到改善。也就是说,实施例1的混合导体(Li4.5Ti4.5Nb0.5O12-δ)、实施例2的混合导体(Li3.5Ti4NbO12-δ)和实施例3的混合导体(Li3.5Ti4TaO12-δ)的带隙为2.0eV或更小,其小于Li4Ti5O12的带隙。因此,发现电子传导性得到改善。
评价实施例5:锂过渡活化能(Ea)的评价
如图3中所示,在具有尖晶石型晶体结构的Li4Ti5O12中,锂位于尖晶石型晶体结构中的四面体8a位点和八面体16d位点处。尽管未在图中示出,但八面体16c位点位于两个相邻的四面体8a位点之间,并且与两个相邻的四面体8a位点共用面。锂传导特性由锂过渡(例如,从四面体8a位点经由八面体16c位点到另外的四面体8a位点)产生。
测量在从四面体8a位点经由八面体16c位点到另外的四面体8a位点过渡时的锂过渡活化能(Ea)。过渡发生在对比例1的Li4Ti5O12、另外包括锂的Li4+xTi5O12(其中0<x)、和其中锂被另外减少的Li4-xTi5O12(其中0<x)中。
基于DFT的框架使用VASP计算活化能。
在Li4Ti5O12中,在从四面体8a位点经由八面体16c位点到另外的四面体8a位点的锂过渡(或锂扩散)时的活化能(Ea,8a->16c->8a)(即,能垒)是约0.7eV或更高。
另一方面,在Li4+xTi5O12(其中0<x)和Li4-xTi5O12(其中0<x)中,在从四面体8a位点经由八面体16c位点到另外的四面体8a位点转换的锂过渡时的活化能(Ea,8a->16c->8a)是约0.5eV或更小。
而且,如评价实施例2的表1中所示,当如在实施例1的混合导体(Li4.5Ti4.5Nb0.5O12-δ)中那样进一步添加锂时,和当如在实施例2的混合导体(Li3.5Ti4NbO12-δ)中那样锂被另外减少时,所述混合导体各自的离子传导性与对比例1的Li4Ti5O12相比得到改善。
因此,可通过对至Li4Ti5O12进一步增加减少的锂而在锂过渡时使能垒降低,且因而,可改善混合导体的离子传导性。
如从前面的描述明晰的,当使用化学稳定的并且同时传输离子和电子的混合导体时,可防止电化学装置的劣化。
应理解,本文中描述的实施方式应仅在描述的意义上考虑且不用于限制的目的。各实施方式内的特征或方面的描述应被认为可用于其它实施方式中的其它类似特征或方面。
尽管已经参照附图描述了一种或多种实施方式,但是本领域普通技术人员将理解,在不背离如由所附权利要求所限定的精神和范围的情况下,可在其中进行形式和细节方面的多种变化。
Claims (27)
1.由式1表示的混合导体:
式1
A4±xTi5-yGzO12-δ
其中,在式1中,
A为单价阳离子,
G为单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr,以及
0<x<2,0.3<y<5,0<z<5,和0<δ≤3。
2.如权利要求1所述的混合导体,其中
A为单价碱金属阳离子,以及
G为二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr。
3.如权利要求2所述的混合导体,其中A为Li、Na、或K的至少一种。
4.如权利要求2所述的混合导体,其中G为如下的至少一种:Mg、Ca、Sr、Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Zr、Hf、V、Nb、Ta、Mo、W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Ge、Sn、Pb、Sb、Bi、Po、As、Se、或Te。
5.如权利要求1所述的混合导体,其中A为Li,以及
G为如下的至少一种:Mg、Ca、Sr、Sc、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Zr、Hf、V、Nb、Ta、Mo、W、Mn、Tc、Re、Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Ge、Sn、Pb、Sb、Bi、Po、As、Se、或Te,以及
其中0.3<x<2,0.3<y<2,0.3<z<2,和0<δ≤3。
6.如权利要求5所述的混合导体,其中所述混合导体包括如下的至少一种:Li4±xTi5- yMgzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yCazO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-ySrzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-ySczO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yYzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yLazO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yCezO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yPrzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yNdzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-ySmzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yEuzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4± xTi5-yGdzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yTbzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yDyzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yHozO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5- yErzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yTmzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yYbzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yLuzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yZrzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yHfzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yVzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yNbzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yTazO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yMozO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yWzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4± xTi5-yMnzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yTczO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yRezO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yFezO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5- yRuzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yOszO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yCozO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yRhzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yIrzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yNizO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yPdzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yPtzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yCuzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yAgzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yAuzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4± xTi5-yZnzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yCdzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yHgzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yAlzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5- yGazO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yInzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yTlzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yGezO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-ySnzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yPbzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-ySbzO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yBizO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yPozO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-yAszO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;Li4±xTi5-ySezO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3;或Li4± xTi5-yTezO12-δ,其中0.4<x≤1,0.4<y≤1,0.4<z≤1,和0<δ≤3。
7.如权利要求1所述的混合导体,其中所述混合导体的电子传导率大于所述混合导体的离子传导率。
8.如权利要求1所述的混合导体,其中在25℃下所述混合导体的电子传导率为1.0×10-6西门子/厘米至1.0西门子/厘米。
9.如权利要求1所述的混合导体,其中在25℃下所述混合导体的离子传导率为1.0×10-7西门子/厘米至1.0×10-1西门子/厘米。
10.如权利要求1所述的混合导体,其中所述混合导体包括具有尖晶石型晶体结构的相。
11.如权利要求10所述的混合导体,其中,在所述混合导体的X射线衍射光谱中,在18°±2.5°的衍射角2θ处的对应于(111)晶面的峰的强度对在23.5°±2.5°的衍射角2θ处的峰的强度的峰强度比为0.001至1。
12.如权利要求10所述的混合导体,其中所述混合导体包括不同于具有尖晶石型晶体结构的相的第二相。
13.如权利要求10所述的混合导体,其中所述具有尖晶石型晶体结构的相属于Fd-3m空间群。
14.如权利要求12所述的混合导体,其中所述第二相包括如下的至少一种:Li2TiO3、Gd2Ti2O7、GdTiO3、LiNbO3、或Nb2O5。
15.如权利要求1所述的混合导体,其中所述混合导体的在价带和导带之间的带隙小于Li4Ti5O12的在价带和导带之间的带隙。
16.如权利要求1所述的混合导体,其中所述混合导体的在价带和导带之间的带隙为0.001电子伏特至2电子伏特。
17.如权利要求1所述的混合导体,其中Ti具有在3和4之间的氧化数。
18.如权利要求1所述的混合导体,其中G具有不同于Ti的氧化数的氧化数。
19.如权利要求1所述的混合导体,其中A设置在尖晶石型晶体结构的四面体8a位点、八面体16c位点、和八面体16d位点的至少一个上,并且当A是锂时,所述混合导体的从四面体8a位点经由八面体16c位点到另外的四面体8a位点的锂过渡的活化能小于Li4Ti5O12的从四面体8a位点经由八面体16c位点到另外的四面体8a位点的锂过渡的活化能。
20.电极,包括如权利要求1-19任一项所述的混合导体。
21.电化学装置,包括:
正极;
包括如权利要求20所述的电极的负极;以及
在所述正极和所述负极之间的隔板。
22.如权利要求21所述的电化学装置,其中所述电化学装置为电池、蓄电池、超级电容器、燃料电池、传感器或电致变色装置。
23.制备混合导体的方法,所述方法包括:
提供包括元素A前体、钛前体和元素G前体的混合物,
其中所述元素A前体提供单价阳离子,且所述元素G前体提供单价阳离子、二价阳离子、三价阳离子、四价阳离子、五价阳离子、或六价阳离子的至少一种,条件是G不是Ti或Cr;以及
热处理所述混合物以制备混合导体。
24.如权利要求23所述的方法,其中所述混合导体是如权利要求1-19任一项中所限定的。
25.如权利要求23所述的方法,其中所述元素A前体为A的盐或A的氧化物,所述钛前体为钛盐或钛氧化物,以及所述元素G前体为G的盐或G的氧化物。
26.如权利要求23所述的方法,其中热处理所述混合物以制备混合导体包括:
干燥所述混合物;
在氧化性气氛下对所述混合物进行一次热处理以提供一次热处理的混合物;
粉碎所述一次热处理的混合物;
将经粉碎的一次热处理的混合物压制以制备片;以及
在还原性气氛、氧化性气氛或氧化性气氛和还原性气氛下对所述片进行二次热处理以制备所述混合导体。
27.如权利要求26所述的方法,其中一次热处理在600℃至1,000℃范围内的温度下进行2小时至10小时,并且二次热处理在700℃至1,400℃范围内的温度下进行6小时至48小时。
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