CN101952223A - 具有石榴石结构的离子导体 - Google Patents
具有石榴石结构的离子导体 Download PDFInfo
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- CN101952223A CN101952223A CN2008800232213A CN200880023221A CN101952223A CN 101952223 A CN101952223 A CN 101952223A CN 2008800232213 A CN2008800232213 A CN 2008800232213A CN 200880023221 A CN200880023221 A CN 200880023221A CN 101952223 A CN101952223 A CN 101952223A
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- ion conductor
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Abstract
本发明涉及具有石榴石型结构的化学稳定固体离子导体在电池、蓄电池、电致变色装置和其它电化学电池中的用途,还涉及适用于这些用途的新化合物。
Description
本发明涉及一种具有石榴石型结构的化学稳定的固体离子导体在电池、超级电容器、蓄电池和电致变色装置、化学传感器及热电转换器中的用途,还涉及适用于这些用途的新化合物。
当需要或期望电子或电气装置至少部分时间独立于电网进行运行时,使用充电(二次)电池。因此,在这方面,用于所述用途的作为电解质材料的固体离子导体的研究成为目前材料研究中的一个重要方面。在仅由固体构成的电池中,需要的优点在于确保不漏电、可小型化、电化学稳定性、相对高的能量密度和相对长的寿命。
近年来,在各种电池技术中,逐渐确立了基于锂离子的电池系统。该电池系统尤其以其高的电能密度和功率而引人关注,这可归因于锂离子高的化学反应性和低的质量以及它们高的移动性。近年来,固体锂离子导体的发展已经吸引了相当多的注意。实例有Li2.9PO3.3N0.46或Li3N和Li-β-铝氧化物。然而,Li2.9PO3.3N0.46与液体电解质相比具有明显较低的离子电导率。Li3N和Li-β-铝氧化物对水分非常敏感。此外,在室温下在低至0.445V的电压,Li3N会分解,而Li-β-铝氧化物不是化学稳定的。
Thangadurai等在其研究中(“Novel Fast Lithium Ion Conduction inGarnet-Type Li5La3M2O12(M=Nb,Ta)”,J.Am.Ceram.Soc.86,437-440,2003)首次描述了具有石榴石型结构的锂离子导体。石榴石型结构Li5La3M2O12化合物具有可观的锂离子电导率。
在结构术语中,石榴石是以立方晶系结晶的通式组成为X3Y2(SiO4)3的原硅酸盐,其中X和Y是八配位和六配位的阳离子位点。各个SiO4四面体经由隙间B阳离子通过离子键与另一SiO4四面体相连。
在上述Thangadurai等研究中描述的式Li5La3M2O12(M=Nb,Ta)的石榴石型化合物与理想的石榴石结构相比含有过量的Li离子。La3+和M5+离子占据八配位和六配位位置,而锂离子占据具有六倍配位的位置。
PCT申请WO2005/085138报道了通常由式Li5La3M2O12(M=Nb或Ta)的化合物通过变价取代而获得的其它石榴石型锂离子导体。La3+位点的变价取代能够增加网络的连接,能够使可用空位的数发生变化。优选通过Li+离子(L)达到电荷平衡。就本发明而言,“变价取代”是指离子被具有不同氧化态的离子取代,由此形成阳离子空位、阴离子空位、隙间阳离子和/或隙间阴离子。固体锂离子导体是化学稳定的,且具有超过3.4×10-6S/cm的离子导电率。由于其高的离子导电率和可忽略的电子导电率,它们能被用于固态电解质。
WO 2005/085138中描述的化合物通常具有化学计量组成L5+xAyGzM2O12,其中L在各种情况下独立地为任何优选的单价阳离子,A在各种情况下独立地为单价、二价、三价或四价阳离子,M在各种情况下独立地为三价、四价或五价阳离子,0<x≤3,0≤y≤3,0≤z≤3,和O能部分或全部被二价和/或三价阴离子(例如N3-)替代。
在所述离子导体中,M在各种情况下是金属Nb和Ta中的一种。没有给出其它金属离子的实例。离子传导通过锂离子(L=Li)进行。
近年来,已经讨论了具有石榴石结构的锂离子导体的其它实例(V.Thangadurai,W.Weppner,Adv.funct.Mater.2005,15,107-112;V.Thangadurai,W.Weppner,J.Power Sources,2005,142,339-344)。其中,在22℃,Li6BaLa2Ta2O12具有最高为4×10-5Scm-1的Li+电导率,活化能为0.40eV。尽管Li6BaLa2Ta2O12对于与金属锂反应、水分、空气和常见电极材料是稳定的,但在室温下体积导电率和总导电率仍然不够高,不能开发出理想的可再充电的固体锂离子电池。
与上述现有技术中离子导体相关的另外一个问题是所建议的金属铌和钽较为昂贵且不易获得。此外,完全由上述石榴石型化合物构成的固体电解质的使用是复杂的且成本高。
因此,本发明的目的之一是提供改进的固体离子导体,其中至少部分地克服上述缺点。
根据本发明,已经发现锆可用作石榴石型离子导体中的金属M。与铌和钽相比,锆容易获得且产生了非常稳定的固态结构。Nb和Ta通常在石榴石结构中以氧化态+V存在,而锆优选以氧化态+IV存在。
因此,在一个实施方案中,本发明提供了具有石榴石型晶体结构且化学计量组成为L7+xAxG3-xZr2O12的固体离子导体,其中
L在各种情况下独立地为单价阳离子,
A在各种情况下独立地为二价阳离子,
G在各种情况下独立地为三价阳离子,
0≤x≤3,和
O可部分或全部被二价或三价阴离子(例如N3-)替代。
L特别优选是碱金属离子,例如Li+、Na+或K+。特别地,L也可以是各种碱金属离子的组合。在本发明的一个特别优选的实施方案中,L=Na+。钠非常廉价,且可以任意量获得。小的Na+离子可以容易地在石榴石型结构中移动,并与锆结合产生化学稳定的晶体结构。
A是任何二价阳离子或这些阳离子的任何组合。二价金属阳离子可优选用作A。特别优选的是碱土金属离子,例如Ca、Sr、Ba和/或Mg,和二价过渡金属阳离子,例如Zn。已发现,这些离子在根据本发明的石榴石型化合物中即使有移动,移动也非常少,因此离子传导基本上通过L进行。
在上述组成中,优选0≤x≤2,尤其优选0≤x≤1。在一个根据本发明的实施方案中,x=0,因而在石榴石型化合物中不存在A。
G是任意三价阳离子或这种阳离子的任意组合。对于G,可优选使用三价金属阳离子。尤其优选G=La。
在上述组成的结构中,O2-可以部分或全部被其它阴离子替代。例如,用其它二价阴离子全部或部分代替O2-是有利的。此外,也可以通过适当的电荷补偿以三价阴离子不等价代替O2-。
在另一方面,本发明提供了化学计量组成为L7+xAxLa3-xZr2O12的固体离子导体,其中A是二价金属,L是Li或Na。因为Na容易获得,所以Na是尤其优选的。在一个优选实施方案中,x=0,因而组成为L7La3Zr2O12。
A优选选自碱土金属,优选选自Ca、Sr、Ba和/或Mg。A也优选选自二价过渡金属,例如A=Zn。最优选A=Sr或Ba。
组成L7+xAxLa3-xZr2O12的离子导体具有石榴石型晶体结构。与已知的组成为L5La3Nb2O12(L=Li)的化合物相比,两个Nb(+V)阳离子通常被两个Zr(+IV)阳离子和两个单价L阳离子代替。此外,La(+III)可以被A(+II)和L(+I)代替。这样,结构中L的总比例增大。L优选为Li或Na,具有石榴石结构的化合物经由Li和Na发生离子传导。这样,通过本发明化合物,可以提供显著改进的离子导体。
与现有技术的化合物相比,组成为L7+xAxLa3-xZr2O12的材料显示出提高的离子导电率。由于本发明化合物的石榴石结构(这是3D各向同性结构),因此在三维而不是在优先方向进行离子传导成为可能。
另一方面,本发明化合物的电子导电率相对较低。本发明化合物的多晶样品也具有低的晶界电阻,因此总导电率几乎完全由体积导电率构成。
该材料的另一优点是其高的化学稳定性。特别地,当与熔融锂接触而加热时,该材料没有表现出可辨别的变化。在最高达350℃的温度和最高达6V的DC电压,没有观察到化学分解。
根据本发明具有石榴石结构的特别优选的化合物的一个实例是Li7La3Zr2O12。高的锂离子导电率、良好的热稳定性和与可能的电极反应方面的化学稳定性、环境相容性、原料的可获得性、低的制造成本和简单的生产和封装,使得Li7La3Zr2O12成为尤其适用于可再充电锂离子电池的有前景的固体电解质。
根据另一方面,本发明提供了制备具有石榴石型结构的固体离子导体的方法。该化合物可以通过存在的元素的适当的盐和/或氧化物的反应形成,例如通过固相反应形成。尤其有用的原料是硝酸盐、碳酸盐和氢氧化物,它们在反应过程中转变成相应的氧化物。
更具体地,本发明涉及制备组成为L7+xAxG3-xZr2O12(例如Na6ALa2Zr2O12)的固体离子导体的方法。该材料可以通过A、G和Zr适当的盐和/或氧化物与L的氢氧化物、硝酸盐或碳酸盐在固相反应中反应而获得。A如上所定义。二价金属A优选以硝酸盐的形式使用。在此,优选Ca(NO3)2、Sr(NO3)2和Ba(NO3)2。至于G,优选使用La,La优选以La2O3的形式使用。有利地,Zr以氧化物形式使用,优选ZrO2。L优选以LOH、LNO3或L2CO3形式使用。例如,可优选使用LiOH·H2O或NaOH·H2O。为了补偿样品的加热过程中L(例如L=Li、Na)的重量损失,优选过量使用各种盐,例如按重量计过量10%。
在第一步骤中将原料混合,并可以例如在球磨机中在2-丙醇中使用氧化锆研磨介质对材料进行研磨。然后在优选400至1000℃的温度范围内在空气中对由此获得的混合物加热数小时,优选2至10小时。600至800℃的温度,例如大约700℃,和4至8小时的热处理时间,例如大约6小时,是尤其合适的。然后再进行研磨,优选同样在球磨机中在2-丙醇中使用氧化锆研磨介质进行。然后对反应产物进行单轴压制或优选等静压制,以获得模制件,例如丸片。然后,在优选700至1200℃的温度、更优选800至1000℃的温度,将它们烧结数小时,优选10至50小时,更优选20至30小时。大约900℃的温度和大约24小时的热处理时间在此是尤为合适的。在该烧结过程中,有利地,用相同组成的粉末覆盖样品,以避免L氧化物的过度损失。
由于所有成分均以可溶性盐存在,因此,可容易地用于制备该化合物的可能方法是前体法,例如Pecchini法、甘氨酸法或沉淀反应。
作为固态电解质,本发明的固体离子导体(例如锂或钠离子导体)是有价值的原料。由于该材料具有格外高的离子导电率和可忽略的电子传导,它们可被用作具有非常高能量密度的电池(例如锂或钠电池)的固体电解质。该材料在化学反应方面(例如与单质锂和常用电极材料的反应)的高稳定性,使得例如本发明固体离子导体能够投入电池的实际应用。
与常用的固体电解质材料相比,本发明固体电解质与电极之间的相界电阻也非常小。因此,使用本发明的材料能够制备具有较高功率(高电流)的电池。与使用液体电解质相比,使用本发明的固态电解质还能提高安全性。当电解质用于机动车辆时,这是尤其有利的。
另一方面,除了用于电池中,本发明还提供了固体离子导体(例如锂离子导体)在电致变色系统(窗口、VDUs、外墙等)中的用途和在超级电容器(超级电容)中用于瞬时能量贮存和释放的用途。当使用本发明离子导体时,可以实现100F/cm3或更高的电容器能量密度。本发明的另一方面是使用石榴石型固体离子导体作为传感器,尤其是用于许许多多气体的优越感器。根据本发明,还可以将该材料用于将热能直接有效转换为电能的热电转换器中。
具有石榴石型的离子导体还可以与其它电解质(例如传统的质子惰性液体电解质)结合用作缓冲层。因此,不必使用完全由石榴石型结构构成的电解质。而是可以与新颖石榴石型离子导体结合使用任何已知的例如以液体、凝胶或固体形式存在的电解质。
因此,另一方面,本发明提供了具有石榴石型晶体结构的固体离子导体作为电极前的保护层的用途,用于提高对于电解质的化学稳定性。为此,不仅可以使用根据本发明的含有锆的石榴石型结构,还可以例如使用WO2005/085138中描述的石榴石型化合物。使用离子导体作为在电极前的缓冲结构防止了短路,并可以产生和施加较高的电压,从而实现明显较大的能量密度和较长的寿命。
附图
图1:
在18℃在空气中对厚丸片(厚1.02厘米,直径0.92厘米)测量Li7La3Zr2O12的AC阻抗曲线。连续线代表使用EQUIVALENT程序(B.A.Boukamp,Equivalent Circuit,Version 4.55,1997,Faculty of ChemicalTechnology,University of Twente,7500 AE Enschede(The Netherlands),Report No.CT 88/265/128/CT89/214/128,May 1989)获得的包括(RbQb)(RgbQgb)(Qel)(其中R是阻抗,Q是恒相位元,符号g、gb和el表示晶粒体积、晶界和电极)的等效电流电路的模拟数据。在插图中显示了在18℃在空气中对薄丸片(厚0.18厘米,直径0.98厘米)测量的Li7La3Zr2O12的AC阻抗曲线。
图2:
a)在两个连续的加热和冷却循环中获得的Li7La3Zr2O12厚丸片的体积电导率和总电导率(体积和晶界)的阿伦尼乌斯曲线。
b)Li7La3Zr2O12厚丸片和薄丸片在第一轮加热(18-300℃)中获得的阿伦尼乌斯曲线的比较。
图3:
Li7La3Zr2O12和其它被考虑用于电池应用的已知锂离子导体的总电导率(体积+晶界)的比较。
图4:
根据粉末衍射标准联合委员会测得的Li7La3Zr2O12的粉末X射线衍射图和已知石榴石相Li5La3Nb2O12(JCPDS:80-0457)的标准图谱。
图5:
在25℃和50℃在空气中对Li7La3Zr2O12厚丸片测得AC阻抗曲线。
图6:
在25℃和50℃在空气中对Li7La3Zr2O12薄丸片测得的AC阻抗曲线。插图中显示了在较高频率下的其它曲线。
图7:在两个连续的加热和冷却循环中获得的Li7La3Zr2O12薄丸片的体积电导率和总电导率(体积和晶界)的阿伦尼乌斯曲线。
图8:
a)与熔融锂接触前的Li7La3Zr2O12丸片和钼坩锅照片,b)Li7La3Zr2O12丸片在熔融锂中的照片,和c)刚刚与熔融锂接触48小时之后的Li7La3Zr2O12丸片和钼坩锅的照片。图c)中照片显示丸片的颜色没有变化(象牙色),且没有形成反应产物。
下述实施例用来阐述本发明特别优选的实施方案。
实施例:
在各种情况下,化学计量量的高纯原料在固态反应中进行反应:
LiOH(Alfa Aesar,>99%),在200℃预干燥6h,按重量计过量10%,以补偿在烧结过程中的Li损失;
La2O3(Alfa Aesar,>99.99%),在900℃预干燥24h;和
ZrO2(Aldrich,>99%)。
使用氧化锆容器和球在2-丙醇中将原料球磨大约12小时。然后在900和1125℃在空气中热处理12小时。然后将获得的产物再次球磨。然后将反应产物等静压制以制成丸片,并在1230℃烧结36小时。在此过程中,为了避免锂的过度损失,用相同组成的粉末覆盖样品。所有处理中的升温速率都是1℃/分钟。用金刚石锯将烧结压制的丸片切割成较薄的丸片。用X-射线粉末衍射(SEIFERT 3000,CuKα,Germany)监视相的形成。用最小二乘法由粉末XRD衍射数据确定晶格常数。
在空气中使用两种不同厚度的丸片(厚丸片:厚1.02厘米,直径0.92厘米,薄丸片:厚0.18厘米,直径0.98厘米)测量电导率。通过阻抗和晶相分析仪(HP 4192A,Hewlett-Packard Co.,Palo Alto,CA)(5Hz-13Hz)在18℃至350℃的温度范围内使用锂离子阻塞的Au电极(在700℃固化1小时的Au糊)进行测量。每次阻抗测试前,将样品在恒定温度下平衡3至6小时。在两个连续的加热和冷却循环中对各丸片进行阻抗测试。在空气中在29-900-20℃的温度范围以2℃/分钟的升温和冷却速率和在等温900℃测量热重分析(TGA)和差热分析(NETZSCH STA 409C/CD)的数据。
在充氩手套箱中通过使丸片与大量过量的熔融锂在钼坩锅中反应48小时,检测Li7La3Zr2O12相对于熔融锂的稳定性。
虽然已经对Li5La3M2O12(M=Nb,Ta)石榴石进行了大量的X-射线衍射(XRD)研究,但在空间群和锂离子的位置方面对结构仍然存在争论(a)D.Mazza,Mater.Lett.1988,7,205-207;b)H.Hyooma,K.Hayashi,Mater.Res.Bull.1988,23,1399-1407;c)J.Isasi,M.L.Veiga,R.Saez-puche,A.jereze,C.Pico,J.Alloys Compd.1991,177,251-257)。最近,中子衍射研究已经表明Li5La3M2O12(M=Nb,Ta)以空间群Ia3d结果,Li位于四面体和八面体位置,且在两类位置中均存在空位(a)E.J.Cussen,Chem.Commun.2006,412-413;b)M.P.O′Callaghan,D.R.Lynham,E.J.Cussen,G.Z.Chen,Chem.Mater.2006,18,4681-4689)。检测出的Li7La3Zr2O12粉末XRD衍射图谱与已知石榴石相Li5La3M2O12的标准图谱一致,且表明石榴石结构能够合并不同氧化态和不同尺寸的阳离子而不过度改变对称性的能力。测定出晶格常数A=12.9682(6)的立方晶胞的衍射图谱。
图1显示了Li7La3Zr2O12厚丸片在18℃获得的典型阻抗曲线。当电极离子阻塞时,在低频区域出现上升,这表明被检测材料是离子导体(a)V.Thangadurai,R.A.Huggins,W.Weppner,J.Power Sources 2002,108,64-69;b)J.T.S.Irvine,D.C.Sinclair,A.R.West,Adv.Mater.1990,2,132-138)。还观察到此前研究的具有石榴石型结构材料具有类似的情形。阻抗曲线可以分为体积、晶界和电极电阻。图1中的连续线表示使用EQUIVALENT程序获得的(RbQb)(RgbQgb)(Qe1)的等效电流电路的数据。在图1的插图中显示了在18℃测量的Li7La3Zr2O12薄丸片的AC阻抗曲线。由高频和低频半弧与轴的交点获得在不同温度下观察到的Li7La3Zr2O12厚丸片(厚1.02厘米,直径0.92厘米)和薄丸片(厚0.18厘米,直径0.98厘米)的体积电导率和总电导率,并摘录在表1中。图1和表1中所示数据表明Li7La3Zr2O12厚丸片和薄丸片具有相似的电性能。与厚丸片相比,薄丸片显示出稍高的体积电导率和总电导率。此外,有意思的是,注意到了对于厚丸片和薄丸片,晶界对总电阻的贡献都小于50%,并随着温度的升高而下降(表1)。在较高温度(对于厚丸片,高于75℃;对于薄丸片,高于50℃),与准确的体积贡献相比,难以确定晶界贡献;因此显示了体积和晶界贡献的总值,用于确定在测试的温度范围内的电导率。具有石榴石型结构的新型结晶快锂离子导体Li7La3Zr2O12在室温下的总电导率(3×10-4S/cm,25℃)优于所有其它固体锂离子导体和所有前述锂石榴石。
这一结果,即总电导率和体积电导率具有相同的数量级,是这里被检测的Li7La3Zr2O12石榴石结构相对于其它陶瓷锂离子导体的尤其有利的性质。对于许多固体电解质在电化学设备(例如电池、传感器、和电致变色显示器)中的应用来说,总电导率应该尽可能的高。此外,通过低温合成Li7La3Zr2O12和通过使用合适的烧结方法进一步致密化,体积和总电导率进一步提高。
图2a显示了在两个加热和冷却循环中获得的Li7La3Zr2O12厚丸片的体积电导率和总电导率的阿伦尼乌斯曲线。在两个循环间没有明显的电导率变化。这意味着被检测的石榴石型结构是热稳定的,且在检测的温度范围(即从室温到350℃)内没有相变发生。对于Li7La3Zr2O12薄丸片,也观察到相似的阿伦尼乌斯曲线。在图2b中,比较了在第一轮加热中获得的Li7La3Zr2O12厚丸片和薄丸片的数据。对于薄丸片的体积和总电导率获得的活化能(18-50℃时0.32eV,18-300℃时0.30eV)略低于对于厚丸片体积和总电导率获得的活化能(18-70℃时0.34eV,18-300℃时0.31eV)。针对由薄丸片获得的电导率略高于针对厚丸片获得的电导率。
除了阻抗分析外,还通过EMF检测证实了电导率的离子性质,在EMF检测中Li7La3Zr2O12被用做单质锂和铝、LiAl之间的固体电解质。将样品的上侧覆盖铝层,并将其置于已经在填充惰性氩气的手套箱中熔融的锂上。通过与锂的化学反应,和通过由与铝相对的锂电极将锂库伦滴定到铝中使铝合金化。产生的电压在理论值的范围内。它们的差别可归因于不均匀的温度分布和不可逆过程造成的相应现象。
图3显示了Li7La3Zr2O12和其它已知的正被考虑用于电池中的锂离子导体的锂离子电导率的比较。电导率高于锂-β-铝氧化物、薄层Lipon(Li2.9PO3.3N0.46)、Li9SiAlO8、Lil+40mol Al2O3、LiZr2(PO4)3、Li3.5Si0.5P0.5O4、Li5La3Ta2O12和Li6BaLa2Ta2O12。比其它含锂的石榴石结构较高的锂电导率和所观测到的低的活化能可能归因于立方晶格常数的增大、锂离子浓度的增加、锂离子和其它形成晶格的离子间化学反应的减少,并可部分归因于提高的密实化(理论密度的92%)。在相对低的温度下,不太稳定的多晶体Li3N的电导率(6.6×10-4S/cm,27℃)可与Li7La3Zr2O12的电导率相比。然而,在较高温度下,Li7La3Zr2O12展示出较高的总电导率。
通过热重分析(TGA)和差热分析(DTA)证实了Li7La3Zr2O12的热稳定性,这是结晶锂离子导体的基本优点。在空气中测定的TG-DTA数据表明,在20-900℃温度范围的加热过程和冷却过程中都没有发生明显的质量变化和可识别的相变化。结果发现,含锆Li7La3Zr2O12对于熔融锂是稳定的,且在数周的观察期内0对于水分和空气的作用也是化学稳定的。
表1
在空气中测得的Li7La3Zr2O12(厚丸片:厚1.02厘米,直径0.92厘米,和薄丸片:厚0.18厘米,直径0.98厘米)的阻抗数据。
丸片类型 | 温度(℃) | σ体积(Scm-1) | σ总(Scm-1) | Rgb/Rb+Rgb [a] |
厚丸片 | 182550 | 3.37×10-44.67×10-41.19×10-3 | 1.90×10-42.44×10-46.15×10-4 | 0.440.480.49 |
薄丸片 | 182550 | 3.97×10-45.11×10-41.45×10-3 | 2.32×10-43.01×10-47.74×10-4 | 0.420.410.47 |
[a]Rgb=晶界电阻,Rb=体积阻电阻
表2:具有石榴石结构的Li7La3Zr2O12的粉末XRD衍射图谱
Claims (20)
1.具有石榴石型晶体结构的固体离子导体的用途,用作电极涂料或电极前的保护层。
2.涂覆有具有石榴石型晶体结构的固体离子导体的电极。
3.包括一个或多个根据权利要求2的电极的电池。
4.具有石榴石型晶体结构且化学计量组成为L7+xAxG3-xZr2O12的固体离子导体,其中
L在各种情况下独立地为单价阳离子,
A在各种情况下独立地为二价阳离子,
G在各种情况下独立地为三价阳离子,
0≤x≤3,和
O可以部分或全部被二价或例如N3-的三价阴离子替代。
5.根据权利要求4的固体离子导体,其中0≤x≤1。
6.根据权利要求4或5的固体离子导体,其中L选自Li、Na和/或K。
7.根据权利要求6的固体离子导体,其中L=Na。
8.根据权利要求4至7任一项的固体离子导体,其中A是二价碱土金属阳离子。
9.根据权利要求4至8任一项的固体离子导体,其中A选自Ca、Sr和/或Ba。
10.根据权利要求4至6任一项的固体离子导体,其中所述化学计量组成为Li7La3Zr2O12。
11.制备根据权利要求4至10任一项的固体离子导体的方法,其特征在于使L、A、G和Zr的盐和/或氧化物互相反应。
12.根据权利要求11的方法,其特征在于所述反应借助例如Pechini法的前体法、甘氨酸法和借助所述组分的溶解盐的沉淀反应进行。
13.根据权利要求11的方法,其特征在于所述反应以固相反应进行。
14.根据权利要求11或13的方法,其特征在于以硝酸盐、碳酸盐或氢氧化物的形式使用L和A,并使它们与G2O3和ZrO2反应。
15.根据权利要求11、13和14任一项的方法,包括下述步骤:
a)将原料混合并球磨,优选在2-丙醇中使用氧化锆容器和球进行球磨,
b)在400至1000℃在空气中将获自a)的混合物加热2至10小时,
c)球磨,优选在2-丙醇中使用氧化锆容器和球进行球磨,
d)将混合物等静压制,以制得所需的形状,和
e)在700至1200℃将覆盖有相同组成的粉末的获自步骤d)的产物烧结10至50小时。
16.根据权利要求15的方法,其中将混合物在步骤b)中在700℃加热6小时和在步骤e)中在900℃烧结24小时。
17.根据权利要求4至10任一项的固体离子导体的用途,用于电池、蓄电池、超级电容器、燃料电池、传感器、热电转换器、和/或例如窗口、VDUs和外墙的电致变色设备中。
18.根据权利要求1的用途,其中使用根据权利要求4至10任一项的离子导体。
19.根据权利要求2的电极,其中使用根据权利要求4至10任一项的离子导体。
20.包括一个或多个根据权利要求19的电极的电池。
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CN102617140A (zh) * | 2012-03-05 | 2012-08-01 | 内蒙古工业大学 | 一种锑掺杂的类石榴石结构的锂离子晶态固体电解质材料及其合成方法 |
CN103682356A (zh) * | 2012-09-18 | 2014-03-26 | 华为技术有限公司 | 一种锂离子电池正极材料及其制备方法 |
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CN107750406B (zh) * | 2015-06-18 | 2021-02-12 | 德克萨斯大学系统董事会 | 水溶剂化玻璃/非晶态固体离子导体 |
CN107750406A (zh) * | 2015-06-18 | 2018-03-02 | 德克萨斯大学系统董事会 | 水溶剂化玻璃/非晶态固体离子导体 |
CN105489927A (zh) * | 2015-11-24 | 2016-04-13 | 青岛能迅新能源科技有限公司 | 一种提高全固态锂离子电解质材料Li7La3Zr2O12常温离子电导的方法 |
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KR101539123B1 (ko) | 2015-07-23 |
US8658317B2 (en) | 2014-02-25 |
CA2694259A1 (en) | 2009-01-08 |
CA2694259C (en) | 2015-06-23 |
US9450271B2 (en) | 2016-09-20 |
EP2176190A2 (de) | 2010-04-21 |
EP2176190B1 (de) | 2018-05-02 |
TWI434452B (zh) | 2014-04-11 |
KR20100053543A (ko) | 2010-05-20 |
DE102007030604A1 (de) | 2009-01-08 |
JP2014241288A (ja) | 2014-12-25 |
WO2009003695A2 (de) | 2009-01-08 |
JP5634865B2 (ja) | 2014-12-03 |
JP2010534383A (ja) | 2010-11-04 |
WO2009003695A3 (de) | 2010-02-04 |
TW200910671A (en) | 2009-03-01 |
US20100203383A1 (en) | 2010-08-12 |
US20140205910A1 (en) | 2014-07-24 |
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