CN113548893A - 锂石榴石复合陶瓷电解质 - Google Patents
锂石榴石复合陶瓷电解质 Download PDFInfo
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- CN113548893A CN113548893A CN202010327279.XA CN202010327279A CN113548893A CN 113548893 A CN113548893 A CN 113548893A CN 202010327279 A CN202010327279 A CN 202010327279A CN 113548893 A CN113548893 A CN 113548893A
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Abstract
本公开涉及锂石榴石复合陶瓷电解质。烧结复合陶瓷为锂石榴石复合陶瓷电解质,包括:锂石榴石主相和富锂次要相;其中,所述富锂次要相包含LixZrO(x+4)/2,2≤x≤10。
Description
技术领域
本公开涉及一种烧结复合陶瓷,具体涉及一种具有改善的极限电流密度(CCD)的锂石榴石复合陶瓷电解质,属于锂离子固体陶瓷电解质领域。
背景技术
常规的锂离子电池已被广泛研究,但是仍然受到能量密度、功率密度和安全性等问题的限制,这也对在电气设备中的大规模应用提出了挑战。基于锂石榴石电解质(LLZO)的固态锂电池解决了安全问题,但由于石榴石刚性陶瓷性质以及表面杂质的存在会造成不良锂润湿性、锂阳极与石榴石电解质之间的接触不足,常常导致大的极化和界面阻抗,从而引起锂的不均匀沉积和锂枝晶的形成。
因此,由于锂阳极和LLZO之间的接触不良,电池可能会经历低的极限电流密度(CCD)并最终短路。
发明内容
本申请公开了一种用于固态锂金属电池中的改进的锂石榴石复合陶瓷电解质,增强了固态锂金属电池中锂阳极/石榴石电解质界面接触。
在一些实施方式中,一种烧结复合陶瓷包括:锂石榴石主相和富锂次要相;其中,所述富锂次要相为LixZrO(x+4)/2,2≤x≤10。
在可与任何其他方面或实施方式组合的一个方面中,锂石榴石主相包含:(i)Li7-3aLa3Zr2LaO12,L=Al、Ga、或Fe,且0<a<0.33;(ii)Li7La3-bZr2MbO12,其中M=Bi、或Y,且0<b<1;(iii)Li7-cLa3(Zr2-c,Nc)O12,其中N=In、Si、Ge、Sn、V、W、Te、Nb、或Ta,且0<c<1;中的一个或者多个。
在可与任何其他方面或实施方式组合的一个方面中,锂石榴石主相与富锂次要相的质量比在100:1至100:12的范围之间。
在可与任何其他方面或实施方式组合的一个方面中,在富锂次要相中,锂与锆的摩尔比率在4至5的范围之间。
在可与任何其他方面或实施方式组合的一个方面中,所述烧结复合陶瓷的相对密度为烧结复合陶瓷理论最大密度的至少90%。
在可与任何其他方面或实施方式组合的一个方面中,所述烧结复合陶瓷的离子电导率至少为0.6mS·cm-1。
在可与任何其他方面或实施方式组合的一个方面中,所述烧结复合陶瓷的极限电流密度(CCD)至少为1.0mA·cm-2。
在可与任何其他方面或实施方式组合的一个方面中,所述烧结复合陶瓷的极限电流密度(CCD)至少为1.4mA·cm-2。
在一些实施方式中,一种烧结复合陶瓷,包括:锂石榴石主相和富锂次要相;其中所述富锂次要相包括Li6Zr2O7和Li8ZrO6中的一种或其组合。
在可与任何其他方面或实施方式组合的一个方面中,锂石榴石主相包含以下组分中至少一种:(i)Li7-3aLa3Zr2LaO12,L=Al、Ga、或Fe,且0<a<0.33;(ii)Li7La3-bZr2MbO12,其中M=Bi、或Y,且0<b<1;(iii)Li7-cLa3(Zr2-c,Nc)O12,其中N=In、Si、Ge、Sn、V、W、Te、Nb、或Ta,且0<c<1。
在可与任何其他方面或实施方式组合的一个方面中,锂石榴石主相与富锂次要相的质量比在100:1至100:12的范围之间。
在可与任何其他方面或实施方式组合的一个方面中,在富锂次要相中锂与锆的摩尔比率在4至5的范围之间。
在可与任何其他方面或实施方式组合的一个方面中,所述富锂次要相包含以下之一:(i)Li6Zr2O7;或(ii)Li6Zr2O7和Li8ZrO6。
在一些实施方式中,一种电池,包括:至少一个锂电极;以及至少一个与锂电极接触的电解质,该电解质是锂石榴石复合陶瓷电解质,其包含如本文所公开的烧结复合陶瓷。
在一些实施方式中,一种制造本文所公开的复合陶瓷的方法包括:首先混合包括锂源化合物和至少一种过渡金属化合物的无机原料以形成第一混合物;第一次研磨该第一混合物并减小原料的粒度;在800至1200℃下煅烧所研磨后的第一混合物,以形成锂石榴石氧化物;将经研磨和煅烧得到的锂石榴石氧化物与至少一种富锂次要相添加剂进行第二次混合,以形成第二混合物;第二次研磨第二混合物以减小第二混合物成分的粒度;将第二次研磨后的第二混合物压实,形成素坯;并在1000℃至1300℃的温度范围内烧结素坯,获得所述的烧结复合陶瓷。
在可与任何其他方面或实施方式组合的一个方面中,所述锂源化合物或次要相添加剂中的至少一种是以相对于化学计量过量的形式存在。
在可与任何其他方面或实施方式组合的一个方面中,所述次要相添加剂包括LixZrO(x+4)/2,2≤x≤10。
在可与任何其他方面或实施方式组合的一个方面中,富锂次要相添加剂包括:Li6Zr2O7和Li8ZrO6的一种或其组合。
在可与任何其他方面或实施方式组合的一个方面中,所述经研磨和煅烧的石榴石氧化物与所述至少一种富锂次要相添加剂的质量比在100:1至100:12的范围之间。
在可以与任何其他方面或实施方式组合的一个方面中,在至少一种次要相添加剂中锂与锆的摩尔比例在4至5的范围之间。
附图说明
通过结合以下附图进行的详细描述,本公开将变得更加易于理解。其中:
图1为具有不同的锂与锆(Li:Zr)摩尔比的富锂添加剂的X-射线衍射(XRD)图谱。
图2为具有富锂添加剂LZO-4(样品2)和LZO-4.5(样品7)的LLZO-LZO复合陶瓷的XRD图谱。
图3为对照样品1的断面扫描电子显微镜(SEM)图像。
图4为样品7的断面SEM图像。
具体实施方式
以下将结合附图对本公开的一些示例性具体实施方式进行详细描述。只要有可能,在所有附图中将使用相同的附图标记指代相同或相似的含义。附图中的组件不是必需要按比例绘制,而是将重点放在所给出示例性实施例的原理上。应当理解,本申请不限于说明书中阐述的或在附图中示出的细节或方法。还应该理解,本公开中所使用的术语仅出于描述的目的,而不应被认为是限制性的。
另外,在本说明书中阐述的任何示例是说明性的,而不是限制性的,并且仅阐述了要求保护的发明中许多可能实施例中的一些。对于本领域技术人员显而易见的,对本领域中通常遇到的各种条件和参数作出的一些非本质的其他合适的修改和调整,均在本公开保护范围内。
术语:
“主要相”、“主相”、“第一相”或类似的术语或短语是指在复合物中按重量比、体积比、摩尔比或类似指标大于50%的锂石榴石的物理存在。
“次要相”、“次相”、“第二相”或类似的术语或短语是指在复合物中按重量比、体积比、摩尔比或类似指标少于50%的锂枝晶生长抑制剂(即,晶界结合增强剂)的物理存在。
“SA”、“第二添加剂”、“第二相添加剂”、“第二相添加剂氧化物”、“相添加剂氧化物”、“添加剂氧化物”、“添加剂”或类似术语是指产生包含在所公开的复合物主相内的次要相或第二相的材料。
“LLZO”或类似术语是指包含锂、镧、锆和氧元素的化合物。例如,锂石榴石电解质包括以下至少一种:(i)Li7-3aLa3Zr2LaO12,L=Al、Ga、或Fe,且0<a<0.33;(ii)Li7La3- bZr2MbO12,其中M=Bi、或Y且0<b<1;(iii)Li7-cLa3(Zr2-c,Nc)O12,其中N=In、Si、Ge、Sn、V、W、Te、Nb、或Ta,且0<c<1。
“包括”、“包含”或类似术语是指包含但不限于,即包括而非排他的。
本文所用的“约”、“大约”、“基本上”和类似术语旨在具有广泛的含义,与本公开的主题涉及的本领域普通技术人员的普通和公认用法相一致。审阅本公开的本领域技术人员应理解,这些术语旨在用于描述所描述和要求保护的某些特征,而不将这些特征的范围限于所提供的精确数值范围。因此,这些术语应被解释为所描述和要求保护的主题的非实质性或无关紧要的修改或变更被认为是在所附权利要求书中所陈述的本发明的范围内。
例如,在改变复合物中组分的数量、浓度、体积、过程温度、过程时间、产率、流速、压力、粘度和类似参量及其范围,或用于描述本公开的实施例中采用的部件的尺寸和类似的值及其范围,“约”或类似术语是指可能发生的数值变化。例如:通过用于制备材料、组合物、复合材料、浓缩物、组成零件、制品或使用配方的典型测量和处理步骤;通过这些步骤中的无意错误;通过用于执行该方法的产品、原料或初始原料或配料的纯度上的差异;以及类似的考虑。术语“约”(或类似术语)也涵盖由于老化组合物或具有特定初始浓度的配方或混合物的过程中的数量变化,以及由于混合或加工组合物或具有特定初始浓度的配方或混合物的过程中的数量变化。
本文所使用的,“可选的”、“可选地”或类似术语旨在表示随后所描述的事件或情况可能发生或不发生,并且该描述事件或情况包括发生和不发生两种情况,并且该描述包括事件或情况发生的实例以及事件或情况没有发生的实例。除非另有说明,否则本文中使用的词语“一个”或“一种”及其类似的词语“所述”是指至少一个或多个。
本文中对元素的位置(例如,“顶部”、“底部”、“上方”、“下方”、“中间”等)的引用仅用于描述附图中各个元素的方向。应当注意,根据其他示例性实施例,各种元件的取向可以不同,并且这种变化旨在被本公开所涵盖。
可以使用本领域普通技术人员众所周知的缩略语(例如,“h”或“hrs”代表一个小时或几个小时,“g”或“gm”代表克,“mL”代表毫升,“RT”或“rt”代表室温,“nm”代表纳米,等类似缩略语)。
公开的关于组分、成分、添加剂、尺寸、条件、时间和类似方面及其范围的具体和优选值仅用于说明;它们不排除其他定义的值或定义范围内的其他值。本公开的组合物、制品和方法可包括本文所述的任何值或任何值的组合、具体值,更具体值和优选值,包括明确或隐含中间值和范围。
本领域普通技术人员众所周知的名词,尽管表述词语或短语存在差异,但描述的实质是相同。例如“极限电流密度”和“临界电流密度”、“埋粉”和“母粉”等。
如上所述,基于锂石榴石电解质(LLZO)的固态锂电池由于锂阳极和LLZO之间的接触不足,导致锂枝晶的形成和生长,电池极限电流密度(CCD)低并最终短路。解决这些问题的常规方法包括:(A)H3PO4酸处理,用于去除杂质,同时形成Li3PO4的保护性中间层,以将电解质的CCD增加到0.8mA·cm-2,以及(B)用SnO2或MoS2修饰电解质-阳极界面并形成Sn或Mo及相关的合金中间层。但是,发现对于这些方法,随着电池循环,中间层逐渐耗尽,并最终导致电池故障。而且,这些中间层不会增加电解质本身对锂枝晶生长的抵抗力。
复合陶瓷电解质有效地改善了主相晶界处的结合,从而通过抑制锂枝晶的生长来改善了CCD。CCD是指LLZO电解质在锂枝晶渗透到电解质中之前可容许的最大电流密度,这会评价电解质的枝晶抑制能力。通过在LLZO烧结过程中添加添加剂,添加剂或其分解产物会在晶界聚集,从而增强晶界结合并阻止锂枝晶的生长。目前研究添加剂的工作包括(i)LLZO中的LiOH·H2O以形成Li2CO3和LiOH的次要相,或(ii)通过将Li3PO4添加到LLZO前体中,并通过控制烧结条件使Li3PO4作为次要相保留在晶界上,或(iii)烧结涂覆有LiAlO2的LLZO颗粒以获得锂石榴石复合陶瓷电解质。然而,(i)至(iii)中的任何一个都不能实现期望的CCD以满足实际应用的要求。
本文公开了一种锂石榴石复合陶瓷电解质,其通过在LLZO陶瓷烧结期间,将富含锂的添加剂(例如,LixZrO(x+4)/2(2≤x≤10,“LZO”)添加到具有任选掺杂元素的LLZO(例如,In、Si、Ge、Sn、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y等中的至少一种)中而制备得到。在一些实施例中,尽管LZO的变体包括Li2ZrO3、Li6Zr2O7和Li8ZrO6,但是烧结气氛主要是Li6Zr2O7和Li8ZrO6提供。Li2ZrO3作为第二相可以聚集在LLZO晶界处。可以使用元素掺杂剂(In、Si、Ge、Sn、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y等中的至少一种或多种)将LLZO稳定成立方相。
该烧结复合陶瓷包括LLZO主相和LZO次要相。在烧结过程中添加富锂添加剂会降低LLZO的烧结温度,并为LLZO烧结创造锂(Li2O)气氛,从而简化了烧结过程并降低了成本。而且,富锂添加剂及其分解产物分布在LLZO晶界处,这增强了LLZO晶界处的结合并阻止了锂枝晶生长的形成。本文所述的锂石榴石复合陶瓷电解质的CCD至少为1.4mA·cm-2。
锂石榴石复合陶瓷电解质的制备方法
第一次混合。在第一次混合步骤中,按照石榴石氧化物的配方将化学计量比的无机原料混合在一起,并且研磨成细粉。无机原料可以是锂源化合物和至少一种过渡金属化合物(例如,La基、Zr基化合物等)。在一些实施方式中,无机材料化合物还可以包含Al、Ga、Fe、Bi、Y、In、Si、Ge、Sn、V、W、Te、Nb、Ta、Mg的至少一种或其组合。
在一些实施方式中,初始原料中可以包含超出化学计量比的锂源材料以补偿在从1000℃至1300℃的高温烧结(例如1100℃至1200℃)期间锂的损失。第一次混合步骤可以是干磨工艺,或使用不溶解无机原料的合适液体为溶剂的湿磨工艺。混料时间可以根据物料规模或程度以及观察到的混合效果来进行调整,例如从几分钟到几小时(例如,1min到48h,或30min到36h,或1h到24h(例如12h),或公开中的任何值或范围)。研磨可以通过行星式球磨机,砂磨机或类似的混合或研磨设备来实现。
煅烧。
在煅烧步骤中,在第一次混合步骤之后,将无机材料的混合物在预定温度(例如在800℃至1200℃包括中间值(例如950℃)在内的温度)下煅烧,以反应并形成目标锂石榴石电解质粉末(或称石榴石氧化物)。该预定温度取决于锂石榴石电解质的种类。煅烧时间一般可为1h至48h(例如2h至36h,或3h至24h,或4h至12h(例如6h),或其中公开的任何值或范围,取决于所选的无机原料或批料的相对反应活性。在一些实施方式中,可以将预混的无机配料研磨,然后根据需要煅烧或烧结。
第二次混合。
将煅烧后的锂石榴石氧化物和次要相添加剂(或称第二相添加剂)混合并研磨以形成均质组成的第二混合物(其混合时间由陶瓷素坯片或者条中的LZO分布与否确定)。LZO次要相通过采用与第一次混合步骤中所述类似的方式(研磨30min至36h(例如24h)和煅烧(例如12h至24h)制备。第二次混合步骤可采用包括以下中的一种或多种:湿磨,干磨或其组合。在混料研磨步骤后,可以在60℃至100℃(例如70℃)的任选低温下加热混合物以除去吸附的水分或溶剂。
成型。
将第二次混合步骤中细化均质的第二混合物在60℃至100℃(例如70℃)的温度下干燥6h至24h(例如12h)。然后,第二混合物通过200目筛并压实成素坯。素坯可以是任何几何形状,可通过冷等静压,热等静压,热压,单向压制或通过任何合适的类似的过程和方法获得。素坯可以具有至少一个尺寸在1mm至30mm的范围内(例如,~20mm)。如下所述,然后在高于煅烧温度的温度下烧结素坯。
烧结。
在烧结步骤中,将素坯置于带盖的坩埚(例如,Pt、ZrO2、Al2O3和MgO坩埚)中。烧结温度可选在1000℃至1300℃范围内任意值,例如中间数值或某个更小的范围数值。在烧结前后,其升温速度(烧结前)和冷却速度(烧结后)可分别为0.5℃·min-1至10℃·min-1(例如5℃·min-1)。
实施例1–锂石榴石(LLZO)电解质的制备
将前驱体LiOH·H2O、La2O3、ZrO2、Ta2O5按照化学计量Li6.5La3Zr1.5Ta0.5O12称量(锂过量2%)。通过使用钇稳定的氧化锆(YSZ)球作为研磨介质,使用异丙醇作为溶剂,以250rpm·min-1的速度进行湿法球磨12小时。将干燥的混合物粉末置于氧化铝坩埚中,在950℃下煅烧6小时,以获得纯立方相锂石榴石电解质粉末(LLZO)。
在一些实施方式中,固体电解质是锂石榴石陶瓷电解质LLZO,其化学式可为Li7- 3aLa3Zr2LaO12(L=Al、Ga或Fe;0<a<0.33),Li7La3-bZr2MbO12(M=Bi或Y;0<b<1),和Li7- cLa3(Zr2-c,Nc)O12(N=In、Si、Ge、Sn、V、W、Te、Nb、或Ta;0<c<1)的一种或多种。
实施例2–富锂次要相添加剂(LZO)的制备
将前驱体LiOH·H2O和ZrO2按照锂和锆摩尔比等于x(2<x<10),使用钇稳定的氧化锆(YSZ)球作为研磨介质,使用异丙醇作为溶剂,以250rpm·min-1的速度进行湿球磨24小时。将干燥的混合物粉末置于氧化铝坩埚中,在950℃下煅烧12-24小时,获得富锂次要相添加剂LZO粉体。
实施例3–锂石榴石复合陶瓷电解质(LLZO-LZO)的制备
将实施例1的LLZO粉末和实施例2的LZO粉末按预定比例称量并使用与上述相同的球磨过程在250rpm·min-1下湿磨12小时。将获得的混合物在70℃下干燥12小时,然后通过200目的筛子。通过在140MPa的压力下单向加压形成直径为18mm的素坯(1.25克)。之后,将素坯置于Al2O3坩埚、MgO坩埚或Pt坩埚中,并在1190℃下烧结30分钟以获得LLZO-LZO。烧结前和烧结后的升温速率和冷却速率均以5℃·min-1进行。在本实验的烧结过程中未使用母粉。
可选地,母粉(Li6.5La3Zr1.5Nb0.5O12)可用于补偿锂石榴石(LLZO)电解质样品在烧结过程中的锂损失。母粉的合成过程类似于本文所述的制备LLZO的方法(例如实施例1),除了前体粉末中锂含量过多(例如15%)。在烧结以制备LLZO-LZO复合材料时,素坯可任选被母粉覆盖,以防止挥发成分(Li2O)损失并避免锂缺乏相(La2Zr2O7)的存在。同时,Li2O气氛的存在促进了LLZO的致密化。
实施例4–纽扣电池的制备
将实施例3中制备的LLZO-LZO电解质片用400目和1200目的SiC砂纸抛光,然后在两面溅射Au层5分钟。在转移到充满氩气的手套箱中之后,在LLZO-LZO片中间贴附上锂金属片并在加热器上,将其加热到250-300℃时,熔融的锂会散布在电解质片的表面。翻转样品,在LLZO-LZO样品另一个表面使用相同处理,贴附锂金属并加热。然后将Li/LLZO/Li对称电池密封在CR2032纽扣电池中。
实施例5–表征技术
形貌和物相分析。
扫描电子显微镜(SEM)图像和元素面映射分析分别通过扫描电子显微镜(Hitachi,S-3400N)及附带的能量色散光谱仪(EDS)进行表征。通过在10-80°的2θ范围内X射线粉末衍射(Rigaku,Ultima IV,经镍过滤的Cu-Kα辐射,)获得X射线粉末衍射(XRD)图谱。通过阿基米德法,以乙醇作为浸没介质来测量陶瓷样品的密度。所有的测试均在室温(例如25℃)下进行。
电化学阻抗谱(EIS)。
通过交流阻抗分析(Autolab,型号PGSTAT302 N),在0.1Hz至1MHz的频率范围测量EIS。
电化学性能。
所有Li对称电池均在LAND CT2001A电池测试系统(武汉,中国)上测试。对实施例4中制备的Li/LLZO-LZO/Li对称电池进行极限电流密度(CCD)测试,电流密度为从0.1mA·cm-2按照0.1mA·cm-2为间隔依次增大到2.0mA·cm-2,每个电流密度下仅一次充电和放电且时间均为30min。所有电池测试均在25℃下进行。
实施例6–样品制备和表征
样品1
将前驱体LiOH·H2O和ZrO2按照锂和锆摩尔比等于4,使用钇稳定的氧化锆(YSZ)球作为研磨介质,使用异丙醇作为溶剂,以250rpm·min-1的速度进行湿法球磨24小时。将干燥的混合物粉末置于氧化铝坩埚中,在950℃下煅烧12小时,获得富锂添加剂粉体(“LZO-4”)。
将锂石榴石电解质LLZO和富锂添加剂LZO-4以100:2的质量比(40g LLZO与0.8gLZO-4和120g异丙醇)进行球磨。以100∶2的质量比称重LLZO粉末和LZO-4粉末,并以250rpm·min-1湿磨12小时。粒度分布(D90)在1.2μm和1.7μm之间。将获得的混合物在70℃下干燥12小时,然后通过200目的筛子。通过在140MPa的压力下单向加压形成直径为18mm的素坯(1.25克)。之后,将素坯放置在MgO坩埚中,并在1190℃下烧结30分钟。
样品2
除了锂石榴石电解质LLZO和富锂添加剂LZO-4质量比为100:4外,制备过程与样品1相同。
样品3
除了锂石榴石电解质LLZO和富锂添加剂LZO-4质量比为100:8外,制备过程与样品1相同。
样品4
除了锂石榴石电解质LLZO和富锂添加剂LZO-4质量比为100:12外,制备过程与样品1相同。
样品5
将前驱体LiOH·H2O和ZrO2按照锂和锆摩尔比等于4.5,使用钇稳定的氧化锆(YSZ)球作为研磨介质,使用异丙醇作为溶剂,以250rpm·min-1的速度进行湿法球磨24小时。将干燥的混合物粉末在氧化铝坩埚中在950℃下煅烧24小时,获得富锂添加剂粉体(“LZO-4.5”)。
将锂石榴石电解质LLZO和富锂添加剂LZO-4.5以100:1的质量比(40g LLZO与0.4gLZO-4.5和120g异丙醇)进行球磨。以100∶1的质量比称重LLZO粉末和LZO-4粉末,并以250rpm·min-1湿磨12小时。粒度分布(D90)在1.2μm和1.7μm之间。将获得的混合物在70℃下干燥12小时,然后通过200目的筛子。通过在140MPa的压力下单向加压形成直径为18mm的素坯(1.25克)。之后,将素坯放置在Pt坩埚中,并在1190℃下烧结30分钟。
样品6
除了锂石榴石电解质LLZO和富锂添加剂LZO-4.5质量比为100:2外,制备过程与样品5相同。
样品7
除了锂石榴石电解质LLZO和富锂添加剂LZO-4.5质量比为100:4外,制备过程与样品5相同。
样品8
除了锂石榴石电解质LLZO和富锂添加剂LZO-4.5质量比为100:8外,制备过程与样品5相同。
对照样品1
除了在锂石榴石电解质LLZO中未添加LZO,并且在烧结过程中将素坯埋入0.4g母粉(Li6.5La3Zr1.5Nb0.5O12,锂过量15%)中之外,制备过程与样品1相同。
对照样品2
除了在锂石榴石电解质LLZO中不添加LZO之外,制备过程与样品1相同。
表1列出样品1-8和对照样品1-2的制备条件和性质总结:
图1给出了根据一些实施例的具有不同的锂与锆(Li:Zr)摩尔比的富锂添加剂的x射线衍射(XRD)图谱。LZO-4的XRD衍射峰与PDF#81-2375标准卡片的XRD特征峰非常匹配,表明LZO-4的化学结构为Li6Zr2O7(即,使用前体原料LiOH·H2O和ZrO2的锂与锆摩尔比等于4,如样品1-4中所使用的)。
当锂与锆的摩尔比提高到4.5(如样品5-8中所用)时,过量的Li2O将与Li6Zr2O7反应形成Li8ZrO6,这导致LZO-4.5为两相体系,包括主相Li6Zr2O7和次要相Li8ZrO6(PDF#26-0867)。图1结果表明LZO的相组成受锂与锆的摩尔比影响。通过改变原料中锂与锆的比例,可以得到组成比不同的Li6Zr2O7和Li8ZrO6。因此,如果锂与锆的摩尔比降低(vs.锂与锆的摩尔比为4),则会出现Li6Zr2O7和Li2ZrO3两相体系。
图2给出了根据一些实施例如样品2和样品7中的锂石榴石复合陶瓷电解质(LLZO-LZO)的XRD图谱,其中添加剂分别为LZO-4和LZO-4.5。因为样品2和7的XRD峰都与立方锂石榴石电解质标准卡片(PDF#45-0109)匹配良好,所以这表明添加LZO不会影响LLZO的相组成。原始LLZO(例如Li7La3Zr2O12)在不同温度下具有立方(c-LLZO)和四方(t-LLZO)相。c-LLZO具有比t-LLZO更高的离子电导率(c-LLZO:10-3至10-4S·cm-1,而t-LLZO:10-5至10-6S·cm-1)。四方相是室温稳定相,经常需要引入掺杂离子(例如,In、Si、Ge、Sn、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y等的至少一种,)以稳定立方相。根据图2的XRD结果,未检测到t-LLZO相。因此,此处使用的LLZO(例如,Li6.5La3Zr1.5Ta0.5O12)可被视为单相材料。
上面的表1给出了样品1-8和对照样品1和2的选定制备条件和性能属性。对照样品2中没有使用母粉和没有添加LZO,烧结效果不佳。与的其他样品(相对密度(与陶瓷的理论最大密度相比)超过90%)相比,具有较低的相对密度(76.99%)。使用母粉但未向锂石榴石粉中添加LZO的对照样品1的相对密度值可与样品1-8的平均值相当(对照样品1:93.6%vs样品1-8的平均值:94.9%),但无法获得与样品1-8的平均值相当的CCD值(对照样品1:0.4mA·cm-2与样品1-8的平均值:0.925mA·cm-2),难以接近到样品2的CCD值(1.4mA·cm-2)。LLZO的烧结机理是气液固过程。Li2O气体在LLZO颗粒的表面冷凝成液相。溶解-沉淀促进物质的运输,导致晶粒长大并增强致密化。母粉和LZO都可以为LLZO烧结提供Li2O气氛,不同的是,LLZO分别从外部和内部获得Li2O气氛。
在1190℃下烧结时,包含LZO添加剂(LZO-4或LZO-4.5)的样品1-8的相对密度增加,这表明LZO可能有助于致密石榴石并降低烧结温度。如实施例3所述样品1-8的锂石榴石复合陶瓷电解质的制备,在样品1-8的烧结过程中未使用母粉。样品1-8的LLZO-LZO复合材料的相对密度还表明,由于LZO的分解将提供Li2O烧结气氛,因此母粉的加入不是烧结过程的关键组分。因此,由于这种Li2O烧结气氛和降低的烧结温度,简化了烧结工艺并且降低了成本。此外,富锂添加剂及其分解产物分布在LLZO晶界处,这增强了LLZO晶界处的结合并阻止了锂枝晶的生长。
所有样品1-8具有至少0.6mS·cm-1的离子电导率,与对照样品1中的电导率相当。对照样品2具有非常低的电导率(0.0123mS·cm-1),这归因于烧结不充分。添加LZO还促使锂石榴石的CCD增加。当LZO和LLZO的质量比为4/100,并且在MgO坩埚中烧结时,CCD达到1.4mA·cm-2。如上所述,LLZO的烧结取决于Li2O气氛。MgO和Pt坩埚与Li2O相对稳定,而Al2O3和ZrO2坩埚在高温下容易与Li2O反应,分别形成LixAlOy和LixZrOy,这使得LLZO难以烧结和致密化。因此,Al2O3和ZrO2坩埚通常需要重复烧结,并且需要在坩埚表面形成钝化层后才可用于LLZO烧结。
图3和图4分别给出对照样品1和样品7的断面SEM图像。如图3所示,在对照样品1的晶界中没有看到明显的杂质。样品7添加LZO时(图4),一些颗粒存在于晶界或晶粒表面中。EDS的结果表明,锆和氧是颗粒的主要成分,几乎没有检测到钽。因此,该颗粒被认为Li6Zr2O7、Li8ZrO6以及它们的分解产物为Li2ZrO3和Li2O之一或其组合。这也证实了图1中的LZO-4.5和图2的样品7的XRD图。对于每个样品1-8,LZO在复合石榴石的晶界中以次要或第二相形式存在,并有助于阻止锂枝晶的生长途径,从而促使CCD的增加。
因此,如本文所述,本公开涉及用于固态锂金属电池应用中的石榴石电解质晶界的改进的锂石榴石复合陶瓷电解质。形成的锂石榴石复合陶瓷电解质的优点包括:(1)更高的极限电流密度(CCD),因为富锂添加剂及其分解产物分布在LLZO晶界处,从而增强了LLZO晶界处的结合和阻止锂枝晶生长;(2)简化烧结工艺并减少成本,(a)通过添加LZO粉末在较低的烧结温度下将锂石榴石致密化;(b)在陶瓷烧结过程中不添加母粉,因为富锂添加剂(LixZrO(x+4)/2,2≤x≤10;LZO)能够提供Li2O烧结气氛。
对于本领域技术人员而言显而易见的是,根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。因此,除非根据所附权利要求及其等同物,否则所要求保护的主题不受限制。
Claims (20)
1.一种烧结复合陶瓷,其特征在于,包括:锂石榴石主相和富锂次要相;其中,所述富锂次要相包含LixZrO(x+4)/2,2≤x≤10。
2.根据权利要求1所述的烧结复合陶瓷,其特征在于,所述锂石榴石主相包括以下组分中至少一种:
(i) Li7-3aLa3Zr2LaO12,其中L = Al、Ga、或Fe,且 0<a<0.33;
(ii) Li7La3-bZr2MbO12,其中M = Bi、或Y,且0<b<1;
(iii) Li7-cLa3(Zr2-c,Nc)O12,其中N = In、Si、Ge、Sn、V、W、Te、Nb、或Ta,且0<c<1。
3.根据权利要求1所述的烧结复合陶瓷,其特征在于,所述锂石榴石主相与富锂次要相的质量比在100:1至100:12的范围之间。
4.根据权利要求1所述的烧结复合陶瓷,其特征在于,所述富锂次要相中锂与锆的摩尔比例在4至5的范围之间。
5.根据权利要求1所述的烧结复合陶瓷,其特征在于,所述烧结复合陶瓷的相对密度至少为烧结复合陶瓷的理论最大密度的90%。
6.根据权利要求1所述的烧结复合陶瓷,其特征在于,所述烧结复合陶瓷的离子电导率至少为0.6mS·cm-1。
7.根据权利要求1所述的烧结复合陶瓷,其特征在于,所述烧结复合陶瓷的极限电流密度CCD至少为1.0mA·cm-2。
8.根据权利要求7所述的烧结复合陶瓷,其特征在于,所述烧结复合陶瓷的极限电流密度CCD至少为1.4mA·cm-2。
9.一种烧结复合陶瓷,其特征在于,包括:锂石榴石主相和富锂次要相,其中,所述富锂次要相包含Li6Zr2O7和Li8ZrO6至少一种。
10.根据权利要求9所述的烧结复合陶瓷,其特征在于,所述锂石榴石主相包含以下组分中的至少一种:
(i) Li7-3aLa3Zr2LaO12,其中L = A、Ga或 Fe,且0<a<0.33;
(ii) Li7La3-bZr2MbO12,其中M = Bi、或Y,且0<b<1;
(iii) Li7-cLa3(Zr2-c, Nc)O12,其中N = In、Si、Ge、Sn、V、W、Te、Nb、或Ta,且0<c<1。
11.根据权利要求9所述的烧结复合陶瓷,其特征在于,所述锂石榴石主相与富锂次要相的质量比在100:1至100:12的范围之间。
12.根据权利要求9所述的烧结复合陶瓷,其特征在于,所述富锂次要相中锂与锆的摩尔比例在4至5的范围之间。
13.根据权利要求9所述的烧结复合陶瓷,其特征在于,所述富锂次要相包括以下之一:
(i) Li6Zr2O7;或者,(ii) Li6Zr2O7和Li8ZrO6。
14.一种电池,其特征在于,包括:
至少一个锂电极;和
与至少一个锂电极接触的电解质,
其中所述电解质为包含权利要求1所述烧结复合陶瓷的锂石榴石复合电解质。
15.一种根据权利要求1所述的烧结复合陶瓷的制备方法,其特征在于,包括:
(1)首先混合无机原料以形成第一混合物,该无机原料包括锂源化合物和至少一种过渡金属化合物;
(2)第一次研磨以减小第一混合物的粒度;
(3)在800℃至1200℃下煅烧经过第一次研磨后的第一混合物,以形成石榴石氧化物;
(4)将所得石榴石氧化物与至少一种次要相添加剂进行第二次混合,以形成第二混合物;
(5)第二次研磨第二混合物以减小第二混合物的粒度;
(6)将经第二次研磨后的第二混合物压制形成素坯;和
(7)在1000℃至1300℃的温度范围内烧结素坯,得到所述烧结复合陶瓷。
16.根据权利要求15所述的制备方法,其特征在于,所述锂源化合物或次要相添加剂中的至少一种是以化学计量过量存在。
17.根据权利要求15所述的制备方法,其特征在于,所述次要相添加剂包括LixZrO(x+4)/2,具有2≤x≤10。
18.根据权利要求15所述的制备方法,其特征在于,所述次要相添加剂包括Li6Zr2O7和Li8ZrO6中的至少一种。
19.根据权利要求15所述的制备方法,其特征在于,所述经研磨和煅烧的石榴石氧化物与所述至少一种次要相添加剂的质量比在100:1至100:12的范围之间。
20.根据权利要求15所述的制备方法,其特征在于,在所述至少一种次要相添加剂中锂与锆的摩尔比例在4至5的范围之间。
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