CN115989206A - 锂-金属氧化物/石榴石复合薄膜及其制造方法 - Google Patents
锂-金属氧化物/石榴石复合薄膜及其制造方法 Download PDFInfo
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- CN115989206A CN115989206A CN202180051629.7A CN202180051629A CN115989206A CN 115989206 A CN115989206 A CN 115989206A CN 202180051629 A CN202180051629 A CN 202180051629A CN 115989206 A CN115989206 A CN 115989206A
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- garnet
- lithium
- composite ceramic
- sintered composite
- metal oxide
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Abstract
烧结复合陶瓷,包括:锂‑石榴石主相;以及锂枝晶生长抑制剂次相,使得基于烧结复合陶瓷的总重量计,锂枝晶生长抑制剂次相具有>0‑10重量%的Li‑金属氧化物。
Description
本申请依据35U.S.C.§119要求于2020年8月21日提交的系列号为63/068,506的美国临时申请的优先权权益,本文以该申请的内容为基础并将其通过引用全文纳入本文。
背景
1.技术领域
本公开涉及具改进的临界电流密度(CCD)的锂-石榴石复合陶瓷电解质。
2.技术
常规的锂(Li)离子电池已经得到了广泛的研究,但是仍具有有限的电容密度、能量密度和安全性问题,从而对在电力设备中大规模应用带来挑战。例如,虽然基于Li-石榴石电解质(LLZO)的固态锂电池解决了安全性问题,但是由于石榴石的刚性陶瓷性质和差的锂润湿性导致的Li阳极与石榴石电解质之间的接触不充分,以及表面杂质常导致大的极化和大的界面阻力,从而造成锂的不均匀沉积和锂枝晶的形成。
因此,由于锂阳极与石榴石电解质之间的不良接触,电池可能经历低的临界电流密度(CCD)并最终短路。
本申请公开了用于在固态锂金属电池应用中增强Li-石榴石电解质的晶界结合的改进的锂-石榴石复合陶瓷电解质。
发明内容
在一些实施方式中,一种烧结复合陶瓷,包含:锂-石榴石主相;以及锂枝晶生长抑制剂次相,其中锂枝晶生长抑制剂次相包含,基于烧结复合陶瓷的总重量计的>0-10重量%的范围中的Li-金属氧化物。
在可与任何其他方面或实施方式组合的一方面中,锂-石榴石主相包含下列的至少一者:(i)Li7-3aLa3Zr2LaO12,其中L=Al、Ga或Fe及0<a<0.33;(ii)Li7La3-bZr2MbO12,其中M=Bi、Ca或Y及0<b<1;(iii)Li7-cLa3(Zr2-c,Nc)O12,其中N=In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca或其组合及0<c<1,或者它们的组合。在可与任何其他方面或实施方式组合的一方面中,锂-石榴石主相包含:Li7-cLa3(Zr2-c,Nc)O12,其中N=Ta、Ga、W或其组合,及0<c<1。在可与任何其他方面或实施方式组合的一方面中,Li-金属氧化物包含:Li-硅酸盐、Li-镓酸盐、Li-铝酸盐、Li-钨酸盐、Li-莫林那特(molinate)、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸盐,或它们的组合。
在可与任何其他方面或实施方式组合的一方面中,金属氧化物包含Li-硅酸盐。在可与任何其他方面或实施方式组合的一方面中,锂-石榴石主相包含至少90重量%的锂石榴石立方晶相。在可与任何其他方面或实施方式组合的一方面中,针对代表至少5%的总晶粒群体的晶粒群体所测量的最大晶粒尺寸不超过总晶粒群体的平均晶粒尺寸的多于20倍。在可与任何其他方面或实施方式组合的一方面中,烧结复合陶瓷包含具有在30-150μm的范围中的厚度的膜。在可与任何其他方面或实施方式组合的一方面中,所述膜具有至少10-4S/cm的Li-离子电导率以及膜的理论最大密度的至少90%的相对密度。
在一些实施方式中,一种电池包含:至少一个锂电极;以及与该至少一个锂电极接触的电解质,其中电解质为包含如本文中所描述的烧结复合陶瓷的锂-石榴石复合电解质。
在一些实施方式中,一种烧结复合陶瓷,包含:锂-石榴石主相;以及锂枝晶生长抑制剂次相,其中:锂-石榴石主相包含:Li7-cLa3(Zr2-c,Nc)O12,其中N=Ta、Ga、W或它们的组合,及0<c<1,以及锂枝晶生长抑制剂次相包含,基于烧结复合陶瓷的总重量计的>0-10重量%的Li-硅酸盐。
在可与任何其他方面或实施方式组合的一方面中,锂-石榴石主相包含至少90重量%的锂石榴石立方晶相。在可与任何其他方面或实施方式组合的一方面中,针对代表至少5%的总晶粒群体的晶粒群体所测量的最大晶粒尺寸不超过总晶粒群体的平均晶粒尺寸的多于20倍。在可与任何其他方面或实施方式组合的一方面中,烧结复合陶瓷包含厚度在30-150μm的范围中的膜。
在一些实施方式中,一种烧结复合陶瓷,包含:锂-石榴石主相;以及锂枝晶生长抑制剂次相,其中烧结复合陶瓷包含下列的至少一者:至少10-4S/cm的Li离子电导率;以及膜的理论最大密度的至少90%的相对密度。
在一些实施方式中,一种方法,其包含:于950℃至1500℃的范围中的温度烧结金属氧化物组分/石榴石生坯带以形成复合陶瓷,复合陶瓷包含:锂-石榴石主相;以及锂枝晶生长抑制剂次相,其中锂枝晶生长抑制剂次相包含,基于烧结复合陶瓷的总重量计的>0-10重量%的Li-金属氧化物。
在可与任何其他方面或实施方式组合的一方面中,烧结包含:自室温加热至温度范围;保持在该温度范围持续1-20分钟的范围中的时间;自温度范围冷却至室温,其中:用于加热步骤的升温速率(HRR)为100℃/分钟<HRR<1000℃/分钟,及用于冷却步骤的冷却速率(CR)为100℃/分钟<CR<1000℃/分钟。在可与任何其他方面或实施方式组合的一方面中,HRR为250℃/分钟<HRR<750℃/分钟,CR为250℃/分钟<CR<750℃/分钟,及温度范围为1100℃至1300℃。在可与任何其他方面或实施方式组合的一方面中,烧结复合陶瓷包含下列的至少一者:至少10-4S/cm的Li-离子电导率;以及膜的理论最大密度的至少90%的相对密度。
在可与任何其他方面或实施方式组合的一方面中,金属氧化物组分/石榴石生坯带藉由下述形成:使过量Li源与添加剂反应以形成Li-金属氧化物(LMO)前体;使LMO前体与钝化石榴石粉末混合以形成石榴石悬浮物;添加分散剂、粘合剂及增塑剂至石榴石悬浮物以形成粉浆组成物(slip composition);以及流延成型(tape casting)粉浆组成物。在可与任何其他方面或实施方式组合的一方面中,添加剂包含下列的至少一者:硅酮、三氧化钨(WO3),及氧化镓(Ga2O3)。在可与任何其他方面或实施方式组合的一方面中,金属氧化物组分/石榴石生坯带藉由以下形成:混合过量Li源、Li-金属氧化物(LMO)前体,及钝化石榴石粉末以形成石榴石悬浮物;添加分散剂、粘合剂,及增塑剂至石榴石悬浮物以形成粉浆组成物;以及流延成型粉浆组成物。
附图说明
结合附图,通过以下具体实施方式能够更完整地理解本公开,其中:
图1根据一些实施方式,例示了用于制造Li-金属-氧化物/LLZO复合薄膜的过程的流程图。
图2根据一些实施方式,例示了刚经喷射研磨的Ta-LLZO石榴石粉末的x射线衍射(XRD)图案。
图3A-3D根据一些实施方式,例示了石榴石带的截面扫描式电子显微镜(SEM)图像,石榴石带包含:0重量%的硅酮(图3A)、2重量%的硅酮(图3B)、5重量%的硅酮(图3C),及10重量%的硅酮(图3D),全部以1050℃/3分钟烧结。生坯带含有70%过量锂(Li)。
图4根据一些实施方式,例示了于1050℃/3分钟烧结之后,经烧结的Ga-W-LLZO带内的Li2O重量%与二氧化硅含量的相互关系。
图5根据一些实施方式,例示了于各种温度烧结持续3分钟及于它们相应的生坯带中包含不同含量的硅酮的Ga-W-LLZO带的Li离子电导率。
图6A-6D根据一些实施方式,例示了于1200℃/5分钟烧结的包含不同量的过量Li及硅酮添加剂的石榴石带的截面SEM图像。
图7A-7D根据一些实施方式,例示了于1200℃/10分钟烧结的包含不同量的过量Li及硅酮添加剂的石榴石带的截面SEM图像。
图8A及8B根据一些实施方式,例示了于1200℃/3分钟烧结的包含不同量的过量Li及硅酮添加剂的石榴石带的截面SEM图像。
图9A及9B根据一些实施方式,例示了于1200℃/15分钟烧结的包含不同量的过量Li及硅酮添加剂的石榴石带的截面SEM图像。
图10根据一些实施方式,例示了在生坯带中具有及不具硅酮添加剂的情况下,来自石榴石膜的电化学阻抗谱(EIS)曲线。
具体实施方式
现在将对示于附图中的示例性实施方式进行详细说明。只要可能,在附图中使用相同的附图标记表示相同或相似的部分。附图中的部件不一定按比例绘制,而是重点在于说明示例性实施方式的原理。应理解的是,本申请不限于说明书中阐述的或附图中例示的细节或方法学。还应理解的是,用辞仅是为了描述目的,而不应被认为是限制性的。
此外,在本说明书中列出的任何实施例都是说明性的而不是限制性的,并且仅列出了要求保护的本发明的诸多可能的实施方式中的一些实施方式。对各种条件和参数进行其他适当的修改和调整在本领域中是常见的,并且对于本领域的技术人员来说是显而易见的,其属于本公开的精神和范围内。
定义
“主相”、“第一相”或类似术语或短语是指大于50重量%的锂石榴石的实体存在。相组分及其浓度可以通过XRD来测量(重量%)。在一些实例中,主相也可以通过在组合物中大于50体积%或大于50摩尔%等的锂石榴石的实体存在来表示。
“次相”、“第二相”等术语或短语是指以重量计,以体积计,以摩尔计或以类似度量计,组合物中的小于50%的锂枝晶生长抑制剂(即,晶界结合增强剂)的实体存在。在一些实例中,不可通过XRD检测到的次相可以通过SEM来测量,以证实次相的存在。
“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”或类似术语是指当被包含在所公开的组合物中时,在主相中产生次相或第二次相的添加剂氧化物。
“LLZO”、“石榴石”或类似术语是指包含锂(Li)、镧(La)、锆(Zr)和氧(O)元素的化合物。任选地,掺杂剂元素可以取代Li、La或Zr中的至少一种。
例如,锂-石榴石电解质包含以下中的至少一种:(i)Li7-3aLa3Zr2LaO12,其中,L=Al、Ga或Fe并且0<a<0.33;(ii)Li7La3-bZr2MbO12,其中,M=Bi、Ca或Y并且0<b<1;(iii)Li7- cLa3(Zr2-c,Nc)O12,其中,N=In、Si、Ge、Sn、V、W、Te、Nb或Ta并且0<c<1;(iv)Li7-xLa3(Zr2-x,Mx)O12,其中,M=In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca或其组合并且0<x<1,或者它们的组合。
“包括”、“包含”或类似术语意为包括但不限于,即,内含而非排他。
如本文所使用的,术语“大约”、“约”、“基本上”和类似术语旨在具有与本公开主题所涉及的领域中的普通技术人员通常及可接受的用法相一致的广泛含义。审阅本公开的本领域技术人员应当理解,这些术语旨在允许对所述及要求保护的某些特征进行描述而不是将这些特征的范围限制于所提供的精确数值范围。因此,这些术语应被解释为表示所述及要求保护的主题的非实质性或微小的修改或变更被认为是在所附权利要求书中所述的本发明的范围内。
例如,在对描述本公开实施方式中所用的组合物中成分的量、浓度、体积、工艺温度、工艺时间、产量、流动速率、压力、粘度等数值及其范围,或者部件的尺寸等数值及其范围进行修饰时,“约”或类似术语是指数量的变化,其可发生在例如:用于制备材料、组合物、复合物、浓缩物、部件零件、制造制品或应用制剂的典型测定和处理步骤中;这些程序中的无意误差中;用来实施所述方法的起始材料或成分的制造、来源、或纯度方面的差异中;以及类似的考虑因素中。术语“约”(或类似术语)还包括由于组合物或制剂的老化而与特定的初始浓度或混合物不同的量,以及由于混合或加工组合物或制剂而与特定的初始浓度或混合物不同的量。
如本文中所使用的,“任选的”或“任选地”等旨在表示随后描述的事件或情况可能发生或者可能不发生,并且该描述包括所述事件或情况发生的实例及不发生的实例。除非另外说明,否则,本文所用的不定冠词“一个”或“一种”及其对应的定冠词“该(所述)”表示至少一(个/种),或者一(个/种)或多(个/种)。
如本文所用,“室温”或“RT”旨在表示在约18℃至25℃范围内的温度。
本文提及的元件位置(例如,“顶”、“底”、“上方”、“下方”等)仅用于描述附图中各个元件的取向。应理解的是,各个元件的取向可以根据其他示例性实施方式而有所不同,并且这种改变旨在涵盖在本公开的范围内。
可采用本领域普通技术人员熟知的缩写(例如,表示小时的“h”或“hrs”;表示克的“g”或“gm”;表示毫升的“mL”;表示室温的“RT”;表示纳米的“nm”以及类似缩写)。
在组分、成分、添加剂、尺寸、条件、时间和类似方面公开的具体和优选的数值及其范围仅用于说明;它们不排除其他限定数值或限定范围内的其他数值。本公开的组合物、制品和方法可包括本文所述的任何数值或者各数值、具体数值、更具体的数值和优选数值的任何组合,包括显义或隐义的中间数值和中间范围。
对于本文中使用的基本上任何的复数和/或单数术语,本领域技术人员可以适当地从复数转换为单数形式和/或从单数转换为复数形式,只要其适用于上下文和/或应用。为了清楚起见,可以在本文中明确说明各种单数/复数排列。
如上所述,基于Li-石榴石电解质(LLZO)的固态锂电池常具有Li阳极与石榴石电解质之间接触不充分的问题,这常导致电池经历低的临界电流密度(CCD)并最终短路。解决这些问题的常规方法已经包括了:(A)H3PO4酸处理以去除杂质,同时形成Li3PO4保护居间层,和(B)改变与SnO2和MoS2的电解质-阳极界面,以形成Sn、Mo和相关的合金居间层。然而,发现对于这些方法,随着电池循环,居间层逐渐耗尽并且导致电池最终失效。另外,这些居间层不增加电解质自身对抗锂枝晶生长的阻力。
复合陶瓷电解质通过最大程度地减少锂枝晶生长,有效地改进了主相晶界处的结合,从而提高了CCD。临界电流密度(CCD)是指在电解质中发生锂枝晶穿透之前,LLZO电解质可承受的最大电流密度,其影响电解质的枝晶抑制能力。通过在LLZO烧结过程期间加入添加剂,所述添加剂或其分解产物在晶界处聚集以增加晶界结合并阻断锂枝晶生长。目前研究添加剂的努力工作包括(i)LLZO中的LiOH·H2O,以形成Li2CO3和LiOH次相,或者(ii)将Li3PO4加入到LLZO前体中并且通过控制烧结条件,使Li3PO4作为次相保留在晶界处,或者(iii)加入经LiAlO2涂覆的LLZO颗粒以获得Li-石榴石复合陶瓷电解质。然而,(i)至(iii)均不可实现期望的CCD来满足实际应用的要求。
石榴石是用于Li金属电池技术的有潜力的固体电解质材料。Li金属阳极允许具有比目前用于常规Li离子电池的碳阳极明显更高的能量密度。在制造薄的石榴石材料的方法中存在挑战。例如,一项挑战是Li枝晶形成,如上所述。第二项挑战是薄膜的强度要求,这由电池组装处理决定。高强度需要细的晶粒微结构。
本文公开了一种用于电解质应用的Li-石榴石复合陶瓷薄膜,其通过将金属氧化物添加到具有任选的元素掺杂(例如,In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Ca等中的至少一种或者其组合)的LLZO中来制备。元素掺杂剂可以用于将LLZO稳定成立方相。
Li-金属-氧化物可用作用于晶粒边界修饰的晶粒边界材料,使得可以不使用或者使用低的Li离子导电材料来填充石榴石晶粒边界,致使Li离子优选地穿透石榴石晶粒,从而抑制Li-枝晶生长通过晶粒边界并且抑制固态电解质临界电流密度(CCD)。第二相材料的低熔化温度亦可以帮助降低石榴石烧结温度及增加晶粒结合强度。
在一些实例中,Li-石榴石复合陶瓷可包含:锂石榴石主相(如,如以上定义的LLZO)及锂枝晶生长抑制剂次相(如,如以上定义的SA)。在一些实例中,主相可掺杂有In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca的至少一者或其组合以及次相包含选自Li-硅酸盐、Li-镓酸盐、Li-铝酸盐、Li-钨酸盐、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸盐或其组合的第二添加剂氧化物,基于陶瓷的总量以自>0-10重量%存在。添加剂可改进陶瓷微结构的均匀性并且增强陶瓷的机械性质。如本文中所使用的“陶瓷微结构的均匀性”意指晶粒尺寸的分布。可以最大程度地减少或消除对机械性质可具有有害影响的异常大的晶粒的存在,并且可以实现细晶粒微结构。例如,对代表至少5%的总晶粒的晶粒群所测得的最大晶粒尺寸不应超过平均晶粒尺寸的多于20倍。
如本文公开的,描述了使用所识别的复合组合物制造致密、细晶粒金属氧化物/石榴石复合薄膜结构的方法,相比于不包含金属氧化物/石榴石复合薄膜的电池单元,所述致密、细晶粒金属氧化物/石榴石复合薄膜结构得到了CCD得到改进的测试电池单元。
以下实施例证明了所公开的陶瓷的制造、使用和分析。
实施例
图1根据一些实施方式,例示了用于制造金属氧化物/LLZO复合薄膜的过程的流程图。
实施例1A—Li-石榴石复合陶瓷粉末的制备(石榴石粉末制造)
步骤1:第一混合步骤
在第一混合步骤中,将化学计量量的石榴石氧化物式中的无机材料混合在一起,并且例如研磨成细粉末。无机材料可以是碳酸盐、磺酸盐、硝酸盐、草酸盐、氢氧化物、氧化物,或者其与化学式中的其他元素的混合物。例如,无机材料例如可以是锂化合物和至少一种过渡金属化合物(例如,La基、Zr基等)。在一些实施方式中,无机材料配混物还可以包括在化学式中的In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca中的至少一种或其组合。
在一些实施方式中,可取的是,在起始无机批料中包括过量的锂源材料,以补偿在1000℃至1300℃(例如1100℃至1200℃)的高温烧结/第二焙烧步骤期间的锂的损失。第一混合步骤可以是干混过程(例如,管式混合随后干法球磨,或反之亦然),干磨过程,或者利用适当液体的湿磨过程,所述适当液体不溶解无机材料。可以调整混合时间,例如,从几分钟到几小时,例如,根据观察到的混合性能的规模或程度来调整[例如,1分钟到48小时,或者30分钟到36小时,或者1小时到24小时(例如12小时),或者在其中公开的任何数值或范围]。研磨可通过例如行星碾磨机、磨碎器、球混合、管式混合或类似混合或碾磨设备来实现。
步骤2:第一焙烧步骤
在第一焙烧步骤中,在第一混合步骤之后,在预定温度下,例如,在800℃至1200℃下(例如,在950℃下)(包括中间的数值和范围),焙烧无机材料的混合物,以反应并形成目标Li-石榴石。预定温度取决于Li-石榴石的类型。煅烧时间例如从1小时到48小时不等[例如,2小时至36小时、或3小时至24小时、或4小时至12小时(例如5小时),或者在其中公开的任何数值或范围],并且还可以取决于选择的无机起始或源批料的相对反应速率。在一些实例中,独立于煅烧时间来选择预定温度,例如,950℃下持续5小时,或者1200℃下持续5小时。在一些实施方式中,需要时,在第一步中,可碾磨无机批料的预混合物,然后煅烧或焙烧。
步骤3:第二焙烧步骤
在第一焙烧步骤后,可以在更高的预定温度下,例如,在1000℃至1300℃(例如1200℃),包括中间的数值和范围对经焙烧的无机材料混合物进行焙烧,并且升温速率(烧结前)和冷却速率(烧结后)为0.5℃/分钟至10℃/分钟(例如5℃/分钟)。第二焙烧的预定温度取决于Li-石榴石的类型。煅烧时间例如从1小时到48小时不等[例如,2小时至36小时、或3小时至24小时、或4小时至12小时(例如5小时),或者在其中公开的任何数值或范围]。
在一些实例中,步骤2和步骤3可以合并成具有两个保持阶段的单个焙烧步骤(第一保持阶段由步骤2代表,第二保持阶段由步骤3代表)。
步骤4:碾磨步骤
在第二焙烧步骤后,可以对粉末进行碾磨,这通过球磨和/或喷射碾磨进行,其中,具有90重量%的上述锂石榴石立方相。当进行球磨时,经球磨的粉末较粗,D50粒度范围在1-5μm之间。当进行喷射碾磨时,经喷射碾磨的粉末较细,D50粒度范围在0.01-1μm之间。粗粉末和细粉末均大致具有双模态粒度分布。对于流延成型,具有单模态分布的较细粉末是优选的。
步骤5:筛分步骤
然后对步骤4的经碾磨的粉末进行过滤,这通过使所述粉末通过100目(grit)筛进行,以获得D50粒度范围在0.01-1μm之间(例如0.6μm)的最终的Li-石榴石复合陶瓷粉末。若粉末形成为任意形状,则粉末的至少一个尺寸可以在0.01-1μm的范围内。
实施例1B
在实施例1B中,分别使用0.5Ta-LLZO和Li4.9La3Zr1.7W0.3Ga0.5O12组成的石榴石制造复合物。
藉由固态反应方法、使用Li2CO3、La2O3、ZrO2及相应的掺杂剂氧化物[如,基于Ta的(如,Ta2O5)、基于W的(如,WO3),或基于Ga的(如,Ga2O3)]作为前体来制备石榴石粉末。由于粉末吸附不同量的吸附物,因此在配料之前,使用TGA(RT-1000C)对粉末(除Li2CO3)进行测量,然后考虑吸附物的量配料粉末中的量。通过管式混合来彻底混合化学计量的批料,随后球磨,然后在单个焙烧步骤中加热,其中,在带有Pt盖板的Pt坩埚中,在950℃下进行5小时的第一保持阶段,并且在1200℃下进行5小时的第二保持阶段。煅烧后,对块状产物进行喷射碾磨,然后用100目筛进行筛分,以获得D50为约0.6μm的最终的石榴石粉末。
图2例示了刚经喷射研磨的Ta-LLZO石榴石粉末的x射线衍射(XRD)图案,以确认组成。
实施例2—石榴石粉末钝化
在一些实施方式中,在粉浆制备(下文有更详细解释)之前,可对实施例1A或1B中制备的石榴石粉末(例如,Ta掺杂的LLZO,或类似地,Ga和/或W掺杂的LLZO)进行空气碳酸化或酸处理以钝化其与其他流延成型粉浆组分的高反应性。这使得当对粉浆进行流延成型时,石榴石是稳定的,因此,最终的生坯带可以稳定长的时间。
通过空气碳酸化对石榴石粉末进行钝化
将制成的石榴石粉末(实施例1A或1B的)暴露于50℃的空气中1个月。使粉末与空气中的H2O和CO2反应以形成H-LLZO(内芯体;H掺杂的LLZO),并且在石榴石粉末颗粒上具有覆盖的Li2CO3外壳。如上所述,这使石榴石钝化以防止在流延成型粉浆时石榴石与粉浆组合物中的有机组分反应。
通过酸处理对石榴石粉末进行钝化
在替代性钝化技术中,添加酸(如,HCl、HF、HNO3、H3PO4、H2SO4、乙酸、硼酸、碳酸、柠檬酸、草酸等)至(实施例1A或1B的)制成的石榴石粉末的浆料中。初始,浆料的pH超过7,但是该值由于加入酸而逐渐下降,直到下降到约6的期望pH。对浆料进行离心分离最终的粉末。所获得的测试粉末为对流延成型粉浆稳定的H-LLZO(质子化石榴石)(即,没有Li2CO3外壳形成—质子化石榴石的一种组成物)。
实施例3—藉由添加Li-金属氧化物(LMO)前体的粉浆制造
在实施方式中,通过制造石榴石粉浆组合物来开始流延成型过程。粉浆包含至少一种溶剂、有机粘合剂、增塑剂、锂石榴石粉末、过量锂源、第二添加剂和分散剂。表1列出了典型的粉浆组合物制剂,但是可以改变锂石榴石粉末、过量锂源、第二添加剂和粘合剂含量,以实现各种高质量的生坯带。
表1
在一些实施例中,粉浆组合物制剂的分散剂可选自包含下列的组:118、142、182、2022、2155、SolsperseTM41090、250、鱼油或其组合。在一些实施例中,粉浆组合物制剂的过量Li可选自包含下列的组:Li2CO3、LiCl、LiNO3、Li-柠檬酸盐、Li-乙酸盐、Li-油酸盐、LiF、Li2SO4,或其组合。
粉浆制造包括下述步骤:于溶剂中分散锂石榴石粉末、过量锂源及第二添加剂以形成石榴石悬浮物。作为参考,添加Li2CO3作为过量锂源(Li前体)。在初始粉浆制造步骤中,含有50重量%SiO2的M97E硅酮(Si前体)用作假性粘合剂/增塑剂(除了于生坯带形成中添加的粘合剂及增塑剂)。在烧结期间,M97E硅酮可分解并且与Li2CO3反应以形成Li-硅酸盐。类似地,针对包含基于钨的化合物(如,WO3)和/或基于镓的化合物(如,Ga2O3)的第二添加剂的粉浆组合物制剂,经由各自与Li2CO3的反应可分别地形成Li-钨酸盐及Li-镓酸盐。在一些实施例中,可添加金属氧化物或其他形式前体(如,WO3、Ga2O3等等)至粉浆中以作为第二添加剂,并流延成型成生坯带。在烧结的步骤期间,这些金属氧化物或前体与Li2CO3反应以分别原位形成Li-钨酸盐、Li-镓酸盐等。随后,Li-硅酸盐、Li-钨酸盐和/或Li-镓酸盐各自在溶剂中与锂石榴石粉末混合以形成石榴石悬浮物。最终,添加分散剂、粘合剂,及增塑剂至石榴石悬浮物,研磨(如,于2000rpm磨碎研磨持续1-5小时(如,2小时))及于真空下除气持续5至10分钟。可于真空下执行研磨及混合并且冷却以防止石榴石和其他粉浆组分之间的无意反应。
实施例4—流延成型
流延成型过程例如包括粉浆制备(如上所述),带铸,以及干燥(烧结,如下所述)。流延成型例如可以使用6密耳至18密耳刀片进行。表1为可用于流延成型Li-硅酸盐/石榴石复合生坯带的粉浆组成物的实施例。
具有及不具硅酮的生坯带
表2显示了用于表征的实验性流延成型条件的比较。来自表2的条件1-3的粉浆组合物藉由在惰性环境(N2)中于950℃首先加热持续2小时而被流延成型。在粉末冷却后,随即为流延成型。表2中定性描述了所得的生坯带的稳定性。当带变得易碎(即,脆性、破裂)时,表示其中含有的有机材料(粘合剂、增塑剂)衰减,其可能为与活性石榴石反应的结果。因此,表2中,“挠性”可归类为当生坯带于90°弯曲且仍然不会开裂。
表2
实施例5—带烧结
在空气及氩(Ar)气氛中烧结石榴石带。在烧结期间,生坯带乘载于拖架上(如,氧化铝、MgO、ZrO2、柔性石墨)或悬浮于空气中。当使用拖架时,生坯石榴石带可夹置于拖架片材之间以维持锂。不需母制粉末(mother powder)。可使用两个类型的烧结方法:常规烧结及快速烧结。在常规烧结中,温度上升速率在100℃/小时至600℃/小时的范围中。在快速烧结中,温度上升速率在100℃/分钟至1000℃/分钟的范围中。在快速烧结中的Li-损失明显降低并因此生坯带可在周围空气中烧结而不需要任何覆盖。为防止热冲击,托架优选为薄膜形式(陶瓷薄片或陶瓷条带)。针对常规烧结,以Ar或氮(N2)气氛为优选。
硅酮/Ga及W掺杂的LLZO带
在一个实施例中,以0.5Ga-0.3W-LLZO石榴石、变化量的硅酮(0重量%至10重量%的范围中)及70%过量Li(作为Li2CO3,相对于石榴石中的Li含量)制备粉浆组成物以及流延成型。流延成型的生坯带于空气中烧结以450℃/分钟的升温速度至1000℃至1200℃的范围中的温度持续3分钟。图3A-3D例示了石榴石带(~70μm)的截面扫描电子显微镜(SEM)图像,包含:0重量%硅酮(即,无Li-硅酸盐)(图3A)、2重量%硅酮(图3B)、5重量%硅酮(图3C),及10重量%硅酮(图3D),全部进行1050℃/3分钟烧结。生坯带含有70%过量锂(Li)。10重量%硅酮样品显示稍微较松散的晶粒结构。
图4例示了由电感耦合等离子体(ICP)测量的于1050℃/3分钟烧结之后,烧结的Ga-W-LLZO带内的Li2O重量%相对二氧化硅含量。当硅酮含量增加,例如自0重量%至2重量%至5重量%至10重量%,烧结的Ga-W-LLZO带内的Li2O重量%也增加。如上文解释的,在烧结期间,硅酮分解并且与Li2CO3反应以形成Li-硅酸盐。因此,通过在烧结的石榴石带中将Li作为Li-硅酸盐保存,Li损失得到了减缓,使得至少一些硅酮含量优于具0重量%硅酮的带。
研究电气性能,图5例示了在各种温度下烧结持续3分钟且相应的生坯带中包含不同含量硅酮的Ga-W-LLZO带的Li离子电导率,如藉由使用金(Au)电极的电化学阻抗谱(EIS)所测量。当于晶粒边界添加第二相时,预期Li离子电导率将严重降低。然而,意外的是,针对包含0重量%至5重量%的范围中的硅酮含量的带,Li离子电导率随带中的硅酮含量增加而增加,自1×10-4至3.5×10-4S/cm变化。Li离子电导率的这种增加可指示样品中保留了更多Li,证实了硅酮或Li-硅酸盐有助于减少Li损失。不受理论所限制,针对较高程度的硅酮(如,10重量%),于较低烧结温度的较低电导率可能是由于烧结制程期间带未充分致密化。这指示(来自硅酮的)太高的硅石含量增加了石榴石的烧结温度。因此,在硅酮含量大于10重量%时,烧结温度可能变为不期望地高。
在一些实施例中,硅酮含量可以下述量存在:>0重量%至10重量%,或>0重量%至8重量%,或>0重量%至5重量%,或5重量%至10重量%,或2重量%至10重量%,或其中公开的任何值或子范围。
表3描述了XRD-测量的具有不同含量硅酮及于不同条件烧结(若未标记,表示带经快速烧结)的薄石榴石烧结膜的相组合物。
表3
所有样品均具有高的石榴石立方相浓度(例如,>90重量%)。高浓度的立方相确保了高的离子传导率。LiGaO2、LaGaO3、La2Zr2O7、Li4WO5、Li2WO4、ZrO2等的存在是Li-Ga、Si-W、Si-Zr等之间的离子交换的副产品。副产品以及Li-硅酸盐第二相留在晶粒边界或三边界点。因为Ga-W-LLZO组合物为低Li组合物并且因为系统含有高的过量Li,石榴石在测试的烧制条件下不分解。
硅酮/Ta掺杂的LLZO带
在一个实施例中,以0.5Ta-LLZO石榴石、不同含量硅酮(于0重量%至10重量%的范围中)及15%或50%过量Li(作为Li2CO3,相对于石榴石中的Li含量)制备粉浆组成物并且流延成型。流延成型的生坯带于空气中烧结,以450℃/分钟的升温速度至1000℃至1200℃的范围中的温度持续3分钟。表4总结了针对各种生坯带组合物的烧结条件。
表4
图6A-9B例示了包含不同含量硅酮添加剂及过量Li以及不同烧结条件的石榴石带(~50μm)的截面SEM图像。如上文所解释的,至少一些硅酮含量优于具0重量%硅酮的带以减缓Li损失。图6A-9B证实了过量Li含量及硅酮含量均影响带烧结。举例来说,针对具有15%过量Li含量的带,具最低添加硅酮含量(2重量%)的那些例证了最致密微结构(图6B及7B)而具最高添加硅酮含量(8重量%)的那些显示最多孔结构(图6D及7D)。根据图8A-9B,显示过量Li(50%)造成不想要的松散晶粒连接(晶粒间断裂)或石榴石中异常及相对大的晶粒生长;细晶粒结构为高强度薄膜的必要条件。因为异常晶粒生长发生于高Li浓度,针对具有或不具有硅酮的样品的SEM图像显示具硅酮的样品在烧结条件下含有更多Li。换句话说,不仅是过量Li,还因为硅酮的存在亦减缓Li损失,从而造成较高Li浓度。此结果再次强调添加硅酮的带保留更多锂。
以下表5提供了Li2O重量%根据在1200℃烧结持续不同时间之后烧结的Ta-LLZO带内的硅石含量而变化的情况,如由电感耦合等离子体(ICP)所测量。数据证明带中的Li-硅酸盐防止Li损失,尤其是针对接近化学计量Li水平(如,11.1% Li2O)的样品。来自石榴石的Li损失较来自诸如Li2CO3、Li2O、LiOH等之类的过量Li物质困难。Li-硅酸盐升高针对这些添加的过量Li物质的Li损失温度并且在较高温度保留更多过量Li。举例来说,在2重量%硅酮带中,仅1重量%为SiO2。由此少量Li-硅酸盐保持的更多的Li可能低于ICP检测灵敏度。
表5
图10例示了在生坯带中具有(5重量%硅酮)及不具硅酮添加剂的情况下,来自于石榴石膜的电化学阻抗谱(EIS)曲线(使用Au电极)。两个样品均于1250℃/3分钟烧结。类似图5的数据,令人意外地,两个带(包含0重量%或5重量%硅酮含量)具有3×10-4S/cm的相同的Li离子电导率(如,在1×10-4至3.5×10-4S/cm的范围内),即便当在晶粒边界添加第二相,预期Li离子电导率将严重降低。这些较高的电导率指示在升高的温度(如,1250℃)烧结足以形成致密化薄膜。具有及不具有Li-硅酸盐的相同Li离子电导率指示Li-硅酸盐留在石榴石的三叉晶粒边界。
表6
表6公开了烧结的Li-硅酸盐/Ta-LLZO带及纯Ta-LLZO带的XRD测量的相组合物。大多数样品具有超过93重量%立方石榴石的高浓度立方晶石榴石相。高立方相确保了高离子电导率。La2Zr2O7及LaTaO4的存在是石榴石分解的副产品。这些不同于期望的Li-硅酸盐第二相,其留在晶粒边界或三边界点。这些副产品呈大团块(数倍的石榴石晶粒大小)及烧结的带中的孔洞。过量的副产品导致电导率下降并减弱带强度。举例来说,针对不具Li-硅酸盐在较高温度烧制较长时间的样品,带损失过多Li,造成立方石榴石相降低至85.4重量%。结果,副产品的增多亦增加。由于Li-硅酸盐减少的Li损失,具有Li-硅酸盐的样品可维持它们的100重量%立方相。此外,具有(2重量%至8重量%)及不具(0重量%)Li-硅酸盐的样品具有大约相同的晶格常数,指示Si未掺杂至石榴石晶格中以及Li-硅酸盐留在晶粒边界或三边界点。
实施例6—烧结过程的比较
常规的烧结涉及1-10℃/分钟(60-600℃/hr)的加热和/或冷却升/降温速率,而本申请中所述的烧结过程(即,“快速烧制”)涉及100-600℃/分钟的加热和/或冷却升/降温速率。
如本文所公开的,石榴石薄带通过下述形成:将过量Li(例如,Li2CO3形式)加入到生坯带中以补偿烧结期间的Li损失,以获得致密烧结的结构(即,相对密度>98%)并具有高的立方石榴石相浓度(接近100%)。快速烧制通过缩短升温时间而抑制了Li损失(当温度大于900℃时,Li损失明显),这能够在更苛刻的条件下实现石榴石带烧结。随着Li损失充分减小,生坯带中所需的过量Li也可以减小。例如,在约100μm厚的0.5Ta-LLZO生坯带中,(A)当在氩气中烧制时,在快速烧制时仅需要5-10%的过量Li,而在常规烧结中需要大于20%的过量Li;或者(B)当在周围空气中烧制时,在快速烧制中仅需要约15-20%的过量Li,而在常规烧结中需要超过50%的过量Li。
实施例7——表征技术
形貌学和相分析
通过扫描电子显微镜(JEOL,JSM-6010PLUS/LA)获得扫描电子显微技术(SEM)图像。藉由于室温在10–80°的2θ范围中的x射线粉末衍射(Bruker,D4,Cu-Kα辐射,)获得X射线粉末衍射(XRD)图案。HF/HClO4冒烟程序(冒烟至干,两次),然后将残余物溶解在HCl中,进行电感耦合等离子体(ICP)测量。使用珀金埃尔默(Perkin Elmer)PinnAAcle 500进行Li分析。
电化学阻抗谱(EIS)
EIS通过AC阻抗分析(Solartron SI 1287)来测得,其中,频率范围为0.1Hz至1MHz。
因此,如本文所述,本公开涉及用于在固态锂金属电池应用中增强Li-石榴石电解质的晶粒边界结合的改进的锂-石榴石复合陶瓷电解质。增强的晶粒边界组合物有助于阻止有害的Li枝晶生长。
具体地,本申请公开了包含锂石榴石立方晶主相(如,LLZO,如上定义)及锂枝晶生长抑制剂次相(如,SA,如上定义)的Li-石榴石复合陶瓷。在一些实施例中,主相可掺杂有In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca的至少一者或其组合,以及次相包含选自下列组的第二添加剂氧化物:Li-硅酸盐、Li-镓酸盐、Li-铝酸盐、Li-钨酸盐、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸盐或其组合,基于陶瓷总量以自>0-10重量%存在。添加剂可改进陶瓷微结构的均匀性并且增强陶瓷的机械性能。因为具有及不具第二相的样品具有类似的晶格常数,这指示第二相(即,次相)(如,Li-硅酸盐)保持于晶粒边界或三边界点并且没有被引入Li-石榴石中。
本申请还公开了制造具致密结构、高立方相及高Li离子电导率的Li-金属氧化物/石榴石复合物的薄膜的过程。该过程包括(1)Li-石榴石复合陶瓷粉末的制备;(2)石榴石粉末钝化;(3)藉由添加Li金属氧化物(LMO)前体的粉浆制造;(4)流延成型;以及(5)将生坯带快速烧制带烧结成为致密带。生坯带中的Li2CO3用作Li源以补偿烧结期间的Li损失。其还可以在高温下产生液相以增强烧结。在1000℃-1300℃的温度范围下进行几分钟的复合石榴石带烧结。本文公开的过程允许大规模烧结带并具有显著改进的密度。
经烧结的石榴石膜具有高的Li离子电导率(>10-4S/cm),厚度为30-150μm,并且相对密度>95%。
优点包括:(1)于生坯带中添加硅酮延长了生坯带寿命(不添加硅酮、非钝化石榴石粉末流延成型的带于1-2周内变脆;添加硅酮,石榴石带可维持数个月);(2)添加硅酮及Li2CO3使得于烧结期间形成Li-硅酸盐;(3)石榴石与Li-硅酸盐稳定;(4)Li-硅酸盐非Li离子导电且可用于阻挡石榴石中的Li-枝晶生长;(5)Li-硅酸盐帮助降低烧结期间的Li损失;以及(6)在石榴石晶粒边界的其他Li金属氧化物,例如Li-镓酸盐、Li-铝酸盐、Li-钨酸盐、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸盐或其组合亦可阻挡Li-枝晶穿透通过晶粒边界。
对本领域的技术人员显而易见的是,可以在不偏离所要求保护的主题的精神或范围的情况下进行各种修改和变动。因此,所要求保护的主题不受所附权利要求书及其等同形式以外的任何内容所限。
Claims (22)
1.一种烧结复合陶瓷,包含:
锂-石榴石主相;以及
锂枝晶生长抑制剂次相,
其中,该锂枝晶生长抑制剂次相包含基于该烧结复合陶瓷的总重量计的>0-10重量%的Li-金属氧化物。
2.如权利要求1所述的烧结复合陶瓷,其中,该锂-石榴石主相包含下列的至少一者:
(i)Li7-3aLa3Zr2LaO12,其中L=Al、Ga或Fe以及0<a<0.33;
(ii)Li7La3-bZr2MbO12,其中M=Bi、Ca或Y以及0<b<1;
(iii)Li7-cLa3(Zr2-c,Nc)O12,其中N=In、Si、Ge、Sn、Sb、Sc、Ti、Hf、V、W、Te、Nb、Ta、Al、Ga、Fe、Bi、Y、Mg、Ca或其组合以及0<c<1,
或它们的组合。
3.如权利要求1或权利要求2所述的烧结复合陶瓷,其中,该锂-石榴石主相包含:
Li7-cLa3(Zr2-c,Nc)O12,其中N=Ta、Ga、W或其组合,以及0<c<1。
4.如权利要求1-3中任一项所述的烧结复合陶瓷,其中,该Li-金属氧化物包含:Li-硅酸盐、Li-镓酸盐、Li-铝酸盐、Li-钨酸盐、Li-莫林那特、Li-Ta氧化物、Li-Nb-氧化物、Li-Sn-氧化物、Li-In-氧化物、Li-As-氧化物、Li-Sb-氧化物、Li-磷酸盐,或其组合。
5.如权利要求1-4中任一项所述的烧结复合陶瓷,其中,该金属氧化物包含Li-硅酸盐。
6.如权利要求1-5中任一项所述的烧结复合陶瓷,其中,该锂-石榴石主相包含至少90重量%的锂石榴石立方相。
7.如权利要求1-6中任一项所述的烧结复合陶瓷,其中,针对代表至少5%的总晶粒群的晶粒群所测量的最大晶粒尺寸不超过该总晶粒群的平均晶粒尺寸的多于20倍。
8.如权利要求1-7中任一项所述的烧结复合陶瓷,包含具有30-150μm的厚度的膜。
9.如权利要求8所述的烧结复合陶瓷,其中,该膜具有至少10-4S/cm的Li离子电导率以及该膜的理论最大密度的至少90%的相对密度。
10.一种电池,包含:
至少一个锂电极;以及
接触该至少一个锂电极的电解质,
其中,该电解质为锂-石榴石复合电解质,其包含如权利要求1-9中任一项所述的烧结复合陶瓷。
11.一种烧结复合陶瓷,包含:
锂-石榴石主相;以及
锂枝晶生长抑制剂次相,
其中:
该锂-石榴石主相包含:
Li7-cLa3(Zr2-c,Nc)O12,其中N=Ta、Ga、W或其组合,以及0<c<1,以及
该锂枝晶生长抑制剂次相包含基于该烧结复合陶瓷的总重量计的>0-10重量%的Li-硅酸盐。
12.如权利要求11所述的烧结复合陶瓷,其中,该锂-石榴石主相包含至少90重量%的锂石榴石立方相。
13.如权利要求11或权利要求12所述的烧结复合陶瓷,其中,针对代表至少5%的总晶粒群的晶粒群所测量的最大晶粒尺寸不超过该总晶粒群的平均晶粒尺寸的多于20倍。
14.如权利要求11-13中任一项所述的烧结复合陶瓷,包含具有30-150μm的厚度的膜。
15.一种烧结复合陶瓷,包含:
锂-石榴石主相;以及
锂枝晶生长抑制剂次相,
其中,该烧结复合陶瓷包含下列的至少一者:
至少10-4S/cm的Li离子电导率;以及
该膜的理论最大密度的至少90%的相对密度。
16.一种方法,所述方法包括:
在950℃至1500℃的范围中的温度烧结金属氧化组分/石榴石生坯带以形成复合陶瓷,该复合陶瓷包含:
锂-石榴石主相;以及
锂枝晶生长抑制剂次相,
其中,该锂枝晶生长抑制剂次相包含基于该烧结复合陶瓷的总重量计的>0-10重量%的Li金属氧化物。
17.如权利要求16所述的方法,其中,该烧结包含:
自室温加热至该温度范围;
保持于该温度范围持续1-20分钟的范围中的时间;
自该温度范围冷却至室温,
其中:
用于该加热步骤的升温速率(HRR)为100℃/分钟<HRR<1000℃/分钟,以及
用于该冷却步骤的冷却速率(CR)为100℃/分钟<CR<1000℃/分钟。
18.如权利要求17所述的方法,其中:
该HRR为250℃/分钟<HRR<750℃/分钟,
该CR为250℃/分钟<CR<750℃/分钟,以及
该温度范围为1100℃至1300℃。
19.如权利要求16-18中任一项所述的方法,其中,该烧结复合陶瓷包含下列的至少一者:
至少10-4S/cm的Li离子电导率;以及
该膜的理论最大密度的至少90%的相对密度。
20.如权利要求16-19中任一项所述的方法,其中,该金属氧化物组分/石榴石生坯带通过下述形成:
使过量Li源与添加剂反应以形成Li金属氧化物(LMO)前体;
使该LMO前体与钝化石榴石粉末混合以形成石榴石悬浮物;
添加分散剂、粘合剂,及增塑剂至该石榴石悬浮物以形成粉浆组合物;以及
流延成型该粉浆组成物。
21.如权利要求20所述的方法,其中,该添加剂包含下列的至少一者:硅酮、三氧化钨(WO3)及氧化镓(Ga2O3)。
22.如权利要求16-21中任一项所述的方法,其中该金属氧化物组分/石榴石生坯带通过下述形成:
混合过量Li源、Li金属氧化物(LMO)前体及钝化的石榴石粉末以形成石榴石悬浮物;
添加分散剂、粘合剂,及增塑剂至该石榴石悬浮物以形成粉浆组成物;以及
流延成型该粉浆组成物。
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CN107848894A (zh) * | 2015-07-29 | 2018-03-27 | 中央硝子株式会社 | 石榴石型氧化物烧结体和其制造方法 |
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CN107787529A (zh) * | 2015-04-14 | 2018-03-09 | 康宁股份有限公司 | 锂氧化物石榴石批料组合物及其固体电解质隔膜 |
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US20170179521A1 (en) * | 2015-12-17 | 2017-06-22 | Jeffrey Sakamoto | Slurry Formulation for the Formation of Layers for Solid State Batteries |
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