CN112789749A - 具有阴离子氧化还原活性的复合阴极的可再充电高能电池的生产方法 - Google Patents
具有阴离子氧化还原活性的复合阴极的可再充电高能电池的生产方法 Download PDFInfo
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- CN112789749A CN112789749A CN201980058292.5A CN201980058292A CN112789749A CN 112789749 A CN112789749 A CN 112789749A CN 201980058292 A CN201980058292 A CN 201980058292A CN 112789749 A CN112789749 A CN 112789749A
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- lithium
- oxide
- transition metal
- metal oxide
- composite cathode
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- 239000000725 suspension Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- WAWVSIXKQGJDBE-UHFFFAOYSA-K trilithium thiophosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=S WAWVSIXKQGJDBE-UHFFFAOYSA-K 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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Abstract
本发明涉及一种具有阴离子氧化还原活性的复合阴极的可再充电高能电池的制造方法,所述复合阴极包含氢氧化锂作为电化学活性组分,将所述氢氧化锂与电子或混合传导性过渡金属和/或过渡金属氧化物混合并接触,从而形成电子或混合传导性网状结构,将这种混合物施加至电流导体上,并将由此形成的复合阴极与隔膜、锂传导性电解质和含锂阳极一起置于电池壳体中,以得到电化学电池,并且对所述电化学电池进行至少一个初始成形循环。
Description
本发明涉及具有阴离子氧化还原活性复合阴极的可再充电高能电池的制造方法。
现有技术
商业可再充电锂离子电池的工作原理是基于插入机制:负极(阳极)和正极(阴极)都由能够嵌入(插入)锂离子而不会从根本上改变微观结构的材料制成。尽管阳极材料是碳基材料(石墨或硬碳),但是阴极活性材料由过渡金属氧化物组成。后者的氧化物中的过渡金属具有氧化还原活性,即它们在充电或放电期间会改变其氧化态。这由以下示例性反应说明:
对于当前使用的阴极材料,当对电池充电/放电时,氧化还原活性金属中心的氧化态仅改变一级。在上述情况下,氧化态在+III与+IV之间变化。出于这个原因,阴极材料的容量相对较低。在传统的阴极材料LiCoO2的情况下,理论容量为274mAh/g,实际上其中仅约135mAh/g可使用。对于极限化学计量LiC6,用于阳极的石墨材料也具有372mAh/g的相对低的容量。因此,石墨(C6)/LiCoO2体系的理论能量密度也低得不令人满意,为约380Wh/g。锂离子电池的另一个缺点是,所使用的阴极材料主要是可用性较低的元素,例如钴和镍。担心这些金属不能以足够的量获得以确保用于全球电动汽车和固定能量存储的锂电池的全面供应。
作为阳离子氧化还原活性正极材料的替代物,正在研究开放式电池体系。这些电池体系包含对环境开放的多孔结构,主要由碳组成,碳的表面涂有含贵金属的催化剂,使得扩散的氧可结合形成氧化锂(氧还原反应):
Li++e-+O2→LiO2
在最初形成的产物超氧化锂(LiO2)中,氧的平均氧化数为-0.5。进一步吸收锂会产生氧的氧化数为-1的过氧化锂(Li2O2)。后者的氧化锂可在催化氧发生氧化的金属催化剂的存在下通过逆转形成反应而再转化为锂和元素氧:
Li2O2→2Li++2e-+O2
缺点在于,上述空气电极仅具有非常中等的功率密度,并且最重要的是,仅具有非常有限的可逆性,因此该阴极形式仍远未在实际应用中使用。另外,在充电电势与放电电势之间存在通常0.5-1V的大差距,使得能量效率(“往返效率”)完全不令人满意。当前的技术挑战意味着锂/空气电池的商业化可预期最早在10-20年内实现。关于综述,参见K.Amine等人,Chem.Reviews 2014,5611-40,114。
也致力于使用锂氧化物(Li2O、Li2O2和LiO2)作为根据阴离子氧化还原原理起作用的活性阴极材料。由于提到的所有锂氧化合物都是电子绝缘体,因此它们必须以细粉状(无定形或纳米颗粒)形式或非常薄的层存在,并且各个粒子必须借助于传导性网状结构进行接触。传导性细粉状金属以及许多金属氧化物和锂金属氧化物可用于此目的。这样的体系在文献中是已知的,并且这里仅提及示例性实施方案。由20%Li2O2、20%炭黑和60%PEO-LiClO4组成的复合阴极可在以锂箔作为反电极的电化学电池中放电/充电三次(M.D.Wardinsky和D.N.Bennion,Proc.Electro chem.Soc.1993,93-23(Proc.Symp.NewSealed Rech.Batt.and Supercapacitors,1993,389-400))。
过氧化锂(Li2O2)可通过与混合传导性LiNi0.33Co0.33Mn0.33O2共研磨而接触并阴极性完全分解(Y.Bie等人,Chem.Commun.2017,53,8324-7)。由Co金属和Li2O的混合物组成的复合材料(都以纳米颗粒形式存在)也可被阴极性完全分解(Y.Sun,Nature Energy,2016年1月,15008)。包含嵌埋在Co3O4基质中的纳米颗粒锂氧化物(Li2O、Li2O2和LiO2的混合物)的完整电池单元的实际功能性是已知的(Z.Zhu,Nature Energy,2016年7月25日,16111)。为了避免从锂氧化物中释放出氧气,不能超过相对于Li/Li+为约3-3.5V的充电电压。
然而,就商业化而言,使用锂氧化物作为阴极活性材料具有实际的缺点。超氧化锂(LiO2)的结晶形式在热力学上不稳定,会分解为Li2O2和氧气(K.C.Lau,Phys.Chem.C 115,23625-33)。过氧化锂是一种强氧化剂并且在与水接触时分解并逸出氧气。因此,上述两种化合物都不能大规模地安全处理。氧化锂Li2O尽管具有热力学稳定性,但不可商购获得。它具有高腐蚀性,只能通过高能耗的工艺获得,例如,在高于约1000℃的温度下Li2CO3的热分解(R.B.Poeppel,Advances in ceramics,第25卷,"Fabrication and properties oflithium ceramics",I.J.Hastings和G.W.Hollenberg编,1989,111-116)。
待解决的问题
本发明要解决的问题是提供一种能够确保至少500Wh/kg的能量密度的制造方法和电化学存储系统,该能量密度特别对于移动应用是足够高的。此外,应使用容易商购获得并且可安全管理的活性材料,其具有尽可能低的稀有或难获得的金属的含量。
问题的解决方案
该问题通过用于制造具有阴离子氧化还原活性复合阴极的可再充电高能电池的方法解决,其中所述阴离子氧化还原活性复合阴极包含氢氧化锂作为电化学活性组分,将所述氢氧化锂与电子或混合传导性过渡金属和/或过渡金属氧化物混合并接触,从而形成电子或混合传导性网状结构,将这种混合物施加至电流导体上,并将由此形成的复合阴极与隔膜、锂传导性电解质和含锂阳极一起置于电池壳体中,因此获得电化学电池。对所述电化学电池进行至少一个初始成形循环。在正极(阴极)由复合材料组成的可再充电高能电池的情况下,所述复合材料包含至少选自以下的锂化合物:作为电化学活性组分的氢氧化锂(LiOH),以及任选地氧化锂(Li2O)、过氧化物(Li2O2)和/或超氧化锂(LiO2),所述阴极至少在第一次放电周期之后(即,处于富锂状态中)包含额外的氢化锂(LiH)。该LiH根据反应式(1)至(3)之一形成,参见下文。电化学活性组分被嵌埋在电子或混合传导性网状结构中,该电子或混合传导性网状结构包含过渡金属颗粒和/或电子传导性过渡金属氧化物以及任选地其他传导率增强材料。
至少锂氧化合物氢氧化锂(LiOH)和任选地选自Li2O、Li2O2和LiO2的另一种锂氧化合物用于生产电化学活性复合阴极材料。氢氧化锂可商购获得并且操作容易且安全。基于上述锂氧化合物的总含量,在复合阴极材料中LiOH的比例为至少10摩尔%,优选至少30摩尔%。
负极(阳极)包含至少一种相对于Li/Li+参比电极的电化学势<2V的供锂组分或化合物。供锂的电化学活性组分或化合物选自金属锂、含锂的金属合金、氮化锂过渡金属化物或复合材料,其电化学活性组分为嵌埋在含过渡金属的电子或混合传导性网状结构中的金属氮化合物。
当制造可再充电的高能电池,优选地包含根据本发明的复合阴极和阳极的二次锂电池时,必须注意所述阳极的活性材料相对于Li/Li+的电化学势<2V,以确保两个电极关于它们各自的电化学活性成分具有适当的平衡(即,重量匹配)。适当的平衡的特征在于,可以尽可能充分地利用电化学活性材料。在当前情况下,这尤其意味着,在第一次放电周期之前,阳极包含一定摩尔量的可电化学活化的、即可从阳极电化学提取的锂,其对应于复合阴极中LiOH含量的摩尔量的至少一半,优选至少相同,并且尤其是优选至少两倍。下面对此进行说明。
当在可再充电锂电池的阴极中使用LiOH时,除了氧化锂(Li2O)、过氧化锂(Li2O2)和/或超氧化锂(LiO2)之外,在第一次放电周期中还形成氢化锂(LiH)。在原电池的第一次放电期间的一般阴极半反应对应于以下三个反应式中的至少一者:
LiOH+2Li++2e-→Li2O+LiH (1)
2LiOH+2Li++2e-→Li2O2+2LiH (2)
2LiOH+Li++e-→LiO2+2LiH (3)
作为第一放电反应的结果,除氢化锂之外,还形成至少一种氧化锂化合物,其具有阴离子氧化还原活性并且是用于后续循环的电化学活性阴极材料。本发明人发现,令人惊讶的是,仅在确保氢氧化锂粒子的充分的电子或混合的电子/离子接触时,才发生反应(1)至(3)。除此之外,氢氧化锂粒子应优选以细粉状形式(纳米颗粒)存在。这同样适用于阴极材料中可能存在的选自Li2O、Li2O2和LiO2的其他锂氧化合物。
由于Li2O在所考虑的锂氧化合物中具有最高的锂含量,因此可形成具有最高理论电化学容量的阴极,LiOH:可从阳极提取(即电化学活性)的锂之间的摩尔比为1∶2的反应方程式(1)是特别优选的。
原则上,在第一次放电周期之后以富锂形式存在的根据本发明的电化学活性阴极材料也可通过将Li2O和/或另一种锂氧化合物和LiH混合来制备。然而,主要由于实际原因,这种制造变型不是非常有利。氢化锂对反应性空气组分如水蒸气和二氧化碳不稳定(分解形成氢氧化锂或碳酸锂)。此外,氧化锂不可商购获得并且需要能量密集型制造方法。
在后续的充放电循环中,此外,电极组成有时发生不可逆的变化。与现有技术(Z.Zhu,Nature Energy,2016年7月25日,16111)相反,根据本发明的阴极至少在第一次放电后(即,处于富锂状态中)包含氢化锂。令人惊讶的是,在第一次放电周期中形成的氢化锂在后续充电周期中平稳地分解,大概是根据以下反应:
LiH→1/2H2+Li++e- (4)
除了氢气外,还会释放锂。
可再充电锂电池需要防止接触金属锂反应性气体和化合物以进行操作。空气成分例如氧气、氮气、二氧化碳、水蒸气和其他微量空气组分对锂具有反应性。因此,可再充电锂电池通常必须在封闭状态下(即,填充在气密密封的壳体中)操作。在当前情况下,至少在第一次充电周期期间形成氢气。所形成的氢气在中等温度下不与金属锂发生反应,但会导致在气密密封的电池单元中形成不希望的压力。为了避免这种不希望的影响,必须在开放状态下执行至少第一次放电/充电循环以及必要时执行进一步的放电/充电循环。在一个或多个第一次循环(所谓的成形循环)期间的这种程序是已知的程序。为了避免电池内容物与环境过度接触,通常借助于开放的毛细管来进行压力平衡,所述毛细管在一个或多个形成气体的反应完成之后封闭。
在第一个充电周期中形成的锂以阳离子形式通过隔膜到达阳极,其在阳极以金属状态沉积或与那里存在的能够接收锂的物质或化合物反应。这可以是至少部分可逆的反应,例如与石墨材料、在形成合金时接收锂的金属、贫锂金属合金和贫锂形式的氮化锂过渡金属化物和/或复合材料反应,其电化学活性组分是金属氮化合物,所述金属氮化合物嵌埋在包含过渡金属的电子或混合传导性网状结构中。然而,也可能涉及不可逆的反应,例如电解质分解和/或在阳极的颗粒或片状金属组分(特别是其电化学活性组分)的表面上形成钝化层。以这种方式不可逆地消耗的锂间接地增加了可再充电锂电池单元的重量容量(gravimetric capacity),因为否则为此目的必须使用来自另一来源的锂,例如选自Li2O、Li2O2、LiO2的锂氧化合物和/或另一种阴极材料如锂过渡金属氧化物。在氢化锂的情况下,在锂释放期间产生的氢气(其相对于其余的电池组件、特别是电解质不具反应性)从电池单元中逸出,而在所述锂氧化合物的情况下,产生与电解质反应的氧气。如果用于钝化或保护层形成的锂源自引入阴极中的锂过渡金属氧化物,则脱锂材料即Lix-δMOy(δ=0至x;x和y可取介于1和10之间的值)或完全无锂的过渡金属氧化物保留。由于缺少锂,它不再能够参与电池氧化还原过程,因此代表了一种降低系统的能量密度的电化学惰性物质。在这种情况下,根据本发明形成的氢化锂用作一流的预锂化剂。
在可再充电电化学电池的环化期间,在阴极中发生的半反应示意如下:
从左至右读取的(5)至(7)是放电反应。双箭头表示这些反应是可逆过程(前提是存在足够的电子或混合接触)。
选自氢氧化锂(LiOH)、氧化锂(Li2O)、过氧化锂(Li2O2)和/或超氧化锂(LiO2)的电化学活性锂化合物以及任选地氢化锂(LiH)必须嵌埋在电子或混合传导性网状结构中,所述网状结构由相对于Li/Li+的电化学势(锂嵌入电势)>2V的细粉状过渡金属粒子和/或细粉状传导性过渡金属氧化物化合物组成。重要的是要确保电化学活性锂化合物与电化学势>2V的过渡金属或传导性过渡金属氧化物之间可能的最紧密接触。后者以及相对于Li/Li+的电化学势>2V的电子或混合传导性过渡金属氧化物化合物以尽可能细粉状即无定形或纳米颗粒形式存在也是有利的。优选的纳米颗粒模制物的确切尺寸取决于机械形状因数(即粒子的三维形状)。在球形(或类似)粒子形状的情况下,它们是0.1-100nm,优选地1-30nm。
阴极复合材料的固体组分可通过优选使用高能研磨机的研磨工艺被压碎并彼此紧密接触。使用行星式球磨机,以这种方式获得了锂氧化合物和相对于Li/Li+的电化学势>2V的电子或混合传导性过渡金属或过渡金属氧化物化合物的纳米颗粒形式。纳米颗粒粒子形态也可通过替代的物理方法(气相沉积、等离子体和激光方法)或化学方法,例如基于溶剂的方法,优选溶胶/凝胶方法来产生。
在阴极中,一方面细粉状过渡金属和/或电子或混合传导性过渡金属氧化物化合物与另一方面基于选自LiOH、Li2O、Li2O2和LiO2的锂氧化合物的活性材料之间的摩尔比在1:100至1:1、优选地1:50至1:1.5的范围内。
过渡金属M优选是元素周期表第3族至第12族的元素,特别优选地M=Sc、Ti、Zr、Hf、V、Cr、Mo、W、Mn、Fe、Ni、Co、Cu、Ag、Zn以及稀土金属La、Ce、Pr、Nd、Sm、Gd、Dy、Ho、Er、TM、Yb和Lu或上述过渡金属的任何混合物。
其中M=元素周期表第3族至第12族金属的电子传导性过渡金属氧化物被用作过渡金属氧化物化合物。可使用二元(MOx)以及三元(MM'yOx)和更高的混合相,其中另一种金属M'至少是元素周期表第3族至第12族的另一种过渡金属和/或元素锂(LiyMOx)。在这种情况下:w、y=0至8;x=0.5至4。
优选使用以下金属氧化物化合物:二元金属氧化物,例如钛氧化物(TiO、Ti2O3)、钒氧化物(V2O3、VO、VO2)、铁氧化物(Fe3O4、FeO)、钴氧化物(CoO2、Co3O4)、镍氧化物(Ni2O3)、锰氧化物(MnO2、Mn3O4)、铬氧化物(CrO2、Cr3O3)、铌氧化物(NbO);层结构的锂金属氧化物(LiCoO2、LiNiO2、Li(Ni,Mn,Co)O2)、LiV3O8;尖晶石结构的锂金属氧化物(LiMn2O4、LiMnNiO2、LiNi0.5Mn1.5O4、LiV3O5);反尖晶石结构的锂金属氧化物(LiNiVO4、LiCoVO4);橄榄石结构的锂金属氧化物(LiFePO4、LiVPO4)。上面列出的化学式表示碱性化合物的理想组成。然而,实际上,它们以稍微或强烈修改的形式使用。这些包括具有结构稳定化掺杂剂的材料(例如,铝稳定化的锂镍钴氧化物,“NCA”)或掺杂有外来金属或非金属以增加传导性的化合物。如果本发明适用,也可使用通过掺杂修饰的母体化合物的此类变体。
特别优选使用可以可逆地释放和插入锂的电子或混合传导性过渡金属氧化物和锂过渡金属氧化物。在这些情况下,如果这些传导率增强剂的电化学势与电化学活性锂氧化合物的电化学势(约3V)大致相同,则可以使用其额外的电化学容量。根据本发明可用的金属氧化物化合物在室温下的电导率为至少10-7S/cm,优选至少10-6S/cm,并且尤其优选至少10-5S/cm。
根据本发明的高能可再充电电池具有负极(阳极),其包含相对于Li/Li+的电化学势<2V的材料。这些可以是:石墨材料(石墨本身、硬碳、石墨烯等);金属锂;能够与锂合金化的元素(例如铝、硅、锗、锡、铅、硼、锌、它们的混合物)和所述金属元素的含锂化合物;过渡金属氮化物(金属氮化物)(MM'yNx ),其中M=元素周期表第3族至第12族的金属,并且M'=元素周期表第3族至第12族的至少一种其他过渡金属和/或元素锂,(LiyMNx)并且其中y=0至8;x=0.5至1;以下通式的金属氮化合物
LiM2 z(NH)0.5x+z (I),和
LimM2 n(NH2)1+n (II),其中
(I)和(II)可以任何混合比率存在,并且
M2=碱土金属元素(Mg、Ca、Sr、Ba或它们的任何混合物),并且
x=0-4;z=0-2
m=1或0;n=1或0,其中(m+n)=1。
在完全充电(最富锂)的状态下,金属氮化合物对应于通式(III)和/或(IV)
Li2z+xM2 z(NH)0.5x+z (III)
Li3N.n(LiM2N).(4-2m)LiH (IV),其中
(III)和(IV)可以任何混合比率存在,并且
M2=碱土金属元素(Mg、Ca、Sr、Ba或它们的任何混合物)
x=0-4;z=0-2
m=1或0;n=1或0,其中(m+n)=1。
金属氮化合物优选用作电化学活性阳极材料,其中所述金属氮化合物嵌埋在含过渡金属的电子或混合传导性网状结构中。电化学活性金属氮化合物具有完全放电(最贫锂)的电荷状态的组成,其由两个通式(I)和/或(II)中的至少一者表示。含过渡金属的电子或混合传导性网状结构包含元素形式的细粉状过渡金属M或相对于Li/Li+的电化学势(锂嵌入电势)<2.5V的细粉状传导性间隙过渡金属化合物。
过渡金属粉末M优选是元素周期表第3族至第12族的元素,特别优选M=Sc、Ti、Zr、Hf、V、Cr、Mo、W、Mn、Fe、Co、Ni、Cu、Ag、Zn以及稀土金属La、Ce、Pr、Nd、Sm、Gd、Dy、Ho、Er、Tm、Yb和Lu或上述过渡金属的任何混合物。
相对于Li/Li+具有<2.5V的电化学势(锂嵌入电势)的电子传导性间隙化合物被用作过渡金属化合物。这些优选是过渡金属氮化物(金属氮化物)和/或过渡金属碳化物,各自其中M=元素周期表第3族至第12族的金属,和/或过渡金属氢化物,其中M=元素周期表第3族至第10族的金属。可以使用二元(MNx、MCx、MHx)以及三元(MM'yNx;MM'yCx;MM'yHx)和更高的混合相,其中另外的金属M'是至少一种来自元素周期表第3族至第12族的另外的过渡金属(MxM'yNz)和/或元素锂(LiyMNx;LiyMCx;LiwMxM'yNz;LiwMxM'yHz;等)。在这种情况下:w、y=0至8;x=0.5至1;z=0至3。
在根据通式(I)的放电(贫锂)状态中,金属氮化物优选由以下化合物中的至少一种组成:Li2NH、MgNH、CaNH、Li2Mg(NH)2、Li2Ca(NH)2、MgCa(NH)2、Li4Mg(NH)3、Li2Mg2(NH)3和/或一种或多种以下根据通式(II)的化合物:LiNH2、Mg(NH2)2、Ca(NH2)2。
如果通过施加外部电压对根据本发明的高能电池进行充电,则含活性N的阳极材料变为更富锂的状态。当完全充电时,形成以下富锂化合物,根据通式(III),优选:Li4NH、Li2MgNH、Li2CaNH、Li6Mg(NH)2、Li6Ca(NH)2、Li4MgCa(NH)2、Li10Mg(NH)3、Li8Mg2(NH)3和/或根据通式(IV),优选:Li3N、MgLiN、CaLiN和LiH。
具有定性组成LiwMxM'yEz(E=N、C、H;w、y=0至8;x=0.5至1;z=0至3)的上述过渡金属化合物属于所谓的间隙金属化合物或合金的组,即作为碳、氮或氢的嵌入外来元素E排列在下面的金属晶格的间隙层(间隙位点)上。所示的化学计量分别表示碳、氮或氢的最高含量(极限化学计量)。然而,间隙化合物并非完全是化学计量的化合物,即,从纯金属开始直至极限化学计量的所有组合物通常是可能的,并且大部分是稳定的。所有外来元素含量较低的化合物,即定性表示为LiwMxM'yEz-δ(δ可取介于0和z之间的任何值)的化合物也都是电子或混合传导性材料,因此适用于制造含氮复合阳极材料。
优选以细分散形式(纳米颗粒)使用电子传导性过渡金属或其相应的电子传导性氮化物、碳化物或氢化物化合物。它们可以通过物理混合工艺与同样纳米颗粒状的含锂氮的阳极材料尽可能均匀地混合,从而通过在阳极剥离生产期间进行后续压制(在技术制造过程中通常通过压延)确保各个粒子之间的良好接触,并且获得完全功能的含氮并含过渡金属的复合阳极材料。合适的复合阳极材料也可通过化学方法,例如与氮源的反应来生产。优选的氮源是元素氮(N2);氨(NH3);肼(N2H4);尿素(CH4N2O)。在用NH3氨解时,金属即锂和所选的过渡金属,优选在升高的温度和压力条件下与氨反应。然后,可通过后续的热解将所获得的酰胺化合物进一步转化为例如酰亚胺化合物和/或氮化物。如果需要非氮化物传导率增强剂,则可以在氨解之前或之后添加适当的过渡金属氢化物和/或过渡金属碳化物。除去过量的氨之后,可将剩余的固体一起研磨。该措施减小了粒度并改善了接触。在大多数升高的温度和压力下与氮气反应期间,立即形成氮化物相。同样在这种情况下,可添加所需的非氮化物传导率增强剂。
在本发明的一个优选的实施方案中,将含锂氮的阳极材料与增强传导率的过渡金属或氮化物、碳化物或氢化物共研磨。使用例如行星式球磨机类型的高能研磨机进行研磨。
可将改善阳极功能的其他材料添加到含氮复合阳极材料中。这些首先包括基于非金属的传导率增强剂、供锂添加剂和粘合剂。元素碳的所有导电形式(石墨、炭黑、石墨烯、碳纳米管)都适合作为基于非金属的传导率增强剂。锂金属(优选经涂布,即表面钝化并呈粉末形式或薄箔状)或富含锂的化合物如锂石墨(LiC6-δ,δ=0-5)或经涂布的硅化锂(LinSiOx@Li2O)可用作供锂添加剂。通常用于电极制造的有机聚酰胺可用作粘合剂。这些包括PTFE、PVdF、聚异丁烯(例如,来自BASF的)和类似材料。在含氮和含过渡金属的复合负极材料中,一方面细粉状过渡金属或电子或混合传导性过渡金属化合物LiwMxM'yEz(E=N、C、H;w、y=0至8;x=0.5至1;z=0至3)与另一方面含氮的电化学活性含氮阳极材料的重量比通常介于1:100与1:2之间。它优选介于1:50至1:5之间。即用型(完全)含氮和过渡金属的复合阳极也可包含其他电导率改进剂(至多30重量%)、粘合剂(至多20重量%)和/或预锂化剂(至多20重量%)。
还优选使用包含金属锂的阳极,其中锂以片状金属或粉末电极的形式或与选自硅、锡、硼和铝的金属的合金形式存在。
作为具有阴离子氧化还原活性复合阴极的根据本发明的可再充电高能电池的电解质,其中在第一次放电之前的状态下,复合阴极包含嵌埋在电子或混合传导性网状结构中的氢氧化锂,并且任选地选自Li2O、Li2O2和LiO2的另外一种或多种锂氧化合物可以是本领域技术人员熟知的类型(液体、凝胶、聚合物和固体电解质)。作为用于液体、聚合物和凝胶-聚合物体系的导电盐,在所使用的基质中使用了具有弱配位、氧化稳定阴离子的可溶性锂盐。这些包括例如LiPF6,氟代烷基磷酸锂,LiBF4,酰亚胺盐(例如LiN(SO2CF3)2),LiOSO2CF3,甲基化物盐(例如LiC(SO2CF3)3),LiClO4,螯合硼酸锂(例如LiB(C2O4)2,也称为“LiBOB”),氟螯合硼酸锂(例如LiC2O4BF2,称为“LiDFOB”),螯合磷酸锂(例如LiP(C2O4)3,称为“LiTOP”)和氟螯合磷酸锂(例如Li(C2O4)2PF2)。特别优选对阴离子解离稳定并且无氟的阴离子的盐。
固体电解质,即锂离子传导性玻璃、陶瓷或结晶无机固体也是特别优选的。这样的材料的实例是:硫代磷酸锂(例如Li3PS4),硫银锗矿(Li6PS5X,其中X=Cl、Br、I),磷硅酸盐(例如Li2SiP2),氮磷酸盐(例如Li2.9PO3.3N0.36),氮硼磷酸盐(例如Li47B3P14N42),金属硫化物磷酸盐(例如Li10GeP2S11),石榴石(例如Li7La3Zr2O12),磷酸钛(Li1.5Al0.5Ti1.5(PO4)3)和硼氢化物化合物(例如LiBH4和Li2B12H12)。
阳极室通过可渗透锂离子但电绝缘的隔膜(例如,由微孔聚烯烃组成)或固体电解质(无机固体或固体聚合物材料类型)与阴极室隔开。
使用以下实施例说明本发明:
实施例1:通过研磨制备含氢氧化锂的复合阴极(过渡金属氧化物和炭黑作为传导率增强剂)
在充满Ar的手套箱中,将0.9g Co3O4(<50nm,供应商Aldrich)、3.6g无水氢氧化锂粉末(供应商Albemarle Germany)和0.2g炭黑(AB 400)在烧杯中预混合。将均质化混合物与约27g 3mm氧化锆陶瓷球一起装入50mL氧化锆陶瓷研磨烧杯中并密封。然后将混合物在行星式球磨机(Pulverisette P7,来自Fritsch)中在900转/分钟(rpm)下研磨240分钟。
将研磨罐放回充满Ar的手套箱中并在那里打开。通过筛分将研磨产物与研磨介质分离。
产量:4.1克细粉
实施例2:通过基于溶剂的方法(过渡金属氧化物作为传导率增强剂)制备含氢氧化锂的复合阴极
将1.2g氯化钴(97%,来自Aldrich)、0.69g过氧化锂(>93%,来自AlbemarleGermany)和3.6g无水氢氧化锂粉末(Albemarle Germany)溶解或悬浮在50ml无水乙醇中,并用高能搅拌器(Ultraturrax IKA T 65)均质化15分钟。将所得悬浮液在室温下磁力搅拌4小时,然后过滤。
首先将过滤残余物在真空中进行预干燥,然后在300℃下在氧气气氛中烧结5小时。
产量:3.6g细粉
所述粉末包含15%Co3O4和约73%LiOH;其余至100%基本上由氧化锂组成。
Claims (15)
1.一种生产具有阴离子氧化还原活性复合阴极的可再充电高能电池的方法,其特征在于,所述电池包含氢氧化锂作为电化学活性成分,将所述氢氧化锂与电子或混合传导性过渡金属和/或过渡金属氧化物混合并接触,从而形成电子或混合传导性网状结构,将这种混合物施加至电流导体上,并将由此形成的所述复合阴极与隔膜、锂传导性电解质和含锂阳极一起置于电池壳体中,以得到电化学电池,并且对所述电化学电池进行至少一个初始成形循环。
2.根据权利要求1所述的方法,其特征在于,将所述氢氧化锂与选自氧化锂、过氧化锂和超氧化锂的其他锂氧化合物混合,基于锂氧化合物的总含量,LiOH在电化学上仍未改性的复合阴极材料中的比例为至少10摩尔%,优选至少30摩尔%。
3.根据权利要求1或2所述的方法,其特征在于,一方面细粉状的电子或混合传导性网状结构组分和另一方面基于选自LiOH、Li2O、Li2O2和LiO2的锂氧化合物的所述阴极活性材料以1:100至1:1、优选1:50至1:1.5的摩尔比使用,形成所述网状结构的所述材料的电导率在室温下为至少10-7S/cm,优选至少10-6S/cm,并且特别优选至少10-5S/cm。
4.根据权利要求1至3所述的方法,其特征在于,所述过渡金属粒子优选地选自元素周期表第3族至第12族的元素,特别优选地M=Sc、Ti、Zr、Hf、V、Cr、Mo、W、Mn、Fe、Co、Ni、Cu、Ag、Zn,以及选自稀土金属La、Ce、Pr、Nd、Sm、Gd、Dy、Ho、Er、Tm、Yb和Lu或所述过渡金属的任何所需混合物。
5.根据权利要求1至4所述的方法,其特征在于,所述传导性过渡金属氧化物选自:二元金属氧化物、层结构的锂金属氧化物、尖晶石结构的锂金属氧化物、反尖晶石结构的锂金属氧化物和/或橄榄石结构的锂金属氧化物。
6.根据权利要求5所述的方法,其特征在于,所述二元金属氧化物选自钛氧化物(TiO、Ti2O3)、钒氧化物(V2O3、VO、VO2)、铁氧化物(Fe3O4、FeO)、钴氧化物(CoO2、Co3O4)、Ni2O3、锰氧化物(MnO2、Mn3O4)、铬氧化物(CrO2、Cr3O3)、NbO;所述层结构的锂金属氧化物选自LiCoO2、LiNiO2、Li(Ni,Mn,Co)O2、LiV3O8;所述尖晶石结构的锂金属氧化物选自LiMn2O4、LiMnNiO2、LiNi0.5Mn1.5O4、LiV3O5;所述反尖晶石结构的锂金属氧化物选自LiNiVO4、LiCoVO4,并且所述橄榄石结构的锂金属氧化物选自LiFePO4、LiVPO4。
7.根据权利要求1至6所述的方法,其特征在于,所述过渡金属粒子和/或所述传导性过渡金属氧化物化合物以及所述电化学活性锂氧化合物以细粉状、无定形或纳米颗粒形式均匀混合存在,其中粒子尺寸在0.1-100nm、优选1-30nm的范围内。
8.根据权利要求1至7所述的方法,其特征在于,将金属锂用作所述阳极,所述锂以片状金属或粉末电极形式或与选自硅、锡、硼和铝的金属的合金形式存在。
9.根据权利要求1至8所述的方法,其特征在于,在第一个放电周期之前,将可从所述阳极电化学提取的摩尔量的可电化学活化的锂引入到所述阳极中,其摩尔量对应于所述复合阴极中存在的所述LiOH含量的摩尔量的至少一半,优选至少相同,并且特别优选至少两倍。
10.根据权利要求1至9所述的方法,其特征在于,将基于非金属的传导率增强剂和粘合剂用于所述阴离子氧化还原活性复合阴极中,并且任选地也用于所述阳极中。
11.根据权利要求10所述的方法,其特征在于,例如石墨、硬碳、炭黑和石墨烯的石墨材料被用作基于非金属的传导率增强剂。
12.根据权利要求1至11所述的方法,其特征在于,所述阴离子氧化还原活性复合阴极和所述阳极都通过压制工艺或压延机压实。
13.根据权利要求1至12所述的方法,其特征在于,所述阴离子氧化还原活性复合阴极的固体组分通过优选使用高能研磨机的研磨工艺粉碎,并彼此紧密接触。
14.一种具有阴离子氧化还原活性复合阴极的高能电池,其特征在于,在第一次电化学放电之前,所述阴极由复合材料组成,所述复合材料至少包含氢氧化锂作为电化学活性组分,并且任选地还包含嵌埋在电子或混合传导性网状结构中的选自氧化锂、过氧化锂和/或超氧化锂的其他锂氧化合物,所述网状结构由电子传导性过渡金属和/或过渡金属氧化物组成,其中一方面所述电子或混合传导性网状结构组分和另一方面基于选自LiOH、Li2O、Li2O2和LiO2的锂氧化合物的所述阴极活性材料以1:100至1:1、优选1:50至1:1.5的摩尔比存在。
15.根据权利要求14所述的高能电池,其特征在于,所述阳极包含至少一种相对于Li/Li+参比电极的电化学势<2V的供锂组分或化合物,所述供锂组分或化合物选自金属锂、含锂的金属合金、氮化锂过渡金属化物或复合材料,其电化学活性组分为金属氮化合物,后者嵌埋在含过渡金属的电子或混合传导性网状结构中。
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