CN101481106A - 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法 - Google Patents

含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法 Download PDF

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CN101481106A
CN101481106A CNA2009100954019A CN200910095401A CN101481106A CN 101481106 A CN101481106 A CN 101481106A CN A2009100954019 A CNA2009100954019 A CN A2009100954019A CN 200910095401 A CN200910095401 A CN 200910095401A CN 101481106 A CN101481106 A CN 101481106A
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oxygen
phosphate
sintering method
solid phase
phase sintering
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金江剑
王国光
徐君
包大新
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Priority to CNA2009100954019A priority Critical patent/CN101481106A/zh
Publication of CN101481106A publication Critical patent/CN101481106A/zh
Priority to US12/622,397 priority patent/US8241521B2/en
Priority to EP10150049A priority patent/EP2207229B1/en
Priority to ES10150049T priority patent/ES2371050T3/es
Priority to CN2010103000236A priority patent/CN101764226B/zh
Priority to AT10150049T priority patent/ATE529907T1/de
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明涉及一种含氧空位和Fe位掺杂型锂离子正极材料磷酸铁锂及其快速微波烧结制备方法。本发明提供一种生产效率高、能耗低、所制备的产物具有优良的极片加工性能、导电性能和电化学性能的一种含氧空位和Fe位掺杂型磷酸铁锂的快速固相微波烧结方法。本发明产物分子式为LiFe1－x－aMeaMxPO4－yNz，其中Me为Mg、Mn或者Nd中的一种或一种以上，M为Li、Na、K、Ag、Cu中的一种或一种以上；0≤x≤0.1，0≤a≤0.1，0＜y≤0.5，0≤z≤0.5，其中x、y、z不能同时为0。

Description

含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法
技术领域
本发明涉及一种锂离子电池材料及制备方法，尤其涉及一种含氧空位和Fe位掺杂型锂离子正极材料磷酸铁锂及其快速微波烧结制备方法。
背景技术
近年来，锂离子电池发展十分迅速，各种便携式电子产品和通讯工具对锂离子电池的需求量不断增加，大型动力锂离子电源也在发展热潮中。正极材料是锂离子电池的重要组成部分，新型正极材料的研制已成为决定锂离子电池发展的关键。目前大规模商品化的LiCoO2，毒性较大，价格昂贵，存在一定的安全问题。LiNiO2成本较低，容量较高，但制备困难，热稳定性差，存在较大的安全隐患。尖晶石LiMn2O4成本低，安全性好，但容量低，高温循环性能差。因此需要开发新型价格低廉性能优良的正极材料以满足日益增长的市场需求。而作为新型锂离子电池正极材料的正交晶系橄榄石型LiFePO4具有容量高，充放电电压平稳特别是其价格低廉，安全性好，热稳定性好，对环境无污染等更使它成为最有潜力的正极材料之一。
LiFePO4在自然界中以磷铁锂矿的形式存在，具有有序的橄榄石结构，属于正交晶系(D162h，Pmnb)。在每个晶胞中有4个LiFePO4单元其晶胞参数为a＝6.0089
Figure A200910095401D0004132618QIETU
，b＝10.334
Figure A200910095401D0004132618QIETU
和c＝4.693
Figure A200910095401D0004132618QIETU
[3]。在LiFePO4中，氧原子近似呈六方紧密堆积，磷原子在四面体的空隙，铁原子、锂原子分别在八面体的空隙。在晶体b-c平面上FeO6八面体共点连结。一个FeO6八面体与两个LiO6八面体共边，而一个PO4四面体则与一个FeO6八面体和两个LiO6八面体共边。且Li+具有二维可移动性，在充放电过程中可以脱出和嵌入。强的P—O共价键形成离域的三维立体化学键，使LiFePO4具有很强的热力学和动力学稳定性。纯LiFePO4存在的主要问题是离子扩散系数和电子传导率均较低。针对这种情况，本发明通过进入Fe位掺杂和引入氧空位来提高磷酸铁锂的电导率和离子扩散系数。
影响磷酸铁锂商品化的两个重要因素是价格和批量稳定性问题，这两个问题目前并没有引起人们的足够重视。当前合成磷酸铁锂的主要方法有高温固相反应法，液相共沉积法，水热法，液相氧化还原法，固相微波烧结法和机械球磨法等。目前广泛采用的高温固相反应法是采用亚铁盐作为铁源，再与锂源及磷源混合，然后在惰性气氛中烧结合成磷酸铁锂。二价铁源价格较贵，而且由于需要防止二价铁源氧化，制备工艺复杂，产物纯度不易控制，从而使成本增加，并且一般烧结时间都在6小时以上。本发明提出使用三价铁源为原料，在烧结过程中采用快速微波固相烧结法，可以大大缩短材料的制备时间，并且生产的产品综合性能高，特别是振实密度较高。
发明内容
本发明针对现有技术在所存在的能耗高、烧结时间长、作为电极时性能低等问题，提供一种生产效率高、能耗低、所制备的产物具有优良的极片加工性能、导电性能和电化学性能的一种含氧空位和Fe位掺杂型磷酸铁锂的快速固相微波烧结方法。
本发明的目的是通过以下技术方案得以实施的：
本发明含氧空位和Fe位掺杂型磷酸铁锂，其分子式为LiFe1-x-aMeaMxPO4-yNz，其中Me为Mg、Mn或者Nd中的一种或一种以上，M为Li、Na、K、Ag、Cu中的一种或一种以上；0≤x≤0.1，0≤a≤0.1，0<y≤0.5，0≤z≤0.5，其中x、y、z不能同时为0。
磷酸铁锂快速微波固相烧结方法步骤如下：
1、配料：将锂化合物，Fe3+化合物，磷酸盐，掺杂物和导电用碳源按比例混合，其中Li：Fe：Me：M：P摩尔比为1：(1-x)：a：x：1。碳源的加入量为混合物总质量的5～20％，优选为10％～15％，碳源的加入可以在高温下与混合物实现分子级的混合，最终以非晶态碳的形态均匀的包覆在磷酸铁锂颗粒周围，增加材料的导电性能，以使材料发挥良好的容量并可提高材料的高倍率放电性能和循环性能。碳源添加量太少可能导致材料导电性能不好，碳源过多可能会使材料振实密度减小且涂覆性能降低，优选10％～15％碳源时，可以获得良好的综合性能。
2、混料。设备采用搅拌机或砂磨机，溶剂可使用去离子水、自来水或酒精、煤油等有机溶剂，混合时间为1～10小时，其中优选时间为1～3小时，混合后的浆料用烘箱烘干或者用喷雾造粒设备烘干，烘干温度采用烘箱时为40～120℃，优选90～110℃，采用喷雾造粒设备时为120～260℃，优选170～220℃。
3、混料烘干后进行压块，压块是使用压力机或者挤压机将上述混合物压制成块状或蜂窝煤状或条状，或者不压块，将上述混合物放入微波反应炉，在流速为0.01～50升/分钟的高纯Ar气和/或H2气混合气保护下加热处理，其中H2气体体积占总气体体积的6～10％。升温速率为40～80℃/分钟，升温至700～800℃，热处理时间为20～60分钟，然后降温到室温。选用的加热处理设备为工业用功率为1.5～5KW的微波烧结炉。
4、粉碎处理，采用二次球磨或气流磨等方法，得到颗粒分布均匀的磷酸铁锂。其中含碳量为1～8wt％。
作为优选，所述锂化合物为碳酸锂，草酸锂，醋酸锂，单水氢氧化锂，磷酸二氢锂中的一种或者一种以上。
作为优选，所述Fe3+化合物为铁红、磷酸铁中的一种或一种以上；铁红主成分为三氧化二铁。
作为优选，所述磷酸盐为磷酸、磷酸氢二铵、磷酸二氢铵、磷酸三铵、磷酸二氢锂中的一种或一种以上。
作为优选，所述碳源为碳黑、乙炔黑、蔗糖、淀粉、葡萄糖、活性炭、聚乙烯醇中的一种或一种以上。
作为优选，所述的混合时加入的溶剂为去离子水或自来水或酒精或煤油。
在半导体中引入氧空位，将导致材料中电子电导的增强，呈现n型电导。在磷酸铁锂中，锂离子的扩散是在磷酸根四面体组成的通道中扩散的，受到0的相互作用的影响。当存在氧空位时，锂离子受到的库仑力减少，从而提高锂离子的扩散系数。由于本发明的正极材料中含氧空位，材料的电子电导率和离子电导率可以显著提高，在电池中作为正极材料应用时，相比现有的体系，其高倍率性能更加优越。在Fe位中掺杂引入金属离子后，可以在不改变材料的橄榄石结构，保持了稳定的循环性能的前提下，大大提高了磷酸铁锂的电导率，改善了材料的高倍率性能。而且本发明使用价格低廉的三价铁源并且采用一步快速微波固相烧结法制备导电性能优异的磷酸铁锂
本发明材料与现有技术相比具有以下优点：
(1)避开了其它合成方法中繁琐的亚铁盐合成步骤，解决了亚铁盐容易氧化导致产物不纯的问题。
(2)使用添加剂将三价铁还原为二价，刚生成的二价铁活性好，与锂源及磷源的反应速度快，结合稳定，生成磷酸铁锂的纯度高，所制备的产物具有优良的极片加工性能、导电性能和电化学性能。
(3)采用微波固相烧结法，将反应所需时间从传统的6～30小时降低到20～60分钟，可以大大提高材料的生产效率，节药能耗。
本发明涉及的正极材料具有广泛的用途，采用该正极材料制备的锂离子电池安全性能好，成本低，可用于电动自行车、电动摩托车、电动汽车、矿灯、滑板车、笔记本电脑、电动工具以及一些非常规的可移动电源等领域。
附图说明
图1是按实施例1所制备的模拟钮扣电池在不同充放电倍率下放电曲线，电压范围为2.0～4.2V，充放电倍率分别为0.1C，0.5C，3C，5C，8C，测试温度为30℃±1℃。
图2是按实施例2所制备的17500圆柱型锂离子电池的循环性能图，电压范围为2.5～4.2V，充放电倍率为0.5C，温度温度为30℃±1℃。
具体实施方式
以下为本发明的具体实施方式，对本发明的技术特征做进一步的说明，但是本发明并不限于这些实施例。
实施例1：制备本发明的磷酸铁锂正极材料LiFe0.8Mg0.1Na0.1PO3.95
首先，按照摩尔比1:0.8:0.1:0.1:1称取单水氢氧化锂，氧化铁，氢氧化镁，氟化钠和磷酸二氢铵，并加入混合料质量比12％的葡萄糖，放入砂磨机中，球料水比例为2：1：1，混合3.5小时。将混合后的浆料用烘箱烘干，然后使用连续式挤压机制成块状，并放入微波反应炉，在10升/分钟的高纯Ar气和氢气混合气，保护下，其中氢气体积比为8％，以50℃/分的速率升温到750℃，保温45分钟，然后降温至室温。将烧结后的材料用破碎机破碎后，在气流磨上分级处理，得到颗粒均匀的磷酸铁锂。
测得材料中含碳量为5.6％。
测得材料的振实密度为1.4g/cm3。测得活性材料的粒度及分布如图1所示。制备材料在激光粒度分布仪上测试，测得的磷酸铁锂颗粒均匀细小，平均粒径1.12微米，D10为0.43微米，D90为2.92微米，粒度分布呈正态。
以82：8：10的质量比分别称取实施例1所得的正极材料：乙炔黑：PVDF，研磨均匀后制成电极，负极选用金属锂片，电解液为溶解在碳酸乙酯和碳酸二乙醋混合溶剂中的1.0mol/l的LiPF6，碳酸乙酯和碳酸二乙醋体积比1：1，隔膜为聚丙烯微孔薄膜，组装成电池。
图1为不同充放电倍率下的放电曲线，在0.1C放电时，材料可逆克容量可达160mAh/g，0.5C放电时可逆克容量为153mAh/g，3C放电时可逆克容量为134mAh/g，5C放电时可逆克容量为120mAh/g，8C放电时克容量为110mAh/g。材料克容量高，放电平台稳定，性能优越。
实施例2、制备本发明的含氧空位的磷酸铁锂材料LiFePO3.94N0.04
含氧空位的磷酸铁锂材料LiFePO3.94N0.04可以通过以下步骤制备。首先，分别称取30.0千克磷酸锂，62.2千克三氧化二铁，68.7千克磷酸氢二铵，803克Li3N和24.0千克蔗糖及12.0千克葡萄糖混合，放入混料机中，加酒精50升，加入玛瑙球200公斤，混合2小时。然后再用超细磨混合1小时，将混合后的浆料用喷雾造粒机烘干，温度控制在120-180℃左右。然后将粉料装入坩锅中，并放入功率为4KW的连续式工业用微波反应炉，在10升/分钟的氮气气氛下，以40℃/分的速率升温到750℃，保温30分钟，然后降温至室温。将烧结后的材料用破碎机破碎后，在气流磨上分级处理，得到颗粒均匀的磷酸铁锂。
将所得材料送锂离子电池厂制备成电极片并组装成17500圆柱电池，在0.5C的充放电倍率下，测得材料的循环性能如图2所示。
实施例3：
制备本发明的含氧空位的磷酸铁锂材料LiFe0.98Mn0.02PO3.97N0.02首先，按照摩尔比0.94:0.49:0.013:1:0.02称取单水氢氧化锂，氧化铁，四氧化三锰，磷酸二氢铵和氮化锂，并加入混合料质量比10％的葡萄糖，放入砂磨机中，球料水比例为2：1：1，混合3小时。将混合后的浆料用喷雾干燥塔喷雾干燥，放入微波反应炉，在10升/分钟的高纯Ar气和氢气混合气，保护下，其中氢气体积比为6％，以50℃/分的速率升温到750℃，保温45分钟，然后降温至室温。将烧结后的材料用破碎机破碎后，在气流磨上分级处理，得到颗粒均匀的磷酸铁锂。
测得材料中含碳量为4.2％。
以85：5：10的质量比分别称取实施例1所得的正极材料：乙炔黑：PVDF，研磨均匀后制成电极，负极选用金属锂片，电解液为溶解在碳酸乙酯和碳酸二乙醋混合溶剂中的1.0mol/l的LiPF6，碳酸乙酯和碳酸二乙醋体积比1∶1，隔膜为聚丙烯微孔薄膜，组装成电池。
在0.2C放电时，材料可逆克容量可达155mAh/g，1C放电时可逆克容量为144mAh/g。材料克容量高，放电平台良好，稳定，性能优越。
本发明中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。
尽管对本发明已作出了详细的说明并引证了一些具体实例，但是对本领域熟练技术人员来说，只要不离开本发明的精神和范围可作各种变化或修正是显然的。

Claims (10)

1.一种含氧空位和Fe位掺杂型磷酸铁锂，其特征在于：其分子式为LiFe1-x-aMeaMxPO4-yNz，其中Me为Mg、Mn或者Nd中的一种或一种以上，M为Li、Na、K、Ag、Cu中的一种或一种以上；0≤x≤0.1，0≤a≤0.1，0<y≤0.5，0≤z≤0.5，其中x、y、z不能同时为0。
2.一种含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，磷酸铁锂的分子式为LiFe1-x-aMeaMxPO4-yNz，其中Me为Mg、Mn或者Nd中的一种或一种以上，M为Li、Na、K、Ag、Cu中的一种或一种以上；0≤x≤0.1，0≤a≤0.1，0<y≤0.5，0≤z≤0.5，其中x、y、z不能同时为0，烧结方法的步骤为：
(1)按上述化学式组成的摩尔比称取锂化合物、Fe3+化合物、Me和M掺杂物和磷酸盐，混合后加入导电用碳源，碳源的加入量为混合物总质量的5～20wt％；
(2)将上述混合物搅拌或者砂磨混合，混合的同时加溶剂，混合1～10小时，然后烘干浆料；
(3)烧结：将烘干后的浆料压块或者直接放入微波烧结炉，在流速为0.01～50升/分钟的Ar气和H2气混合气体保护下加热处理，升温速率为40～80℃/分钟，升温至700～800℃，热处理时间为20～60分钟，然后降温到室温；
(4)制粉：采用二次球磨或气流磨方法粉磨，得到磷酸铁锂。
3.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于所述Fe3+化合物选自三氧化二铁或磷酸铁或其混合物。
4.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的锂化合物为碳酸锂、草酸锂、醋酸锂、单水氢氧化锂、磷酸二氢锂中的至少一种。
5.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的磷酸盐为磷酸、磷酸氢二铵、磷酸二氢铵、磷酸三铵、磷酸二氢锂中至少一种。
6.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的碳源的加入量为混合物总质量的10wt％～15wt％。
7.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的碳源为碳黑、乙炔黑、蔗糖、淀粉、葡萄糖、活性炭、聚乙烯醇中的一种或一种以上。
8.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的Ar气和H2气混合气体中，H2的气体积比为总体积的6～10％。
9.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的混合时加入的溶剂为去离子水或自来水或酒精或煤油，混合时间为1～3小时。
10.根据权利要求2所述的含氧空位和Fe位掺杂型磷酸铁锂的快速固相烧结方法，其特征在于，所述的烘干为用烘箱烘干或者用喷雾造粒设备烘干，烘干温度采用烘箱时为40～120℃，采用喷雾造粒设备时为120～260℃。
CNA2009100954019A 2009-01-08 2009-01-08 含氧空位和Fe位掺杂型磷酸铁锂及其快速固相烧结方法 Pending CN101481106A (zh)

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US12/622,397 US8241521B2 (en) 2009-01-08 2009-11-19 Lithium iron phosphate having oxygen vacancy and doped in the position of Fe and method of quick solid phase sintering for the same
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AT10150049T ATE529907T1 (de) 2009-01-08 2010-01-04 Lithiumeisenphosphat, das eine sauerstoffleerstelle aufweist und in der fe- stellung dotiert ist, und verfahren zum schnellen festphasensintern für das lithiumeisenphosphat

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