CN112028650A - 一种锂离子电池正极材料用匣钵 - Google Patents

一种锂离子电池正极材料用匣钵 Download PDF

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CN112028650A
CN112028650A CN202010917259.8A CN202010917259A CN112028650A CN 112028650 A CN112028650 A CN 112028650A CN 202010917259 A CN202010917259 A CN 202010917259A CN 112028650 A CN112028650 A CN 112028650A
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sagger
lithium ion
ion battery
positive electrode
thermal expansion
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宋海利
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Guangzhou yueci New Material Co.,Ltd.
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Shenzhen Feiyue New Material Technology Co ltd
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Abstract

本发明公开一种锂离子电池正极材料用匣钵，由低热膨胀材料和/或负热膨胀材料与耐锂离子电池正极材料侵蚀材料组成，低热膨胀材料和/或负热膨胀材料与耐锂离子电池正极材料侵蚀材料混合后成型为匣钵胚体，经烧成后制得锂离子电池正极材料用匣钵。本发明的匣钵具有耐热冲击性和耐锂离子电池正极材料侵蚀的特性，大大提高了匣钵的使用寿命，减少了锂离子电池正极材料对耐火材料的消耗，保护了环境。本发明的匣钵不需要额外的涂层来保护匣钵，大幅减少了生产流程、所需设备和人工的使用，仅需要简单的成型设备和退火设备就能够进行生产，提高了生产效率。

Description

一种锂离子电池正极材料用匣钵
技术领域
本发明涉及锂离子电池技术领域，具体涉及一种锂离子电池正极材料用匣钵。
背景技术
近年来，随着技术的不断进步以及锂离子电池性能的不断提升，锂离子电池逐渐在电动汽车，笔记本电脑，智能手机，航天科技等领域得到广泛应用。锂离子电池一般是由正极材料，负极材料和电解质溶液三部分组成。其中，锂离子电池的正极材料主要有钴酸锂(LiCoO2)、锰酸锂(LiMn2O4)、镍酸锂(LiNiO2)以及磷酸锂铁(LiFePO4)等材料组成。这些锂离子电池正极材料大都是用耐火匣钵在窑炉中以高温固相合成的方法制成。目前，锂离子电池正极材料制备用的耐火匣钵大体是以堇青石、莫来石，以及氧化铝为原料制备而成。在锂离子电池正极材料高温制备时，正极材料中的Li2O与匣钵材料中的Al2O3和SiO2发生了化学反应,生成了LiAlSiO4，γ-LiAlO2和LiAlSi2O4反应产物层。由于LiAlSiO4、γ-LiA1O2和LiAlSi2O4反应产物层厚度可以达到1mm左右，反应产物层与莫来石和堇青石的热膨胀不匹配，再加上反应产物生成所带来的体积变化，形成了局部应力，导致了匣钵壁面裂纹的产生和剥落，大大缩短匣钵的使用寿命。
在匣钵使用寿命的后半段，生成的新的矿物成分和匣钵本身结合力有限，所以在反复使用的时候，生成的新的矿物质容易从匣钵表面脱落进而附着在锂离子电池正极材料上，严重影响了锂离子电池的性能。
由于三元锂离子电池阳极材料的能量密度高，原料成本低及原料元素丰度高等优点，逐渐成为锂离子电池正极材料的重要组成部分。与锻烧一元电池正极材料(如LiCoO2/LiMn2O4/LiNiO2)的相比，烧成三元电池正极材料(LiNixCoyMn1-x-yO2，LNCM)的温度更高，为940～1100℃。因此，锻烧三元电池正极材料用匣钵所遭受的化学侵蚀不仅由LiCoO2/LiMn2O4/LiNiO2的侵蚀转变为LiNixCoyMri1-x-yO2的多元侵蚀，而且反应温度由800～900℃升高到940～1100℃使反应大大加剧，造成了匣钵材料壁面被侵蚀而出现了开裂和逐层剥落，使匣钵的使用寿命缩短。
为了延长匣钵的使用寿命，专利文献CN103884190A中使用了莫来石或者莫来石-堇青石为母材，然后用氧化锆、氧化铝、氮化硅、尖晶石、氧化镁等材料对匣钵母材进行涂覆进而隔绝了母材和锂离子电池正极材料的反应。但是氧化锆、尖晶石、氧化镁的热膨胀系数和母材的莫来石或者莫来石-堇青石相比差异巨大，在反复使用的过程中涂层很容易出现裂纹，附着力下降。另外，氮化硅的热膨胀系数虽然很小，但是价格偏高，提高了匣钵的生产成本。
为了降低涂层和母材热膨胀系数不匹配的问题，专利文献CN103311498A中采用了在堇青石-莫来石母材上用二次压制的方法附着了氧化锆和锂辉石的混合附着层。氧化锆和锂辉石和锂离子电池正极材料都很难反应，并且锂辉石的热膨胀系数低，可以和氧化锆在一定比例范围内配合使用。但是该专利文献中所使用的二次压制的方法不仅复杂，而且还存在着压制涂层不均匀导致匣钵底面和侧面的强度降低从而出现裂纹等问题。
专利文献CN108302942A的匣钵保护层包括传统上经常使用的氧化铝、氧化镁、镁铝尖晶石、氧化锆、硅酸锆、锂辉石等，并且还包括了莫来石-堇青石和锂离子电池正极材料反应后的产物包括铝酸锂(LiAlO2)和锂霞石(Li2O·Al2O3·2SiO2)。但是该专利文献所采用的涂层涂布方法为浸渍涂布，喷涂法或者刷涂法进行涂布，不但需要特殊的喷涂设备或者耗费人工，并且在涂层涂布以后还要等待涂层干燥，大大降低了生产效率。
综上所述，现在主流的提高匣钵使用寿命的方法主要是在堇青石-莫来石匣钵表面附着一层保护层，阻止了匣钵和锂离子正极材料的反应。但是，这种方法本身具有很多缺点：第一，莫来石-堇青石质的匣钵本身热膨胀系数很低，但是传统上认为的和碳酸锂或者氧化锂不反应的物质如氧化锆、氧化镁、氧化铝、镁铝尖晶石等的热膨胀系数都非常高，在反复不断加热冷却的时候，匣钵的母材和保护层会因为热膨胀系数不匹配进而出现开裂或者脱落等情况，并不能真正有效的提高匣钵的使用寿命；第二，不论是浸渍涂布，喷涂法或者刷涂法进行涂布，不但需要特殊的喷涂设备或者耗费人工，并且在涂层涂布以后还要等待涂层干燥，大大降低了生产效率，提高了生产成本。第三，一般的匣钵母材是由干式成型法成形，成形后的母材本身堆积密度很大，后期烧结的时候收缩率非常小。但是现有的保护层技术主体为两种，第一种为匣钵母材烧结后喷涂，干燥后直接就可以用来烧结锂离子电池正极材料，这种方法成膜简单，但是保护膜层的强度低下，在最开始的几次使用当中，容易发生保护层脱落的情况。另一种保护层技术为匣钵母材成形后直接在其表面附着保护膜，在整体干燥后进行烧结处理。这样做的好处是匣钵母材和保护层的结合力高，不容易脱落，但缺点是保护膜和母材的烧结收缩率不同，造成在烧结的时候就出现开裂起皮等现象，大大降低了成品率，提高了生产成本。
发明内容
本发明的目的在于提供一种锂离子电池正极材料用匣钵，其耐腐蚀性高、耐热冲击、抗弯折强度大、气孔率低，并且只需要一次成型，不需要特殊的保护层，生产工艺简便，生产效率高。
本发明当中所述锂离子电池正极材料包括但不局限于有层状结构金属氧化物锂盐，包括钴酸锂、镍钴锰三元材料、富锂锰基材料等；具有橄榄石结构的磷酸铁锂、磷酸钴锂、磷酸锰锂、磷酸锰铁锂等；具有尖晶石结构的锰酸锂、镍锰二元材料等正极材料。
为达此目的，本发明采用以下技术方案：
提供一种锂离子电池正极材料用匣钵，由低热膨胀材料和/或负热膨胀材料与耐锂离子电池正极材料侵蚀材料组成，所述低热膨胀材料和/或负热膨胀材料与所述耐锂离子电池正极材料侵蚀材料混合后成型为匣钵胚体，经烧成后制得锂离子电池正极材料用匣钵。
所述低热膨胀材料选自石英(SiO2)、透锂长石(Li2O·Al2O3·8SiO2)、锂辉石(Li2O·Al2O3·4SiO2)中的一种或两种以上，所述负热膨胀材料选自锂霞石(Li2O·Al2O3·2SiO2)和/或钨酸锆(ZrO2·2WO4)。
本发明通过使用低热膨胀材料和/或负热膨胀材料与耐锂离子电池正极材料侵蚀材料(简称耐蚀材)来制备匣钵，不但控制了匣钵的热膨胀系数，使其可以在急冷急热的情况下使用，并且在匣钵中提高了和耐锂离子电池正极材料侵蚀材料的比例，最大限度的减缓了匣钵和碳酸锂或者氢氧化锂的反应，延长了匣钵的使用。并且本发明不需要在匣钵表面装配保护层，降低了生产难度和设备的投入，并且解决了保护层和匣钵母材间结合力的问题，更进一步降低了匣钵在使用当中可能出现问题的概率。
本发明所使用的这些低热膨胀材料的热膨胀系数为0/K～0.9*10-6/K，负热膨胀材料的热膨胀系数为-9*10-6/K～0/K，所述耐锂离子电池正极材料侵蚀材料的热膨胀系数为4.5*10-6/K～13.1*10-6/K，低热膨胀材料和/或负热膨胀材料可以很好地和耐锂离子电池正极材料侵蚀材料(简称耐蚀材)进行配合，控制匣钵整体的热膨胀系数。并且，本发明所使用的低热膨胀材料和/或负热膨胀材料不包括和锂离子电池正极材料容易反应的莫来石和堇青石，进而有效地控制了匣钵的被侵蚀性。
所述低热膨胀材料与所述耐锂离子电池正极材料侵蚀材料的重量比为0.15～6.0，优选为0.2～2.0，通过对低热膨胀材料与耐锂离子电池正极材料侵蚀材料的配比调整平衡，以更好地控制匣钵整体的热膨胀系数，使其可以在急冷急热的情况下使用。
本发明所使用的低热膨胀材料优选透锂长石(Li2O·Al2O3·8SiO2)和/或锂辉石(Li2O·Al2O3·4SiO2)，所述负热膨胀材料选自锂霞石(Li2O·Al2O3·2SiO2)。因为这些矿物质是包含锂的矿物质，和碳酸锂或者氢氧化锂很难进行反应，本身就是性能良好的耐锂离子电池正极材料侵蚀材料，可以同时承担控制热膨胀系数和耐锂离子电池正极材料侵蚀的热性，一举两得。
进一步地，所述耐锂离子电池正极材料侵蚀材料选自氧化铝(Al2O3)、氧化锆(ZrO2)、氧化镁(MgO)、镁铝尖晶石(Al2O3·MgO)、硅酸锆(ZrO2·SiO2)、镁橄榄石(2MgO·SiO2)、顽火辉石(MgO·SiO2)中的一种或两种以上。这些材料本身和锂离子电池正极材料很难反应，热膨胀系数在4.5～13.1*10-6/K之间，属于中高热膨胀材料，和上述低热膨胀材料配合使用时，添加的比例要适当，否则在急冷急热的情况下使用容易产生开裂等问题。
进一步地，按质量百分比计，本发明的锂离子电池正极材料用匣钵由以下组份组成：
Figure BDA0002665455530000041
一般情况下，匣钵的堆积密度越大，气孔率就会越小，本发明中的所述锂离子电池正极材料用匣钵的堆积密度为1.5～5.0g/cm3；为了平衡气孔率和匣钵本身的重量，锂离子电池正极材料用匣钵的堆积密度优选为2.0～4.0g/cm3。
一般情况下，材料的耐热冲击性和热膨胀系数，抗弯折强度，还有材料本身的性质如厚度和杨氏模量有关。为了避免匣钵在急冷急热的使用条件下过早出现开裂等情况，所述锂离子电池正极材料用匣钵的热膨胀系数为6.0*10-6/K以下，抗弯折强度为5MPa以上；进一步地，所述锂离子电池正极材料用匣钵的热膨胀系数为-1.0*10-5/K～4.0*10-6/K，抗弯折强度为9～150MPa以上，可以使锂离子电池正极材料用匣钵具有更好的耐热冲击性。
本发明的发明人认为，匣钵的耐锂离子电池正极材料的侵蚀性主要表现在两个方面：第一、匣钵本身的材料中容易和碳酸锂或氢氧化锂反应的物质的比例，如果匣钵中容易和锂离子电池正极材料反应的莫来石的比例太高，就会严重影响匣钵的使用寿命；第二、匣钵本身的气孔率；由于锂离子电池正极材料所使用的锂源大多为碳酸锂，而碳酸锂在725℃以上烧成条件下会变成液态。如果匣钵的气孔率太大，在高温退火的时候，碳酸锂就会从固态转化为液态进而渗透到匣钵当中。如果匣钵的气孔率非常高，那么锂离子在匣钵当中的扩散率就会非常大，进而提高了和匣钵当中的易反应物质的结合概率，降低匣钵的使用寿命。所以为了防止锂离子的损失，并且为了减小液态锂离子对匣钵的侵蚀，所述锂离子电池正极材料用匣钵的气孔率为50％以下，优选为5～30％，可以获得更高的耐侵蚀效果。
进一步地，所述匣钵胚体的成型方法包括干法压制成型法、注浆成型法、等静压成型法。
进一步地，烧成温度为900～1600℃；
优选地，烧成之前还包括干燥步骤：在室温下或在50～120℃的条件下干燥0.5～96h。
具体地，本发明的锂离子电池正极材料制备用的匣钵可以通过以下方法制备，该方法包括以下步骤：
第一，将上述低热膨胀材料、耐蚀材根据成型的方法加入不同比例的水进行混合；
第二，在干法压制成型法、注浆成型法、等静压成型法当中选取一种来对匣钵进行成型；
第三，成型后的匣钵胚体，在室温下或者在50～120℃的条件下经过0.5～96小时干燥后，在700～1600℃下烧成1～48小时；
第四，对烧结后的匣钵不进行加工或者进行未加工剔除表面的不均匀部分，进而得到最后的匣钵成品。
本发明的有益效果：本发明所使用的低热膨胀材料和/或负热膨胀材料不包含和锂离子电池正极材料容易反应的堇青石或者莫来石，本身就具有很强的耐蚀性，所以本发明的匣钵本身就具有耐热冲击性和耐锂离子电池正极材料侵蚀的特性，大大提高了匣钵的使用寿命，减少了锂离子电池正极材料对耐火材料的消耗，保护了环境。本发明的匣钵本身具备非常好的耐锂离子电池正极材料的侵蚀的特性，所以不需要额外的涂层来保护匣钵，大幅减少了生产流程、所需设备和人工的使用，仅需要简单的成型设备和退火设备就能够进行生产，提高了生产效率。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
如无具体说明，本发明的各种原料均可市售购得，或根据本技术领域的常规方法制备得到。
实施例1
按照表1所示组份的重量百分比备好原料。将原料加水混合搅拌，形成具有和易性的浆料，其中加入的水占所有粉末原料重量的10％。将所述浆料倒入模具中，并将模具移动至振动台上，震动至泛浆找平。
将注入至模具中的胚体(注浆成型)在模具中自然养护15h后脱模，并将脱模后的匣钵胚体在105℃下干燥15h。
将干燥后的胚体放置在高温电炉中(烧成温度参考表1)，在1350℃下退火3h，冷却至150℃以下后开炉取出，即可得到锂离子电池正极材料用匣钵。
实施例2～13
各实施例所用的原料及其百分比、成型方法及烧成条件分别参考表1，其余步骤均与上述实施例1相同，具体不再赘述。
表1.实施例1～13工艺参数
Figure BDA0002665455530000061
Figure BDA0002665455530000071
比较例1～10
各比较例所用的各原料及其百分比、成型方法及烧成温度分别参考表2，其余步骤均与上述实施例1相同，具体不再赘述。
表2.比较例1～10工艺参数
Figure BDA0002665455530000072
测试
对实施例1～13所述匣钵的堆积密度、弯折强度、化学成分的重量比、热膨胀系数、真密度、气孔率以及耐用次数进行测试，测试结果见表3。
对比较例1～10所述匣钵的堆积密度、弯折强度、化学成分的重量比、热膨胀系数、真密度、气孔率以及耐用次数进行测试，测试结果见表4。
其中，匣钵的堆积密度通过重量和体积的测算可获得；采用三点弯折强度试验(试验机：株式会社岛津制作所AG-Xplus)测定匣钵的弯折强度；通过X射线分析装置(株式会社岛津制作所PDA-8000)测定匣钵的化学成分的重量百分比；采用热膨胀系数测定仪(株式会社NETZSCH，DIL 402C)检测匣钵的热膨胀系数；通过液相置换法(株式会社セイシン企業，AUTO TRUE DENSER MAT-7000)测定匣钵的真密度和气孔率。
耐用次数测试：将碳酸锂粉末和氧化钴粉末按照Li和Co的摩尔比1:1在球磨机中进行1h的高速混合。将混合均匀的碳酸锂氧化钴混合物堆积至匣钵的顶部平行(大约6kg)。然后将装满混合物的匣钵放置在大电炉当中，用3h从室温升至800℃，并在800℃保持5h，然后让匣钵及其当中的锂离子电池正极材料在大电炉中自然冷却至150℃(约6h)取出，并进行观察。如果所烧的锂离子电池正极材料可以轻松从匣钵中倒出，匣钵表面没有锂离子电池正极材料残留物，并且匣钵本身没有出现开裂脱皮等不良反应，则视为匣钵可以继续进行锂离子电池正极材料的烧结实验。如果发现锂离子电池正极材料不能顺利从匣钵中倒出，或者匣钵中少量残留锂离子电池正极材料，或者匣钵本身出现开裂脱皮等状况，则视为匣钵已经到了使用寿命，终止锂离子电池正极材料的烧结实验。
表3.实施例1～13测试结果
Figure BDA0002665455530000081
表4.比较例1～10测试结果
Figure BDA0002665455530000082
Figure BDA0002665455530000091
从表3可知，上述实施例1制得的匣钵可以使用的循环次数为45次。当进行了第46次循环烧结实验后，发现该匣钵表面出现了脱皮开裂，可能会影响锂离子电池正极材料的使用性能。比传统的莫来石-堇青石匣钵的使用寿命提高了一倍左右(表4)。
在“比较例1”当中，是传统上的莫来石-堇青石-氧化铝配合，由于堇青石和莫来石非常容易被锂离子电池正极材料侵蚀，所以耐用次数非常短，只有18次。在“比较例2”当中，由于匣钵的热膨胀系数很大，在使用一次后就出现了开裂，无法继续使用。在“比较例3”当中，由于匣钵的化学成分中有大量的氧化硅，所以非常容易被锂离子电池正极材料所侵蚀，使用寿命只有3次。在“比较例4”到“比较例7”当中，由于匣钵的热膨胀系数很大，所以在使用一次后就都出现了开裂，无法继续使用。在“比较例8”和“比较例9”当中，由于匣钵的堆积密度较小，气孔率都超过了50％，高温固相合成的时候，液态的锂离子电池正极材料非常容易侵入到匣钵并在内部扩散，从而让使用寿命大大缩短。在“比较例10”当中，含有部分堇青石，在锂离子电池循环烧结时，匣钵不断被侵蚀，最终使用寿命只有19次，远不如本发明所述匣钵的使用寿命。
上述实施例1～13及比较例1～10中所使用的各原料的来源、密度以及热膨胀系数参见下表：
表5.各原料的来源、密度以及热膨胀系数
Figure BDA0002665455530000092
Figure BDA0002665455530000101
上述实施例1～13及比较例1～10中所使用的各原料的化学成分的重量比参见下表：
表6.各原料的化学成分的重量比
原料 SiO<sub>2</sub>(％) Al<sub>2</sub>O<sub>3</sub>(％) Li<sub>2</sub>O(％) ZrO<sub>2</sub>(％) MgO(％) WO<sub>3</sub>(％) 其他(％)
石英(SiO<sub>2</sub>) 99.5 0.1 0.0 0.0 0.1 0.0 0.3
透锂长石(Li<sub>2</sub>O·Al<sub>2</sub>O<sub>3</sub>·8SiO<sub>2</sub>) 78.4 16.6 4.8 0.0 0.1 0.0 0.1
锂辉石(Li<sub>2</sub>O·Al<sub>2</sub>O<sub>3</sub>·4SiO<sub>2</sub>) 64.5 27.4 8.0 0.0 0.0 0.0 0.1
锂霞石(Li<sub>2</sub>O·Al<sub>2</sub>O<sub>3</sub>·2SiO<sub>2</sub>) 47.6 40.5 11.9 0.0 0.0 0.0 0.0
钨酸锆(ZrO<sub>2</sub>·2WO<sub>4</sub>) 0.0 0.0 0.0 20.9 0.0 79.0 0.1
铝酸锂(Li<sub>2</sub>O·Al<sub>2</sub>O<sub>3</sub>) 0.0 77.2 22.7 0.0 0.0 0.0 0.1
氧化铝(Al<sub>2</sub>O<sub>3</sub>) 0.1 99.5 0.0 0.0 0.0 0.0 0.4
氧化锆(ZrO<sub>2</sub>) 0.1 0.1 0.0 99.7 0.0 0.0 0.1
氧化镁(MgO) 0.1 0.1 0.0 0.0 99.8 0.0 0.0
镁铝尖晶石(Al<sub>2</sub>O<sub>3</sub>·MgO) 0.1 71.8 0.0 0.0 28.1 0.0 0.0
硅酸锆(ZrO<sub>2</sub>·SiO<sub>2</sub>) 32.6 0.1 0.0 67.0 0.0 0.0 0.3
镁橄榄石(2MgO·SiO<sub>2</sub>) 42.8 0.1 0.0 0.0 57.0 0.0 0.1
顽火辉石(MgO·SiO<sub>2</sub>) 59.7 0.1 0.0 0.0 39.8 0.0 0.4
堇青石(2MgO·2Al<sub>2</sub>O<sub>3</sub>·5SiO<sub>2</sub>) 51.3 34.9 0.0 0.0 13.6 0.0 0.2
莫来石(3Al<sub>2</sub>O<sub>3</sub>·2SiO<sub>2</sub>) 28.1 71.8 0.0 0.0 0.0 0.0 0.1
以上实施例仅用来说明本发明的详细方法，本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明白，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

1.一种锂离子电池正极材料用匣钵，其特征在于，由低热膨胀材料和/或负热膨胀材料与耐锂离子电池正极材料侵蚀材料组成，所述低热膨胀材料和/或负热膨胀材料与所述耐锂离子电池正极材料侵蚀材料混合后成型为匣钵胚体，经烧成后制得锂离子电池正极材料用匣钵。
2.根据权利要求1所述低热膨胀材料选自石英、透锂长石、锂辉石中的一种或两种以上，所述负热膨胀材料选自锂霞石和/或钨酸锆；
优选地，所述耐锂离子电池正极材料侵蚀材料选自氧化铝、氧化锆、氧化镁、镁铝尖晶石、硅酸锆、镁橄榄石、顽火辉石中的一种或两种以上。
3.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，所述低热膨胀材料的热膨胀系数为0/K～0.9*10-6/K，所述负热膨胀材料的热膨胀系数为-9*10-6/K～0/K，所述耐锂离子电池正极材料侵蚀材料的热膨胀系数为4.5*10-6/K～13.1*10-6/K。
4.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，所述低热膨胀材料与所述耐锂离子电池正极材料侵蚀材料的重量比为0.15～6.0，优选为0.2～2.0。
5.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，所述低热膨胀材料选自透锂长石和/或锂辉石，所述负热膨胀材料选自锂霞石。
6.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，按质量百分比计，由以下组份组成：
Figure FDA0002665455520000011
7.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，所述锂离子电池正极材料用匣钵的堆积密度为1.5～5.0g/cm3，优选为2.0～4.0g/cm3。
8.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，所述锂离子电池正极材料用匣钵的热膨胀系数为6.0*10-6/K以下，优选为-1.0*10-5/K～4.0*10-6/K；
优选地，所述锂离子电池正极材料用匣钵的抗弯折强度为5MPa以上，进一步优选为9～150MPa；
优选地，所述锂离子电池正极材料用匣钵的气孔率为50％以下，进一步优选为5～30％。
9.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，所述匣钵胚体的成型方法包括干法压制成型法、注浆成型法、等静压成型法。
10.根据权利要求1所述的锂离子电池正极材料用匣钵，其特征在于，烧成温度为900～1600℃；
优选地，烧成之前还包括干燥步骤：在室温或者在50～120℃的条件下干燥0.5～96h。
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