CN113387683B - 一种锂钴锰氧化物靶材及其制备方法 - Google Patents

一种锂钴锰氧化物靶材及其制备方法 Download PDF

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CN113387683B
CN113387683B CN202110652019.4A CN202110652019A CN113387683B CN 113387683 B CN113387683 B CN 113387683B CN 202110652019 A CN202110652019 A CN 202110652019A CN 113387683 B CN113387683 B CN 113387683B
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lithium cobalt
cobalt manganese
manganese oxide
lithium
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CN113387683A (zh
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吴隽
付豪
王凯丰
黄成彬
张绍奇
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Wuhan University of Science and Engineering WUSE
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Abstract

本发明公开了一种锂钴锰氧化物靶材及其制备方法。其技术方案是：按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶(0.417～0.667)∶(1.25～2)配料，于球磨罐中球磨，得到混合料；将所述混合料置入马弗炉中，在空气气氛中加热至1000～1200℃，保温18～30h，得到锂钴锰氧化物产物：Li(3+2x)/3Co(3‑x)/3Mn(3‑x)/3O4，其中：0≤x≤0.5；将所述锂钴锰氧化物产物在1000～1200℃和75～125MPa条件下，热压烧结1～3h，得到锂钴锰氧化物胚料；对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材。本发明具有生产成本低、操作简单、产品形状和尺寸均可控的特点，制备的锂钴锰氧化物靶材密度高，适用于各种物理气相沉积法制备锂钴锰氧化物薄膜。

Description

一种锂钴锰氧化物靶材及其制备方法
技术领域
本发明属于陶瓷靶材技术领域。具体涉及一种锂钴锰氧化物靶材及其制备方法。
背景技术
目前，锂钴锰氧化物薄膜主要是通过化学气相沉积法或物理气相沉积法制得：化学气相沉积法(Chemical Vapor Deposition简称CVD)是利用气态或蒸汽态的物质在气相或气固界面上发生反应生成固态沉积物的过程；物理气相沉积法(Physical VapourDeposition，PVD)是指在真空条件下，采用物理方法，将材料源——固体或液体表面气化成气态原子、分子或部分电离成离子，并通过低压气体(或等离子体)过程，在基体表面沉积具有某种特殊功能的薄膜的技术。物理气相沉积的主要方法有真空蒸镀、溅射镀膜、电弧等离子体镀、离子镀膜和分子束外延等方法。通过物理气相沉积法制备锂钴锰氧化物薄膜均首先需要制得锂钴锰氧化物靶材，故锂钴锰氧化物靶材及其制备方法已引起本领域技术人员的广泛关注。
“一种钴酸锂靶材及其制备方法”(CN102181840A)的专利技术，公开了一种先液压成型，再冷等静压得到钴酸锂胚料，最后高温烧结制得钴酸锂靶材的方法。而高温烧结会改变钴酸锂胚料形状尺寸，因此该方法制得的钴酸锂靶材仍需通过磨加工方法制成所要求的尺寸，且该方法在高温烧结时需抽真空加入保护气氛，工艺复杂，成本高。
“一种陶瓷靶材的制备方法”(CN107188555A)的专利技术，公开了一种依次烘料、配料、球磨、干燥、煅烧、球磨、制胚、烧结、冷却制得[(Bi1/2Na1/2)0.9118Ba0.0582La0.02]Ti0.96M0.04O3陶瓷靶材的方法。该方法虽然是一种绿色制备技术，但是工艺复杂，生产周期长。
“一种锂离子电池锰钴锂氧化物正极材料及其制备方法”(CN102583583B)的专利，公开了一种用锂盐、锰盐和钴盐共沉淀法制备锰钴锂氧化物粉末的方法。该方法的原料采用三种盐，得到的是锂钴锰氧化物粉末(未制得纳米级锂钴锰氧化物薄膜)。
游美玲等人(游美玲等.尖晶石LiCo1+xMn1-xO4(x＝0,0.05,0.1)材料的制备及电化学性能的研究.广州化工.2013,41(12):109-112.)采用化学气相沉积法，以碳酸锂、醋酸钴和醋酸锰为原料，在750℃和空气气氛条件下恒温煅烧24小时，得到锂钴锰氧化物正极材料(未制得纳米级锂钴锰氧化物薄膜)。
日本大阪城市大学的Kingo Ariyoshi(Kingo Ariyoshi等.High dimensionalstability of LiCoMnO4 as positive electrodes operating at high voltage forlithium-ion batteries with a long cycle life.Electrochimica Acta,260(2018),498–503.)采用化学气相沉积法，以LiOH·H2O和双氢氧化钴锰为原料，在900℃加热12小时，然后在700℃冷却24小时，在650℃加热24小时，然后在600℃冷却，得到LiCoMnO4正极材料(未制得纳米级LiCoMnO4薄膜)。
日本东北大学Naoaki Kuwata(Naoaki Kuwata等.Fabrication of thin-filmlithium batteries with 5-V-class LiCoMnO4 cathodes.Solid State Ionics,262(2014),166-169.)，以碳酸锂、氧化钴和碳酸锰为原料，分别在800℃的空气中烧结24小时，在600℃的空气中烧结3天，制得LiCoMnO4靶材，由于其制备方法的温度较低，两种碳酸盐原料容易分解且不易充分反应，致使制得的LiCoMnO4靶材密度只有3.28g/cm3，且相对密度仅是LiCoMnO4理论密度(4.69g/cm3)的70％，因而此方法得到的LiCoMnO4靶材的质量较差。
发明内容
本发明旨在克服现有技术缺陷，目的在于提供一种生产成本低、操作简单、产品形状和尺寸均可控的锂钴锰氧化物靶材制备方法；用该方法制备的锂钴锰氧化物靶材密度高，适用于各种物理气相沉积法制备锂钴锰氧化物薄膜。
为了解决上述技术问题，本发明采用的技术方案是：
步骤一、按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶(0.417～0.667)∶(1.25～2)配料，将所述氧化锂、四氧化三钴和二氧化锰加入球磨罐中，以300～400r/min的转速球磨2～4h，得到混合料。
步骤二、将所述混合料置入马弗炉中，在空气气氛中，以1～3℃/min的速率加热至1000～1200℃，保温18～30h，得到锂钴锰氧化物产物：Li(3+2x)/3Co(3-x)/3Mn(3-x)/3O4，其中：0≤x≤0.5。
步骤三、将所述锂钴锰氧化物产物在空气气氛、1000～1200℃和75～125MPa条件下，热压烧结1～3h，得到锂钴锰氧化物胚料。
步骤四、对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材。
所述氧化锂的纯度大于等于99.9％，平均粒径为0.5～50μm。
所述四氧化三钴的纯度大于等于99.9％，平均粒径为0.5～50μm。
所述二氧化锰粉末的纯度大于等于99.9％，平均粒径为0.5～50μm。
由于采用上述技术方案，本发明与现有技术相比具有以下优点：
1、本发明以氧化锂、四氧化三钴和二氧化锰三种粉末为原料，经球磨混合后，在空气气氛高温固相合成锂钴锰氧化物产物，于空气气氛中热压烧结制得锂钴锰氧化物胚料，经机械精加工后制得锂钴锰氧化物靶材；还能通过不同的热压模具来控制锂钴锰氧化物胚料的尺寸和形状，不仅产品的形状和尺寸均可控，且工艺简单，操作方便。
2、本发明的热处理过程均在空气气氛中完成，不需抽真空加入保护气氛，生产成本低，操作简单。
3、本发明制备的锂钴锰氧化物靶材经检测：相对密度均在锂钴锰氧化物靶材理论密度的85％以上；制备的锂钴锰氧化物靶材密度，高使用时不易开裂和掉渣，适用于各种物理气相沉积法制备锂钴锰氧化物薄膜。
因此，本发明具有生产成本低、操作简单、产品形状和尺寸均可控的特点，制备的锂钴锰氧化物靶材密度高，适用于各种物理气相沉积法制备锂钴锰氧化物薄膜。
附图说明
图1为本发明制备的一种锂钴锰氧化物靶材的X射线衍射图谱。
具体实施方式
下面结合附图和基体实施方式对本发明作进一步的描述，并非对其保护范围的限制。
一种锂钴锰氧化物靶材及其制备方法。本具体实施方式所述制备方法的步骤是：
步骤一、按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶(0.417～0.667)∶(1.25～2)配料，将所述氧化锂、四氧化三钴和二氧化锰加入球磨罐中，以300～400r/min的转速球磨2～4h，得到混合料。
步骤二、将所述混合料置入马弗炉中，在空气气氛中，以1～3℃/min的速率加热至1000～1200℃，保温18～30h，得到锂钴锰氧化物产物：Li(3+2x)/3Co(3-x)/3Mn(3-x)/3O4，其中：0≤x≤0.5。
步骤三、将所述锂钴锰氧化物产物在空气气氛、1000～1200℃和75～125MPa条件下，热压烧结1～3h，得到锂钴锰氧化物胚料。
步骤四、对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材。
本具体实施方式中：
所述氧化锂的纯度大于等于99.9％，平均粒径为0.5～50μm；
所述四氧化三钴的纯度大于等于99.9％，平均粒径为0.5～50μm；
所述二氧化锰粉末的纯度大于等于99.9％，平均粒径为0.5～50μm。
实施例中不再赘述。
实施例1
一种锂钴锰氧化物靶材及其制备方法。本具体实施方式所述制备方法的步骤是：
步骤一、按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶0.667∶2配料，将所述氧化锂、四氧化三钴和二氧化锰加入球磨罐中，以400r/min的转速球磨2h，得到混合料。
步骤二、将所述混合料置入马弗炉中，在空气气氛中，以1℃/min的速率加热至1200℃，保温18h，得到锂钴锰氧化物产物：LiCoMnO4。
步骤三、将所述锂钴锰氧化物产物在空气气氛、1000℃和125MPa条件下，热压烧结3h，得到锂钴锰氧化物胚料。
步骤四、对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材。
本实施例制备的锂钴锰氧化物靶材经检测：密度为4.09g/cm3；相对密度是锂钴锰氧化物靶材的理论密度(4.69g/cm3)的87.2％。
实施例2
一种锂钴锰氧化物靶材及其制备方法。本具体实施方式所述制备方法的步骤是：
步骤一、按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶0.5∶1.5配料，将所述氧化锂、四氧化三钴和二氧化锰加入球磨罐中，以350r/min的转速球磨3h，得到混合料。
步骤二、将所述混合料置入马弗炉中，在空气气氛中，以2℃/min的速率加热至1100℃，保温24h，得到锂钴锰氧化物产物：Li1.2Co0.9Mn0.9O4。
步骤三、将所述锂钴锰氧化物产物在空气气氛、1100℃和100MPa条件下，热压烧结2h，得到锂钴锰氧化物胚料。
步骤四、对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材。
本实施例制备的锂钴锰氧化物靶材经检测：密度为3.81g/cm3，相对密度是锂钴锰氧化物靶材的理论密度(4.40g/cm3)的86.6％。
实施例3
一种锂钴锰氧化物靶材及其制备方法。本具体实施方式所述制备方法的步骤是：
步骤一、按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶0.417∶1.25配料，将所述氧化锂、四氧化三钴和二氧化锰加入球磨罐中，以300r/min的转速球磨4h，得到混合料。
步骤二、将所述混合料置入马弗炉中，在空气气氛中，以3℃/min的速率加热至1000℃，保温30h，得到锂钴锰氧化物产物：Li1.333Co0.833Mn0.833O4。
步骤三、将所述锂钴锰氧化物产物在空气气氛、1200℃和75MPa条件下，热压烧结1h，得到锂钴锰氧化物胚料。
步骤四、对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材。
本实施例制备的锂钴锰氧化物靶材经检测：密度为3.59g/cm3，相对密度是锂钴锰氧化物靶材的理论密度(4.20g/cm3)的85.5％。
本具体实施方式与现有技术相比具有以下优点：
1、本具体实施方式以氧化锂、四氧化三钴和二氧化锰三种粉末为原料，经球磨混合后，在空气气氛高温固相合成锂钴锰氧化物产物，于空气气氛中热压烧结制得锂钴锰氧化物胚料，经机械精加工后制得锂钴锰氧化物靶材；还能通过不同的热压模具来控制锂钴锰氧化物胚料的尺寸和形状，不仅产品的形状和尺寸均可控，且工艺简单，操作方便。
2、本具体实施方式的热处理过程均在空气气氛中完成，不需抽真空加入保护气氛，生产成本低，操作简单。
3、本具体实施方式制备的锂钴锰氧化物靶材如附图所示，图1是实施例1制备的锂钴锰氧化物靶材，经X射线衍射图谱显示，合成的锂钴锰氧化物靶材具有尖晶石型结构。
本具体实施方式制备的锂钴锰氧化物靶材经检测：相对密度均在锂钴锰氧化物靶材理论密度的85％以上；制备的锂钴锰氧化物靶材密度高，使用时不易开裂和掉渣，适用于各种物理气相沉积法制备锂钴锰氧化物薄膜。
因此，本具体实施方式具有生产成本低、操作简单、产品形状和尺寸均可控的特点，制备的锂钴锰氧化物靶材密度高，适用于各种物理气相沉积法制备锂钴锰氧化物薄膜。

Claims (5)

1.一种锂钴锰氧化物靶材的制备方法，其特征在于，该方法包括以下步骤：
步骤一、按氧化锂∶四氧化三钴∶二氧化锰的摩尔比为1∶(0.417～0.667)∶(1.25～2)配料，将所述氧化锂、四氧化三钴和二氧化锰加入球磨罐中，以300～400r/min的转速球磨2～4h，得到混合料；
步骤二、将所述混合料置入马弗炉中，在空气气氛中，以1～3℃/min的速率加热至1000～1200℃，保温18～30h，得到锂钴锰氧化物产物：Li(3+2x)/3Co(3-x)/3Mn(3-x)/3O4，其中：0≤x≤0.5；
步骤三、将所述锂钴锰氧化物产物在空气气氛、1000～1200℃和75～125MPa条件下，热压烧结1～3h，得到锂钴锰氧化物胚料；
步骤四、对所述锂钴锰氧化物胚料进行精加工，清洗，制得锂钴锰氧化物靶材；
所述氧化锂的平均粒径为0.5～50μm；
所述四氧化三钴的平均粒径为0.5～50μm；
所述二氧化锰粉末的平均粒径为0.5～50μm。
2.根据权利要求1所述的锂钴锰氧化物靶材的制备方法，其特征在于所述氧化锂的纯度大于等于99.9％。
3.根据权利要求1所述的锂钴锰氧化物靶材的制备方法，其特征在于所述四氧化三钴的纯度大于等于99.9％。
4.根据权利要求1所述的锂钴锰氧化物靶材的制备方法，其特征在于所述二氧化锰粉末的纯度大于等于99.9％。
5.一种锂钴锰氧化物靶材，其特征在于所述锂钴锰氧化物靶材是根据权利要求1～4项中任一项所述锂钴锰氧化物靶材的制备方法制备的锂钴锰氧化物靶材。
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