CN113548884B - 含堇青石和复合尖晶石莫来石的匣钵及其制备方法 - Google Patents
含堇青石和复合尖晶石莫来石的匣钵及其制备方法 Download PDFInfo
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Abstract
本发明涉耐火窑具技术领域,具体涉及含堇青石和复合尖晶石莫来石的匣钵及其制备方法,所述匣钵的原料含有以下重量份的成分:尖晶石25份、堇青石15份、复合尖晶石莫来石40份、高岭土6份、电熔98氧化镁2份、煅烧氧化铝粉12份、黄糊精1份、水3.2份。本申请提供的匣钵耐腐蚀性好,循环使用次数多,寿命长。
Description
技术领域
本申请涉及耐火窑具技术领域,尤其涉及一种锂电池正极材料用含堇青石和复合尖晶石莫来石的匣钵及其制备方法。
背景技术
目前,钴酸锂和普通三元正极材料(523)是国内目前广泛使用锂电池的正极材料,而大部分的正极材料的生产都是在耐火窑炉中以高温固相合成法制成,在合成过程中,承烧用的匣钵材料一般以堇青石、莫来石、石英和刚玉质为主,在这些材料中以堇青石复合莫来石质匣钵的产品应用最广。
堇青石复合莫来石质匣钵是以堇青石、莫来石以及刚玉为原料,加入部分粘土及微粉作为结合剂,在高吨位压机下压制成型,经常温养护后,再入耐火窑炉进行高温烧成制得产品。
随着锂电降低成本的要求,特别是电动车电池的需求,正极材料向磷酸铁锂和高镍三元材料发展,要求尽量降低钴的含量,甚至不含钴,高镍三元正极材料(811)应运而成,其钴含量大幅度降低,同时锂离子组分的引入采用氢氧化锂,氢氧化锂分解温度远低于碳酸锂,因此,材料烧结温度也大幅度从钴酸锂(1100℃)和523(950℃)降到800~850℃。但是,磷酸铁锂和高镍三元材料对匣钵的腐蚀性能要求也大幅度提高,523正极材料用匣钵在811上用,寿命从50次降到12~15次。
匣钵生产企业经过2~3年的努力,通过配方调整优化,目前能达到20~25次,还是达不到523的使用寿命(40~60次)和磷酸铁锂的使用寿命(70~90次),需要不断努力创新,引入新原料和采用创新工艺,来提高高镍三元正极材料用匣钵的使用寿命,为国家节材降耗做出贡献,为企业降低生产成本做出努力。
201711323738.1(公开号为CN108046792A)公开了一种堇青石-尖晶石匣钵,以高岭土6-12份,滑石6-10份,α-氧化铝3-8份,粒径不大于46.9μm的尖晶石20-30份,以及粒径不大于1mm的尖晶石40-60份作为原料,制备的匣钵具有耐腐蚀性强、热稳定性好、使用寿命长和使用成本低的优点。实验中发现,莫来石抗三元正极材料523性能不好,在三元正极材料811中抗腐蚀性能更差。
202110311784.X(公开号为CN113135745A)公开了一种轻质莫来石-尖晶石空心球匣钵,其原料是:苏州二号泥2-6份,硅微粉4-6份,α-氧化铝粉4-8份,α-氧化铝微粉4-6份,铝酸钙水泥6-10份,电熔莫来石粉11-21份,电熔刚玉粉3-11份,电熔尖晶石空心球0.2-1mm10-20份,电熔尖晶石空心球1-3mm4-6份,轻质莫来石颗粒0-1mm10-20份,轻质莫来石颗粒1-3mm10-20份,三聚磷酸钠0.2-0.3份。上述配方中采用电熔尖晶石和电熔莫来石、电熔刚玉粉等混合,该专利是设计用于在使用场合温度高于1500℃的匣钵,其利用轻质莫来石和尖晶石空心球的孔隙提高使用寿命,产品本身并不具有良好的抗锂离子腐蚀性能。
解决方案,进一步降低堇青石和莫来石含量,提高尖晶石含量,本申请则是采用复合尖晶石莫来石原料来提高综合抗锂离子腐蚀性能。
发明内容
本申请所要解决的技术问题在于如何克服现有的匣钵在高镍三元正极材料中抗腐蚀性能差、使用寿命短的问题,延长使用寿命。
为了解决上述技术问题,本申请提供了一种含堇青石-复合尖晶石莫来石匣钵,所述原料含有以下重量份的成分:尖晶石25份、堇青石15份、复合尖晶石莫来石40份、高岭土6份、电熔98氧化镁2份、煅烧氧化铝粉12份、黄糊精1份、水3.2份。
上述成分中:
所述复合尖晶石莫来石的原料含有以下重量份的成分:轻烧镁粉9-21份、工业氧化铝70-80份和石英粉8-20份。
优选的,所述复合尖晶石莫来石的原料含有以下重量份的成分:轻烧镁粉12-21份、工业氧化铝70-80份和石英粉8.4-18份。
进一步优选,所述复合尖晶石莫来石的原料含有以下重量份的成分:轻烧镁粉15-21份、工业氧化铝70-75份和石英粉8.4-16份。
所述复合尖晶石莫来石,由以下方法制备:按照配比称取各原料,然后混匀,加入矿热炉中,在2200-2500℃电弧加热熔融5-15分钟,然后倾斜矿热炉倒入水槽中快速冷却,捞出干燥,粉碎,得到复合尖晶石莫来石。
优选的,复合尖晶石莫来石选择尖晶石和莫来石晶相比为70:30和30:70的复合物复配,或晶相比为40:60和60:40的复合物复配,或晶相比为50:50不同粒径的复合物进行复配,上述晶相比中两种复合物的粒径选自1-2mm或0-1mm。
晶相比复配时的重量比为1-2:1,优选为1:1。
所述尖晶石的粒径为0-1mm;
所述堇青石的粒径为0.5-1.25mm。
所述高岭土和煅烧氧化铝粉的粒径分别为320目;
所述电熔98氧化镁的粒径为200目。
本申请还提供了上述匣钵的制备方法,包括以下步骤:
1)按照配比称取各成分,先将粒径不大于200目的粉料混匀,得到混匀的粉料,备用;
2)把除黄糊精和水的其他粒径的颗粒料加入碾压搅拌机后,依次加入黄糊精、水混匀,在加入混匀的粉料,混匀;
3)压力为850~1000吨,保压时间为6~9秒,得到生坯,再放入窑中1380-1410℃烧制,烧制时间为3~6小时,即得。
本申请提供的匣钵具有以下有益效果:
1、本申请的匣钵中的复合尖晶石莫来石,是以轻烧镁粉、工业氧化铝粉和高纯石英粉为原料,经矿热炉高温冶炼熔融之后,熔体倒入水槽中快速冷却,保持微晶结构,从而提升复合尖晶石莫来石材料的抗锂离子腐蚀能力,从动力学角度来讲,与锂离子在高温下的反应变得缓慢,从而在同样的时间范围内,生成的反应物变少,从而防止因生成物过多,造成的体积膨胀,从而在匣钵表层表现为脱皮、剥落现象,从而造成报废。
采用复合尖晶石莫来石材料后,反应速度变缓,从而使之具有更长的使用寿命,表现出同样的脱皮、剥落现象出现时,产品比以前同样组分的匣钵使用次数更多。
2、本申请匣钵的原料中:
目前锂电池正极材料匣钵用材料主要有堇青石、莫来石、刚玉、尖晶石氧化铝粉及粘土等,其中在骨料中,莫来石的抗腐蚀能力相对弱,但是抗热震性能好,尖晶石可以抗腐蚀性,如何提高莫来石的抗锂离子腐蚀性能,又不降低抗热震性能,仅仅靠降低莫来石的用量,或提升尖晶石的用量,很难解决上述问题。
申请人经过大量的实验,发现复合尖晶石莫来石取代莫来石可有效提高抗锂离子腐蚀性能,从而提高匣钵的使用寿命。
从尖晶石、莫来石和复合尖晶石莫来石原料中与锂离子的腐蚀反应中可以发现,尖晶石性能最好,复合尖晶石莫来石原料次之,莫来石最差,但在抗热震方面则反之,因此采用复合尖晶石莫来石取代全部的莫来石和部分尖晶石,在确保抗热震性能的前提下,尽可能多用尖晶石,防止使用寿命降低。
尖晶石用量增加,寿命延长,但是过多会造成匣钵开裂,严重的没等腐蚀报废,其就破碎报废。
因此,适量的尖晶石莫来石组合,效果较好。
3、本申请提供的匣钵耐腐蚀性好,循环使用多次,寿命长。
具体实施方式
以下实施例用于说明本申请,但不用来限制本申请的范围。
原料来源:
轻烧镁粉,购自营口鑫垚镁业有限公司;
工业氧化铝粉,购自中铝中州铝业有限公司;
高纯石英粉,购自江苏润弛太阳能材料科技有限公司;
莫来石,购自河南特耐工程材料股份有限公司;
尖晶石,购自河南特耐工程材料股份有限公司,牌号为AM-70;
堇青石,购自淄博鲁宏沃尔森陶瓷有限公司;
高岭土,购自中国高岭土有限公司,是手选2号泥;
电熔98氧化镁,购自营口兴北耐火材料有限公司;
黄糊精,购自山东开普勒生物科技有限公司。
实施例1:复合尖晶石莫来石
1、配方见表1:
表1:实施例1-1到1-5的原料(单位为g、kg或mg,原料中的粒径均为200目)
2、制备方法:
1)按照配比称取工业氧化铝粉、轻烧镁粉与高纯石英粉,预混,搅拌时间为30分钟;
2)把预混好的粉体加入矿热炉中采用电弧加热融化,最后融化温度为2500℃,熔融后再继续加热熔炼10分钟;
3)把熔体导入带循环水冷却304不锈钢钢槽中,循环水直接冲进击矿热炉倒入的熔体,使之快速冷却,同时部分颗粒化(遇水爆裂形成颗粒);
4)熔体倒入结束后,循环冷却水继续冷去15分钟,把不锈钢槽吊出,复合尖晶石莫来石颗粒沥干送入干燥窑干燥。
尖晶石莫来石复合耐火材料可以根据需要进行粉碎,如破碎机破碎,破碎后分选出0~1mm颗粒,1~2mm颗粒,其中部分0~1mm颗粒拿出研磨成320目粉料。
实验例1:
1、样品,见实施例1-1到1-5、对比例1(采用质量比为50:50的尖晶石和莫来石为原料,采用实施例1的方法制备)、对比例2(采用质量比为30:70的尖晶石和莫来石为原料,采用实施例1的方法制备)、对比例3(采用质量比为70:30的尖晶石和莫来石为原料,采用实施例1的方法制备)、对比例4(单独使用尖晶石)和对比例5(单独使用莫来石)。
2、检测方法:
采用复合尖晶石莫来石与高镍LNCM电池正极材料(811生料)化学反应来测试抗腐蚀能力,主要通过样品尺寸变化来确定抗锂离子腐蚀性能。
按复合耐火原料与高镍LNCM电池正极材料(811生料)按质量比70:30混合均匀,外加上述混合物料总质量的3%的黄糊精作为结合剂,在球磨机中干磨2h,再加入去离子水湿磨10min。将混制完成的原料在50MPa下压制为圆片,直径为30mm,放入烘箱110℃下24h。得到干燥后的样品,在将其置于800℃到1100℃下热处理4h,用游标卡尺测量热处理前后圆片试样直径尺寸的变化。
3、结果:
表1:膨胀尺寸检测结果
表1结果显示:
单独使用尖晶石或莫来石时,在800℃时,尖晶石几乎没有膨胀,而莫来石为1.9%,(30.58/30=1.019)到1100℃时尖晶石最大膨胀为2.2%(30.7/30=1.022),而莫来石则达到4.3%(31.29/30=1.043),由此可以看出莫来石比尖晶石更容易反应,表面锂离子腐蚀性能差。
采用本申请方法制备的复合尖晶石莫来石复合物,其性能介于纯尖晶石和莫来石之间,且随着尖晶石含量的增加,抗腐蚀性能越好。
尖晶石和莫来石含量相同的样品进行比较:从膨胀尺寸可以看出,对比例1在不同的温度条件下均比实施例1-1大,实施例1-2和实施例1-3提供的尖晶石和莫来石也是同样小于对比例2、3。
结果表明:本申请方法提供的复合尖晶石莫来石复合物比单一莫来石产品抗腐蚀性能有较大的提高,从而为延长制品使用寿命奠定基础。
实施例2:一种含堇青石和复合尖晶石莫来石的匣钵
1、组成:见表2-1和2-2
表2-1:对比例、实施例2-1到2-5的配方(单位为g、kg或mg)
表2-2:实施例6-9的配方(单位为g、kg或mg)
注,本文中涉及的尖晶石和莫来石的比例为晶相含量比。
2、制备方法:
步骤1、按照配比成称取各成分,先把小于200目的粉料在搅拌机中预混30分钟,备用;
步骤2、将其他粒径的颗粒料和黄糊精加入碾压搅拌机,预混合10分钟,然后加水预混5分钟,再加入步骤1预混好的粉料,搅拌混合25分钟,然后出料备用,捆料24~36小时;
步骤3、把捆料后的匣钵料加入压机模具中,加压成型(压力是950吨),保压8秒,得到匣钵生坯。
步骤4、把匣钵生坯放入干燥窑中干燥或室外晾干,
步骤5、干燥好的生坯放入窑中烧制,烧成温度在1380~1410℃烧制,烧制时间3-6小时,即得。
(词语解释:捆料,就是把搅拌好的料,堆放在桶里,让水分均匀润湿料和结合剂,成型不会出现层裂现象)
实验例2:膨胀系数和耐腐蚀性检测:
1、样品:对比例、实施例2-1到2-9提供的样品;
2、检测方法:
1)匣钵的膨胀系数采用高温热膨胀测试仪RPZ-03P直接测量,将各实施例制备成330mm*330mm*110mm尺寸匣钵,每种匣钵4只,送到高镍三元正极材料811生产隧道窑中试用,根据每个匣钵的次数,平均得到。
2)匣钵的抗腐蚀性,即平均使用次数:
采用匣钵与高镍LNCM电池正极材料(811生料)化学反应来测试抗腐蚀能力,主要通过样品尺寸变化来确定抗锂离子腐蚀性能。
3、结果:见表2-1、2-2中的检测数据。
实施例2-1到2-5的膨胀系数和循环使用次数是较好的。
实施例2-6到2-9中,但是随着堇青石用量的减少,30:70复合尖晶石莫来石与40:60复合尖晶石莫来石的复配用量的增加,也即尖晶石用量的增加,循环多次使用后,匣钵会开裂,甚至没有等腐蚀完就直接碎裂,报废。
结果显示:含有堇青石-复合尖晶石莫来石的匣钵,采用特定配比的尖晶石莫来石的复合物进行组合,能够明显降低膨胀系数,增加循环使用次数。
Claims (9)
1.一种含堇青石和复合尖晶石莫来石的匣钵,其特征在于,所述原料含有以下重量份的成分:尖晶石25份、堇青石15份、复合尖晶石莫来石40份、高岭土6份、电熔98氧化镁2份、煅烧氧化铝粉12份、黄糊精1份、水3.2份;
所述复合尖晶石莫来石的原料含有以下重量份的成分:轻烧镁粉9-21份、工业氧化铝70-80份和石英粉8-20份;
所述复合尖晶石莫来石由以下方法制备:按照配比称取各原料,然后混匀,加入矿热炉中,在2200-2500℃电弧加热熔融5-15分钟,然后倾斜矿热炉倒入水槽中快速冷却,捞出干燥,粉碎,得到复合尖晶石莫来石。
2.根据权利要求1所述的匣钵,其特征在于,所述复合尖晶石莫来石的原料含有以下重量份的成分:轻烧镁粉12-21份、工业氧化铝70-80份和石英粉8.4-18份。
3.根据权利要求2所述的匣钵,其特征在于,所述复合尖晶石莫来石的原料含有以下重量份的成分:轻烧镁粉15-21份、工业氧化铝70-75份和石英粉8.4-16份。
4.根据权利要求1所述的匣钵,其特征在于,所述复合尖晶石莫来石选自尖晶石和莫来石晶相比为70:30和30:70,或晶相比为40:60和60:40,或晶相比为50:50不同粒径的复合物进行复配,上述晶相比中两种复合物的粒径选自1-2mm或0-1mm。
5.根据权利要求4所述的匣钵,其特征在于,晶相比复配时的重量比为1-2:1。
6.根据权利要求5所述的匣钵,其特征在于,晶相比复配时的重量比为1:1。
7.根据权利要求1所述的匣钵,其特征在于,所述尖晶石的粒径为0-1mm、所述堇青石的粒径为0.5-1.25mm。
8.根据权利要求1所述的匣钵,其特征在于,所述高岭土和煅烧氧化铝粉的粒径为320目;所述电熔98氧化镁的粒径为200目。
9.一种如权利要求1-8任一所述的匣钵的制备方法,其特征在于,该方法包括以下步骤:
1)按照配比称取各成分,先将粒径不大于200目的粉料混匀,得到混匀的粉料,备用;
2)把除黄糊精和水的其他粒径的颗粒料加入碾压搅拌机后,依次加入黄糊精、水混匀,再加入步骤1)混匀的粉料,混匀;
3)压力为850~1000吨,保压时间为6~9秒,得到生坯,再放入窑中1380-1410℃烧制,烧制时间为3~6小时,即得。
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