CN103964839B - 一种正温度系数热敏电阻材料及其制备方法 - Google Patents

一种正温度系数热敏电阻材料及其制备方法 Download PDF

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CN103964839B
CN103964839B CN201310034876.3A CN201310034876A CN103964839B CN 103964839 B CN103964839 B CN 103964839B CN 201310034876 A CN201310034876 A CN 201310034876A CN 103964839 B CN103964839 B CN 103964839B
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sintering
weight part
preparation
temperature
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CN103964839A (zh
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赵严帅
周维
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BYD Co Ltd
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BYD Co Ltd
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Priority to CN201310034876.3A priority Critical patent/CN103964839B/zh
Priority to US14/762,078 priority patent/US9805847B2/en
Priority to JP2015555572A priority patent/JP6181207B2/ja
Priority to PCT/CN2014/071418 priority patent/WO2014117689A1/en
Priority to EP14746818.5A priority patent/EP2951134B1/en
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Abstract

本发明提供了一种正温度系数热敏电阻材料及其制备方法，该正温度系数热敏电阻材料为混合物混炼而得到的产物，所述混合物包括BaTiO3、B2O3、SiO2、Li2O、P2O5、Cs2O、Nd2O3、Al2O3及TiO2，制备的产品的居里温度高，耐压高，而且热敏电阻的室温电阻显著降低，升阻比高，同时制备的材料的晶粒和晶界电阻小，工艺简单易实现，烧结条件要求低，烧结条件优，易控制，也降低了成本，提高了良品率和产品一致性，制备的PTC热敏电阻的性能更完美。本发明制得的PTC热敏电阻材料，特别能稳定有效的应用于高压加热器环境。

Description

一种正温度系数热敏电阻材料及其制备方法
技术领域
本发明涉及一种正温度系数（PTC）热敏电阻材料及其制备方法。
背景技术
正温度系数（PTC）热敏电阻材料广泛应用于计算机及其外部设备、移动电话、电池组、远程通讯和网络装备、变压器、工业控制设备、汽车及其它电子产品中，起到过电流或过温保护的作用。特别是钛酸钡系正温度系数热敏电阻拥有比较大的温度系数，其产生的一系列特性而在众多行业中拥有较好的应用。
现有钛酸钡系正温度系数热敏电阻材料的居里温度为120℃，为提高热敏电阻的工作温度，可通过掺杂等对钛酸钡粉体进行半导化，现有公开的有Pb、Sr、Ca、Y、Nb、Bi、Ce、La等施主掺杂及Mn、Fe、Mg等受主掺杂，得到具有半导化的热敏电阻来改善PTC的高耐压特性和提高其居里点，但上述掺杂却导致热敏电阻的室温电阻变大，同时现有在施主或受主单掺杂进行半导化时，烧结工艺不易控，不能够均匀对钛酸钡进行半导化，导致烧结过程中钛酸钡粉体颗粒尺寸不均匀，晶粒和晶界电阻较大，从而也导致产品室温电阻较大，升阻比降低，制约了其发展和应用。
发明内容
本发明为了克服现有技术的正温度系数热敏电阻材料的晶粒和晶界电阻较大，制备的热敏电阻的室温电阻较大，升阻比低的技术问题，提供一种晶粒和晶界电阻小，制备的热敏电阻的室温电阻显著降低，升阻比高，且居里温度高、耐压高的正温度系数热敏电阻材料及其制备方法。
本发明的第一个目的是提供一种正温度系数热敏电阻材料，该正温度系数热敏电阻材料为混合物混炼而得到的产物，所述混合物包括BaTiO3、B2O3、SiO2、Li2O、P2O5、Cs2O、Nd2O3、Al2O3及TiO2。
本发明的第二个目的是提供上述正温度系数热敏电阻材料的制备方法，其步骤包括：
S1，按质量比BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3=94.85%~97.75%：0.4%~2.5%：0.5%~0.9%：0.08%~0.2%：0.2%~0.3%:0.6%~0.725%:0.325%~0.565%将钛酸钡和氧化物混合，球磨；
S2，包括将步骤S1所得粉体物质于800-900℃下进行第一烧结；
S3，将步骤S2所得粉体物质与相对于钛酸钡质量0.06-0.08%的Al2O3、相对于钛酸钡质量0.04-0.08%的TiO2及烧结助剂混合，球磨；
S4，将步骤S3所得的粉体物质与有机粘结剂混合造粒；
S5，将步骤S4所得粒子物质压片成型；
S6，包括将步骤S5所得成型物质于580-600℃下进行第一热处理，除去有机粘结剂；后于1150-1180℃下进行第二热处理，进行补充合成；再于1200-1270℃下进行第三热处理，进行第二烧结；后于1100-1175℃下进行第四热处理，进行氧化。
本发明的发明人意外发现，通过本发明的氧化物掺杂，不仅能提高制备的产品的居里温度，提高其耐压，而且热敏电阻的室温电阻显著降低，升阻比高，同时制备的材料的晶粒和晶界电阻小，工艺简单易实现，烧结条件要求低，烧结条件优，易控制，也降低了成本，提高了良品率和产品一致性。本发明的氧化物为复合掺杂，既有施主掺杂氧化物也存在受主掺杂氧化物，从而多方面改善钛酸钡的体系，本发明的施主掺杂离子和受主掺杂离子取代钛酸钡中的钛和钡离子，改善的钛酸钡体系具有很好的低室温电阻，同时PTC热敏电阻的其它性能也得到了改善，制备的PTC热敏电阻的性能更完美。本发明制得的PTC热敏电阻材料，室温时电阻甚至可以为十几欧，工作电压可以达到大于400V，击穿电压达到900V，居里点为200℃，升阻比可达6以上，特别能稳定有效的应用于高压加热器环境。同时本发明的施主和受主复合掺杂能够均匀的对钛酸钡进行半导化，且本发明的烧结工艺优，烧结过程中钛酸钡粉体颗粒尺寸均匀，晶粒和晶界电阻较小，能进一步降低产品室温电阻，提高升阻比。
附图说明
图1为本发明实施例1制备的PTC材料的SEM（扫描电镜）图。
图2为本发明实施例2制备的PTC材料的SEM图。
图3为本发明实施例3制备的PTC材料的SEM图。
图4为本发明对比例1制备的PTC材料的SEM图。
具体实施方式
本发明提供了一种正温度系数热敏电阻材料，为混合物混炼而得到的产物，其中，混合物包括BaTiO3、B2O3、SiO2、Li2O、P2O5、Cs2O、Nd2O3、Al2O3及TiO2。
优选，相对于100重量份的BaTiO3，所述B2O3的含量为1.05~2.64重量份；所述SiO2的含量为0.52~0.94重量份；所述Li2O的含量为0.084~0.21重量份；所述P2O5的含量为0.21~0.32重量份；所述Cs2O的含量为0.63~0.764重量份；所述Nd2O3的含量为0.343~0.596重量份；所述Al2O3的含量为0.06~0.08重量份；所述TiO2的含量为0.04~0.08重量份。
进一步优选，相对于100重量份的BaTiO3，所述B2O3的含量为1.08~2.60重量份；所述SiO2的含量为0.55~0.90重量份；所述Li2O的含量为0.088~0.20重量份；所述P2O5的含量为0.25~0.30重量份；所述Cs2O的含量为0.65~0.75重量份；所述Nd2O3的含量为0.35~0.55重量份；所述Al2O3的含量为0.06~0.08重量份；所述TiO2的含量为0.04~0.08重量份。
更进一步优选，相对于100重量份的BaTiO3，所述B2O3的含量为1.10~2.60重量份；所述SiO2的含量为0.55~0.0.88重量份；所述Li2O的含量为0.1~0.20重量份；所述P2O5的含量为0.28~0.30重量份；所述Cs2O的含量为0.68~0.75重量份；所述Nd2O3的含量为0.36~0.5重量份；所述Al2O3的含量为0.06~0.08重量份；所述TiO2的含量为0.04~0.08重量份，进一步优化产品的性能。
本发明同时提供了上述正温度系数热敏电阻材料的制备方法，步骤包括：
S1，按质量比BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3=94.85%~97.75%：0.4%~2.5%：0.5%~0.9%：0.08%~0.2%：0.2%~0.3%:0.6%~0.725%:0.325%~0.565%将钛酸钡和氧化物混合，球磨，其中，各物质的混合顺序及方式本发明没有限制，球磨本发明可以采用本领域技术人员公知的各种球磨技术，例如可以采用行星式球磨机。
S2，包括将步骤S1所得粉体物质于800-900℃下进行第一烧结，优选第一烧结的时间为100-120min，升温到第一烧结的温度的升温速率为4.2-5.2℃/min，
较佳情况下，第一烧结可以采用非一段式烧结，即优选步骤S2包括多段烧结，优选多段烧结包括两段烧结，包括先于500-620℃下进行第三烧结，后于800-900℃下进行第四烧结，进一步优选，第三烧结的时间为50-70min；第四烧结的时间为60-70min，升温到第三烧结的温度的升温速率为4.5~5.0℃/h，第三烧结的温度升温到第四烧结的温度的升温速率为4.2-5.2℃/min。
S3，将步骤S2所得粉体物质与相对于钛酸钡质量0.06-0.08%的Al2O3、相对于钛酸钡质量0.07-0.08%的TiO2、及烧结助剂混合，球磨；优选，烧结助剂为酸性SiO2溶胶，其中，酸性SiO2溶胶可以采用市售，也可以采用如下方式配制：将乙醇、水和正硅酸乙脂按40：4：1混合，于水浴60℃中磁力搅拌5h，同时在搅拌过程中滴加1.1mol的盐酸，搅拌完成后，静置陈放24h，得到酸性SiO2溶胶。一般烧结助剂的用量为步骤S2所得粉体物质的质量的0.02%-0.04%。
S4，将步骤S3所得的粉体物质与有机粘结剂混合造粒，优选，有机粘结剂为聚乙烯醇溶液，较佳情况下，聚乙烯醇溶液的质量百分含量为5-6wt%，具体可以为5wt%。优选，聚乙烯醇溶液的质量为步骤S3所得的粉体物质的质量的0.1%-0.15%，具体可以为0.1wt%。优选，造粒的方法为喷雾造粒，进一步优化材料的性能。较佳情况下，造粒后所得粒子粒径为200μm-1000μm。
S5，将步骤S4所得粒子物质压片成型；压片成型的压力为20-30MPa，进一步提高颗粒的致密性。
S6，包括将步骤S5所得成型物质于580-600℃下进行第一热处理，除去有机粘结剂；后于1150-1180℃下进行第二热处理，进行补充合成；再于1200-1270℃下进行第三热处理，进行第二烧结；后于1100-1175℃下进行第四热处理，进行氧化。优选，第一热处理的时间为60-120min；第二热处理的时间为20-40min；第三热处理的时间为50-70min；第四热处理的时间为50-70min。优选，升温到所述第一热处理的温度的升温速率为4.0-5.2℃/min；升温到所述第三热处理的温度的升温速率为3.0-10℃/min；降温到所述第四热处理的温度的降温速率为1.1-3.5℃/min。优选，步骤S6还包括于600-610℃下进行第五热处理90-110min，还可再降温到200℃，后自然冷却到室温。
本发明进一步优选本发明的制备方法步骤还包括退火，优选，退火的条件为从室温以250-300℃/h的升温速率升温至1125-1250℃，保温1-1.5h；后以300-350℃/h的速率降至室温，进一步优化材料的性能。
其中，钛酸钡可以采用市售，也可以优选采用本发明的方法制备得到，优选BaTiO3可以通过共沉淀法制得，其中，共沉淀法包括步骤：A、将钡盐、钛酸酯与草酸溶液在pH=2.5~3.5的条件下混合，制得草酸钛钡前驱体；B、将草酸钛钡前驱体于720-820℃下煅烧0.8-1.2h制得钛酸钡粉体。较佳情况下，其制备的具体步骤可以为：（a）将分析纯氯化钡、草酸分别用去离子水配成0.5mol/L和1.0mol/L溶液，混匀后静置。（b）取1000ml的草酸溶液置于60℃电子恒温水浴槽中，然后将氯化钡溶液和分析纯钛酸丁酯以50ml/min加入草酸溶液中，并开启磁力搅拌器进行搅拌，其中原料配比为氯化钡：钛酸丁酯：草酸=1：1：2，同时用氨水调节溶液PH值控制在2.5~3.5之间。（c）控制共沉淀反应时间为1h左右，反应结束后，关闭磁力搅拌器恒温水浴，将沉淀物静置老化后得草酸钛钡前驱体。然后进行洗涤过滤，以除去沉淀物中的氯离子和其它杂质，一般控制洗涤次数为4~6次，将洗涤后的前驱体放入100℃烘箱中进行干燥。（d)最后将干燥的草酸钛钡前驱体在800℃煅烧1h可制得超细钛酸钡粉体。
较佳情况下，热敏电阻材料的具体的制备步骤可以为：
（1）称量和混料：将钛酸钡粉料和氧化物按BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3=94.85%~97.75%：0.4%~2.5%：0.5%~0.9%：0.08%~0.2%：0.2%~0.3%:0.6%~0.725%:0.325%~0.565%重量百分比进行称量，混合，球磨，其中，球磨可以将料:玛瑙球:水质量比按1:2:1进行球磨，优选球磨时间为10小时，优选玛瑙球的直径为2mm，混料球磨后可通过过筛等得粉体物体，可采用80目筛，一般可将粉体物质干燥后再进行后续步骤，可于烘箱中80℃烘干。
（2）将粉体物质进行预烧结：优选，将粉体物质放入烧结炉中，先以5℃/min的升温速率升温到620℃保温60min，再以4.5~5.2℃/min的升温速率升温到850℃保温60min。
（3）二次球磨：称取相对于钛酸钡质量0.06%-0.08%的Al2O3、相对于钛酸钡质量0.07%-0.08%的TiO2及相对于步骤S2所得粉体物质的质量的0.02%-0.04%的烧结助剂SiO2溶胶与步骤（2）所得的预烧结后粉体物质混合，球磨，球磨可以将料:玛瑙球:水质量比按1:2:2进行球磨，优选球磨时间为24h，优选玛瑙球的直径为2mm，一般可将二次球磨之后的粉体物质烘干，过筛，优选，过100目筛。
（4）造粒：在上述所得粉体物质中加入聚乙烯醇溶液（PVA）进行造粒，优选，PVA溶液的质量分数为5wt%，优选，加入的PVA的量为粉体物质质量的0.1wt%。较佳情况下，造粒的粒子粒径在200-1000um之间。
（5）压片：在预先做好的模子里，填入粉体物质，压片成型，压力为25MPa。（6）烧结：将（5）所得的成型压片放入高温烧结炉中进行烧结，升温速率为4.1℃/min，600℃保温60min，除去有机粘合剂，1175℃保温40min，进行补充合成，快速升到烧结温度1250℃，保温60min，以3.3℃/min速率进行降温，降温到1100℃，保温50min，充分氧化，再降温到600℃，保温50min，再次降温到200℃，自然冷却到室温。
（7）退火：将烧结好后的瓷片进行退火处理，退火的条件为从室温以4.2-5℃/min的升温速率升温至1125℃，保温60min。
下面将结合具体的实施例来进一步详述本发明所提供的正温度系数热敏电阻材料及其制备方法。
实施例1
1、BaTiO3粉体的制备：
（a)将分析纯氯化钡、草酸分别用去离子水配成0.5mol/L和1.0mol/L溶液，混匀后静置。
（b)取1000ml的草酸溶液置于60℃电子恒温水浴槽中，然后将氯化钡溶液和分析纯钛酸丁酯以50ml/min加入草酸溶液中，并开启磁力搅拌器进行搅拌，其中原料配比为氯化钡：钛酸丁酯：草酸=1：1：2，同时用氨水调节溶液PH值始终控制在2.5~3.5之间。
（C）控制共沉淀反应时间为1h左右，反应结束后，关闭磁力搅拌器恒温水浴，将沉淀物静置老化后得草酸钛钡前驱体。然后进行洗涤过滤，以除去沉淀物中的氯离子和其它杂质，洗涤次数为5次。将洗涤后的前驱体放入100℃烘箱中进行干燥。
（d)最后将干燥的草酸钛钡前驱体在800℃煅烧60min得超细钛酸钡粉体。
2、PTC材料的制备
（a)称量和混料：将上述制备好的钛酸钡粉料和分析纯的氧化物按BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3按96.65%：1.3%：0.7%：0.1%：0.25%:0.625%:0.375%的质量百分比进行称量，并按照料:玛瑙球:水质量比为1:2:1进行球磨，球磨时间10小时，其中玛瑙球的直径为2mm。
（b）过筛并干燥：将球磨后的混料过80目筛，并于烘箱中80℃烘干。
（c）预烧结：将过筛后的粉体预烧结，预烧温度为620℃下保温2h，850℃下保温2h，其中，升温速率为5℃/min。
（d)配制SiO2溶胶：分别称取乙醇、水、正硅酸乙脂按40：4：1混合，水浴60℃，磁力搅拌5h，在搅拌过程中滴加1.1mol的盐酸，搅拌完成后，静置陈放24h，得到酸性SiO2溶胶。
（e）二次球磨：称取0.061g的Al2O3、0.074gTiO2及上述制备的0.056gSiO2溶胶加入到上述预烧结后的粉料中，并按照料:玛瑙球:水质量比为1:2:2进行球磨，球磨时间24h，其中玛瑙球的直径为2mm。
（f）过筛并干燥：将二次球磨之后的粉体烘干，过100目筛。
（g）造粒：在粉体中加入PVA进行喷雾造粒，使用质量分数为5wt%的PVA溶液，加入粉体中，加入PVA的量为粉体质量的0.1wt%，造粒的粒子粒径为200~300um。
（h）压片：在预先做好的模子里，填入上述造粒后的粉体，压片成型，压力为20MPa。
（i）烧结：将上述得到的成型压片放入高温烧结炉中进行烧结，升温速率为4.1℃/min，600℃保温120min，除去有机粘合剂，1175℃保温40min，进行补充合成，10℃/min升到烧结温度1250℃，保温20min，以3.3℃/min速率进行降温，降温到1100℃，保温50min，充分氧化，再次降温到200℃，自然冷却到室温。
（j）退火：将烧结好后的瓷片进行退火处理，退火的条件为从室温以4.7℃/min的升温速率升温至1125℃，保温60min。制得PTC材料样品S1。
采用FESEM/EDS—场发射扫描电镜及附件能谱仪对制得的PTC材料样品S1进行扫描电镜分析，电镜图如图1。
实施例2
采用与实施例1相同的方法制备PTC材料样品S2，不同的是步骤2中的（i）烧结：将上述得到的成型压片放入高温烧结炉中进行烧结，升温速率为5℃/min，600℃保温100min，除去有机粘合剂，1150℃保温40min，进行补充合成，8℃/min升到烧结温度1225℃，保温70min，以2.3℃/h速率进行降温，降温到1100℃，保温50min，充分氧化，再次降温到200℃，自然冷却到室温。
采用FESEM/EDS—场发射扫描电镜及附件能谱仪对制得的PTC材料样品S2进行扫描电镜分析，电镜图如图2。
实施例3
采用与实施例1相同的方法制备PTC材料样品S3，不同的是步骤2中的（a）称量和混料：将上述制备好的钛酸钡粉料和分析纯的氧化物按BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3按94.85%：2.5%：0.87%：0.20%：0.30%:0.725%:0.555%的质量百分比进行称量，并按照料:玛瑙球:水质量比为1:2:1进行球磨，球磨时间10小时，其中玛瑙球的直径为2mm。
采用FESEM/EDS—场发射扫描电镜及附件能谱仪对制得的PTC材料样品S3进行扫描电镜分析，电镜图如图3。
实施例4
采用与实施例1相同的方法制备PTC材料样品S4，不同的是步骤2中的（a）称量和混料：将上述制备好的钛酸钡粉料和分析纯的氧化物按BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3按94.92%：2.44%：0.9%：0.20%：0.28%:0.705%:0.558%的质量百分比进行称量，并按照料:玛瑙球:水质量比为1:2:1进行球磨，球磨时间10小时，其中玛瑙球的直径为2mm。
实施例5
采用与实施例1相同的方法制备PTC材料样品S5，不同的是步骤2中的（a）称量和混料：将上述制备好的钛酸钡粉料和分析纯的氧化物按BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3按96.65%：1.6%：0.5%：0.08%：0.20%:0.605%:0.365%的质量百分比进行称量，并按照料:玛瑙球:水质量比为1:2:1进行球磨，球磨时间10小时，其中玛瑙球的直径为2mm。
实施例6
采用与实施例1相同的方法制备PTC材料样品S6，不同的是步骤2中的（a）称量和混料：将上述制备好的钛酸钡粉料和分析纯的氧化物按BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3按96.65%：1.0%：0.8%：0.2%：0.30%:0.675%:0.375%的质量百分比进行称量，并按照料:玛瑙球:水质量比为1:2:1进行球磨，球磨时间10小时，其中玛瑙球的直径为2mm。
实施例7
采用与实施例1相同的方法制备PTC材料样品S7，不同的是步骤2中的（c）预烧结：将过筛后的粉体预烧结，预烧温度为850℃下保温2h，升温速率为5℃/min。
实施例8
采用与实施例1相同的方法制备PTC材料样品S8，不同的是步骤2中的（g）造粒：在粉体中加入PVA进行手工造粒，使用质量分数为5wt%的PVA溶液，加入粉体中，加入PVA的量为粉体质量的0.2wt%，造粒的粒子粒径为400~600um。
实施例9
采用与实施例1相同的方法制备PTC材料样品S9，不同的是步骤2中的（h）压片：在预先做好的模子里，填入上述造粒后的粉体，压片成型，压力为30MPa。
对比例1
PTC材料的制备
（a)称量和混料：将BaCO3、TiO2、SiO2、Pb3O4、Mn(NO3)2、Al2O3、Nb2O5按质量百分比45.72%、27.70%、0.49%、25.49%、0.024%、0.07%、0.5%进行称量，并按照料:玛瑙球:水质量比为1:2:2进行球磨，球磨时间7小时，其中玛瑙球的直径为2mm。
（b）过筛并干燥：将球磨后的混料过100目筛，并于烘箱中80℃烘干。
（c）预烧结：将过筛后的粉体预烧结，预烧温度为600℃下保温140min，再于965℃下保温60min，其中，升温速率为4.5℃/min。
（d)配制SiO2溶胶：分别称取乙醇、水、正硅酸乙脂按40：4：1混合，水浴60℃，磁力搅拌5h，在搅拌过程中滴加1.1mol的盐酸，搅拌完成后，静置陈放24h，得到酸性SiO2溶胶。
（e）二次球磨：称取0.028g的Mn及上述制备的0.042gSiO2溶胶加入到上述预烧结后的粉料中，并按照料:玛瑙球:水质量比为1:2:1进行球磨，球磨时间7h，其中玛瑙球的直径为2mm。
（f）过筛并干燥：将二次球磨之后的粉体烘干，过100目筛。
（g）造粒：在粉体中加入PVA进行喷雾造粒，使用质量分数为5wt%的PVA溶液，加入粉体中，加入PVA的量为粉体质量的0.2wt%，造粒的粒子粒径为800-900um。
（h）压片：在预先做好的模子里，填入上述造粒后的粉体，压片成型，压力为25MPa。
（i）烧结：将上述得到的成型压片放入高温烧结炉中进行烧结，升温速率为5℃/min，600℃保温120min，900℃保温70min，1180℃保温30min，1260℃保温60min，1175℃保温60min，再降温到600℃保温100min，后自然冷却到室温。
（j）退火：将烧结好后的瓷片进行退火处理，退火条件为从0℃110min升温到550℃保温30min，130min升温到1200℃保温80min，130min升温到550℃保温50min，制得PTC材料样品DS1。
采用FESEM/EDS—场发射扫描电镜及附件能谱仪对制得的PTC材料样品DS1进行扫描电镜分析，电镜图如图4。
性能测试
1、阻抗分析：使用温科精密阻抗分析仪,型号6510B，测试频率为20Hz~10MHz,的阻抗分析仪对实施例1-9及对比例1制备的样品S1-S9及DS1进行阻抗测试，测试结果如表1。
2、室温电阻：室温下，使用万用表测试实施例1-9及对比例1制备的样品S1-S9及DS1的电阻，测试结果如表1。
3、居里温度：用万用表测量电阻，电阻达到最大时对应的温度，测试结果如表1。
4、升阻比：lg(居里点电阻/室温电阻)，测试结果如表1。
5、耐压：采用BYD-GN-02的耐压测试仪，测试实施例1-9及对比例1制备的样品S1-S9及DS1的击穿电压，测试结果如表1。
表1
样品 晶粒电阻（Ω） 晶界电阻（KΩ） 室温电阻（Ω） 居里温度(℃) 升阻比 耐压(ν)
S1 3.11 2 5.4 204 6.6 1050
S2 10.1 28 18 200 6.2 1018
S3 50 101 17 201 6.0 960
S4 20 23.2 27 198 5.8 987
S5 19 24 21 212 6.3 1012
S6 3.45 4.65 5.7 192 6.2 1008
S7 14.3 12 11 202 5.7 923
S8 11.2 19.7 23 191 5.4 956
S9 10.2 27.8 18 187 5.9 943
DS1 125 2000 91 192 5.3 812
本发明制备的产品的居里温度高，耐压高，而且热敏电阻的室温电阻显著降低，升阻比高，同时制备的材料的晶粒和晶界电阻小，工艺简单易实现，烧结条件要求低，烧结条件优，易控制，也降低了成本，提高了良品率和产品一致性，制备的PTC热敏电阻的性能更完美。本发明制得的PTC热敏电阻材料，室温时电阻为十几欧，工作电压可以达到大于400V，击穿电压达到900V，居里点为200℃，升阻比可达6以上，特别能稳定有效的应用于高压加热器环境。

Claims (12)

1.一种正温度系数热敏电阻材料，其特征在于，所述正温度系数热敏电阻材料为混合物混炼而得到的产物，所述混合物包括BaTiO3、B2O3、SiO2、Li2O、P2O5、Cs2O、Nd2O3、Al2O3及TiO2；相对于100重量份的BaTiO3，所述B2O3的含量为1.05~2.64重量份；所述SiO2的含量为0.52~0.94重量份；所述Li2O的含量为0.084~0.21重量份；所述P2O5的含量为0.21~0.32重量份；所述Cs2O的含量为0.63~0.764重量份；所述Nd2O3的含量为0.343~0.596重量份；所述Al2O3的含量为0.06~0.08重量份；所述TiO2的含量为0.04~0.08重量份。
2.根据权利要求1所述的正温度系数热敏电阻材料，其特征在于，相对于100重量份的BaTiO3，所述B2O3的含量为1.08~2.60重量份；所述SiO2的含量为0.55~0.90重量份；所述Li2O的含量为0.088~0.20重量份；所述P2O5的含量为0.25~0.30重量份；所述Cs2O的含量为0.65~0.75重量份；所述Nd2O3的含量为0.35~0.55重量份；所述Al2O3的含量为0.06~0.08重量份；所述TiO2的含量为0.04~0.08重量份。
3.一种根据权利要求1所述的正温度系数热敏电阻材料的制备方法，其特征在于，步骤包括：
S1，按质量比BaTiO3:B2O3:SiO2:Li2O:P2O5:Cs2O:Nd2O3=100：1.05~2.64：0.52~0.94：0.084~0.21：0.21~0.32：0.63~0.764：0.343~0.596将钛酸钡和氧化物混合，球磨；
S2，包括将步骤S1所得粉体物质进行第一烧结，所述第一烧结采用非一段式烧结，包括于500-620℃下进行第三烧结，后于800-900℃下进行第四烧结；
S3，将步骤S2所得粉体物质与相对于钛酸钡质量0.06%-0.08%的Al2O3、相对于钛酸钡质量0.04%-0.08%的TiO2及烧结助剂混合，球磨；
S4，将步骤S3所得的粉体物质与有机粘结剂混合造粒；
S5，将步骤S4所得粒子物质压片成型；
S6，包括将步骤S5所得成型物质于580-600℃下进行第一热处理，除去有机粘结剂；后于1150-1180℃下进行第二热处理，进行补充合成；再于1200-1270℃下进行第三热处理，进行第二烧结；后于1100-1175℃下进行第四热处理，进行氧化。
4.根据权利要求3所述的制备方法，其特征在于，所述第一热处理的时间为60-120min；第二热处理的时间为20-40min；第三热处理的时间为50-70min；第四热处理的时间为50-70min。
5.根据权利要求3所述的制备方法，其特征在于，升温到所述第一热处理的温度的升温速率为4.0-5.2℃/min；升温到所述第三热处理的温度的升温速率为3.0-10℃/min；降温到所述第四热处理的温度的降温速率为1.1-3.5℃/min。
6.根据权利要求3所述的制备方法，其特征在于，所述步骤S6还包括于600-610℃下进行第五热处理90-110min。
7.根据权利要求3所述的制备方法，其特征在于，所述第三烧结的时间为50-70min；所述第四烧结的时间为60-70min，升温到所述第四烧结的温度的升温速率为4.2-5.2℃/min。
8.根据权利要求3所述的制备方法，其特征在于，所述烧结助剂为酸性SiO2溶胶，所述有机粘结剂为聚乙烯醇溶液，所述聚乙烯醇溶液的质量百分含量为5-6wt%，所述聚乙烯醇溶液的质量为步骤S3所得的粉体物质的质量的0.1-0.2wt%。
9.根据权利要求3所述的制备方法，其特征在于，所述造粒的方法为喷雾造粒，所述造粒后所得粒子粒径为200μm-1000μm。
10.根据权利要求3所述的制备方法，其特征在于，所述压片成型的压力为20-30MPa。
11.根据权利要求3所述的制备方法，其特征在于，所述步骤还包括退火，所述退火的条件为以250-300℃/h的升温速率升温至1125-1250℃，保温1-1.5h；后以300-350℃/h的速率冷却。
12.根据权利要求3所述的制备方法，其特征在于，所述BaTiO3通过共沉淀法制得，所述共沉淀法包括步骤：A、将钡盐、钛酸酯与草酸溶液在pH=2.5~3.5的条件下混合，制得草酸钛钡前驱体；
B、将草酸钛钡前驱体于720-820℃下煅烧0.8-1.2h制得钛酸钡粉体。
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