CN104821398A - 一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法 - Google Patents

一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法 Download PDF

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CN104821398A
CN104821398A CN201510042074.6A CN201510042074A CN104821398A CN 104821398 A CN104821398 A CN 104821398A CN 201510042074 A CN201510042074 A CN 201510042074A CN 104821398 A CN104821398 A CN 104821398A
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吴明铂
李朋
刘婧妍
刘阳
吴文婷
尹令红
孙启乾
李忠涛
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China University of Petroleum East China
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Abstract

一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法，属新材料制备技术的范畴，属于炭素材料与电化学交叉的技术领域。本发明的特征是以量大价廉的石油沥青为碳源，纳米氧化锌为模板，制备沥青基多孔炭，洗涤烘干后加入六水合硝酸锌和硝酸锰，低温干燥后惰性气体保护下煅烧，即得锂离子电池沥青基多孔炭/ZnMn2O4负极材料，产品放电比容量高、循环性能好，是一种应用前景非常好的锂离子二次电池负极材料。

Description

一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法
技术领域
一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法,属新材料制备技术的范畴，属于炭素材料与电化学交叉的技术领域。本发明的特征是以量大价廉的石油沥青为碳源，纳米氧化锌为模板，制备沥青基多孔炭，洗涤烘干后加入六水合硝酸锌和硝酸锰，低温干燥后惰性气体保护下煅烧，即得锂离子电池沥青基多孔炭/ZnMn2O4负极材料，该材料具有高的比电容和好的循环性，是一种应用前景看好的锂离子二次电池负极材料。
背景技术
相对于其他电池，锂离子二次电池具有很多独特优势，如工作电压高、应用温度范围广、自放电率低、无污染等，目前已广泛应用于便携式通讯设备、相机、混合动力汽车等电源，并在航天、小型医疗器械及军用通讯等方面逐步替代传统的电源。锂离子电池负极材料的电化学性能是提升锂电整体性能的关键因素之一。
锌锰矿(ZnMn2O4)具有较高的理论比容量，其在锂离子电池负极材料中的应用是当今研究的热点之一，但充放电过程中出现的积聚与坍塌限制了其广泛应用。对ZnMn2O4进行改性，以提高其电化学性能成为锂离子电池研究领域的重要研究方向之一。
发明内容
一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法，以量大价 廉的石油沥青为碳源，纳米氧化锌为模板，制备沥青基多孔炭，洗涤烘干后加入六水合硝酸锌和硝酸锰，低温干燥后惰性气体保护下煅烧，即得锂离子电池沥青基多孔炭/ZnMn2O4负极材料。其特征在于其制备的步骤和工艺条件如下：
(1)称取一定量的石油沥青溶于100mL甲苯，再加入一定量纳米氧化锌，且m(纳米氧化锌)：m(石油沥青)＝0.2～0.8，110℃下搅拌蒸干。
(2)将蒸干后的混合物在700～800℃惰性气体保护下焙烧1h，自然冷却后用2M的盐酸洗去纳米氧化锌模板，抽滤干燥。
(3)所得的沥青基多孔炭经浓硝酸80℃预处理1h后，加入一定量的六水合硝酸锌和六水合硝酸锰，使m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.3～0.7，60℃下干燥12h。
(4)将烘干产物于350～500℃惰性气体保护下焙烧1～3h。将产物研磨并用200目筛分后即得锂离子电池负极材料沥青基多孔炭/ZnMn2O4。
所制沥青基多孔炭/ZnMn2O4用作锂离子电池负极材料时，产品形貌好、结构稳定、放电容量高、循环性能好，是一种应用前景非常好的锂离子二次电池负极材料。
附图说明
图1是所得样品的X射线衍射图。
图2是所得样品与纯ZnMn2O4的循环性能曲线图。
具体实施方式
下面将结合具体实施例来详叙本发明的技术特点。
实施例1
称取2g石油沥青溶于100mL甲苯中，按照质量比m(纳米氧化锌)：m(沥青)＝2:5称取相应量的氧化锌并于110℃下搅拌蒸干。将蒸干后的混合物在800℃，氮气保护下焙烧1h，自然冷却后用2M的盐酸洗去纳米氧化锌模板，抽滤干燥。将所得的沥青基多孔炭用浓硝酸于80℃预处理1h后，按照m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.3加入六水合硝酸锌和硝酸锰，并于60℃下干燥12h。将烘干产物在400℃氮气保护下焙烧3h，产物经研磨过200目筛后即得到锂离子电池负极材料沥青基多孔炭/ZnMn2O4。
实施例2
沥青基多孔炭的制备同实施例1。将沥青基多孔炭用浓硝酸于80℃预处理1h后，按照m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.5加入六水合硝酸锌和硝酸锰。其余步骤与实例1相同，得到锂离子电池沥青基多孔炭/ZnMn2O4负极材料。
实施例3
沥青基多孔炭的制备同实施例1。将沥青基多孔炭用浓硝酸于80℃预处理1h后，按照m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.7加入六水合硝酸锌和硝酸锰。其余步骤与实例1相同，得到锂离子电池沥青基多孔炭/ZnMn2O4负极材料。
对实施例1～3中合成的沥青基多孔炭/ZnMn2O4进行XRD分析，如图1所示，锌锰矿在复合材料中的质量百分含量分别为30、50和70％时，对应的衍射峰基本一致，各个衍射峰的衍射角也大体相同，图中未发现明显杂峰。
对合成的沥青基多孔炭/ZnMn2O4负极材料做成电池，进行恒流充放电测试。由图2可得，相对于纯的ZnMn2O4，沥青基多孔炭/ZnMn2O4负极材料的比容量显著提高。当m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.3时，循环 30次后，容量保持在400mA hg-1左右；当m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.7时，虽然首次放电达到1300mA hg-1以上，但是容量很快衰减到了600mA hg-1以下；当m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.5时，沥青基多孔炭/ZnMn2O4负极材料首次放电容量达到1400mA hg-1，循环30次后仍然保持在750mA hg-1以上，并且可逆性良好，具有非常好的综合电化学性能。

Claims (2)

1.一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法，以量大价廉的石油沥青为碳源，纳米氧化锌为模板，制备沥青基多孔炭，洗涤烘干后加入六水合硝酸锌和硝酸锰，低温干燥后惰性气体保护下煅烧，即得锂离子电池沥青基多孔炭/ZnMn2O4负极材料。其特征在于其制备的步骤和工艺条件如下：
(1)称取一定量的石油沥青溶于100mL甲苯，再加入一定量纳米氧化锌，110℃下搅拌蒸干；
(2)将蒸干后的混合物在700～800℃高温、惰性气体保护下焙烧，自然冷却后用2M的盐酸洗去纳米氧化锌模板，抽滤干燥；
(3)所得的沥青基多孔炭经浓硝酸80℃预处理1h后，加入一定量的六水合硝酸锌和六水合硝酸锰，60℃下干燥12h；
(4)将烘干产物于350～500℃惰性气体保护下焙烧1～3h。将产物研磨并用200目筛分后即得锂离子电池负极材料沥青基多孔炭/ZnMn2O4。
2.根据权利要求1所述的一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法，其特征在于，m(纳米氧化锌)：m(石油沥青)＝0.2～0.8，m(ZnMn2O4)/m(沥青基多孔炭+ZnMn2O4)＝0.3～0.7。
CN201510042074.6A 2015-01-26 2015-01-26 一种锂离子电池负极材料沥青基多孔炭/ZnMn2O4的制备方法 Pending CN104821398A (zh)

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