CN115140730A - 低取向度储热石墨、制备低取向度储热石墨的组合物及其制备方法 - Google Patents

低取向度储热石墨、制备低取向度储热石墨的组合物及其制备方法 Download PDF

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CN115140730A
CN115140730A CN202110355151.9A CN202110355151A CN115140730A CN 115140730 A CN115140730 A CN 115140730A CN 202110355151 A CN202110355151 A CN 202110355151A CN 115140730 A CN115140730 A CN 115140730A
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graphite
heat storage
average particle
spherical
spherical graphite
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段春婷
卫昶
梁文斌
刘均庆
郑冬芳
高光辉
盛英
文成玉
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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National Institute of Clean and Low Carbon Energy
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Priority to PCT/CN2021/133577 priority patent/WO2022205972A1/zh
Priority to EP21934608.7A priority patent/EP4317355A1/en
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Abstract

本发明涉及储热材料技术领域，公开了一种制备低取向度储热石墨、制备低取向度储热石墨的组合物及其制备方法，以所述储热石墨的总质量计，所述储热石墨包括65‑85wt％的分散相石墨和15‑35wt％的连续相石墨；其中，所述分散相石墨为球形石墨，所述球形石墨的球度为0.5‑1；所述储热石墨的垂直热导率/面向热导率的比值为0.4‑0.8，所述储热石墨的面向热导率为50‑150W/mK。本发明提供的储热石墨具有取向度低且面向热导率高的优点。

Description

低取向度储热石墨、制备低取向度储热石墨的组合物及其制 备方法
技术领域
本发明涉及储热材料技术领域，具体涉及一种低取向度储热石墨、制备低取向度储热石墨的组合物及低取向度储热石墨的制备方法。
背景技术
现有储热炭材料一般由粘接剂(例如沥青)和填料(例如天然石墨)经过模压成型后烧结而成。由于天然石墨自身是取向结构，经历压制过程之后，天然石墨大范围的取向，得到的块体材料往往具有较强的各向异性，因而热导率高。但是高度取也会导致垂直热导率与面向热导率数值相差较大，二者比值一般小于0.2。较大的各向异性不利于储放热过程的温度传递和温度均匀性。
因此，亟待提供一种取向度低且热导率高的储热炭材料。
发明内容
本发明的目的是为了克服现有技术存在的储热炭材料各向异性强的问题，提供一种低取向度储热石墨、制备储热石墨的组合物及其制备方法，该储热石墨具有取向度低且热导率高、抗压强度大的优点。
为了实现上述目的，本发明第一方面提供了一种低取向度储热石墨，以所述储热石墨的总质量计，所述储热石墨包括65-85wt％的分散相石墨和15-35wt％的连续相石墨；其中，所述分散相石墨为球形石墨，所述球形石墨的球度为0.5-1；所述储热石墨的垂直热导率/面向热导率的比值为0.4-0.8，所述储热石墨的面向热导率为50-150W/mK。
本发明第二方面提供了一种制备低取向度储热石墨的组合物，所述组合物包括60-80重量份的球形石墨和20-40重量份的沥青，其中，所述球形石墨的球度为0.5-1。
本发明第三方面提供了一种低取向度储热石墨的制备方法，所述方法包括以下步骤：
(1)将包含球形石墨和沥青的组合物热压成型，得到成型材料；
(2)将所述成型材料先进行碳化处理后进行石墨化处理，得到储热石墨。
通过上述技术方案，本发明所取得的有益技术效果如下：
1)本发明所提供的低取向度储热石墨的热导率高，抗压强度大，取向度低，垂直热导率/面向热导率的比值高于0.4，储热放热过程的温度传递稳定；
2)本发明所制备的低取向度储热石墨的制备方法，操作简单，适合工业化推广。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供了一种低取向度储热石墨，以所述储热石墨的总质量计，所述储热石墨包括65-85wt％的分散相石墨和15-35wt％的连续相石墨；其中，所述分散相石墨为球形石墨，所述球形石墨的球度为0.5-1；所述储热石墨的垂直热导率/面向热导率的比值为0.4-0.8，所述储热石墨的面向热导率为50-150W/mK。
其中，本发明的发明人经过研究发现，将球度为0.5-1的球形石墨均匀的分散在连续相石墨中，可以降低储热石墨的取向度，增大垂直热导率/面向热导率的比值(λ⊥/λ∥)，使得储热材料的储热放热过程的温度传递更加稳定。
在一个优选的实施方式中，以所述储热石墨的总质量计，所述储热石墨包括75-85wt％的分散相石墨和15-25wt％的连续相石墨。
在一个优选的实施方式中，所述储热石墨的球度为0.8-1。
在一个优选的实施方式中，所述储热石墨的垂直热导率/面向热导率的比值为0.6-0.8。
在一个优选的实施方式中，所述储热石墨的面向热导率为80-120W/mK。
在一个优选的实施方式中，所述储热石墨的密度为1.6-2.1g/cm3，优选为1.8-2.1g/cm3；抗压强度为10-50MPa，优选为20-40MPa。
本发明第二方面提供了一种制备低取向度储热石墨的组合物，所述组合物包括60-80重量份的球形石墨和20-40重量份的沥青，其中，所述球形石墨的球度为0.5-1。
在一个优选的实施方式中，所述组合物包括70-80重量份的球形石墨和20-30重量份的沥青，其中，所述球形石墨的球度为0.8-1。
在一个优选的实施方式中，所述球形石墨的平均粒径为25-2000μm。
在进一步优选的实施方式中，所述球形石墨选自平均粒径为10-25μm的球形石墨、平均粒径为25-50μm的球形石墨、平均粒径为50-100μm的球形石墨、平均粒径为100-300μm的球形石墨、平均粒径为300-600μm的球形石墨、平均粒径为600-1000μm的球形石墨中的至少2种。
在本发明中，25-50μm，50-100μm，100-300μm，300-600μm指的是包括最小值，但是不包括最大值的区间，600-1000μm指的是包括最小值，也包括最大值的区间。
在更优选的实施方式中，所述球形石墨选自平均粒径为10-25μm的球形石墨、平均粒径为25-50μm的球形石墨、平均粒径为50-100μm的球形石墨、平均粒径为100-300μm的球形石墨、平均粒径为300-600μm的球形石墨、平均粒径为600-1000μm的球形石墨中的至少3种。
在进一步更优选的实施方式中，所述球形石墨选自平均粒径为10-25μm的球形石墨、平均粒径为25-50μm的球形石墨、平均粒径为50-100μm的球形石墨、平均粒径为100-300μm的球形石墨、平均粒径为300-600μm的球形石墨、平均粒径为600-1000μm的球形石墨中的任意3种，其中，小范围粒径、中范围粒径与大范围粒径的球形石墨的质量比为1：0.1-15：0.1-30，优选为1：0.5-10：1-15，进一步优选为1：1-4：2-8。其中，小范围粒径、中范围粒径与大范围粒径依据所选取的三种球形石墨的粒径范围的数值大小做区分。优选地，所述小范围粒径的球形石墨选自平均粒径为10-25μm的球形石墨和/或平均粒径为25-50μm的球形石墨；中范围粒径的球形石墨选自平均粒径为50-100μm的球形石墨和/或平均粒径为100-300μm的球形石墨；大范围粒径的球形石墨选自平均粒径为300-600μm的球形石墨和/或平均粒径为600-1000μm的球形石墨。
在一个优选的实施方式中，所述球形石墨的含碳量≥95wt％，优选≥97wt％；石墨化度≥85％，优选≥90％。
本发明中，所述球形石墨可以商购获得，例如，球形石墨具有球度0.9、含碳量99.5％、石墨化度99％，平均粒径为25-50μm，100-300μm，600-1000μm等参数。当球度不满足使用要求时，可通过球磨、筛分的方式对材料筛选。
在一个优选的实施方式中，所述沥青为非中间相沥青或中间相沥青。其中，所述非中间相沥青中间相含量为0，软化点为130-250℃，优选为140-200℃，残炭率≥60wt％，优选≥65wt％。所述中间相沥青的中间相含量为50-100wt％，优选为75-100wt％；H/C摩尔比为0.5-0.7，优选为0.55-0.65；软化点为200-350℃，优选230-325℃；残碳率≥70wt％，优选≥75wt％。
本发明中，所述非中间相沥青和中间相沥青可以商购获得，例如，非中间相沥青具有中间相含量为0，软化点165℃，残炭率65wt％等参数；中间相沥青具有中间相含量为100wt％；H/C摩尔比为0.64；软化点为285℃；残碳率75wt％等参数。
本发明第三方面提供了一种储热石墨的制备方法，所述方法包括以下步骤：
(1)将包含球形石墨和沥青的组合物热压成型，得到成型材料；
(2)将所述成型材料先进行碳化处理后进行石墨化处理，得到储热石墨。
在一个优选的实施方式中，所述热压成型的条件包括成型温度为250-600℃，优选300-550℃；成型压力为10-100MPa，优选为20-80MPa，成型时间为1-5h，优选为1.5-2h。
在一个优选的实施方式中，所述碳化处理的条件包括：碳化温度为800-1600℃，优选为1200-1600℃；碳化时间为0.5-3h，优选为0.5-1h。
在一个优选的实施方式中，所述石墨化处理在2700-3200℃下进行0.5-2h；进一步优选地，所述石墨化处理在2800-3200℃下进行0.5-1h。
在一个优选的实施方式中，所述碳化处理和石墨化处理在惰性气体保护下进行，其中，所述惰性气体可以是氮气和/或氩气。
以下将通过实施例对本发明进行详细描述。其中，球形石墨的球度采用BT-2800动态图像粒度粒形分析系统进行测量。实施例和对比例中的垂直导热率和面向导热率按照ASTM E1461进行测试，垂直导热率指的是x、y、z三个方向中最低的热导率，面向导热率指的是x、y、z三个方向中最高的热导率；孔隙率采用压汞法进行测试，抗压强度按照GBT1431-2019进行测试，体积密度按照GB/T24528-2009进行测试，储热石墨中分散相(球形石墨)的含量通过公式计算：储热石墨中分散相(球形石墨)的含量＝原料中球形石墨的质量/(原料中球形石墨的质量+沥青的质量*沥青残炭率)。
以下实施例和对比例中，球形石墨、中间相沥青、非中间相沥青均为市售商品，商品参数满足实施例和对比例中的参数。
实施例1
(1)将70g的球形石墨(球度0.9、含碳量99.5％、石墨化度99％，其中平均粒径25-50μm的球形石墨为10g，平均粒径100-300μm的球形石墨为15g，平均粒径600-1000μm的球形石墨为45g)，和30g的中间相沥青(中间相含量为100wt％；H/C摩尔比为0.64；软化点为285℃；残碳率75wt％)的组合物混合均匀后模压成型，成型温度为550℃，成型压力为80MPa，成型时间为2h，得到成型材料；
(2)在氮气保护下，将上述成型材料先在1500℃下碳化处理1h，然后在3000℃下石墨化处理0.5h，得到储热石墨。
实施例2
与实施例1不同的是，用非中间相沥青(中间相含量为0，软化点165℃，残炭率65wt％)替换中间相沥青。
实施例3
与实施例1不同的是，球形石墨的球度为0.6。
实施例4
与实施例1相似，区别在于：成型压力为25MPa。
实施例5
与实施例1相似，区别在于：球形石墨的添加量为60g，中间相沥青(中间相含量为50wt％；H/C摩尔比为0.6；软化点为245℃；残碳率70wt％)的添加量为40g；成型温度400℃，压力50MPa；石墨化温度为2800℃。
实施例6
与实施例1相似，区别在于：75g球形石墨(球度0.9、含碳量99.5％、石墨化度99％，其中，平均粒径10-25μm的球形石墨为20g，平均粒径25-50μm的球形石墨为25g，平均粒径50-100μm的球形石墨为25g)，25g中间相沥青。
对比例1
与实施例1相似，区别在于：利用天然鳞片石墨(平均粒径500μm、含碳量99.5％、石墨化度99％)替换球形石墨。
对比例2
与实施例1相似，区别在于：利用球度0.3、含碳量99.5％、石墨化度99％，平均粒径600-1000μm的球形石墨替换实施例1中的球形石墨。
对比例3
与实施例1相似，区别在于：球形石墨的添加量90g，中间相沥青的添加量10g。
测试例1
对实施例1-6以及对比例1-3所制备的储热材料进行垂直导热率、面向导热率、抗压强度和密度的测试，测试结果如表1所示
表1
Figure BDA0003002591410000081
通过表1中实施例1-6的结果可以看出，本发明制备的储热石墨具有取向度低且热导率高、抗压强度大的优点。通过对比实施例1和对比例1和对比例2可知，当采用鳞片石墨或球形石墨的球度比较小时，得到的储热石墨虽然面向导热率大，但是取向度高，垂直热导率过低，不利于储放热过程的温度传递和温度均匀性。
通过对比实施例1和对比例3可知，当沥青用量过少时，不能实现有效粘接，得到的储热石墨的抗压强度差，热导率低。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

1.一种低取向度储热石墨，其特征在于：以所述储热石墨的总质量计，所述储热石墨包括65-85wt％的分散相石墨和15-35wt％的连续相石墨；其中，所述分散相石墨为球形石墨，所述球形石墨的球度为0.5-1；所述储热石墨的垂直热导率/面向热导率的比值为0.4-0.8，所述储热石墨的面向热导率为50-150W/mK。
2.根据权利要求1所述的储热石墨，其中，所述储热石墨的密度为1.6-2.1g/cm3，优选为1.8-2.1g/cm3；抗压强度为10-50MPa，优选为20-40MPa。
3.一种制备低取向度储热石墨的组合物，其特征在于：所述组合物包括60-80重量份的球形石墨和20-40重量份的沥青，其中，所述球形石墨的球度为0.5-1。
4.根据权利要求3所述的组合物，其中，所述球形石墨的平均粒径为10-2000μm；
优选地，所述球形石墨选自平均粒径为10-25μm的球形石墨、平均粒径为25-50μm的球形石墨、平均粒径为50-100μm的球形石墨、平均粒径为100-300μm的球形石墨、平均粒径为300-600μm的球形石墨、平均粒径为600-1000μm的球形石墨中的至少2种；
优选地，所述球形石墨的含碳量≥95wt％，优选≥97wt％；石墨化度≥85％，优选≥90％。
5.根据权利要求3或4所述的组合物，其中，所述沥青为非中间相沥青或中间相沥青；
优选地，所述非中间相沥青中间相含量为0，软化点为130-250℃，优选为140-200℃，残炭率≥60wt％，优选≥65wt％；
优选地，所述中间相沥青的中间相含量为50-100wt％，优选为75-100wt％；H/C摩尔比为0.5-0.7，优选为0.55-0.65；软化点为200-350℃，优选230-325℃；残碳率≥70wt％，优选≥75wt％。
6.一种储热石墨的制备方法，其特征在于：所述方法包括以下步骤：
(1)将包含球形石墨和沥青的组合物热压成型，得到成型材料；
(2)将所述成型材料先进行碳化处理后进行石墨化处理，得到储热石墨。
7.根据权利要求6所述的制备方法，其中，所述热压成型的条件包括成型温度为250-600℃，优选为300-550℃；成型压力为10-100MPa，优选为20-80MPa，成型时间为1-5h，优选为1.5-2h。
8.根据权利要求6或7所述的制备方法，其中，所述碳化处理的条件包括：碳化温度为800-1600℃，优选为1200-1600℃；碳化时间为0.5-3h，优选为0.5-1h。
9.根据权利要求6-8中任意一项所述的制备方法，其中，所述石墨化处理在2700-3200℃下进行0.5-2h；进一步优选地，所述石墨化处理在2800-3200℃下进行0.5-1h。
10.根据权利要求6-9中任意一项所述的制备方法，其中，所述碳化处理和石墨化处理在惰性气体保护下进行。
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