CN113636843A - 一种超轻陶瓷泡沫复合储热材料及制备方法 - Google Patents
一种超轻陶瓷泡沫复合储热材料及制备方法 Download PDFInfo
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Abstract
本发明公开了一种超轻陶瓷泡沫复合储热材料及制备方法,由碳化硅泡沫陶瓷与掺杂纳米颗粒的相变材料组成;相变材料负载于碳化硅泡沫陶瓷的孔隙中。碳化硅泡沫陶瓷是在金属镍泡沫模板上进行化学气相沉积生长石墨,并利用高温硅蒸汽法对提取的石墨中间体进行化学反应制备而成,相变材料是将纳米颗粒均匀分散在无机盐或多元共晶盐溶液中进行超声处理并烘干后制备得到的。采用溶液辅助浸渍法和真空浸渍法将相变材料紧密地填充于陶瓷泡沫的孔隙中,即得超轻陶瓷泡沫复合储热材料。本发明实现了复合材料导热系数与储热密度的同时提升,可以采用不同形态的镍模板得到相应形态的碳化硅泡沫,制备方法简单,成本低,可调控性范围广,实用性高。
Description
技术领域
本发明属于复合储热材料,尤其涉及一种超轻泡沫陶瓷、纳米颗粒与相变材料复合的储热材料及制备方法。
背景技术
相变材料在熔点附近温度不会发生显著的变化,但能吸收大量的热,并且在凝固时能释放出同等的热量,因而受到了广泛关注。传统相变材料虽然能够存储大量热,但是导热系数非常低(通常在0.1~1W/mK之间),导致储热系统在工质与储热材料的热交换过程中热传输效率低,能量损失严重,不能直接规模化、产业化。通过将一定体积分数的(通常在20%~50%之间)高导热材料多孔骨架嵌入到相变材料中制备成复合材料可以增强其导热系数。现有的高导热骨架以金属、陶瓷等为主要材料,这些材料导热系数高,但在工作温度范围内不发生相变,使得复合材料的潜热大幅低于纯相变材料,另外骨架材料的比热容相比也更小,导致复合材料的显热也大大降低,这两个的缺陷使骨架复合材料的储热密度严重受限。
发明内容
发明目的:本发明的第一目的是提供一种储热密度与导热率同时提高的超轻陶瓷泡沫复合储热材料;本发明的第二目的在于提供一种超轻泡沫陶瓷-纳米颗粒-相变材料复合的储热材料制备方法。
技术方案:本发明的一种超轻陶瓷泡沫复合储热材料,由碳化硅泡沫陶瓷与掺杂纳米颗粒的相变材料组成;所述相变材料负载于碳化硅泡沫陶瓷的孔隙中,所述碳化硅泡沫陶瓷的孔隙率为92~99%,所述相变材料的负载率为90~99%,所述纳米颗粒为相变材料总质量的0.5~1.5%。
进一步的,所述相变材料为硝酸锂和氯化钠组成的共晶盐,其中,氯化钠的摩尔分数为5.9~17.2 mol%,硝酸锂和氯化钠的摩尔分数之和为100%。
进一步的,所述纳米颗粒为Al2O3、AlN、CuO、MgO、SiC和SiO2中的任一种,纳米颗粒直径在1~100nm之间。
本发明还保护一种超轻陶瓷泡沫复合储热材料的制备方法,包括以下步骤:
(1)制备碳化硅泡沫陶瓷;
(2)制备相变材料:取硝酸锂、氯化钠和纳米颗粒溶解与水中进行超声分散,随后将均匀分散的溶液加热至水分蒸发,烘干后得到相变材料;
(3)采用溶液浸渍和真空浸渍联合的方式将相变材料填充在碳化硅泡沫陶瓷的孔隙中,得到复合储热材料。
进一步的,步骤(1)中的碳化硅泡沫陶瓷包括以下制备步骤:
(11)取金属镍泡沫板置于含H2的混合气体中进行还原去除表面氧化层;
(12)将还原后的金属镍泡沫板置于含CH4的混合气体中进行化学气相沉积,在金属镍泡沫板表面并生成石墨;
(13)将步骤(12)得到的产物置于蚀刻剂中进行刻蚀,去除金属镍,得到石墨泡沫;
(14)将硅粉置于石墨泡沫底部,石墨泡沫与硅粉不接触,进行硅蒸发得到碳化硅泡沫陶瓷。
进一步的,所述步骤(14)中,硅粉与石墨泡沫的质量比为2.4~3:1,蒸发温度为1600~1800℃,蒸发时间为5~6h。
进一步的,所述步骤(13)中,刻蚀剂为盐酸、氯化铁溶液、硝酸铁溶液或过硫酸铵溶液中的任一种,刻蚀剂的浓度为0.5~3mol/L,刻蚀温度为50~80℃。
进一步的,所述步骤(11)中,金属镍泡沫板的孔隙率为30~135ppi,厚度为1~5mm。
进一步的,步骤(3)中,溶液浸渍具体是指:将相变材料配置成饱和溶液,对碳化硅泡沫陶瓷进行滴浸5~10次,然后蒸干水分。
进一步的,步骤(3)中,真空浸渍具体是指:将溶液浸渍之后的碳化硅泡沫陶瓷与相变材料混合,然后在相变材料熔点以上50℃的温度进行真空加热并保温2~3h。
进一步的,氢气还原、化学气相沉积以及硅蒸汽法升降温速率均≤10℃/min。
参见图1的碳化硅泡沫陶瓷制备流程,在金属镍泡沫模板上先进行氢气还原去除表面的氧化层,混合气氛采用氩气与氢气或氮气与氢气,优选的温度为1000~1050℃,并保温30 min~60 min;随后进行化学气相沉积,混合气氛为氩气、氢气和甲烷或者氮气、氢气和甲烷,使CH4在高温下裂解,C元素可以在金属镍泡沫模板上沉积生成石墨,石墨沉积的时间由镍泡沫的质量以及需要的产物壁厚决定,当反应进行足够时间后,将温度降至室温,石墨将覆盖整个镍泡沫表面,厚度将不断增加;随后利用刻蚀剂去除金属镍,去除金属镍的时间由金属镍自身决定,金属镍去除后得到石墨泡沫,随后采用硅蒸汽法形成碳化硅结构,蒸发过程中石墨泡沫不与硅粉接触,非接触时,蒸汽形态的硅与石墨反应,反应后的表面不存在单质硅,减少了单质硅的去除步骤。
本发明的制备原理为,优化了制备碳化硅泡沫的方法,得到的泡沫孔隙率高,可以大大减小骨架对材料潜热的削减,另外在相变材料中掺杂的纳米颗粒使相变材料显热得到显著提升,在复合过程中采用溶液浸渍和真空浸渍相结合的方法,使得相变材料能紧密填充满泡沫的孔隙,使得孔隙率在90~99%,得到的复合材料的储热密度和导热率同时提升,可以直接以太阳光作为热源,吸光后碳化硅泡沫迅速传热,相变材料蓄热。
本发明的超轻碳化硅陶瓷泡沫为复合材料提供了良好的导热通道,使复合材料导热率相比于相变材料明显提升,而低体积占比,高孔隙率使复合材料的相变焓削弱程度大大降低。纳米颗粒与无机盐之间的微尺度效应增强了相变材料的比热容,从而提升了材料的显热储热性能。通过陶瓷泡沫和纳米颗粒对复合材料热物性的促进作用,实现了复合材料导热系数与储热密度的同时提升。
有益效果:与现有技术相比,本发明的显著优点为:(1)本发明采用碳化硅作为导热材料,能稳定、耐高温、耐腐蚀,改善了熔融盐对金属基材的腐蚀问题;(2)本发明采用超轻泡沫结构,提升复合材料总体热导率的同时,降低了导热材料对复合材料储热密度的削减;(3)本发明在无机盐中掺杂纳米颗粒,大大提高了相变材料的定压比热容,同时提高了材料总体储热密度;(4)本发明所述制备方法可以采用不同形态的镍模板得到相应形态的碳化硅泡沫,制备方法简单,成本低,可调控性范围广,实用性高。
附图说明
图1为碳化硅泡沫陶瓷的合成过程;
图2为实施例4中不同反应时间的碳化硅泡沫及石墨中间体的XRD图像;
图3为实施例1中不同样品的SEM图像;f:纳米颗粒在相变材料中的分布,及其尺寸;
图4为实施例1中纳米颗粒在相变材料中的分布;
图5为实施例5中样品的SEM图像;
图6为不同样品比热容随温度的变化;
图7为不同样品导热系数随温度的变化;
图8为实施例6中不同比例共晶盐的潜热对比。
具体实施方式
下面结合附图和实施例对本发明的技术方案作进一步详细说明。
实施例1
第一步、将孔隙率为95ppi的金属镍泡沫修剪成15 × 15 × 5 mm3大小的块体,将其置于管式炉中,在Ar/H2氛围下,以10℃/min的升温速率,将温度升至1050℃,并进行氢气还原30min。随后关闭Ar/H2混合气,并打开Ar/H2/CH4混合气,在1050℃下进行化学气相沉积180min,在以10℃/min的降温速率,将温度降至室温,得到包覆石墨的镍泡沫,孔隙率为97%。
第二步、将包覆石墨的镍泡沫置于1mol/L的盐酸中,在50℃下,蚀刻48h,随后将蚀刻完成的石墨泡沫置于去离子水中,反复清洗。接着放入干燥箱中,以80℃干燥30min,得到石墨泡沫。
第三步、将石墨泡沫置于刚玉支架上,并放入盛有硅粉的带盖坩埚中,硅粉与石墨泡沫的质量比为2.4:1,在管式炉中在Ar氛围下,以小于10℃/min的升温速率,将温度升至1600℃,并保温5h,随后以小于10℃/min的降温速率将温度降至室温,即得到碳化硅陶瓷泡沫。
第四步、称取物质的量之比为92.5:7.5的硝酸锂和氯化钠共30g,与0.3g 平均粒径为50nm 的SiO2纳米颗粒混合,并加入100mL去离子水充分溶解。将溶液放入超声振荡器中超声处理2h,随后将溶液置与140℃的油浴锅中蒸干水分。蒸干后,将得到的掺杂纳米颗粒的共晶盐放入干燥箱中,以90℃干燥12h,得到干燥的相变材料。
第五步、取适量干燥的相变材料再次溶解于去离子水中,将碳化硅泡沫放置于180℃的加热台上,使用滴管对泡沫进行滴浸,反复10次后,将其中的水分蒸干。随后将溶液辅助浸渍的泡沫放入瓶中,并加入过量的相变材料,置于管式炉中真空加热到300℃,保温180min,去除多余相变材料后,即得到超轻泡沫陶瓷-纳米颗粒-相变材料复合储热材料。
参见图3,a为金属镍泡沫模板,b为第三步制备的碳化硅泡沫,c为碳化硅泡沫的局部示意图,由图可以看到泡沫状的Ni形貌,蚀刻后的SiC泡沫依然保持了良好的形貌特点,说明了该方法制备SiC泡沫具有良好的保形性,因此可以通过不同的镍泡沫模板制备处具有不同形貌特点的SiC泡沫。
参见图4,可以看到添加了1wt% 50nm SiO2颗粒的LiNO3-NaCl共晶盐表面的形貌,纳米颗粒在相变材料中是均匀分布的,不存在明显的团聚现象,充分分散的纳米颗粒可以有效提高相变材料的比热容。
对制备的复合储热材料进行导热性能测试,参见图6和图7,当碳化硅泡沫孔隙率为97%时,复合材料热导率可达2.78W/(m•K),相变焓高达331.9 kJ/kg,在50℃~300℃的温差下储能密度可达672.4 kJ/kg。本实施例采用碳化硅作为导热材料,性能稳定、耐高温、耐腐蚀,解决了熔融盐对金属基材的腐蚀问题。并采用超轻泡沫结构,提升复合材料总体热导率的同时,削减了常规导热材料对复合材料储热密度的影响。其中,复合后的材料潜热可以达到纯相变材料的97%,而且平均比热容提升了4.86%,在150℃的温差下,储热密度已经超过纯相变材料。同时,泡沫的嵌入使复合材料的热导率提升了159%。因此该复合材料储热密度和导热率得到了同时提升。
实施例2
第一步、将孔隙率为30ppi的金属镍泡沫修剪成15 × 15 × 5 mm3大小的块体,将其置于管式炉中,在N2/H2氛围下,以10℃/min的升温速率,将温度升至1050℃,并进行氢气还原30min。随后关闭N2/H2混合气,并打开N2/H2/CH4混合气,在1050℃下进行化学气相沉积180min,在以10℃/min的降温速率,将温度降至室温,得到包覆石墨的镍泡沫,孔隙率为90%。
第二步、将包覆石墨的镍泡沫置于3mol/L的过硫酸铵溶液中,在80℃下,蚀刻48h,随后将蚀刻完成的石墨泡沫置于去离子水中,反复清洗。接着放入干燥箱中,以80℃干燥30min,得到石墨泡沫。
第三步、将石墨泡沫置于刚玉支架上,并放入盛有硅粉的带盖坩埚中,硅粉与石墨泡沫的质量比为3:1,在管式炉中在Ar氛围下,以小于10℃/min的升温速率,将温度升至1800℃,并保温6h,随后以小于10℃/min的降温速率将温度降至室温,即得到碳化硅陶瓷泡沫。
第四步、称取物质的量之比为92.5:7.5的硝酸锂和氯化钠共30g,与0.3g 平均粒径为50nm 的Al2O3纳米颗粒混合,并加入100mL去离子水充分溶解。将溶液放入超声振荡器中超声处理2h,随后将溶液置与140℃的油浴锅中蒸干水分。蒸干后,将得到的掺杂纳米颗粒的共晶盐放入干燥箱中,以90℃干燥12h,得到干燥的相变材料。
第五步、取适量干燥的相变材料再次溶解于去离子水中,将碳化硅泡沫放置于180℃的加热台上,使用滴管对泡沫进行滴浸,反复10次后,将其中的水分蒸干。随后将溶液辅助浸渍的泡沫放入瓶中,并加入过量的相变材料,置于管式炉中真空加热到300℃,保温180min,去除多余相变材料后,即得到超轻泡沫陶瓷-纳米颗粒-相变材料复合储热材料。
实施例3
第一步、将孔隙率为130ppi的金属镍泡沫修剪成15 × 15 × 5 mm3大小的块体,将其置于管式炉中,在Ar/H2氛围下,以10℃/min的升温速率,将温度升至1050℃,并进行氢气还原30min。随后关闭Ar/H2混合气,并打开Ar/H2/CH4混合气,在1050℃下进行化学气相沉积180min,在以10℃/min的降温速率,将温度降至室温,得到包覆石墨的镍泡沫。
第二步、将包覆石墨的镍泡沫置于0.5mol/L的盐酸中,在70℃下,蚀刻48h,随后将蚀刻完成的石墨泡沫置于去离子水中,反复清洗。接着放入干燥箱中,以80℃干燥30min,得到石墨泡沫。
第三步、将石墨泡沫置于刚玉支架上,并放入盛有硅粉的带盖坩埚中,硅粉与石墨泡沫的质量比为2.5:1,在管式炉中在Ar氛围下,以小于10℃/min的升温速率,将温度升至1700℃,并保温5h,随后以小于10℃/min的降温速率将温度降至室温,即得到碳化硅陶瓷泡沫。
第四步、称取物质的量之比为92.5:7.5的硝酸锂和氯化钠共30g,与0.3g 平均粒径为50nm 的AlN纳米颗粒混合,并加入100mL去离子水充分溶解。将溶液放入超声振荡器中超声处理2h,随后将溶液置与140℃的油浴锅中蒸干水分。蒸干后,将得到的掺杂纳米颗粒的共晶盐放入干燥箱中,以90℃干燥12h,得到干燥的相变材料。
第五步、取适量干燥的相变材料再次溶解于去离子水中,将碳化硅泡沫放置于180℃的加热台上,使用滴管对泡沫进行滴浸,反复10次后,将其中的水分蒸干。随后将溶液辅助浸渍的泡沫放入瓶中,并加入过量的相变材料,置于管式炉中真空加热到300℃,保温180min,去除多余相变材料后,即得到超轻泡沫陶瓷-纳米颗粒-相变材料复合储热材料。
实施例4
具体制备过程同实施例1,不同之处在于,第三步中保温时间不同,分别为3h和4h。
参见图2,当保温为5h时,所得产物的XRD结果上可以明显看见在2theta为36.7°、41.4°、59.9°、71.7°、76°处出现了SiC的特征峰,说明了可以成功制备SiC,当温度低于5h的时候,XRD结果显示在33.6°出现了一个特征峰,改出的特征峰表示碳化硅晶体中存在层错,层错将导致晶界间产生界面,会降低材料的导热率,而保温5h以上的XRD图像中没有该特征峰,说明晶体中的层错大大减少,可以有效提高泡沫的导热率,因此硅蒸发的温度和时间直接影响所形成的碳化硅结构,当温度应高于1600℃,保温时间应大于5小时,可以获得良好的晶体堆积结构,导热率更高。
实施例5
具体制备过程同实施例1,不同之处在于,第五步中仅采用单一的真空浸渍法制备。
参见图5,图中a为单一浸渍法,图中b为溶液辅助浸渍和真空浸渍相结合的方式,由图可知a中获得的是堆积疏松复合材料,而b中获得的是紧密堆积的复合材料,说明了若仅选用单一浸渍方法,相变材料不能紧密填充满泡沫的孔隙,因而导致复合材料导热系数和储热密度降低。
实施例6
具体制备过程同实施例1,不同之处在于,第四步中硝酸锂和氯化钠的物质的量之比不同。其中,氯化钠的摩尔分数分别为5.9 mol%、7.5 mol%、17.2 mol%、18.2 mol%和38.8mol%。
参见图8,当氯化钠的摩尔分数过高,相变材料的潜热明显降低,因此相变材料中硝酸锂和氯化钠的物质的量最优之比为92.5:7.5,高于或低于该比例将导致材料潜热降低。
Claims (10)
1.一种超轻陶瓷泡沫复合储热材料,其特征在于:由碳化硅泡沫陶瓷与掺杂纳米颗粒的相变材料组成;所述相变材料负载于碳化硅泡沫陶瓷的孔隙中,所述碳化硅泡沫陶瓷的孔隙率为92~99%,所述相变材料的负载率为90~99%,所述纳米颗粒为相变材料总质量的0.5~1.5%。
2.根据权利要求1所述的一种超轻陶瓷泡沫复合储热材料,其特征在于:所述相变材料为硝酸锂和氯化钠组成的共晶盐,其中,氯化钠的摩尔分数为5.9~17.2 mol%,硝酸锂和氯化钠的摩尔分数之和为100%。
3.根据权利要求1所述的一种超轻陶瓷泡沫复合储热材料,其特征在于:所述纳米颗粒为Al2O3、AlN、CuO、MgO、SiC和SiO2中的任一种,纳米颗粒直径在1~100nm之间。
4.一种权利要求1-3任一项所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于,包括以下步骤:
(1)制备碳化硅泡沫陶瓷;
(2)制备相变材料:取硝酸锂、氯化钠和纳米颗粒溶解与水中进行超声分散,随后将均匀分散的溶液加热至水分蒸发,烘干后得到相变材料;
(3)采用溶液浸渍和真空浸渍联合的方式将相变材料填充在碳化硅泡沫陶瓷的孔隙中,得到复合储热材料。
5.根据权利要求4所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于,步骤(1)中的碳化硅泡沫陶瓷包括以下制备步骤:
(11)取金属镍泡沫板置于含H2的混合气体中进行还原去除表面氧化层;
(12)将还原后的金属镍泡沫板置于含CH4的混合气体中进行化学气相沉积,在金属镍泡沫板表面并生成石墨;
(13)将步骤(12)得到的产物置于蚀刻剂中进行刻蚀,去除金属镍,得到石墨泡沫;
(14)将硅粉置于石墨泡沫底部,石墨泡沫与硅粉不接触,进行硅蒸发得到碳化硅泡沫陶瓷。
6.根据权利要求5所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于:所述步骤(14)中,硅粉与石墨泡沫的质量比为2.4~3:1,蒸发温度为1600~1800℃,蒸发时间为5~6h。
7.根据权利要求5所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于:所述步骤(13)中,刻蚀剂为盐酸、氯化铁溶液、硝酸铁溶液或过硫酸铵溶液中的任一种,刻蚀剂的浓度为0.5~3mol/L,刻蚀温度为50~80℃。
8.根据权利要求5所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于:所述步骤(11)中,金属镍泡沫板的孔隙率为30~135ppi,厚度为1~5mm。
9.根据权利要求4所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于,步骤(3)中,溶液浸渍具体是指:将相变材料配置成饱和溶液,对碳化硅泡沫陶瓷进行滴浸5~10次,然后蒸干水分。
10.根据权利要求4所述的超轻陶瓷泡沫复合储热材料的制备方法,其特征在于,步骤(3)中,真空浸渍具体是指:将溶液浸渍之后的碳化硅泡沫陶瓷与相变材料混合,然后在相变材料熔点以上50℃的温度进行真空加热并保温2~3h。
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CN114196380A (zh) * | 2021-12-13 | 2022-03-18 | 南京金合能源材料有限公司 | 一种高潜热高导热性的中高温相变储热复合材料及其制备方法 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1357591A (zh) * | 2001-12-28 | 2002-07-10 | 昆明理工大学 | 一种复合蓄热材料的制备工艺及复合充填蓄热室 |
CN1830901A (zh) * | 2006-03-30 | 2006-09-13 | 中国科学院山西煤炭化学研究所 | 一种生物结构球形多孔碳化硅陶瓷材料的制备方法 |
US20090305017A1 (en) * | 2006-02-01 | 2009-12-10 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Impregnated ceramic foam made of recrystallized silicon carbide |
US20180102543A1 (en) * | 2016-10-06 | 2018-04-12 | Nanotek Instruments, Inc. | Lithium Ion Battery Anode Containing Silicon Nanowires Grown in situ in Pores of Graphene Foam and Production Process |
CN108598431A (zh) * | 2018-04-28 | 2018-09-28 | 江苏科技大学 | 石墨烯泡沫-氧化镍复合电极材料及其制备方法 |
JP2019137819A (ja) * | 2018-02-15 | 2019-08-22 | 国立大学法人名古屋大学 | 複合構造体、複合構造体の製造方法、及び蓄熱方法 |
KR20190111657A (ko) * | 2018-03-23 | 2019-10-02 | 한국신발피혁연구원 | 다공성 잠열 축열재의 제조방법 |
CN111621264A (zh) * | 2020-05-21 | 2020-09-04 | 国电南瑞科技股份有限公司 | 一种纳米改性三水醋酸钠相变储热材料及其制备方法 |
CN112521153A (zh) * | 2020-11-27 | 2021-03-19 | 南京航空航天大学 | 一种生物形态碳化硅陶瓷高温光热储存材料 |
-
2021
- 2021-09-10 CN CN202111062076.3A patent/CN113636843A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1357591A (zh) * | 2001-12-28 | 2002-07-10 | 昆明理工大学 | 一种复合蓄热材料的制备工艺及复合充填蓄热室 |
US20090305017A1 (en) * | 2006-02-01 | 2009-12-10 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Impregnated ceramic foam made of recrystallized silicon carbide |
CN1830901A (zh) * | 2006-03-30 | 2006-09-13 | 中国科学院山西煤炭化学研究所 | 一种生物结构球形多孔碳化硅陶瓷材料的制备方法 |
US20180102543A1 (en) * | 2016-10-06 | 2018-04-12 | Nanotek Instruments, Inc. | Lithium Ion Battery Anode Containing Silicon Nanowires Grown in situ in Pores of Graphene Foam and Production Process |
JP2019137819A (ja) * | 2018-02-15 | 2019-08-22 | 国立大学法人名古屋大学 | 複合構造体、複合構造体の製造方法、及び蓄熱方法 |
KR20190111657A (ko) * | 2018-03-23 | 2019-10-02 | 한국신발피혁연구원 | 다공성 잠열 축열재의 제조방법 |
CN108598431A (zh) * | 2018-04-28 | 2018-09-28 | 江苏科技大学 | 石墨烯泡沫-氧化镍复合电极材料及其制备方法 |
CN111621264A (zh) * | 2020-05-21 | 2020-09-04 | 国电南瑞科技股份有限公司 | 一种纳米改性三水醋酸钠相变储热材料及其制备方法 |
CN112521153A (zh) * | 2020-11-27 | 2021-03-19 | 南京航空航天大学 | 一种生物形态碳化硅陶瓷高温光热储存材料 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114196380A (zh) * | 2021-12-13 | 2022-03-18 | 南京金合能源材料有限公司 | 一种高潜热高导热性的中高温相变储热复合材料及其制备方法 |
CN114196380B (zh) * | 2021-12-13 | 2023-11-03 | 南京金合能源材料有限公司 | 一种高潜热高导热性的中高温相变储热复合材料及其制备方法 |
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