CN112479176B - 一种3d碳泡沫材料、制备方法及其应用 - Google Patents
一种3d碳泡沫材料、制备方法及其应用 Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000006261 foam material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims abstract description 12
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 12
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 12
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 7
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Abstract
本发明涉及纳米材料和电化学储能领域,特别涉及一种3D碳泡沫材料、制备方法及其应用。本发明以廉价易得的聚丙烯酸钠作为碳前驱体,通过控制前驱体六偏磷酸钠的用量,实现无模板法制备一种3D碳泡沫材料。所制备的3D碳泡沫材料具有丰富介孔结构,结构高度均一。作为锂硫电池电极材料由相互连接的碳支架形成的丰富内部空隙有利于电解液的渗透,为充放电过程中硫阴极体积膨胀提供了充足的内部空腔。同样制备的3D碳泡沫材料应用在超级电容器中也表现出优异的性能,这得益于其具有丰富的孔隙结构,大比表面积和适量的磷掺杂。本发明其工艺简单易操作,可控性高,原料廉价易得,绿色环保。
Description
技术领域
本发明涉及纳米材料和电化学储能领域,特别涉及一种3D碳泡沫材料、制备方法及其应用。
背景技术
碳原子之间通过不同的杂化态(如sp、sp2、sp3杂化)形成独特的σ和π键。这种特性提供了多种碳的同素异向结构,从单分子到层状结构,再到复杂的介孔结构。显然,原子排列的多样性可以提供不同碳的同素异向结构,这些结构在物理和功能性质上是不同的。在这一事实的推动下,人们对发明具有不同维度(如0D、1D、2D和3D)的新型纳米结构碳同素异形体进行了开创性的探索。低维碳纳米结构(0D、1D和2D)由于其优秀的内在物理化学性质已被广泛应用在各个领域,然而也常常遭受劣质的外在特征影响,比如较低的电气和热导率、低的比表面积和不可靠的机械性能。三维介孔碳材料结构可能会提供理想的骨架支撑,增强催化剂活性位点,多维导电网络改善电子传输,并扩大体积以适应电解质/反应物扩散,从而显著提高机械稳定性。
3D介孔碳材料具有良好的导电性和高的比表面积成为优良的储能电极材料候选之一。在3D介孔碳材料中碳泡沫因其具有较高的比表面积,良好的抗腐蚀性、热稳定性和柔韧性,以及高度开放的孔道结构等特点,是一种非常有发展前途的电极材料。
目前文献和已有专利中报道的具有3D网络结构的泡沫碳的制备方法有:Liu等人(Adv. Funct. Mater. 2017, 27 (37), 1702573)报道了一种新型3D多功能氧化镁修饰的碳泡沫@碳纳米管用于锂硫电池正级。超薄MgO纳米片的修饰促进了反应过程中对多硫化锂的化学吸附,而原位氮掺杂有利于对多硫化锂的捕捉,因此提高了硫的利用率和电池倍率性能。但是其采用工艺复杂,耗能耗时的模板法制备策略,增加了工艺成本限制其商业化应用。专利CN107834078A通过热解异原子前驱体和两种尺寸的SiO2的混合物,经过HF刻蚀除去SiO2模板得到杂原子掺杂的蜂窝状分级多孔碳材料。虽然,该方法通过牺牲SiO2模板有利于构建多级孔结构,但成本贵且酸刻蚀步骤危险性高,环境污染大。此外,专利CN108767272A报道一种钴氮共掺杂多孔碳材料及其制备和应用,其采用核黄素为碳源和氮源,结合醋酸钴和氯化钠模板,通过冷冻干燥碳化得到了钴氮共掺杂的多孔碳材料。其采用氯化钠作为模板,成本低且容易去除和回收利用,但核黄素(维生素B2)价格较为昂贵,限制了其商业化前景。
综上,由于现有技术存在的不足,如何实现简便有效地制备三维泡沫碳材料仍具有非常重要的意义。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种3D碳泡沫材料、制备方法及其应用。
本发明的第一方面,提供一种3D碳泡沫材料的制备方法,包括以下步骤:将六偏磷酸钠溶解于水中,然后在搅拌下加入聚丙烯酸钠,反应得到果冻状的前驱体;冷冻干燥去除所述的果冻状的前驱体中的溶剂,在惰性气体氛围下退火处理;用盐酸水溶液对退火产物进行洗涤去除钠化合物,抽滤,烘干,得到3D的碳泡沫材料。
该制备方法无需模板,且原料廉价易得,孔结构可调,制备方法简单。
进一步地,六偏磷酸钠与聚丙烯酸钠的质量比为1-20:20。
进一步地,六偏磷酸钠与聚丙烯酸钠的质量比为7:20。
进一步地,所述的退火处理中,退火温度为700 ℃~1000 ℃,升温速率1~5 ℃min-1,保温1~3 h。
本发明的第二方面,提供如上述的3D碳泡沫材料的制备方法所制备的3D碳泡沫材料,其介孔尺寸在8-23 nm之间,具有丰富的孔隙结构(微孔、中孔、大孔),比表面积为300-600 m2 g-1。
本发明的第三方面,提供一种锂硫电池正极,包括如上述的3D碳泡沫材料。
本发明的第四方面,提供一种如上述的锂硫电池正极的制备方法,包括以下步骤:
(1)将如上述的3D碳泡沫材料与单质硫研磨混合,在烘箱中加热反应得到3D碳泡沫/硫复合材料;
(2)将3D碳泡沫/硫复合材料、粘合剂、导电添加剂分散到溶剂中形成浆状,涂覆在集流体上,干燥、轧压、切片得到锂硫电池正极。
粘合剂可以采用本领域已知的所有可用于锂硫电池的粘合剂。
导电剂可以用于增加电极导电性,降低电池的内阻,可以选择导电炭黑、乙炔黑、镍粉、铜粉和导电石墨中的一种或多种,导电剂的含量一般为正极材料中的0-15%重量,优选为0-10%重量。
集流体可以是本领域技术人员所公知的各种集流体,如铝箔、铜箔、镀镍钢带等。
进一步地,3D碳泡沫材料与单质硫的质量比为1:3-2:3。
进一步地,3D碳泡沫/硫复合材料、粘合剂、导电添加剂的质量比为8:1:1。
本发明的第五方面,提供如上述的3D碳泡沫材料作为超级电容器的电极材料的应用。
本发明的有益效果如下:
1、本发明以一种廉价易得的强吸水性高分子材料聚丙烯酸钠(PAAS)作为碳前驱体,利用水为调节剂,结合冷冻干燥技术,通过控制前驱体六偏磷酸钠的用量,实现无模板法制备一种3D碳泡沫材料。
2、所制备的3D碳泡沫材料具有丰富介孔结构,结构高度均一。利用六偏磷酸钠作为造孔剂,比表面积由494 m2 g-1增加至603 m2 g-1,孔容由0.44增加到1.75。多孔泡沫碳形成了一个3D的导电网络,缩短了传质距离,提高电极整体的导电性。由相互连接的碳支架形成的丰富内部空隙有利于电解液的渗透,同时也为充放电过程中硫阴极体积膨胀提供了充足的内部空腔。此外,有效的杂原子掺杂协同改善物化性能和电容行为。
3、本发明其工艺简单易操作,可控性高,原料廉价易得,绿色环保。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,根据这些附图获得其他的附图仍属于本发明的范畴。
图1中(a)-(d)依次为对比例1和实施例1-3所获得样品的SEM图;
图2为对比例1和实施例1-3所获得样品的BET图,(a)为吸附-脱附等温线,(b)为孔径分布曲线,(c)为比表面积和孔容值汇总表;
图3为对比例1和实施例1-3所获得样品的TGA图;
图4为对比例1和实施例1-3所获得样品作为锂硫电池正极时,在充放电不同倍率下放电容量图;
图5为对比例1和实施例1-3所获得样品作为锂硫电池正极时,在充放电循环稳定性及库伦效率图;
图6为对比例1和实施例1-3所获得样品作为超级电容器的电极材料,在不同电流密度下的容量对比图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明作进一步地详细描述。
对比例1
首先将100 mL的去离子水加入到圆底烧瓶中,在慢速搅拌的过程中将2 g聚丙烯酸钠(PAAS)均匀分散在水中,快速搅拌2 h使其形成均匀的果冻状溶液。将分散均匀的混合溶液放入冰箱中冷冻凝结后放进冷冻干燥器中将水分抽干,在氩气氛围下高温退火处理,以5 ℃ min-1的速率升温至800 ℃,保温2 h后自然冷却,用1 M HCl洗涤去除钠化合物,抽滤,烘干,获得碳纳米片(PCNS)。
小结:碳纳米片表面没有明显的孔隙结构形成(如图1a),比表面积为494 m2 g-1,孔容为0.44 cm3 g-1(见图2)。
实施例1
将0.2 g六偏磷酸钠溶解在100 mL的去离子水中,然后加入2 g聚丙烯酸钠,超声分散并搅拌溶解。将分散均匀的混合溶液放入冰箱中冷冻凝结后放进冷冻干燥器中将水分抽干,在氩气氛围下高温退火处理,以5℃ min-1的速率升温至800 ℃,保温2 h后自然冷却,用1 M HCl洗涤去除钠化合物,抽滤,烘干,得到3D碳泡沫材料(P-CF-0.2)。(如图1b)
小结: 比表面积为498 m2 g-1,孔容为1.19 cm3 g-1(见图2)。
实施例2
将0.7 g六偏磷酸钠溶解在100 mL的去离子水中,然后加入2 g聚丙烯酸钠,超声分散并搅拌溶解。将分散均匀的混合溶液放入冰箱中冷冻凝结后放进冷冻干燥器中将水分抽干,在氩气氛围下高温退火处理,以5℃ min-1的速率升温至800℃,保温2 h后自然冷却,用1 M HCl洗涤去除钠化合物,抽滤,烘干,得到3D碳泡沫材料(P-CF-0.7)。
小结: 比表面积为603.6 m2 g-1,孔容为1.75 cm3 g-1(见图2)。
实施例3
将1.5 g六偏磷酸钠溶解在100 mL的去离子水中,然后加入2 g聚丙烯酸钠,超声分散并搅拌溶解。将分散均匀的混合溶液放入冰箱中冷冻凝结后放进冷冻干燥器中将水分抽干,在氩气氛围下高温退火处理,以5℃ min-1的速率升温至800℃,保温2 h后自然冷却,用1M HCl洗涤去除钠化合物,抽滤,烘干,得到3D碳泡沫材料(P-CF-1.5)。
小结: 比表面积为301.82 m2 g-1,孔容为1.13 cm3g-1(见图2)。
实施例4
步骤一、碳/硫复合材料的制备
取实施例1、2、3、4中的碳材料0.08 g置于玛瑙研钵中,混合0.187 g硫粉,置于165℃烘箱中加热,12 h后冷却取出,获得碳/硫(PCNS@S和P-CF-X@S)复合材料,通过图3(热重图)分析,其硫的含量为70 wt%。
步骤二、锂硫电池正极的制备及电池组装
将上述的碳/硫复合材料、导电炭、PVDF按质量比8:1:1分散在吡咯烷酮中并搅拌24 h,成浆状,在涂布机上涂覆在铝箔上,60 ℃下真空干燥12 h,取出切成直径为1.5 cm的圆片,得到自制的锂硫电池正极,按常规组装锂电池方法组装电池,其电解液为含1 mol/L双三氟甲基磺酸酰亚胺锂、1%硝酸锂的乙二醇二甲醚和1,3-二氧六环的混合溶液。
步骤三、电池性能常规测试
采用LAND测试系统对所有实施例进行不同电流密度下充放电测试,充放电的电压区间是1.5-3 V,在不同的倍率下(0.2-5 C)下评估其电化学性能。从中得出在0.2 C下,P-CF-0.7@S电池的初始容量可以达到1352.4 mAh g-1。在5 C下,电池的容量可以达到685.6mAh g-1。PCNS@S电池的初始容量为940.2 mAh g-1,在5 C下,电池的容量可以达到524.8mAh g-1(见图4)。同时本发明的3D碳泡沫具有优异的循环性能,P-CF-0.7@S在1 C的倍率下,循环1200次后仍具有469.7 mAh g-1的容量,容量衰减率为0.04%且库伦效率接近100%(见图5),优于PCNS@S电池。
实施例5
将上述碳材料(PCNS和P-CF-X)作为超级电容器的电极材料,在常规三电极体系评价其电化学性能,以铂片为对电极,饱和甘汞为参比电极,电解液为6 M KOH。活性物质(80wt%),乙炔黑(10 wt%)和聚四氟乙烯(10 wt%)混合。涂敷在镍泡沫(1 * 1厘米)集电器上,用于工作电极。将泡沫镍放在100 ℃烘箱中烘干12 h,取出泡沫镍,压成薄片制得电极片。然后将电极片立即称重,标号记录。测试前先将电极片浸泡在电解液中5 h,使电解液充分与电极材料接触。在三电极体系中测量各种电化学性能,其中红色夹对电极,绿色夹工作电极,白色夹参比电极。对实施例1-4中的碳材料进行不同电流密度下充放电测试,充放电的电压区间是-1-0 V,在不同的电流密度下(0.5-100 A g-1)下评估其电化学性能。在电流密度为0.5 A g-1时,P-CF-0.7电极比容量达到275.5 F g-1,PCNS比容量达到158 F g-1。增大电流密度至100 A g-1,P-CF-0.7电极比电容仍达到172 F g-1,而PCNS电极比电容仅为62F g-1(见图6),表明了3D泡沫结构对倍率性能具有很好地提升作用。
以上所揭露的仅为本发明较佳实施例而已,当然不能以此来限定本发明之权利范围,因此依本发明权利要求所作的等同变化,仍属本发明所涵盖的范围。
Claims (4)
1.一种3D碳泡沫材料的制备方法,其特征在于包括以下步骤:
将六偏磷酸钠溶解于水中,然后在搅拌下加入聚丙烯酸钠,反应得到果冻状的前驱体;冷冻干燥去除所述的果冻状的前驱体中的溶剂,在惰性气体氛围下退火处理;用盐酸水溶液对退火产物进行洗涤去除钠化合物,抽滤,烘干,得到3D的碳泡沫材料。
2.根据权利要求1所述的3D碳泡沫材料的制备方法,其特征在于:六偏磷酸钠与聚丙烯酸钠的质量比为1-20:20。
3.根据权利要求2所述的3D碳泡沫材料的制备方法,其特征在于:六偏磷酸钠与聚丙烯酸钠的质量比为7:20。
4.根据权利要求1所述的3D碳泡沫材料的制备方法,其特征在于:所述的退火处理中,退火温度为700 ℃~1000 ℃,升温速率1~5 ℃min-1,保温1~3 h。
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