CN113307250B - 有序木质素碳-碳纳米管复合材料的制备方法及其应用 - Google Patents
有序木质素碳-碳纳米管复合材料的制备方法及其应用 Download PDFInfo
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- CN113307250B CN113307250B CN202110480222.8A CN202110480222A CN113307250B CN 113307250 B CN113307250 B CN 113307250B CN 202110480222 A CN202110480222 A CN 202110480222A CN 113307250 B CN113307250 B CN 113307250B
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- lignin
- carbon
- salt
- carbon nanotube
- nanotube composite
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- 229920005610 lignin Polymers 0.000 title claims abstract description 131
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 70
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- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003763 carbonization Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 28
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- 239000012018 catalyst precursor Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
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- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 19
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- 239000000243 solution Substances 0.000 description 35
- 229910052799 carbon Inorganic materials 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 238000004090 dissolution Methods 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
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- 239000004475 Arginine Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
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- 229910017061 Fe Co Inorganic materials 0.000 description 1
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- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
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- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
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- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
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- 238000005554 pickling Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
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- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
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- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及一种有序木质素碳‑碳纳米管复合材料的制备方法及其应用,属于碳材料载体制备领域。所述制备方法包括S1.制备改性木质素;S2.采用蒸发诱导自组装技术制备木质素/催化剂前驱体;S3.控制木质素/催化剂前驱体的碳化和催化过程,使得碳纳米管有序自生长,得到木质素碳‑碳纳米管‑催化剂复合物;S4.通过稀酸刻蚀去除催化剂后形成大量的均匀的介孔孔道,从而获得高介孔率的高有序化木质素碳‑碳纳米管基材。和现有技术相比,本发明方法制备的高附加值的有序化木质素碳‑碳纳米管复合材料具有一定的比表面积、多级孔道和高导电性,作为锂硫电池正极活性材料具有高的能量密度、体积比容量、良好的倍率性能和循环稳定性。
Description
技术领域
本发明公开了一种有序木质素碳-碳纳米管复合材料的制备方法及其应用,属于碳材料载体制备领域。
背景技术
随着世界能源越发紧缺、科技高速发展及人们环保意识的提高,绿色可持续生物质资源的开发引起全球愈加广泛而强烈的关注。木质素是自然界中第二大丰富可再生资源(1500亿吨/年),具有高芳香性、高碳含量、官能团丰富等特点,其高值资源化利用成为新的研究热点。工业上,木质素主要来自制浆造纸和生物乙醇行业的废弃物,全球产量高达7000万吨/年,其资源化工业应用的突出瓶颈在于回收再利用效率不理想、产品附加值低且易产生二次污染等,严重阻碍了生物质资源产业的高速发展。以工业木质素为原料研制附加值极高的碳材料并应用于储能领域,可为生物质资源化提供新途径,同时对于缓解全球能源危机和资源紧缺具有重大战略意义和经济效益。
锂硫电池作为新一代储能器件,其理论能量密度(2600Wh·Kg-1)是锂离子电池的3~5倍,同时硫阴极的理论比容量高达1675mAh·g-1。由于硫单质的绝缘性和循环过程中多硫化锂(Li2Sx,8≥x>4)的“穿梭效应”,多孔碳材料作为阴极基材可以提高电极导电性并限制多硫化锂溶出/穿梭,从而提高锂硫电池的循环稳定性能、倍率性能和循环寿命。以工业木质素为原料制备的木质素多孔碳(LPC)表现出孔隙发达、高孔容积、物理化学性质稳定等特点,其高硫负载率的显著优势使其在锂硫电池中的应用成为新的研究热点。然而,由于木质素结构复杂且水溶性差,常规碳化活化法制备的LPC存在形貌无规、孔道结构不可控和导电性差等结构缺陷,无法完全抑制多硫化锂的“穿梭效应”,导致容量不断衰减极大限制了其在锂硫电池中的应用。碳纳米管(CNTs)具有优异的结构稳定性、规整的纳米结构、高导电性和显著的纳米尺寸效应,常被用来调控电极材料的微观结构。为了获得CNTs有序排列的碳杂化材料,清华大学魏飞教授利用FeMo催化剂,首先使用C2H4为碳源在750℃下经CVD生成同一取向的CNTs,然后使用CH4在950℃下经CVD生成垂直于CNTs且被隔开的石墨烯层,合成过程中同时使用NH3作为氮源,最后构建得到结构可控的三维N-ACNT/G杂化材料,这种分级多孔且CNTs同一取向稳定排列结构可以显著促进锂硫电池中电子快速传输及电解质渗透扩散(ACS Nano,2012,6(12):10759-10769;Advanced Materials,2014,26(35):6100-6105)。南洋理工大学沈泽祥教授课题组首先利用C2H4为碳源经CVD得到石墨烯薄膜,继而在石墨烯薄膜上负载FeCo催化剂并利用CH4为碳源经CVD得到垂直石墨烯的CNTs阵列,最后在CNT-G薄膜上水热负载Fe2O3得到具有优异库伦效率、超高倍率性能和高电极稳定性的无支撑三维Fe2O3/CNT–G复合薄膜材料(Nano Energy,2014,9:364-372)。经过不断深入研究,广西大学童张法教授开发出利用碳酸钙作为绿色模板剂,聚多巴胺和三聚氰胺分别作为碳源和氮源在H2环境下经Fe-Co基催化剂一步碳化催化得到均一针状N-AHPC@H-CNTs复合材料(Chemical Engineering Journal,2019,361:278-285)。广东工业大学蔡俊杰利用纳米碳酸钙为模板剂,三聚氰胺甲醛树脂为碳源和氮源,经Fe-Co催化碳化后得到富氮的N-HPC-CNTs复合材料,CNTs的引入提供了更多的导电通道并使CNTs与HPC相互连接,从而使得介孔复合材料不仅可以促进多硫化物的物理化学吸附,而且确保电子的快速传输(ACS AppliedMaterials&Interfaces,2017,9(39):33876-33886)。此外,为了构建CNTs有序排列且硫单质与碳原子紧密连接的结构,苏州大学邓照教授将聚丙烯腈、CNTs及硫单质进行共纺丝,在分子或原子水平上使得硫在聚丙烯腈环化过程中共聚形成共价键,这个碳和硫共纺丝方法协同增加材料的孔隙和导电通道,提高阴极的电化学性能(Energy Storage Materials,2019,16:194-202)。
发明内容
本发明是针对上述现有技术的不足,提供一种高有序化且内部以C-C键连接的有序木质素碳-碳纳米管复合材料的制备方法。以该方法制备的木质素碳-碳纳米管复合材料具有以均匀介孔为主,兼具大孔和微孔的多级孔道结构。
在本发明中,所述的高介孔率应该理解是多级孔碳材料(有序木质素碳-碳纳米管复合材料)的介孔率不低于60%,多级孔应该理解是含有大孔、微孔和介孔;载硫量为60%以上。
在本发明中,所述木质素为工业木质素,包括麦草碱木质素、竹浆碱木质素、芦苇碱木质素、木浆碱木质素、棉浆碱木质素、玉米芯酶解木质素、木质素磺酸钠和蔗渣碱木质素中的至少一种。
本发明的技术任务是按以下方式实现的:有序木质素碳-碳纳米管复合材料的制备方法,以工业木质素为原料,利用自组装-自催化制备高有序化木质素碳-碳纳米管复合材料。首先,基于改性后木质素的三维网络结构和带电性,采用蒸发诱导自组装技术制备木质素/催化剂前驱体。然后,控制碳化和催化过程,利用木质素自身热分解产生的甲烷和小分子有机物间的自催化作用,使得碳纳米管有序自生长;同时,利用纳米级催化剂作为硬模板剂,高温碳化后通过稀酸刻蚀去除后形成大量的均匀的介孔孔道,从而获得高介孔率的高有序化木质素碳-碳纳米管复合材料。
具体包括:
S1.在碱性条件下对木质素进行化学改性,制备改性木质素;
S2.采用蒸发诱导自组装技术制备木质素/催化剂前驱体;
S3.控制木质素/催化剂前驱体的碳化和催化过程,利用木质素自身热分解产生的甲烷和小分子有机物间的自催化作用,使得碳纳米管有序自生长,得到木质素碳-碳纳米管-催化剂复合物;
S4.利用纳米级催化剂作为硬模板剂,通过稀酸刻蚀去除后形成大量的均匀的介孔孔道,从而获得高介孔率的高有序化木质素碳-碳纳米管基材。
木质素的溶解过程是一个溶胀过程,木质素分子中的羧基、羟基、酚羟基等官能团在溶解过程中逐渐电离必须在强碱性环境中才会溶解。因此,这里必须先对木质素进行改性,改变原有官能团种类和数量,改善木质素亲疏水性,提高电离强度,拓宽木质素在溶液中可溶解的pH范围(pH=3~10)。如果不进行改性处理,在强碱性环境下加入金属盐时会使得金属盐迅速沉淀,不能与木质素形成均一分散的木质素-催化剂前驱体混合物,无法进一步催化得到有序的碳纳米管阵列。
为了改善工业木质素在水溶液中的溶解局限性(仅可溶解于强碱性溶液体系),本发明先对工业木质素进行化学改性,最大限度的扩宽工业木质素在溶液中的溶解范围;同时,改善工业木质素自身的带电性和带电量,为将催化剂均匀分散在木质素聚集体中做前期准备。
作为优选,步骤S1在pH=11~12条件下对木质素进行化学改性,得到不同改性程度的改性木质素。
所述化学改性方法可以是任意一种能够使木质素形成三维网络结构和带电性的改性方法,包括羧甲基化改性、磺酸化改性、季铵化改性、胺化改性、硝化改性、醚化反应或偶氮化改性等可行的接枝/共聚化学改性方法。
改性程度优选为接枝改性试剂用量占木质素的质量比重为10%~60%。
作为优选,步骤S2中木质素/催化剂前驱体的制备方法为:将改性木质素溶解于水溶液中,加入催化剂,搅拌均匀后加入一定量弱碱性铵盐,加热条件下反应一定时间后蒸发、干燥得到木质素/催化剂前驱体混合物固体粉末。
所述催化剂为可溶性金属盐,可以是钴盐、铝盐、镍盐、锌盐、铁盐、铜盐、锰盐、银盐、铂盐、钯盐中的两种或多种。例如氯化铝、氯化钴、氯化镍、氯化锌、氯化铁、氯化亚铁、氯化铜、氯化锰、乙酸铝、乙酸钴、乙酸镍、乙酸锌、乙酸铁、乙酸亚铁、乙酸锰、硝酸铝、硝酸钴、硝酸镍、硝酸锌、硝酸铁、硝酸亚铁、硝酸铜、硝酸锰、硝酸银、硝酸铂、硝酸钯等。
特别是,当可溶性金属盐中包括钴盐时,即催化剂采用钴盐与其它可溶性金属盐的混合使用时,反应效果最佳。此时得到的催化剂前驱体为复合型催化剂前驱体,如铁钴催化剂、铁钴镍催化剂、铁钴铝催化剂等的前驱体。可溶性金属盐中钴盐的质量百分含量优选为不低于20%。
以重量计,改性木质素:可溶性金属盐:弱碱性铵盐的配比为100:(10~100):(10~100),特别优选为100:(50~100):(50~100)。若重量比过低会使步骤S4中碳化所得碳纳米管的产量过低,难以获得碳纳米管有序排列的复合材料;如果质量比大于100,导致所得到的木质素/催化剂前驱体复合物中催化剂前驱体含量过高,易造成步骤S4中催化剂聚集严重,催化效果不佳,致使难以形成内部以C-C键连接的木质素碳-碳纳米管复合材料。
所述弱碱性铵盐为尿素、氨水、碳酸氢铵和/或碳酸铵。反应体系中加入弱碱性铵盐后加热至50~80℃,反应1~3小时。
作为优选,步骤S3通过控制加热碳化的加热升温速率和恒温加热保持时间,控制碳化和催化过程。
碳化温度应控制在500~700℃范围内,时间在0.5~6h,若温度过低或时间短低则会导致碳化不完全,过高不仅会提升生产成本,还造成木质素碳-碳纳米管复合材料结构不稳定。另外,严格控制升温速率是此步骤的关键之处,如果在升温速率过快则会导致木质素热解生产的甲烷和小分子有机物迅速逸出,在催化剂上停留时间过短难以催化生长碳纳米管。
控制碳化和催化过程的具体方法优选为:第一段以5~10℃/min升温至200~400℃,保持10~60min;第二段以0.1~5℃/min升温至500~700℃,保持0.5~5h,降温至室温。特别优选为:第一段以5~7℃/min升温至300~400℃,保持20~40min;第二段以0.1~2℃/min升温至550~650℃,保持1~3h,降温至室温。
碳化和催化过程优选在惰性气体(如氮气、氩气等)保护下进行。第一段升温过程中惰性气体的气流量为0.1~1m3/h,更优选为0.4m3/h;第二段升温过程中惰性气体气流量控制在0.01~0.05m3/h,更优选为0.02m3/h。
作为优选,步骤S4稀酸刻蚀的具体方法为:将木质素碳-碳纳米管-催化剂复合物浸泡在一定质量浓度的稀酸溶液中进行酸洗,洗涤去除其中的催化剂,然后离心、干燥后获得木质素碳-碳纳米管复合材料。
所述稀酸溶液优选为浓度0.1~2mol/L的硝酸和/或盐酸溶液,酸洗时间不少于4小时。如果酸液浓度过低或酸洗时间过短,则会导致金属氧化物残余过多,孔道结构较少,其循环性能和倍率性能会大幅度降低,酸洗浓度过高,导致成本增加。
进一步的,本发明提供上述有序木质素碳-碳纳米管复合材料的应用。
本发明方法以工业木质素为原料,通过自催化法制备碳纳米管有序排列的三维木质素碳-碳纳米管复合材料(木质素碳-碳纳米管复合材料)的表面积范围为200~1000m2·g-1,孔径大小为0.1~100nm,孔容积为0.5~3.5cm3/g,微孔和介孔孔容积占80%以上。可应用于制备气体吸附剂、锂离子电池负极材料、超级电容器或催化剂载体,特别适用于制备锂硫电池。样品比表面积和孔道结构的测试使用全自动比表面及孔隙度分析仪(Micromeritics ASAP 2020instrument)。
用于制备锂硫电池时,木质素碳-碳纳米管复合材料以载硫材料的形式被应用,作为高稳定性基材可抑制多硫化锂溶解/扩散,可提高电极的导电性和稳定性,并提高锂硫电池的质量比容量、体积比容量和倍率性能,最终实现提高锂硫电池综合性能并达到实际应用的目的。
一种锂硫电池,其载硫材料为本发明方法制备的木质素碳-碳纳米管复合材料。
例如,可以采用型号为CR2032的电池进行锂硫电池组装。以本发明制备得到的木质素碳-碳纳米管复合材料作为载硫基材,通过低温蒸镀发负载硫单质后用作锂硫电池正极电极,其中活性物质70wt%,炭黑20%,聚偏氟乙烯(PVDF)10%(溶解于N-甲基吡咯烷酮)。锂金属电极作为负极电极,电解液为溶解于碳酸二乙酯和碳酸亚乙酯(体积比1:1)中的LiPF6(1mol·L-1)溶液。锂硫电池的整个安装过程在氩气保护的手套箱中操作完成。
和现有技术相比,本发明的有序木质素碳-碳纳米管复合材料的制备方法及其应用具有以下突出的有益效果:
一、本发明制备的高有序化木质素碳-碳纳米管复合材料与碳纳米管杂化材料相比,具有高占比的介孔孔道,以及一定量的微孔结构;特别是自催化过程可以使得木质素碳与碳纳米管间通过C-C键连接,增强结构稳定性,提高材料导电性;负载硫单质后作为锂硫电池正极材料具有更高的可逆容量、良好的循环性能和倍率性能,应用前景广阔。
二、本发明是以工业木质素作为碳源来自催化制备木质素碳-碳纳米管复合材料,所采用的自组装-自催化法具有操作简单、成本低的优势。利用木质素自身热解生产的甲烷等有机小分子作为碳源来催化生长碳纳米管可以大大的节约成本,该方法对设备无腐蚀、绿色环保,具有普适性。
三、以可溶性金属盐为催化剂,反应完成后可通过简易的沉淀法进行回收并重复利用,以免造成二次污染,即通入二氧化碳气体或者加入碳酸盐进行沉淀滤液中的金属催化剂离子。
附图说明
附图1是实施例1所得木质素碳-碳纳米管复合材料的扫描电镜照片;
附图2是实施例1所得木质素碳-碳纳米管复合材料的透射电镜照片;
附图3是实施例1所得木质素碳-碳纳米管复合材料的氮气吸/脱附等温线;
附图4是实施例1所得木质素碳-碳纳米管复合材料的孔径分布曲线。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,但不作为对本发明的限定。
本发明所有实施例中涉及的物料均可从商业渠道获得。
如无特别说明,下述所用各成分的含量为质量百分比含量。
实施例1
称取5g纯化的麦草碱木质素加入到100ml的20%氢氧化钠溶液(pH略大于11)中,超声分散并不断搅拌得到木质素溶液,加入2g氯乙酸钠在65℃下反应6h,旋蒸、离心、冷冻干燥得到羧甲基化木质素;
称取2g上述羧甲基化木质素并溶解100ml去离子水中,加入1g硝酸钴粉末和1g硝酸铁粉末。将上述溶液在常温下搅拌30min后,加入0.5g尿素和1g氨水,在常温下搅拌2h后升温到100℃下蒸发至晶体析出。将上述晶体样品研磨至微米级固体颗粒,得到木质素/铁钴催化剂前驱体混合物固体粉末。
将上述混合物置于3cm×6cm的瓷舟中,并将装好样品的瓷舟置于管式炉中进行碳化。整个碳化过程中在N2(99.9%)保护下进行,碳化温度由常温升以5℃/min温至350℃,并保持30min,N2流速为0.4m3/h;再以0.2℃/min升温至600℃,保持2h,N2流速为0.02m3/h,碳化后降到室温得到黑色粉末。
将碳化后所得到的黑色粉末分散到50ml的1mol/L盐酸溶液中,在磁力搅拌下搅拌4h。对上述溶液进行过滤后经去离子水反复洗涤去除残余盐分后,在110℃下干燥6h即获得木质素碳-碳纳米管复合材料。
由图1的扫描电镜照片可以看出复合材料呈层状结构,碳纳米管有序排列。
由图2的透射电镜照片可以看出复合材料内部碳纳米管有序排列,并与木质素碳纳米片紧密连接。
由图3的氮气脱吸附曲线可以看出,木质素多级孔碳为Ⅳ型吸附并具有回滞环,说明碳材料具有多孔性和介孔结构,一定的吸附量指出材料具有较高的比表面积(260m2·g-1)。
由图4的孔径分布曲线可以看出,木质素多孔碳在0.5~100nm的孔径范围内具有显著的孔道分布,尤其是在5~10nm具有显著的介孔孔道分布。微孔和大孔的出现与木质素自身热解作用有关。介孔的出现与铁钴催化剂的自模板作用有关,由于纳米级铁钴催化剂对木质素碳起到硬模板的作用,且氧化物粒径为5~10nm,所以去除氧化锌颗粒后可以生成均一的介孔孔道。
实施例2
称取5g纯化的玉米芯酶解木质素加入到100ml的20%氢氧化钠溶液(pH略大于11)中,超声分散并不断搅拌得到木质素溶液,加入2g的3-氯2-羟丙基三甲基氯化铵,在85℃下反应6h,旋蒸、离心、冷冻干燥得到季铵化木质素。
称取2g上述季铵化木质素并溶解100ml去离子水中,加入0.5g硝酸钴粉末、1g硝酸铁和0.5g硝酸铝粉末。将上述溶液在常温下搅拌30min后,加入1g碳酸氢铵和1g氨水,在常温下搅拌2h后升温到100℃下蒸发至晶体析出。将上述晶体样品研磨至微米级固体颗粒,得到木质素/铝铁钴催化剂前驱体混合物固体粉末。
将上述混合物置于3cm×6cm的瓷舟中,并将装好样品的瓷舟置于管式炉中进行碳化。整个碳化过程中在N2(99.9%)保护下进行,碳化温度由常温升以5℃/min温至350℃,并保持30min,N2流速为0.4m3/h;再以0.2℃/min升温至600℃,保持2h,N2流速为0.02m3/h,碳化后降到室温得到黑色粉末。
将碳化后所得到的黑色粉末分散到50ml的1mol/L盐酸溶液中,在磁力搅拌下搅拌4h。对上述溶液进行过滤后经去离子水反复洗涤去除残余盐分后,在110℃下干燥6h即获得木质素碳-碳纳米管复合材料。
实施例3
称取5g纯化的木质素磺酸钠加入到100ml的20%氢氧化钠溶液(pH略大于11)中,超声分散并不断搅拌得到木质素溶液,加入0.5g甲醛和2g的精氨酸,在65℃下反应6h,旋蒸、离心、冷冻干燥得到胺化木质素。
称取2g上述胺化木质素并溶解100ml去离子水中,加入0.5g硝酸镍粉末、1g硝酸钴和0.5g硝酸铝粉末。将上述溶液在常温下搅拌30min后,加入0.5g碳酸铵和1g氨水,在常温下搅拌2h后升温到100℃下蒸发至晶体析出。将上述晶体样品研磨至微米级固体颗粒,得到木质素/铝钴镍催化剂前驱体混合物固体粉末。
将上述混合物置于3cm×6cm的瓷舟中,并将装好样品的瓷舟置于管式炉中进行碳化。整个碳化过程中在N2(99.9%)保护下进行,碳化温度由常温升以5℃/min温至350℃,并保持30min,N2流速为0.5m3/h;再以0.2℃/min升温至650℃,保持2h,N2流速为0.01m3/h,碳化后降到室温得到黑色粉末。
将碳化后所得到的黑色粉末分散到50ml的1mol/L盐酸溶液中,在磁力搅拌下搅拌4h。对上述溶液进行过滤后经去离子水反复洗涤去除残余盐分后,在110℃下干燥6h即获得木质素碳-碳纳米管复合材料。
实施例4
称取5g纯化的蔗渣碱木质素加入到100ml的20%氢氧化钠溶液(pH略大于11)中,超声分散并不断搅拌得到木质素溶液,加入0.5g甲醛和2g的精氨酸,在65℃下反应6h,旋蒸、离心、冷冻干燥得到胺化木质素。
称取2g上述胺化木质素并溶解100ml去离子水中,加入2g硝酸钴粉末。将上述溶液在常温下搅拌30min后,加入2g氨水,在常温下搅拌2h后升温到100℃下蒸发至晶体析出。将上述晶体样品研磨至微米级固体颗粒,得到木质素/铝铁镍催化剂前驱体混合物固体粉末。
将上述混合物置于3cm×6cm的瓷舟中,并将装好样品的瓷舟置于管式炉中进行碳化。整个碳化过程中在N2(99.9%)保护下进行,碳化温度由常温升以5℃/min温至350℃,并保持30min,N2流速为0.5m3/h;再以0.2℃/min升温至650℃,保持2h,N2流速为0.01m3/h,碳化后降到室温得到黑色粉末。
将碳化后所得到的黑色粉末分散到50ml的1mol/L盐酸溶液中,在磁力搅拌下搅拌4h。对上述溶液进行过滤后经去离子水反复洗涤去除残余盐分后,在110℃下干燥6h即获得木质素碳-碳纳米管复合材料。
实施例5
采用型号为CR2032的电池进行锂硫电池组装。以实施例1-4所制备得到的木质素碳-碳纳米管复合材料作为载硫基材,通过低温蒸镀发负载硫单质后用作锂硫电池正极电极,其中活性物质70wt%,炭黑20%,聚偏氟乙烯(PVDF)10%(溶解于N-甲基吡咯烷酮)。锂金属电极作为负极电极,电解液为溶解于碳酸二乙酯和碳酸亚乙酯(体积比1:1)中的LiPF6(1mol·L-1)溶液。锂硫电池的整个安装过程在氩气保护的手套箱中操作完成。
通过电化学工作站和深圳新威尔电池测试系统测试其循环性能、倍率性能和电化学性能,具体结果见表1。
表1.不同实施例制备的木质素碳-碳纳米管基材载硫后的锂硫电池循环性能
注:Neware电池性能测试系统在0.001V~3.0V电压范围内以1C电流密度下进行电池的恒电流充电/放电性能测试,倍率性能测试在0.1C、0.2C、0.5C、1C和2C电流密度下完成。
由表1的测试结果可以看出,本发明方法制备的木质素碳-碳纳米管基材均表现出较为优异的载硫性能和储锂性能。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.有序木质素碳-碳纳米管复合材料的制备方法,其特征在于包括:
S1.在pH=11~12条件下对木质素进行化学改性,制备改性木质素,所述化学改性方法包括羧甲基化改性、磺酸化改性、季铵化改性、胺化改性、硝化改性、醚化反应或偶氮化改性;
S2.采用蒸发诱导自组装技术制备木质素/催化剂前驱体:
将改性木质素溶解于水溶液中,加入可溶性金属盐,搅拌均匀后加入一定量弱碱性铵盐,加热条件下反应一定时间后蒸发、干燥得到木质素/催化剂前驱体混合物固体粉末,以重量计,改性木质素:可溶性金属盐:弱碱性铵盐的配比为100:(10~100):(10~100),
所述可溶性金属盐为钴盐、铝盐、镍盐、锌盐、铁盐、铜盐、锰盐、银盐、铂盐和钯盐中的两种或多种,且钴盐的质量百分含量不低于20%;
S3.控制木质素/催化剂前驱体的碳化和催化过程,利用木质素自身热分解产生的甲烷和小分子有机物间的自催化作用,使得碳纳米管有序自生长,得到木质素碳-碳纳米管-催化剂复合物;
S4.利用纳米级催化剂作为硬模板剂,通过稀酸刻蚀去除后形成大量的均匀的介孔孔道,从而获得高介孔率的高有序化木质素碳-碳纳米管基材。
2.根据权利要求1所述的有序木质素碳-碳纳米管复合材料的制备方法,其特征在于,
以重量计,改性木质素:可溶性金属盐:弱碱性铵盐的配比为100:(10~100):(10~100);
所述弱碱性铵盐为尿素、氨水、碳酸氢铵和/或碳酸铵。
3.根据权利要求1所述的有序木质素碳-碳纳米管复合材料的制备方法,其特征在于,加入弱碱性铵盐后加热至50~80℃,反应1~3小时。
4.根据权利要求1所述的有序木质素碳-碳纳米管复合材料的制备方法,其特征在于,步骤S3通过控制碳化的加热升温速率和恒温加热保持时间,控制碳化和催化过程。
5.根据权利要求4所述的有序木质素碳-碳纳米管复合材料的制备方法,其特征在于,碳化和催化过程在惰性气体保护下进行;
控制碳化和催化过程的具体方法为:第一段以5~10℃/min升温至200~400℃,保持10~60min;第二段以0.1~5℃/min升温至500~700℃,保持0.5~5h,降温至室温。
6.根据权利要求1所述的有序木质素碳-碳纳米管复合材料的制备方法,其特征在于,步骤S4稀酸刻蚀的具体方法为:将木质素碳-碳纳米管-催化剂复合物浸泡在一定质量浓度的稀酸溶液中进行酸洗,洗涤去除其中的催化剂,然后离心、干燥后获得木质素碳-碳纳米管复合材料。
7.根据权利要求6所述的有序木质素碳-碳纳米管复合材料的制备方法,其特征在于,所述稀酸溶液为浓度0.1~2mol/L的硝酸和/或盐酸溶液,酸洗时间不少于4小时。
8.权利要求1-7中任意一项所述制备方法得到的有序木质素碳-碳纳米管复合材料在制备气体吸附剂、锂离子电池负极材料、超级电容器或催化剂载体中的应用。
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