CN106183142A - 一种基于石墨烯纤维无纺布的自热膜 - Google Patents
一种基于石墨烯纤维无纺布的自热膜 Download PDFInfo
- Publication number
- CN106183142A CN106183142A CN201610573992.6A CN201610573992A CN106183142A CN 106183142 A CN106183142 A CN 106183142A CN 201610573992 A CN201610573992 A CN 201610573992A CN 106183142 A CN106183142 A CN 106183142A
- Authority
- CN
- China
- Prior art keywords
- woven fabrics
- graphene
- graphene fiber
- fiber non
- hotting mask
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 87
- 239000000835 fiber Substances 0.000 title claims abstract description 74
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000004744 fabric Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 239000010408 film Substances 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 238000009288 screen filtration Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/002—Inorganic yarns or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Resistance Heating (AREA)
- Surface Heating Bodies (AREA)
Abstract
本发明公开了一种基于石墨烯纤维无纺布的自热膜及其制备方法。该自热膜由光伏薄膜作为能量层提供电压和电流,并利用石墨烯纤维无纺布的电致发热效应构成发热层,能量层与发热层中间由隔热材料隔开。由于石墨烯纤维无纺布具有高的导电率和相对较低的密度,因此能够在较低的工作电压下获得较大的发热温度和较高的升温、降温速率。同时,石墨烯纤维无纺布具有高柔性和结构稳定性,该自热膜在弯曲状态下依然能够表现出稳定的发热行为,因此这种基于石墨烯纤维无纺布的自热膜可用于新型清洁能源的可穿戴式发热器件。
Description
技术领域
本发明涉及电热膜,尤其涉及一种基于石墨烯纤维无纺布作为发热元件的自热膜。
背景技术
电致发热是电流通过导体时使导体产生热量的现象,从而将电能转化成导体的内能。电流所产生的热量遵循焦耳定律,即热量与电流的平方、电阻值和通电时间成正比(Q=I2Rt)。在纯电阻电路中,热量与施加的电压的平方成正比,与导体的电阻值成反比(Q=(U2/R)t)。由碳材料制成的电致发热材料具有电热转换效率高,使用寿命长等优异性能,并且能够发出对人体有益的远红外线辐射。因此与传统的金属等电热材料相比,呈现出较为明显的优势。
石墨烯作为近年来备受关注的碳纳米材料,可由石墨为原料通过化学剥离法大量制备,其宏观组装体如薄膜等还原后的导电性较高,将其用作电热材料时具有均匀的温度分布,加之石墨烯薄膜良好的柔性,因此是一种理想的电致发热材料,可应用于玻璃除雾、机翼除冰等用途(Nano Lett.,2011,11(12):5154-5158;Chem.Mater.,2014,26(23):6786-6795)。其在可穿戴柔性电热膜方面的应用同样具有较大的潜力,相关器件的制备有待开发。
发明内容
本发明针对目前石墨烯电热薄膜材料工作电压高、发热速度慢、饱和温度低等不足提出一种基于石墨烯纤维无纺布的自热膜,石墨烯纤维无纺布作为该自热膜的发热层材料具有导电率高、密度低的优势,因此可在较低的工作电压下快速发热,达到高的饱和温度。同时,将柔性的光伏薄膜作为能量层与石墨烯纤维无纺布发热层整合,能够得到柔性的自发热膜,在弯曲时发热性能不发生变化。
本发明通过以下技术方案实现:一种基于石墨烯纤维无纺布的自热膜,所述自热膜包括能量层和发热层,以及位于能量层和发热层之间的隔离层,所述能量层的两极分别与发热层的两端相连,形成闭合回路;所述能量层由柔性光伏薄膜构成,所述发热层由石墨烯纤维无纺布构成。
进一步地,所述能量层的一端与发热层的一端通过开关相连。
进一步地,所述隔离层由热隔离材料构成。
进一步地,所述石墨烯纤维无纺布由直径为1~1000μm的石墨烯纤维相互搭接形成网络结构,网格节点处的石墨烯纤维之间相互融合,所述石墨烯纤维由石墨烯片沿轴向定向排列而成。
进一步地,所述石墨烯纤维无纺布通过以下方法制备得到:
(1)配置浓度为1~15mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.01~10mL/min挤出速度通过直径为10~1000μm的纺丝管进入乙酸乙酯凝固液中,凝固液中浸泡30~200min后凝固成丝,真空抽滤收集,室温放置5-30h,60℃真空干燥,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇的混合液(水:乙醇的体积比=3:1~1:3)中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布还原,得到石墨烯纤维无纺布。
进一步地,凝固液置于可旋转的容器中,通过控制容器的旋转速度与纺丝液挤出速度的比值,使得石墨烯纤维的长度在2mm以上。
进一步地,收集石墨烯短纤维的滤网为孔径在0.2~100μm范围的微孔滤膜、纱网或不锈钢金属网。
进一步地,还原方法为使用氢碘酸、水合肼、维他命C、硼氢化钠等化学还原剂进行还原或100~3000℃热还原。
本发明与现有技术相比,具有的优势如下:
(1)基于溶液法连续纺丝得到的石墨烯纤维无纺布制备工艺简单,易于得到大面积的面状电热材料。
(2)制得的自热膜可在远低于人体安全电压的范围内高效率工作,升温和降温速率快,饱和温度高。
(3)制得的自热膜柔性好,在弯曲状态下发热性能不改变。
(4)光伏薄膜使用清洁能源,使自热膜器件工作时更节能环保。
附图说明
图1是自热膜器件的示意图,光伏薄膜为能量层,石墨烯纤维无纺布为发热层,中间为隔热材料构成的隔离层。能量层的两极与发热层的两端相连,在一端设有开关。
图2为发热层的扫描电镜图。
具体实施方式
本发明公开了一种基于石墨烯纤维无纺布的自热膜,包括能量层和发热层,以及位于能量层和发热层之间的隔离层,所述能量层的两极分别与发热层的两端相连,形成闭合回路;所述能量层由柔性光伏薄膜构成,所述发热层由石墨烯纤维无纺布构成。石墨烯纤维无纺布的纤维之间相互融合,接触电阻较低,因此无纺布整体的导电性和导热性都较高,同时,石墨烯纤维无纺布是一种多孔的二维薄膜状材料,其密度与之前的石墨烯薄膜和石墨烯纸相比相对较低。将其用作电致发热材料,该电热织物在较低的工作电压下即可达到快速的电热响应和高的饱和温度。另一方面,石墨烯纤维无纺布具有较好的柔性和结构稳定性,在弯曲状态下不发生结构破坏和由此而导致的电阻变化,因此该电热织物在自然状态和弯曲状态下的发热行为相同。
为搭建仅由石墨烯构成的网络结构的无纺布,本发明通过将湿纺得到的氧化石墨烯纤维组成的薄膜重新分散、沉积,得到纤维搭接、形状平整的氧化石墨烯无纺布结构,重新分散、沉积(即步骤3)使步骤2得到的团聚的石墨烯纤维重新分散在溶液中,同时纤维含有的溶剂量大大减少,从而显著降低氧化石墨烯纤维在干燥过程中的体积收缩,使得氧化石墨烯纤维无纺布的结构能够保持,解决了湿纺纤维溶剂脱除过程中由于严重的体积收缩而无法成型为无纺布的技术问题,最终得到的石墨烯纤维无纺布显现出密度低,孔隙率高,比表面积大的特点。此外,重新分散后的氧化石墨烯纤维呈低程度的溶胀状态,纤维表面结构疏松,因此沉积时在相互搭接的节点处会发生融合,纤维之间不再是较弱的摩擦力,能提供更多的强π-π相互作用。同时,纤维融合后形成整体式的传导网络,避免了传导过程中在纤维搭接处跃迁所导致的能量损耗,因此具有更好的导电导热性能。
本发明进一步将石墨烯纤维无纺布用作发热层,并由现有的柔性的光伏薄膜提供能量,中间添加隔热材料,得到了具有柔性和优良发热效率的自热膜。
下面通过实施例对本发明进行具体描述,本实施例只用于对本发明做进一步的说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整,均属于本发明的保护范围。
实施例1:
(1)配置浓度为5mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.04mL/min挤出速度通过直径为130μm的纺丝管进入乙酸乙酯旋转凝固液中,凝固液中浸泡30min后凝固成长度在2mm以上的氧化石墨烯短纤维,真空抽滤收集,室温放置10h,60℃真空干燥3h,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇按表1所示的体积比组成的混合液中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布经3000℃热还原得到石墨烯纤维无纺布。得到的无纺布的性质如表1所示。
表1水和乙醇体积比对制备石墨烯纤维无纺布的影响
(5)以水和乙醇按体积比3:1组成的混合液条件下获得的产物作为发热层,将其裁成条状,两端刷涂导电银胶并粘贴导电铜箔作为电极。
(6)将封装在聚合物薄膜中的1.5V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关,由此得到柔性自热膜。
经过以上步骤,得到的自热膜发热温度为40℃,通电时升温速率20℃s-1,断电时降温速率10℃s-1。自热膜弯曲时发热温度和速率不变。
实施例2:
(1)配置浓度为5mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.06mL/min挤出速度通过直径为200μm的纺丝管进入乙酸乙酯旋转凝固液中,凝固液中浸泡30min后真空抽滤收集,室温放置10h,60℃真空干燥3h,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇按体积比3:1的混合液中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布经3000℃热还原得到石墨烯纤维无纺布,如图2所示。
(5)将步骤4得到的石墨烯纤维无纺布裁成条状,两端刷涂导电银胶并粘贴导电铜箔作为电极。
(6)将封装在聚合物薄膜中的2V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关,由此得到柔性自热膜。
经过以上步骤,得到的自热膜发热温度为45℃。自热膜弯曲时发热温度和速率不变。
实施例3:
步骤1-5同实施例1。
(6)将封装在聚合物薄膜中的2V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关,由此得到柔性自热膜。
经过以上步骤,得到的自热膜发热温度为50℃,通电时升温速率55℃s-1,断电时降温速率58℃s-1。自热膜弯曲时发热温度和速率不变。
实施例4:
步骤1-5同实施例1。
(6)将3V太阳能电池片粘贴在石墨烯纤维无纺布的表面,并用导线连接光伏薄膜和无纺布的电极,电路的一侧安装开关。
经过以上步骤,得到的自热膜发热温度为79℃,通电时升温速率135℃s-1,断电时降温速率134℃s-1。
Claims (8)
1.一种基于石墨烯纤维无纺布的自热膜,其特征在于,所述自热膜包括能量层和发热层,以及位于能量层和发热层之间的隔离层等部件,所述能量层的两极分别与发热层的两端相连,形成闭合回路;所述能量层由柔性光伏薄膜构成,所述发热层由石墨烯纤维无纺布构成。
2.根据权利要求1所述的自热膜,其特征在于,所述能量层的一端与发热层的一端通过开关相连。
3.根据权利要求1所述的自热膜,其特征在于,所述隔离层由热隔离材料构成。
4.根据权利要求1所述的自热膜,其特征在于,所述石墨烯纤维无纺布由直径为1~1000μm的石墨烯纤维相互搭接形成网络结构,网格节点处的石墨烯纤维之间相互融合,所述石墨烯纤维由石墨烯片沿轴向定向排列而成。
5.根据权利要求1所述的自热膜,其特征在于,所述石墨烯纤维无纺布通过以下方法制备得到:
(1)配置浓度为1~15mg/mL的氧化石墨烯分散液,溶剂为N,N-二甲基甲酰胺,并将其作为纺丝液。
(2)使纺丝液以0.01~10mL/min挤出速度通过直径为10~1000μm的纺丝管进入乙酸乙酯凝固液中,凝固液中浸泡30~200min后凝固成丝,真空抽滤收集,室温放置5-30h,60℃真空干燥,得到氧化石墨烯纤维组成的薄膜。
(3)将步骤2得到的薄膜在水和乙醇的混合液(水:乙醇的体积比=3:1~1:3)中重新分散,得到氧化石墨烯纤维的悬浮液,经过滤网过滤沉积,在过滤网上得到氧化石墨烯纤维无纺布;将氧化石墨烯纤维无纺布用乙醇洗涤三遍,80℃干燥。
(4)将干燥后的氧化石墨烯纤维无纺布还原,得到石墨烯纤维无纺布。
6.根据权利要求5所述的石墨烯纤维无纺布制备方法,其特征在于,凝固液置于可旋转的容器中,通过控制容器的旋转速度与纺丝液挤出速度的比值,使得石墨烯纤维的长度在2mm以上。
7.根据权利要求5所述的石墨烯纤维无纺布制备方法,其特征在于,收集石墨烯短纤维的滤网为孔径在0.2~100μm范围的微孔滤膜、纱网或不锈钢金属网。
8.根据权利要求5所述的石墨烯纤维无纺布制备方法,其特征在于,还原方法为使用氢碘酸、水合肼、维他命C、硼氢化钠等化学还原剂进行还原或100~3000℃热还原。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610573992.6A CN106183142B (zh) | 2016-07-18 | 2016-07-18 | 一种基于石墨烯纤维无纺布的自热膜 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610573992.6A CN106183142B (zh) | 2016-07-18 | 2016-07-18 | 一种基于石墨烯纤维无纺布的自热膜 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106183142A true CN106183142A (zh) | 2016-12-07 |
CN106183142B CN106183142B (zh) | 2018-02-09 |
Family
ID=57493642
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610573992.6A Active CN106183142B (zh) | 2016-07-18 | 2016-07-18 | 一种基于石墨烯纤维无纺布的自热膜 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106183142B (zh) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018014583A1 (zh) * | 2016-07-18 | 2018-01-25 | 浙江大学 | 一种石墨烯纤维无纺布及其制备方法 |
CN107761249A (zh) * | 2017-11-18 | 2018-03-06 | 杭州高烯科技有限公司 | 一种石墨烯‑玻璃纤维复合材料及其制备方法 |
CN108315877A (zh) * | 2018-03-09 | 2018-07-24 | 欧阳业东 | 一种石墨烯无纺布及其生产制造工艺 |
CN109098362A (zh) * | 2018-09-25 | 2018-12-28 | 浙江明烁节能科技股份有限公司 | 用于融化冰雪的柔性卷材贴及其冰雪融化系统、方法 |
WO2019066492A3 (en) * | 2017-09-28 | 2019-05-02 | Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) | JULY EFFECT GRAPHENE FIBER FIBER AND METHOD FOR MANUFACTURING THE SAME |
CN109734468A (zh) * | 2019-02-26 | 2019-05-10 | 航天材料及工艺研究所 | 一种石墨烯纸增强碳/碳复合材料及其制备方法 |
CN109888190A (zh) * | 2019-04-19 | 2019-06-14 | 河北工业大学 | 一种钠离子储能用石墨烯/钛酸钠无纺布材料的制备方法 |
CN110219095A (zh) * | 2019-06-24 | 2019-09-10 | 山东天厚新材料科技有限公司 | 一种石墨烯纤维阻燃导电无纺布及其制备方法 |
WO2019182351A1 (ko) * | 2018-03-20 | 2019-09-26 | 한양대학교 산학협력단 | 펄스 전류가 인가된 그래핀 파이버 및 그 제조 방법 |
CN111411451A (zh) * | 2020-04-27 | 2020-07-14 | 成都新柯力化工科技有限公司 | 一种柔性石墨烯无纺布发热材料及制备方法 |
US11542411B2 (en) | 2017-05-27 | 2023-01-03 | Hangzhou Gaoxi Technology Co., Ltd. | Method for preparing composites on basis of graphene bonding |
US11661677B2 (en) | 2017-09-28 | 2023-05-30 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Graphene fiber manufactured by joule heating and method of manufacturing the same |
WO2023108378A1 (zh) * | 2021-12-14 | 2023-06-22 | 浙江大学 | 具有特定截面形态特征的气凝胶纤维及其制备方法与装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN203813982U (zh) * | 2014-04-22 | 2014-09-03 | 常州二维碳素科技有限公司 | 一种自除雾透明体 |
CN104229783A (zh) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | 一种高导热石墨烯膜的制备方法 |
US20150064463A1 (en) * | 2013-09-02 | 2015-03-05 | Enerage Inc. | Graphene fiber and method of manufacturing the same |
CN105113127A (zh) * | 2015-09-26 | 2015-12-02 | 武汉纺织大学 | 一种大面积的柔性压电自发热无纺布及其制备方法 |
CN105615522A (zh) * | 2016-04-01 | 2016-06-01 | 无锡市翱宇特新科技发展有限公司 | 一种保温水杯 |
-
2016
- 2016-07-18 CN CN201610573992.6A patent/CN106183142B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150064463A1 (en) * | 2013-09-02 | 2015-03-05 | Enerage Inc. | Graphene fiber and method of manufacturing the same |
CN203813982U (zh) * | 2014-04-22 | 2014-09-03 | 常州二维碳素科技有限公司 | 一种自除雾透明体 |
CN104229783A (zh) * | 2014-09-10 | 2014-12-24 | 浙江碳谷上希材料科技有限公司 | 一种高导热石墨烯膜的制备方法 |
CN105113127A (zh) * | 2015-09-26 | 2015-12-02 | 武汉纺织大学 | 一种大面积的柔性压电自发热无纺布及其制备方法 |
CN105615522A (zh) * | 2016-04-01 | 2016-06-01 | 无锡市翱宇特新科技发展有限公司 | 一种保温水杯 |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018014583A1 (zh) * | 2016-07-18 | 2018-01-25 | 浙江大学 | 一种石墨烯纤维无纺布及其制备方法 |
US11542411B2 (en) | 2017-05-27 | 2023-01-03 | Hangzhou Gaoxi Technology Co., Ltd. | Method for preparing composites on basis of graphene bonding |
WO2019066492A3 (en) * | 2017-09-28 | 2019-05-02 | Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) | JULY EFFECT GRAPHENE FIBER FIBER AND METHOD FOR MANUFACTURING THE SAME |
US11661677B2 (en) | 2017-09-28 | 2023-05-30 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Graphene fiber manufactured by joule heating and method of manufacturing the same |
CN107761249A (zh) * | 2017-11-18 | 2018-03-06 | 杭州高烯科技有限公司 | 一种石墨烯‑玻璃纤维复合材料及其制备方法 |
CN108315877A (zh) * | 2018-03-09 | 2018-07-24 | 欧阳业东 | 一种石墨烯无纺布及其生产制造工艺 |
WO2019182351A1 (ko) * | 2018-03-20 | 2019-09-26 | 한양대학교 산학협력단 | 펄스 전류가 인가된 그래핀 파이버 및 그 제조 방법 |
CN109098362A (zh) * | 2018-09-25 | 2018-12-28 | 浙江明烁节能科技股份有限公司 | 用于融化冰雪的柔性卷材贴及其冰雪融化系统、方法 |
CN109734468A (zh) * | 2019-02-26 | 2019-05-10 | 航天材料及工艺研究所 | 一种石墨烯纸增强碳/碳复合材料及其制备方法 |
CN109888190A (zh) * | 2019-04-19 | 2019-06-14 | 河北工业大学 | 一种钠离子储能用石墨烯/钛酸钠无纺布材料的制备方法 |
CN109888190B (zh) * | 2019-04-19 | 2021-04-20 | 河北工业大学 | 一种钠离子储能用石墨烯/钛酸钠无纺布材料的制备方法 |
CN110219095A (zh) * | 2019-06-24 | 2019-09-10 | 山东天厚新材料科技有限公司 | 一种石墨烯纤维阻燃导电无纺布及其制备方法 |
CN111411451A (zh) * | 2020-04-27 | 2020-07-14 | 成都新柯力化工科技有限公司 | 一种柔性石墨烯无纺布发热材料及制备方法 |
WO2023108378A1 (zh) * | 2021-12-14 | 2023-06-22 | 浙江大学 | 具有特定截面形态特征的气凝胶纤维及其制备方法与装置 |
Also Published As
Publication number | Publication date |
---|---|
CN106183142B (zh) | 2018-02-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106183142B (zh) | 一种基于石墨烯纤维无纺布的自热膜 | |
CN107502995B (zh) | 一种褶皱的石墨烯纤维和石墨烯纤维无纺布及其制备方法 | |
CN106192201B (zh) | 一种石墨烯纤维无纺布及其制备方法 | |
CN103607795B (zh) | 一种石墨烯发热膜的制备方法 | |
CN109537105A (zh) | 一种多孔中空纤维导电材料及其制备方法 | |
CN108707998A (zh) | 一种褶皱的石墨烯纤维和石墨烯纤维无纺布及其制备方法 | |
CN106868715A (zh) | 一种模压成型石墨烯无纺布的制备方法 | |
CN109281224A (zh) | 一种多孔石墨烯纤维无纺布及其制备方法 | |
CN108315877A (zh) | 一种石墨烯无纺布及其生产制造工艺 | |
CN105366661A (zh) | 一种超级电容器用卷曲状多孔炭纳米片的制备方法 | |
CN108774808A (zh) | 一种具有交联形貌的表面包覆二氧化锆的聚酰亚胺纳米纤维膜及其制备方法 | |
CN105110312A (zh) | 碳纳米管石墨复合材料及其制备方法和装置 | |
CN109355799A (zh) | 一种氮掺杂的石墨烯纤维无纺布及其制备方法 | |
CN105405960B (zh) | 一种石墨烯驻极体纳米发电机 | |
Zhao et al. | Cloth-derived anisotropic carbon scroll attached with 2D oriented graphite layers for supporting phase change material with efficient thermal storage | |
CN109065367A (zh) | 一种石墨烯/二氧化锰基非对称同轴纤维超级电容器及其制备和应用 | |
CN105970715A (zh) | 一种三层复合过滤纸及其制备方法 | |
CN107687090A (zh) | 一种石墨烯交联的碳纤维丝束、织物及其制备方法 | |
CN107523891A (zh) | 一种碳纳米管定向增强的纳米pva纤维复合材料及其制备方法 | |
CN103103870B (zh) | 一种功能化碳纤维复合电热纸的制备方法 | |
Leng et al. | Porous biological carbon fiber foam combined by aluminum phosphate for enhancing electric heating and electric thermal storage performance | |
KR20200126693A (ko) | 발열기능을 구비한 그래핀 코팅 탄소섬유 의류 | |
CN105887244A (zh) | 一种石墨烯纤维 | |
CN101140828A (zh) | 一种规模化生产的超级电容器 | |
CN110452494A (zh) | 一种复合导热材料及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20190903 Address after: 313100 Room 830, 8th Floor, Changxing World Trade Building, 1278 Mingzhu Road, Changxing Economic Development Zone, Huzhou City, Zhejiang Province Patentee after: Changxin de Technology Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: Zhejiang University |
|
TR01 | Transfer of patent right |