CN112614933B - Pvdf压电材料的制备方法及pvdf压电材料 - Google Patents
Pvdf压电材料的制备方法及pvdf压电材料 Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 315
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 313
- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 75
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 11
- 238000001523 electrospinning Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 5
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 5
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000000051 modifying effect Effects 0.000 claims description 4
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 4
- -1 2- (phosphoryloxy) ethyl Chemical group 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 230000008054 signal transmission Effects 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 238000009987 spinning Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 238000010586 diagram Methods 0.000 description 4
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 3
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- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
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- 239000002052 molecular layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HARFJRFDECVESO-UHFFFAOYSA-N 2-hydroxyethyl dihydrogen phosphate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCOP(O)(O)=O HARFJRFDECVESO-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BFYJDHRWCNNYJQ-UHFFFAOYSA-N oxo-(3-oxo-3-phenylpropoxy)-(2,4,6-trimethylphenyl)phosphanium Chemical compound CC1=CC(C)=CC(C)=C1[P+](=O)OCCC(=O)C1=CC=CC=C1 BFYJDHRWCNNYJQ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
一种PVDF压电材料的制备方法及PVDF压电材料,该方法包括如下步骤:S1:制备PVDF原溶液,以及制备带电荷的改性分子与PVDF的混合溶液;S2:使PVDF原溶液形成第一PVDF层,使带电荷的改性分子与PVDF的混合溶液形成第二PVDF层及第三PVDF层,并使第二PVDF层及第三PVDF层分别位于第一PVDF层的两个表面上,以形成PVDF材料基体,在形成PVDF基体时,使第二PVDF层及第三PVDF层内的改性分子与PVDF形成带电荷的交联网络;S3:在第二PVDF层及第三PVDF层上施加带有电荷的电极催化剂溶液,电极催化剂溶液所带电荷的种类与改性分子及PVDF的混合溶液中的电荷的种类相反;S4:对施加有带电荷的催化剂溶液的PVDF材料基体进行化学镀处理,以使第二PVDF层及第三PVDF层上形成电极。该PVDF压电材料的两个电极间能够具有较好地信号传输性能。
Description
技术领域
本发明涉及柔性技术领域,尤其是一种PVDF压电材料的制备方法及PVDF压电材料。
背景技术
PVDF(聚偏氟乙烯,polyvinylidene fluoride)材料因其具有很好的压电活性,广泛地应用于压电器件内。在制备PVDF压电材料时,需要在一层PVDF膜的两个表面上制备电极。在现有技术中,一般会通过粘贴的方式将电极固定于PVDF膜的两个表面上。粘贴界面性能会影响两个电极间压电信号的传输,继而影响压电器件的性能。
发明内容
有鉴于此,本发明提供了一种PVDF压电材料的制备方法及PVDF压电材料,该PVDF压电材料的两个电极间能够具有较好地信号传输性能。
本发明提供了一种PVDF压电材料的制备方法,该方法包括如下步骤:
S1:制备PVDF原溶液,以及制备带电荷的改性分子与PVDF的混合溶液;
S2:使所述PVDF原溶液形成第一PVDF层,使所述带电荷的改性分子与PVDF的混合溶液形成第二PVDF层及第三PVDF层,并使所述第二PVDF层及所述第三PVDF层分别位于所述第一PVDF层的两个表面上,以形成PVDF材料基体,在形成所述PVDF基体时,使所述第二PVDF层及所述第三PVDF层内的改性分子与PVDF形成带电荷的交联网络;
S3:在所述第二PVDF层及第三PVDF层上施加带有电荷的电极催化剂溶液,所述电极催化剂溶液所带电荷的种类与改性分子及PVDF的混合溶液中的电荷的种类相反;
S4:对施加有带电荷的催化剂溶液的PVDF材料基体进行化学镀处理,以使所述第二PVDF层及所述第三PVDF层上形成电极。
进一步地,在S1步骤中,所述带电荷的改性分子与PVDF的混合溶液中的电荷由改性分子引入混合溶液。
进一步地,所述改性分子所带电荷为正电荷或负电荷,所述带正电荷的改性分子包括丙烯酰氧乙基三甲基氯化铵或甲基丙烯酰氧乙基三甲基氯化铵,所述带负电荷的改性分子包括二[2-(甲基丙烯酰氧基)乙基]磷酸酯、2-(磷酰氧基)乙基丙烯酸酯或2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯。
进一步地,在S1步骤中,该方法还包括在所述带电荷的改性分子与PVDF的混合溶液中加入使所述改性分子与所述PVDF形成交联网络的引发剂。
进一步地,在所述带电荷的改性分子与PVDF的混合溶液中,以质量百分比计,所述PVDF含量为5-25wt%,所述改性分子含量为0.5-5wt%,所述引发剂含量为0.002-0.02wt%。
进一步地,在形成所述第二PVDF层及所述第三PVDF层时,该步骤还包括施加与所述引发剂相适应的改性因素。
进一步地,在所述PVDF原溶液中,所述PVDF的含量为8-30wt%。
进一步地,在S2步骤中,通过电纺丝或喷墨打印工艺以形成所述第一PVDF层、所述第二PVDF层及所述第三PVDF层。
进一步地,所述带有电荷的电极催化剂溶液中的电荷由电极催化剂引入,所述电极催化剂的种类与S4步骤中,引入电极的种类相适应。
进一步地,当所述电极为金属铜时,所述电极催化剂为钯催化剂,所述带有电荷的钯催化剂溶液为四氨基二氯化钯溶液或四氯钯酸钠溶液。
进一步地,在进行S3步骤时,该方法包括:
将S2步骤中的所述PVDF材料基体浸入带有相反种类电荷的所述电极催化剂溶液中;
取出所述PVDF材料基体,并进行清洗;
在进行S4步骤时,该方法包括:
将施加有带电荷的电极催化剂溶液的所述PVDF材料基体放入化学镀反应液中,进行化学镀;
取出进行化学镀后的PVDF材料基体,并对其进行清洗;
对PVDF材料基体进行烘干处理。
本发明还提供了一种PVDF压电材料,所述PVDF压电材料由上述PVDF压电材料的制备方法制备而成。
综上所述,在本发明中,由于第二PVDF层及第三PVDF层内形成有改性分子与PVDF的带有电荷的交联网络,且电极催化剂溶液内含有与其相反的电荷,因此,在分子层面上,电极金属能够通过化学镀的方式进入到改性分子与PVDF形成的二维或三维网络结构内,也即,第二PVDF层及第三PVDF层内的改性分子与PVDF二维或三维体系能够原位自催化升程导电层以作为PVDF压电材料的电极,进一步地,由于第二PVDF层及第三PVDF层设置于第一PVDF层的两个表面上,PVDF压电材料的电极与第一PVDF层形成统一结构的界面,这保证了PVDF压电材料的压电性能不受界面的影响,提高PVDF压电材料的性能。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下特举较佳实施例,并配合附图,详细说明如下。
附图说明
图1所示为本发明实施例提供的PVDF压电材料的截面结构示意图。
图2所示为本发明实施例提供的PVDF压电材料的制备方法中各步骤的流程示意图。
图3所示为电纺装置的结构示意图。
具体实施方式
为更进一步阐述本发明为达成预定发明目的所采取的技术手段及功效,以下结合附图及较佳实施例,详细说明如下。
本发明提供了一种PVDF(聚偏氟乙烯,polyvinylidene fluoride)压电材料的制备方法及PVDF压电材料,该PVDF压电材料的两个电极间能够具有较好地信号传输性能。
图1所示为本发明实施例提供的PVDF压电材料的截面结构示意图,图2所示为本发明实施例提供的PVDF压电材料的制备方法中各步骤的流程示意图,图3所示为电纺装置的结构示意图。如图1至图3所示,本发明提供的PVDF压电材料的制备方法包括如下步骤:
S1:制备PVDF原溶液,以及制备带电荷的改性分子与PVDF的混合溶液;
在配置PVDF原溶液时,称取一定量的PVDF,然后加入溶剂进行溶解,在配置好的PVDF原溶液中,以质量百分比计,PVDF的含量为8-30wt%。在本实施例中,PVDF原溶液的溶剂可以为N,N-二甲基甲酰胺(DMF)和丙酮,在配置好的PVDF原溶液中,DMF与丙酮的质量比为3:7-9:1。
在该步骤中,带电荷的改性分子与PVDF的混合溶液中的电荷可以由改性分子引入溶液,改性分子所带电荷可以为正电荷或负电荷。带正电荷的改性分子包括丙烯酰氧乙基三甲基氯化铵(CAS:44992-01-0)或甲基丙烯酰氧乙基三甲基氯化铵(CAS:5039-78-1)等;带负电荷的改性分子包括二[2-(甲基丙烯酰氧基)乙基]磷酸酯(CAS:32435-46-4)、2-(磷酰氧基)乙基丙烯酸酯(CAS:32120-16-4)或2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯(CAS:52628-03-2)等。上述的材料因其自身的溶解而使溶液带有不同种类的电荷。
进一步地,在本实施例中,将带有电荷的改性分子与PVDF形成混合溶液的目的,是为了使改性分子与PVDF形成带电荷的交联网络。为了使该交联网络更容易形成,该方法还包括,在改性分子与PVDF的混合液中加入引发剂,如光引发剂,以便后续在对改性分子与PVDF的混合溶液施加改性因素处理,如紫外线照射时,改性分子与PVDF进行交联,使二者形成带电荷的交联网络。
光引发剂可以包括苯基双(2,4,6-三甲基苯甲酰基)氧膦(819)、2,4,6-三甲基苯甲酰基乙氧基苯基氧化膦(TEPO)或2,4,6-三甲基苯甲酰基二苯基氧化膦(TPO)等。
在配制带有电荷的改性分子与PVDF的混合溶液时,可以将改性分子加入到PVDF原溶液中,也可以先将改性分子与PVDF混合,然后进行溶液的制备。在配置好的改性分子与PVDF的混合溶液中,以质量百分比计,PVDF含量为5-25wt%,带电荷的改性分子含量为0.5-5wt%,引发剂含量为0.002-0.02wt%。在本实施例中,带电荷的改性分子与PVDF的混合溶液的溶剂同样可以为N,N-二甲基甲酰胺(DMF)和丙酮,在配置好的带电荷的改性分子与PVDF的混合溶液中,DMF与丙酮的质量比为3:7-9:1。
S2:使PVDF原溶液形成第一PVDF层11,使带电荷的改性分子与PVDF的混合溶液形成第二PVDF层12及第三PVDF层13,并使第二PVDF层12及第三PVDF层13分别位于第一PVDF层11的两个表面上,以形成PVDF材料基体。在形成PVDF材料基体时,使得第二PVDF层12及第三PVDF层13内的改性分子与PVDF形成带电荷的交联网络。
在该步骤中,可以先形成第二PVDF层12,以第二PVDF层12为衬底,在第二PVDF层12上形成第一PVDF层11,然后在第一PVDF层11上形成第三PVDF层13。同样地,也可以先形成第一PVDF层11,然后在第一PVDF层11的两个表面上分别形成第二PVDF层12及第三PVDF层13。
在本实施例中,可以通过电纺丝工艺形成第一PVDF层、第二PVDF层及第三PVDF层,在进行电纺丝时,如图3所示,先将带有电荷的改性分子与PVDF的混合溶液装入注射器21中,并将注射器21在可移动的基台22上进行固定,设定注射器21的推进速率、基台22的移动速率、收集滚筒23的转速及纺丝电压,然后进行纺丝成膜,以形成第二PVDF层12。当改性分子与PVDF的混合溶液内添加有光引发剂时,可以在纺丝过程中,对其进行紫外线处理,以使改性分子与PVDF形成带电荷的交联网络。也即,改性分子的引入是为了在该步骤中对PVDF进行改性,使改性分子与PVDF形成带电荷的二维或三维网络结构。可以理解地,在其它实施例中,引发剂还可以为其它种类的引发剂,如热引发剂,与之相应地,在进行纺丝的过程中需要施加热处理等影响因素。
在本实施例中,注射泵推进速率为0.01-1mm/min,基台的移动速率为100-500mm/min,收集滚筒的转速为100-1000r/min,纺丝电压为10-30kV。
在进行第一PVDF层11的制备时,可以将带电荷的改性分子与PVDF的混合溶液替换为PVDF原溶液,其余步骤不变,并使第一PVDF层11形成于第二PVDF层12上。可以理解地,由于PVDF原溶液中不再需要形成改性分子与PVDF的带电荷的交联网络,其可以不再施加改性影响,如不再进行紫外线照射等。
在进行第三PVDF层13的制备时,其步骤与第二PVDF层12相同,并使第三PVDF层13形成于第一PVDF层11远离第二PVDF层12的一侧上。
在其它实施例中,还可以通过喷墨打印的方式形成第一PVDF层、第二PVDF层及第三PVDF层。可以理解地,各层也可以通过不同的工艺来形成。
S3:在第二PVDF层12与第三PVDF层13上施加带电荷的电极催化剂溶液,该电极催化剂溶液所带电荷的种类与S1步骤中,改性分子与PVDF的混合溶液中的电荷的种类相反。
在本步骤中,当改性分子与PVDF的混合溶液中带有正电荷时,电极催化剂溶液应选用带有负电荷的电极催化剂,当改性分子与PVDF的混合溶液中带有负电荷时,电极催化剂溶液应选用带有正电荷的电极催化剂。
在本实施例中,电极催化剂溶液的施加是为了在第二PVDF层12及第三PVDF层13上形成电极,因此,电极催化剂的种类需要与电极金属的种类相适应,在本实施例中,若需要在第二PVDF层12及第三PVDF层13上形成铜电极,则该电极催化剂溶液可以为钯催化剂溶液。在其它实施例中,第二PVDF层12及第三PVDF层上的电极均可以为银电极或镍电极,同样地,其电极催化剂也可以为钯催化剂。
在本步骤中,可以将上述的PVDF材料基体浸入带有相反种类电荷的电极催化剂溶液中,由于第二PVDF层12及第三PVDF层13内形成有改性分子与PVDF的带有电荷的交联网络,且电极催化剂溶液内含有与其相反种类的电荷,因此电极催化剂能够浸入第二PVDF层12及第三PVDF层13内,并与之较好地结合。在本实施例中,浸泡时间可以为1-30min。在取出PVDF材料基体后,还可以用去离子水对其进行清洗,以去除未与第二PVDF层12及第三PVDF层13结合的电极催化剂。
在本实施例中,带电荷的电极催化剂内的电荷由电极催化剂引入。在制备电极催化剂溶液时,以钯催化剂溶液为例,称取一定量的四氨基二氯化钯(带正电荷的钯催化剂)或四氯钯酸钠(带负电荷的钯催化剂),然后加入去离子水进行溶解,在形成电极催化剂溶液后,以质量百分比计,电极催化剂溶液的含量为0.05-0.5wt%。
需要说明的是,在本实施例中,PVDF原溶液的含义为无法在第二PVDF层或第三PVDF层的制备过程中,形成改性分子与PVDF的带电荷的交联网络的溶液,其不代表不能够包含其他的材料。
S4:对施加有带电荷的电极催化剂溶液的PVDF材料基体进行化学镀处理,以使第二PVDF层12及第三PVDF层13上形成电极。
在本实施例中,以电极为铜金属为例,可以将施加有正电荷或负电荷的电极催化剂溶液的PVDF材料基体浸泡入化学镀铜的反应液中,当第二PVDF层12及第三PVDF层13上有气泡产生时,说明化学镀铜的反应已经发生,在进行化学镀后,取出PVDF材料基体,用去离子水清洗后,放入烘箱中烘干,完成PVDF压电材料的制备。其中,化学镀铜液可以为双组份镀铜液,使用前将A组分及B组分按照体积比1:1进行混合。化学镀的反应时间为1-30min,烘干温度为40-80℃,烘干时间可以为5-30min。
在本发明中,由于第二PVDF层12及第三PVDF层13内形成有改性分子与PVDF的带有电荷的交联网络,且电极催化剂溶液内含有与其相反的电荷,因此,在分子层面上,电极金属能够通过化学镀的方式进入到改性分子与PVDF形成的二维或三维网络结构内,也即,第二PVDF层12及第三PVDF层13内的改性分子与PVDF二维或三维体系能够原位自催化生成导电层以作为PVDF压电材料的电极,进一步地,由于第二PVDF层12及第三PVDF层13设置于第一PVDF层11的两个表面上,PVDF压电材料的电极与第一PVDF层11形成统一结构的界面,这保证了PVDF压电材料的压电性能不受界面的影响,提高PVDF压电材料的性能。
以下以具体实施例对该制备方法进行说明:
实施例1:
配制PVDF原溶液的步骤:称取一定量PVDF(分子量为60万)放入烧杯中,加入N,N-二甲基甲酰胺(DMF)和丙酮进行溶解。PVDF含量为10wt%,其余为DMF和丙酮,DMF与丙酮的质量比为6:4。
配制含有正电荷改性分子与PVDF的混合溶液的步骤:称取一定量的PVDF(分子量为60万)放入烧杯中,加入N,N-二甲基甲酰胺(DMF)和丙酮进行溶解,最后加入带正电荷的丙烯酰氧乙基三甲基氯化铵、光引发剂苯基双(2,4,6-三甲基苯甲酰基)氧膦(819)搅拌溶解。最终体系中PVDF含量为10wt%,带正电荷的改性分子含量为2wt%,光引发剂含量为0.012wt%,其余为DMF和丙酮,DMF与丙酮的质量比为6:4。
电纺成膜步骤:
1、将含有正电荷的改性分子与PVDF混合溶液装入注射器,并放置于可移动的基台上固定,设置注射泵的推进速率、基台移动速率、收集滚筒转速、纺丝电压后,进行纺丝成膜。电纺过程中,DMF和丙酮逐渐挥发;在紫外光源照射下,改性分子与PVDF共混形成带电荷的交联网络。注射泵推进速率为0.15mm/min,基台移动速率为200mm/min,收集滚筒转速为600r/min,纺丝电压为18kV。
2、将含有正电荷的改性分子与PVDF混合溶液替换成PVDF原溶液,纺丝步骤同步骤1,纺丝过程中关闭紫外光源,不需要光照,以最终形成第一PVDF层。
3、第三PVDF层也是由带有正电荷的改性分子与PVDF混合溶液制成,纺丝步骤同步骤1。
化学镀铜步骤:
将纺丝完成的PVDF材料基体从设备上取下,放在带正电荷的钯催化剂溶液中浸泡10min后取出,用去离子水清洗后浸泡在化学镀铜反应液中,5min后取出,在去离子水清洗后放入60℃烘箱中10min烘干得到PVDF压电材料。
钯催化剂配制方法:称取一定量四氯钯酸钠(带负电荷的钯催化剂)放入烧杯中,加去离子水进行溶解。四氯钯酸钠的含量为0.09wt%,其余为水。
测试:
用四探针进行镀铜后上下电极的导电性能测试,方阻为430mΩ/sq。
实施例2:
配制PVDF原溶液的步骤:称取一定量PVDF(分子量为80万)放入烧杯中,加入N,N-二甲基甲酰胺(DMF)和丙酮进行溶解。PVDF含量为15wt%,其余为DMF和丙酮,DMF与丙酮的质量比为5:5。
配制含有负电荷的改性分子与PVDF混合溶液的步骤:称取一定量的PVDF(分子量为80万)溶液放入烧杯中,加入N,N-二甲基甲酰胺(DMF)和丙酮进行溶解,最后加入带负电荷的改性分子二[2-(甲基丙烯酰氧基)乙基]磷酸酯、光引发剂2,4,6-三甲基苯甲酰基二苯基氧化膦(TPO)搅拌溶解。最终体系中PVDF含量为15wt%,带负电荷的改性分子含量为1.5wt%,光引发剂含量为0.005wt%,其余为DMF和丙酮,DMF与丙酮的质量比为5:5。
电纺成膜步骤:
1、将含有负电荷的改性分子与PVDF混合溶液装入注射器,并放置于可移动的基台上固定,设置注射泵的推进速率、基台移动速率、收集滚筒转速、纺丝电压后,进行纺丝成膜。电纺过程中,DMF和丙酮逐渐挥发;在紫外光源照射下,改性分子与PVDF共混形成带电荷的交联网络。注射泵推进速率为0.3mm/min,基台移动速率为300mm/min,收集滚筒转速为500r/min,纺丝电压为20kV。
2、将含有负电荷的改性分子与PVDF混合溶液替换成PVDF原溶液,纺丝步骤同步骤1,纺丝过程中关闭紫外光源,不需要光照,以最终形成第一PVDF层。
3、第三PVDF层也是由带有负电荷的改性分子与PVDF混合溶液制成,纺丝步骤同步骤1。
化学镀铜步骤:
将成型的PVDF材料基体从设备上取下,放在带正电荷的钯催化剂溶液中浸泡20min后取出,用去离子水清洗后浸泡在化学镀铜反应液中,50min后取出,在去离子水清洗后放入70℃烘箱中8min烘干得到PVDF压电材料。
钯催化剂配制方法:称取一定量四氨基二氯化钯(带正电荷的钯催化剂)放入烧杯中,加去离子水进行溶解。四氨基二氯化钯的含量为0.12wt%,其余为水。
测试:
用四探针进行镀铜后上下电极的导电性能测试,方阻为790mΩ/sq。
对比例1:制备PVDF膜,然后在PVDF膜的上下两侧粘贴铜电极,如铜胶带。用四探针进行镀铜后上下电极的导电性能测试,方阻为20mΩ/sq。
本发明还提供了一种PVDF压电材料,该压电材料由上述的PVDF压电材料制备方法制备而成。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (11)
1.一种PVDF压电材料的制备方法,其特征在于:该方法包括如下步骤:
S1:制备PVDF原溶液,以及制备带电荷的改性分子与PVDF的混合溶液,所述改性分子为对所述PVDF进行改性,以使所述改性分子与所述PVDF形成二维或三维交联网络的改性分子,所述带电荷的改性分子与PVDF的混合溶液中的电荷由改性分子引入混合溶液;
S2:使所述PVDF原溶液形成第一PVDF层,使所述带电荷的改性分子与PVDF的混合溶液形成第二PVDF层及第三PVDF层,并使所述第二PVDF层及所述第三PVDF层分别位于所述第一PVDF层的两个表面上,以形成PVDF材料基体,在形成所述PVDF基体时,使所述第二PVDF层及所述第三PVDF层内的改性分子与PVDF形成带电荷的交联网络;
S3:在所述第二PVDF层及所述第三PVDF层上施加带有电荷的电极催化剂溶液,所述电极催化剂溶液所带电荷的种类与改性分子及PVDF的混合溶液中的电荷的种类相反;
S4:对施加有带电荷的催化剂溶液的PVDF材料基体进行化学镀处理,以使所述第二PVDF层及所述第三PVDF层上形成电极。
2.根据权利要求1所述的PVDF压电材料的制备方法,其特征在于:所述改性分子所带电荷为正电荷或负电荷,所述带正电荷的改性分子包括丙烯酰氧乙基三甲基氯化铵或甲基丙烯酰氧乙基三甲基氯化铵,所述带负电荷的改性分子包括二[2-(甲基丙烯酰氧基)乙基]磷酸酯、2-(磷酰氧基)乙基丙烯酸酯或2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯。
3.根据权利要求1所述的PVDF压电材料的制备方法,其特征在于:在S1步骤中,该方法还包括在所述带电荷的改性分子与PVDF的混合溶液中加入使所述改性分子与所述PVDF形成交联网络的引发剂。
4.根据权利要求3所述的PVDF压电材料的制备方法,其特征在于:在所述带电荷的改性分子与PVDF的混合溶液中,以质量百分比计,所述PVDF含量为5-25wt%,所述改性分子含量为0.5-5wt%,所述引发剂含量为0.002-0.02wt%。
5.根据权利要求3所述的PVDF压电材料的制备方法,其特征在于:在形成所述第二PVDF层及所述第三PVDF层时,该步骤还包括施加与所述引发剂相适应的改性因素。
6.根据权利要求1所述的PVDF压电材料的制备方法,其特征在于:在所述PVDF原溶液中,所述PVDF的含量为8-30wt%。
7.根据权利要求1所述的PVDF压电材料的制备方法,其特征在于:在S2步骤中,通过电纺丝或喷墨打印工艺以形成所述第一PVDF层、所述第二PVDF层及所述第三PVDF层。
8.根据权利要求1所述的PVDF压电材料的制备方法,其特征在于:所述带有电荷的电极催化剂溶液中的电荷由电极催化剂引入,所述电极催化剂的种类与S4步骤中,引入电极的种类相适应。
9.根据权利要求8所述的PVDF压电材料的制备方法,其特征在于:当所述电极为金属铜时,所述电极催化剂为钯催化剂,所述带有电荷的钯催化剂溶液为四氨基二氯化钯溶液或四氯钯酸钠溶液。
10.根据权利要求1所述的PVDF压电材料的制备方法,其特征在于:在进行S3步骤时,该方法包括:
将S2步骤中的所述PVDF材料基体浸入带有相反种类电荷的所述电极催化剂溶液中;
取出所述PVDF材料基体,并进行清洗;
在进行S4步骤时,该方法包括:
将施加有带电荷的电极催化剂溶液的所述PVDF材料基体放入化学镀反应液中,进行化学镀;
取出进行化学镀后的PVDF材料基体,并对其进行清洗;
对PVDF材料基体进行烘干处理。
11.一种PVDF压电材料,其特征在于:所述PVDF压电材料由权利要求1至10中任意一项所述的PVDF压电材料的制备方法制备而成。
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