WO2022048165A1 - Motif-structured cellulose based nanofluid ion conductor and preparation method and application - Google Patents

Motif-structured cellulose based nanofluid ion conductor and preparation method and application Download PDF

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WO2022048165A1
WO2022048165A1 PCT/CN2021/089394 CN2021089394W WO2022048165A1 WO 2022048165 A1 WO2022048165 A1 WO 2022048165A1 CN 2021089394 W CN2021089394 W CN 2021089394W WO 2022048165 A1 WO2022048165 A1 WO 2022048165A1
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cellulose
parts
conductor material
ionic conductor
nanofluidic
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叶冬冬
邹捷
李琦华
郑格格
郑双
林泽婉
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五邑大学
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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Definitions

  • the present invention relates to the field of nanofluid, in particular to a cellulose-based nanofluid ion conductor material of elementary order structure, a preparation method and application thereof.
  • Li Tian et al. (Sci. Adv. 2019, 5, u4238) used the natural oriented nano-microstructure of wood to prepare a wood film with nanofluid effect from top to bottom; Hu Liangbing of the University of Maryland et al. designed a class based on wood. Nanofluidic wood membrane realizes low heat recovery (Nat. Mater. 2019, 18, 608), osmotic power generation with salt concentration gradient (Adv. Energy Mater. 2019, 1902590).
  • the invention is based on the wide application of nanomaterials in the fields of energy conversion materials, energy storage materials, conductive materials, biomedical materials and the like.
  • a “top-down” strategy that is, from the molecular chain level of cellulose, prepared by dissolving cotton, chemical modification, etc.
  • An environmentally friendly, renewable, and degradable functional cellulose-based nanofluid ion conductor material, and its application in the field of salt gradient concentration osmotic power generation is realized.
  • An object of the present invention is to provide a cellulose-based nanofluidic ionic conductor material of elementary ordered structure, which can be realized by the following technical means:
  • a cellulose-based nano fluid ionic conductor material which is prepared from the following raw materials in parts by mass:
  • the cellulose solvent contains alkali, urea and water
  • the first functional nanofiller includes one or both of carbon nanotubes or carboxylated carbon nanotubes
  • the second functional nanofiller includes one or more of graphene, graphene oxide, MXene, boron nitride nanosheets or hydroxylated boron nitride nanosheets.
  • the cellulose solvent includes the following components in parts by mass:
  • the first functional nanofiller includes the following components in parts by mass:
  • the second functional nanofiller includes the following components in parts by mass:
  • Another object of the present invention is to provide a method for preparing the above-mentioned elementary ordered cellulose-based nanofluidic ionic conductor material, which can be achieved by the following technical means:
  • a method for preparing a cellulose-based nanofluidic ionic conductor material with a primitive order structure comprising the following steps:
  • the stirring temperature is -20--10°C
  • the stirring speed is 1000-5000 rpm.
  • the stirring time is 2-10min.
  • the chemical crosslinking agent is selected from one or more of epichlorohydrin, epichlorobutane, glutaraldehyde or polyethylene glycol glycidyl ether.
  • the coagulation bath is selected from one or more of sulfuric acid, hydrochloric acid, citric acid, phytic acid, acetic acid, methanol, ethanol or water.
  • Another object of the present invention is to provide the application of the above-mentioned elementary ordered cellulose-based nanofluid ionic conductor material in a cellulose-based nanofluid osmotic energy generator.
  • the invention discloses a cellulose-based nano-fluid ion conductor material of elementary order structure. Due to the addition of functional nano-fillers, the material has excellent electrochemical properties and strong mechanical stability.
  • the invention also discloses a preparation method of the above-mentioned elementary-order structured cellulose-based nano-fluid ion conductor material, which has the characteristics of low cost, simple process and environmental protection.
  • the invention also discloses the application of the elementary ordered cellulose-based nanofluid ion conductor material in the cellulose-based nanofluid osmotic energy generator, which expands the application of natural polymer materials in optics, electricity, energy storage and special Application in the field of functionalized biomedical materials.
  • Example 1 is a schematic diagram of the preparation of a cellulose nanofluidic ionic conductor material with a primitive ordered structure in Example 1 of the present invention
  • Fig. 2 is a picture of cellulose/nano-element composite solution in Example 1 of the present invention.
  • Fig. 3 is the SEM image of the cellulose-based nanofluidic ionic conductor material of elementary ordered structure in Example 1 of the present invention
  • Fig. 4 is the AFM image of the cellulose-based nanofluidic ionic conductor material of the elementary ordered structure in Example 2 of the present invention.
  • Figure 5 shows the ionic conductivity of the elementary-ordered cellulose-based nanofluidic ionic conductor material in different concentrations of KCl solution in Example 1 of the present invention, and the ordered cellulose/functional elementary composite membrane (Comparative Example 1) , the measurement diagram of the structured cellulose membrane (Comparative Example 2);
  • Example 6 is the graph of the gradient salt concentration diffusion potential and diffusion current in the application of the elementary-ordered cellulose-based nanofluid ionic conductor material in the cellulose-based nanofluid osmotic energy generator in Example 3 of the present invention.
  • MXene refers to a class of two-dimensional inorganic compounds. These materials consist of transition metal carbides, nitrides or carbonitrides several atomic layers thick.
  • the source of cellulose selected from one or more of cotton linter pulp, wood pulp, bamboo pulp and straw pulp;
  • the carbon nanotubes described in the embodiments of the present invention are purchased from NANOCYL TM , and the model is NC7000;
  • carboxylated carbon nanotubes described in the embodiment of the present invention are purchased from Pioneer Nano, and the model is XFM72;
  • the graphene described in the embodiment of the present invention is purchased from Pioneer Nano, and the model is XF001H;
  • the graphene oxide described in the embodiment of the present invention is purchased from Pioneer Nano, and the model is XF002-3;
  • the MXene described in the embodiment of the present invention is purchased from Pioneer Nano, and the model is XFK08;
  • the boron nitride nanosheets described in the embodiment of the present invention are purchased from Pioneer Nano, and the model is XFBN03-1;
  • hydroxylated boron nitride nanosheets described in the embodiments of the present invention are obtained by ultrasonically treating the above boron nitride in isopropanol (300W, 1h).
  • a fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
  • the preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
  • the composite alkali gel is drawn by external force (the drawing strain is 160%), and then placed in a 10 wt% sulfuric acid coagulation bath for 1 min to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • Example 1 is a flow chart of the preparation of the nano-element-ordered cellulose nanofluidic ionic conductor membrane material prepared in Example 1 of the present invention, illustrating that the present invention is based on a bottom-up strategy to construct nano-element-ordered fibers
  • the preparation process is simple and controllable, which is different from the cumbersome bottom-up construction methods such as wood-based materials.
  • Example 2 is a photo of the composite solution of the cellulose-based nanofluidic ionic conductor material prepared in Example 1 of the present invention, which shows that the cellulose solution in which the nano-elements are dispersed has good stability and good fluidity.
  • Fig. 3 is the SEM image of the cellulose-based nanofluid ionic conductor material in Example 1 of the present invention, which shows that the structure of the nano-element-ordered cellulose nanofluid ionic conductor film after dehydration and drying is very dense, and the surface is flat, Highly oriented with nanoscale ion channels.
  • Figure 5 illustrates that the cellulose functional membrane with the basic element order structure prepared in Example 1 has higher ionic conductivity than the ordered structure composite membrane without chemical modification and the oriented cellulose membrane, which is more conducive to the selective transport of ions.
  • a fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
  • the preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
  • the composite alkali gel is drawn by external force (the drawing strain is 180%), and then placed in a 2wt% phytic acid coagulation bath for 10 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • Example 4 is an AFM image of the cellulose-based nanofluidic ionic conductor material in Example 2 of the present invention, which shows that there are a large number of long-range ordered nanofibers in the functional cellulose membrane, showing a highly oriented and highly densified structure, which is Ions produce better transport properties in nanoscale channels.
  • a fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
  • a preparation method of a cellulose nanofluid ionic conductor membrane material with a primitive order structure comprising the following steps:
  • the composite alkali gel is drawn by external force (drawing strain is 200%), and then placed in a coagulation bath of absolute ethanol for 20 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • Figure 6 illustrates the diffusion voltage and diffusion current that the functional cellulose nanofluidic film prepared in Example 3 can generate under 10-fold, 100-fold, 100-fold, and 1000-fold salt concentration gradients. Simulations verify the feasibility of salt concentration gradient power generation.
  • a fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
  • the preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
  • the composite alkali gel is drawn by external force (drawing strain is 140%), and then placed in a 10wt% hydrochloric acid coagulation bath for 1 min to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • a fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
  • the preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
  • the composite alkali gel is drawn by external force (the drawing strain is 170%), and then placed in a 10 wt% phytic acid coagulation bath for 10 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • a fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
  • the preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
  • the composite alkali gel is drawn by external force (the drawing strain is 160%), and then placed in a 10wt% citric acid coagulation bath for 5 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • Comparative Example 1 is a regenerated cellulose/functional element composite membrane without chemical modification, while Example 1 is TEMPO oxidized, and the cellulose molecular chain is negatively charged. Structured cellulose/functional motif composite membranes.
  • a preparation method of a structured cellulose/functional element composite membrane material comprising the following steps:
  • the composite alkali gel is drawn by external force (the drawing strain is 160%), and then placed in a 10 wt% sulfuric acid coagulation bath for 1 min to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
  • Comparative Example 2 The difference between the components of Comparative Example 2 and Example 1 is that the components in Comparative Example 2 are only regenerated cellulose, while the components in Example 1 contain regenerated cellulose and nano-functional primitives.
  • a preparation method of a sequenced cellulose membrane material comprising the following steps:
  • the alkali gel is drawn by external force (drawing strain is 160%), and then placed in a 10wt% sulfuric acid coagulation bath for 1min to fix the orientation to obtain a highly oriented cellulose hydrogel;
  • Test method prepare six concentrations of potassium chloride solutions of 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 and 10 -1 M, and test the conductivity values of the bulk solutions of the six concentrations respectively. Next, the conductance of nano-element-structured cellulose nanofluidic ionic conductor membranes immersed in 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 , and 10 -1 M potassium chloride solution were tested. Rate. Two parallel test probes are placed at both ends of the sample to be tested, then a certain potential is applied to both ends of the probes, and then the current through the sample is measured. An IV image was made with the obtained current and potential, fitted, and the slope was taken as the conductivity.
  • the formula for calculating conductivity ( ⁇ ) is as follows:
  • G is the measured conductance (ie, the slope of the I-V curve)
  • l is the length of the measured composite film
  • h is the measured height of the film
  • w is the measured width of the composite film.
  • Test method Two parallel test probes are placed on both ends of the sample to be tested, and the inside of the sample is immersed in 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 , 10 -1 M chloride respectively. The potassium solution then applies a certain potential across the probe, and the current through the ordered cellulose/functional motif composite membrane is then measured. An IV image was made with the obtained current and potential, fitted, and the slope was taken as the conductivity.
  • the formula for calculating conductivity ( ⁇ ) is as follows:
  • G is the measured conductance (ie, the slope of the IV curve)
  • l is the length of the sequenced structured cellulose/functional motif composite membrane
  • h is the height of the sequenced structured cellulose/functional motif composite membrane
  • w is The width of the sequenced structured cellulose/functional motif composite membrane.
  • Test method Two parallel test probes are placed on both ends of the sample to be tested, and the inside of the sample is immersed in 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 , 10 -1 M chloride respectively. The potassium solution then applies a potential across the probe and the current through the structured cellulose membrane is then measured. An IV image was made with the obtained current and potential, fitted, and the slope was taken as the conductivity.
  • the formula for calculating conductivity ( ⁇ ) is as follows:
  • G is the measured conductance (ie, the slope of the I-V curve)
  • l is the length of the sequenced textured cellulose membrane
  • h is the height of the sequenced textured cellulose membrane
  • w is the width of the sequenced textured cellulose membrane.
  • a system of mixing seawater (0.5M NaCl) and river water (0.01M NaCl) is designed, with seawater and river water on both sides, and a highly oriented functional cellulose nanofluid material in the middle, which can obtain a certain voltage and current.
  • the above-mentioned functional film is placed between the two grooves; finally, the two test electrodes of the digital source meter are immersed in the above-mentioned two grooves respectively to test and record the diffusion voltage and diffusion current generated by the functional cellulose film.
  • Example 1 has different degrees of advantages in electrical conductivity at different solution concentrations.

Abstract

The present invention relates to a cellulose based nanofluid ion conductor material, which is prepared from the following raw materials: cellulose, a cellulose solvent, and a first or second functional nanofiller. The material disclosed in the present invention has excellent electrochemical properties and strong mechanical stability. Further disclosed in the present invention is a preparation method for the cellulose based nanofluid ion conductor material, and the method has the characteristics of low cost, simple process, and environmental friendliness. Further disclosed in the present invention is an application of the cellulose based nanofluid ion conductor material in a cellulose based nanofluid osmotic energy generator, and an application of a natural polymer material in the fields of optical, electrical, energy storage, and special functionalized biomedical materials is expanded.

Description

基元序构化纤维素基纳米流体离子导体材料和制备方法及应用Motif-ordered cellulose-based nanofluidic ionic conductor material and preparation method and application 技术领域technical field
本发明涉及纳米流体领域，具体地涉及一种基元序构化纤维素基纳米流体离子导体材料和制备方法及应用。The present invention relates to the field of nanofluid, in particular to a cellulose-based nanofluid ion conductor material of elementary order structure, a preparation method and application thereof.
背景技术Background technique
近年来，纳米流体离子导体***的研究引起了广泛的关注，其中纳米流体通道内的离子，表现出与电解质溶液中离子明显不同的输运行为。这是由纳米流体通道的高度以及通道形成的双电层所决定的。这种离子的快速传输是一种理想的创新能源利用，在生物传感、能量储存和转换以及水处理等有很大的研究价值。纳米碳材料常用于功能化高分子材料以获得特殊功能的高分子复合材料，广泛应用于能源转换材料、储能材料、导电材料和生物医用材料等领域，是一种理想的高附加值填料。Hu等(J.Am.Chem.Soc.2019，141，17830)从木材中提取纳米纤维素，并促使纳米纤维素包裹住纳米厚度的石墨烯片，形成多个二维约束空间，制备了一种生物质纳米流体通道。本发明利用绿色溶剂体系(碱/尿素水体系)，通过分别在纤维素溶液中掺杂纳米碳材料石墨烯和碳纳米管制备了一种高附加值功能化纤维素基材料。制备工艺简单且绿色环保。In recent years, research on nanofluidic ionic conductor systems has attracted extensive attention, in which ions within nanofluidic channels exhibit significantly different transport behaviors from those in electrolyte solutions. This is determined by the height of the nanofluidic channel and the electric double layer formed by the channel. This fast transport of ions is an ideal innovative energy utilization with great research value in biosensing, energy storage and conversion, and water treatment. Carbon nanomaterials are often used to functionalize polymer materials to obtain polymer composite materials with special functions. They are widely used in energy conversion materials, energy storage materials, conductive materials, and biomedical materials. They are an ideal high value-added filler. Hu et al. (J.Am.Chem.Soc.2019, 141, 17830) extracted nanocellulose from wood, and promoted nanocellulose to wrap nano-thick graphene sheets to form multiple two-dimensional confined spaces, and prepared a Biomass nanofluidic channels. In the present invention, a green solvent system (alkali/urea water system) is used to prepare a high value-added functionalized cellulose-based material by doping nano-carbon materials graphene and carbon nanotubes in a cellulose solution respectively. The preparation process is simple and environmentally friendly.
以往大多数具有纳米流体通道的材料是由聚乙烯亚胺、聚乙烯醇、聚苯乙烯磺酸盐等石油基合成聚合物组成的。然而，它们都是不可再生，不可降解的材料，长此以往会造成严重的环境问题；此外，尽管在实验室条件下有序纳米通道的制备已经取得了很大的进展，但常常需要高成本、复杂和耗时的光刻工艺、原子层沉积等制造方法，在可扩展的商业应用方面仍然存在挑战。因此，利用自然界储量最丰富、低成本和可再生的纤维素材料，设计具有优异离子传输性能的取向纳米结构离子膜还有待开发。目前一些科研人员从自然取材，利用天然木材设计纳米流体材料，解决了高成本及环境污染等问题。例如，李恬等(Sci.Adv.2019，5，u4238)利用木材的天然取向纳米微结构，自上而下的制备了具有纳米流体效应的木膜；马里兰大学的胡良兵等基于木材设计一类纳米流体木膜实现了低热量的再回收(Nat.Mater.2019，18，608)、盐浓度梯度的渗透发电(Adv.Energy Mater.2019，1902590)。Most previous materials with nanofluidic channels are composed of petroleum-based synthetic polymers such as polyethyleneimine, polyvinyl alcohol, and polystyrene sulfonate. However, they are all non-renewable, non-degradable materials, which will cause serious environmental problems in the long run; moreover, although great progress has been made in the preparation of ordered nanochannels under laboratory conditions, they often require high cost, complex and time-consuming photolithography processes, atomic layer deposition and other fabrication methods, there are still challenges in scalable commercial applications. Therefore, utilizing the most abundant, low-cost and renewable cellulose material in nature, the design of oriented nanostructured ionic membranes with excellent ion transport properties remains to be developed. At present, some researchers draw from natural materials and use natural wood to design nano-fluid materials, which solves the problems of high cost and environmental pollution. For example, Li Tian et al. (Sci. Adv. 2019, 5, u4238) used the natural oriented nano-microstructure of wood to prepare a wood film with nanofluid effect from top to bottom; Hu Liangbing of the University of Maryland et al. designed a class based on wood. Nanofluidic wood membrane realizes low heat recovery (Nat. Mater. 2019, 18, 608), osmotic power generation with salt concentration gradient (Adv. Energy Mater. 2019, 1902590).
因此，亟需找到一种新的基元序构化纤维素基纳米流体离子导体材料及其制备方法，以克服上述性能缺陷。Therefore, there is an urgent need to find a new element-ordered cellulose-based nanofluidic ionic conductor material and its preparation method to overcome the above-mentioned performance defects.
发明内容SUMMARY OF THE INVENTION
本发明基于纳米材料在能源转换材料、储能材料、导电材料和生物医用材料等领域广泛的应用。我们通过对纤维素溶液分别掺杂第一和/或第二功能性纳米填料，利用“自上而下”的策略，即从纤维素的分子链层次，通过溶解棉花、化学修饰等方法制备了一种绿色环保、可再生、可降解的功能性的纤维素基纳米流体离子导体材料，并实现其在盐梯度浓度渗透发电领域的应用。The invention is based on the wide application of nanomaterials in the fields of energy conversion materials, energy storage materials, conductive materials, biomedical materials and the like. By doping the cellulose solution with the first and/or the second functional nanofillers respectively, we used a "top-down" strategy, that is, from the molecular chain level of cellulose, prepared by dissolving cotton, chemical modification, etc. An environmentally friendly, renewable, and degradable functional cellulose-based nanofluid ion conductor material, and its application in the field of salt gradient concentration osmotic power generation is realized.
本发明的一个目的在于提供一种基元序构化纤维素基纳米流体离子导体材料，其通过以下技术手段得以实现：An object of the present invention is to provide a cellulose-based nanofluidic ionic conductor material of elementary ordered structure, which can be realized by the following technical means:
一种纤维素基纳米流体离子导体材料，其由以下质量份数的原料制得：A cellulose-based nano fluid ionic conductor material, which is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000001
Figure PCTCN2021089394-appb-000001
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经氧化处理；Wherein, before the elementary ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to be oxidized;
纤维素溶剂中包含碱、尿素和水；The cellulose solvent contains alkali, urea and water;
第一功能性纳米填料包括碳纳米管或羧基化碳纳米管的一种或两种；The first functional nanofiller includes one or both of carbon nanotubes or carboxylated carbon nanotubes;
第二功能性纳米填料包括石墨烯、氧化石墨烯、MXene、氮化硼纳米片或羟基化氮化硼纳米片的一种或多种。The second functional nanofiller includes one or more of graphene, graphene oxide, MXene, boron nitride nanosheets or hydroxylated boron nitride nanosheets.
进一步地，所述纤维素溶剂包括以下质量份数的成分：Further, the cellulose solvent includes the following components in parts by mass:
碱6-12份；尿素10-17份；水71-84份。Alkali 6-12 parts; urea 10-17 parts; water 71-84 parts.
进一步地，所述第一功能性纳米填料包括以下质量份数的成分：Further, the first functional nanofiller includes the following components in parts by mass:
碳纳米管0.09-4份；羧基化碳纳米管0.09-10份。0.09-4 parts of carbon nanotubes; 0.09-10 parts of carboxylated carbon nanotubes.
进一步地，所述第二功能性纳米填料包括以下质量份数的成分：Further, the second functional nanofiller includes the following components in parts by mass:
石墨烯0.09-6份；氧化石墨烯0.09-8份；MXene 0.09-8份；氮化硼纳米片0.09-8份；羟基化氮化硼纳米片0.09-10份。0.09-6 parts of graphene; 0.09-8 parts of graphene oxide; 0.09-8 parts of MXene; 0.09-8 parts of boron nitride nanosheets; 0.09-10 parts of hydroxylated boron nitride nanosheets.
本发明的另一个目的在于提供上述基元序构化纤维素基纳米流体离子导体材料的制备方法，其通过以下技术手段得以实现：Another object of the present invention is to provide a method for preparing the above-mentioned elementary ordered cellulose-based nanofluidic ionic conductor material, which can be achieved by the following technical means:
一种基元序构化纤维素基纳米流体离子导体材料的制备方法，包括如下步骤：A method for preparing a cellulose-based nanofluidic ionic conductor material with a primitive order structure, comprising the following steps:
S1.将纤维素溶解在纤维素溶剂中，并向其中掺杂第一或第二功能性纳米填料，搅拌形成纤维素/纳米基元复合溶液；S1. Dissolving cellulose in a cellulose solvent, doping it with the first or second functional nano-filler, and stirring to form a cellulose/nano-primitive composite solution;
S2.将上述复合溶液离心后，加入化学交联剂反应，生成粗产物；S2. after the above-mentioned composite solution is centrifuged, a chemical cross-linking agent is added to react to generate a crude product;
S3.将上述粗产物离心、定型，得到碱凝胶；S3. above-mentioned crude product is centrifuged and shaped to obtain an alkaline gel;
S4.将上述碱凝胶牵伸取向，浸泡在凝固浴中进行固定取向；S4. the above-mentioned alkali gel is drawn and oriented, and immersed in a coagulation bath for fixed orientation;
S5.对上述取向凝胶进行TEMPO氧化处理、水洗，干燥，得到纳米基元序构化纤维素基纳米流体离子导体材料。S5. Perform TEMPO oxidation treatment on the above-mentioned oriented gel, wash with water, and dry to obtain a nano-element-ordered cellulose-based nano-fluid ionic conductor material.
进一步地，所述S1中，搅拌温度为-20--10℃，搅拌速度为1000-5000rpm。Further, in the S1, the stirring temperature is -20--10°C, and the stirring speed is 1000-5000 rpm.
进一步地，所述S1中，搅拌时间为2-10min。Further, in the S1, the stirring time is 2-10min.
进一步地，所述化学交联剂选自环氧氯丙烷、环氧氯丁烷、戊二醛或聚乙二醇缩水甘油醚的一种或多种。Further, the chemical crosslinking agent is selected from one or more of epichlorohydrin, epichlorobutane, glutaraldehyde or polyethylene glycol glycidyl ether.
进一步地，所述凝固浴选自硫酸、盐酸、柠檬酸、植酸、醋酸、甲醇、乙醇或水的一种或多种。Further, the coagulation bath is selected from one or more of sulfuric acid, hydrochloric acid, citric acid, phytic acid, acetic acid, methanol, ethanol or water.
本发明的另一个目的在于提供上述基元序构化纤维素基纳米流体离子导体材料在纤维素基纳米流体渗透能发电器中的应用。Another object of the present invention is to provide the application of the above-mentioned elementary ordered cellulose-based nanofluid ionic conductor material in a cellulose-based nanofluid osmotic energy generator.
本发明有益效果在于：The beneficial effects of the present invention are:
本发明公开了一种基元序构化纤维素基纳米流体离子导体材料，由于功能性纳米填料加入，这种材料具有优异的电化学性质，也兼具较强的力学稳定性。本发明还公开了上述基元序构化纤维素基纳米流体离子导体材料的制备方法，其具有低成本、工艺简单、绿色环保的特点。本发明还公开了所述基元序构化纤维素基纳米流体离子导体材料在纤维素基纳米流体渗透能发电器中的应用，其拓展了天然高分子材料在光学、电学、储能及特殊功能化生物医用材料领域的应用。The invention discloses a cellulose-based nano-fluid ion conductor material of elementary order structure. Due to the addition of functional nano-fillers, the material has excellent electrochemical properties and strong mechanical stability. The invention also discloses a preparation method of the above-mentioned elementary-order structured cellulose-based nano-fluid ion conductor material, which has the characteristics of low cost, simple process and environmental protection. The invention also discloses the application of the elementary ordered cellulose-based nanofluid ion conductor material in the cellulose-based nanofluid osmotic energy generator, which expands the application of natural polymer materials in optics, electricity, energy storage and special Application in the field of functionalized biomedical materials.
附图说明Description of drawings
图1为本发明实施例1中基元序构纤维素纳米流体离子导体材料的制备示意图；1 is a schematic diagram of the preparation of a cellulose nanofluidic ionic conductor material with a primitive ordered structure in Example 1 of the present invention;
图2为本发明实施例1中纤维素/纳米基元复合溶液图片；Fig. 2 is a picture of cellulose/nano-element composite solution in Example 1 of the present invention;
图3为本发明实施例1中基元序构化纤维素基纳米流体离子导体材料的SEM图；Fig. 3 is the SEM image of the cellulose-based nanofluidic ionic conductor material of elementary ordered structure in Example 1 of the present invention;
图4为本发明实施例2中基元序构化纤维素基纳米流体离子导体材料的AFM图；Fig. 4 is the AFM image of the cellulose-based nanofluidic ionic conductor material of the elementary ordered structure in Example 2 of the present invention;
图5为本发明实施例1中基元序构化纤维素基纳米流体离子导体材料在不同浓度的KCl溶液中离子电导率，与序构化纤维素/功能基元复合膜(对比例1)、序构化纤维素膜(对比例2)的测量图；Figure 5 shows the ionic conductivity of the elementary-ordered cellulose-based nanofluidic ionic conductor material in different concentrations of KCl solution in Example 1 of the present invention, and the ordered cellulose/functional elementary composite membrane (Comparative Example 1) , the measurement diagram of the structured cellulose membrane (Comparative Example 2);
图6为本发明实施例3中基元序构化纤维素基纳米流体离子导体材料在纤维素基纳米流体渗透能发电器的应用中，其梯度盐浓度扩散电势和扩散电流图。6 is the graph of the gradient salt concentration diffusion potential and diffusion current in the application of the elementary-ordered cellulose-based nanofluid ionic conductor material in the cellulose-based nanofluid osmotic energy generator in Example 3 of the present invention.
具体实施方式detailed description
本发明说明书所记载的内容中，Among the contents described in the specification of the present invention,
术语“MXene”是指一类二维无机化合物。这些材料由几个原子层厚度的过渡金属碳化物、氮化物或碳氮化物构成。The term "MXene" refers to a class of two-dimensional inorganic compounds. These materials consist of transition metal carbides, nitrides or carbonitrides several atomic layers thick.
纤维素的来源，选自棉短绒浆、木浆、竹浆和草浆中的一种或多种；The source of cellulose, selected from one or more of cotton linter pulp, wood pulp, bamboo pulp and straw pulp;
本发明实施例所述碳纳米管采购自NANOCYL TM，型号为NC7000； The carbon nanotubes described in the embodiments of the present invention are purchased from NANOCYL TM , and the model is NC7000;
本发明实施例所述羧基化碳纳米管采购自先锋纳米，型号为XFM72；The carboxylated carbon nanotubes described in the embodiment of the present invention are purchased from Pioneer Nano, and the model is XFM72;
本发明实施例所述石墨烯采购自先锋纳米，型号为XF001H；The graphene described in the embodiment of the present invention is purchased from Pioneer Nano, and the model is XF001H;
本发明实施例所述氧化石墨烯采购自先锋纳米，型号为XF002-3；The graphene oxide described in the embodiment of the present invention is purchased from Pioneer Nano, and the model is XF002-3;
本发明实施例所述MXene采购自先锋纳米，型号为XFK08；The MXene described in the embodiment of the present invention is purchased from Pioneer Nano, and the model is XFK08;
本发明实施例所述氮化硼纳米片采购自先锋纳米，型号为XFBN03-1；The boron nitride nanosheets described in the embodiment of the present invention are purchased from Pioneer Nano, and the model is XFBN03-1;
本发明实施例所述羟基化氮化硼纳米片通过上述氮化硼在异丙醇中超声处理(300W，1h)获得。The hydroxylated boron nitride nanosheets described in the embodiments of the present invention are obtained by ultrasonically treating the above boron nitride in isopropanol (300W, 1h).
本发明实施例所涉及的成分，除特别提及，均为常见的市售材料；The components involved in the embodiments of the present invention, unless otherwise mentioned, are common commercially available materials;
TEMPO氧化处理所采用的具体步骤为：将20g水凝胶，90g去离子水、0.010g TEMPO(四甲基哌啶)，0.2g溴化钠。6.203g次氯酸钠混合，维持溶液PH＝10，氧化2h。The specific steps adopted in the TEMPO oxidation treatment are: 20g of hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), and 0.2g of sodium bromide. 6. Mix 203g of sodium hypochlorite, maintain the solution pH=10, and oxidize for 2h.
实施例1Example 1
一种基元序构化纤维素基纳米流体离子导体材料，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000002
Figure PCTCN2021089394-appb-000002
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经TEMPO氧化处理。Wherein, before the element-ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to undergo TEMPO oxidation treatment.
上述基元序构化纤维素纳米流体离子导体膜材料的制备方法，包括如下步骤：The preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
S1.按质量份数纤维素溶剂82份(其中氢氧化钠4.92份、尿素份8.2、去离子水68.88份配置)，碳纳米管(第一功能性纳米填料)0.09份，-20℃冷肼下预冷，加入3份纤维素木浆，5000rpm下搅拌2min，得到纤维素/纳米基元复合溶液；S1. 82 parts by mass of cellulose solvent (including 4.92 parts of sodium hydroxide, 8.2 parts of urea, and 68.88 parts of deionized water), 0.09 parts of carbon nanotubes (the first functional nanofiller), and -20°C cold hydrazine Under pre-cooling, 3 parts of cellulose wood pulp were added, and stirred at 5000 rpm for 2 min to obtain a cellulose/nano-primitive composite solution;
S2.随后加入0.05份化学交联剂环氧氯丙烷，恒温-5℃，350rpm搅拌3h，得 到化学交联后的粗产物；S2. add 0.05 part of chemical crosslinking agent epichlorohydrin subsequently, constant temperature-5 ℃, 350rpm stirs 3h, obtains the crude product after chemical crosslinking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在-5℃下放置5h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, poured into the mold gel and placed at -5°C for 5h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变160％)，然后置于10wt％硫酸凝固浴1min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (the drawing strain is 160%), and then placed in a 10 wt% sulfuric acid coagulation bath for 1 min to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.将20g复合纤维素水凝胶、90g去离子水、0.010g TEMPO(四甲基哌啶)、0.2g溴化钠、6.203g次氯酸钠混合，维持溶液PH＝10，氧化1h，洗净后二端夹持，25℃限域干燥，获得基元序构化纤维素纳米流体离子导体材料。S5. Mix 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide, and 6.203g of sodium hypochlorite, maintain the solution pH=10, oxidize for 1h, and wash The two ends were clamped and dried at 25°C to obtain the fundamentally ordered cellulose nanofluid ionic conductor material.
图1为本发明实施例1所制得的纳米基元序构化纤维素纳米流体离子导体膜材料的制备流程图，说明了本发明是基于自下而上策略构筑纳米基元序构化纤维素纳米流体离子导体膜材料，制备过程简便、可控，区别于木材基等自下而上的繁琐构筑方法。1 is a flow chart of the preparation of the nano-element-ordered cellulose nanofluidic ionic conductor membrane material prepared in Example 1 of the present invention, illustrating that the present invention is based on a bottom-up strategy to construct nano-element-ordered fibers The preparation process is simple and controllable, which is different from the cumbersome bottom-up construction methods such as wood-based materials.
图2为本发明实施例1中制备纤维素基纳米流体离子导体材料的复合溶液照片，其表明分散纳米基元的纤维素溶液稳定性好，具有良好的流动性。2 is a photo of the composite solution of the cellulose-based nanofluidic ionic conductor material prepared in Example 1 of the present invention, which shows that the cellulose solution in which the nano-elements are dispersed has good stability and good fluidity.
图3为本发明实施例1中纤维素基纳米流体离子导体材料的SEM图，其表明失水干燥后的纳米基元序构化纤维素纳米流体离子导体膜的结构非常致密，且表面平整、高度取向，具有纳米尺度的离子通道。Fig. 3 is the SEM image of the cellulose-based nanofluid ionic conductor material in Example 1 of the present invention, which shows that the structure of the nano-element-ordered cellulose nanofluid ionic conductor film after dehydration and drying is very dense, and the surface is flat, Highly oriented with nanoscale ion channels.
图5说明了实施例1制备的基元序构纤维素功能膜相比无化学修饰序构复合膜和取向纤维素膜具有更高离子电导率，更有利于离子选择性运输。Figure 5 illustrates that the cellulose functional membrane with the basic element order structure prepared in Example 1 has higher ionic conductivity than the ordered structure composite membrane without chemical modification and the oriented cellulose membrane, which is more conducive to the selective transport of ions.
实施例2Example 2
一种基元序构化纤维素基纳米流体离子导体材料，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000003
Figure PCTCN2021089394-appb-000003
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经TEMPO氧化处理。Wherein, before the element-ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to undergo TEMPO oxidation treatment.
上述基元序构化纤维素纳米流体离子导体膜材料的制备方法，包括如下步骤：The preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
S1.按质量份数纤维素溶剂96.72份(其中氢氧化钠11.61份、尿素份16.44、去离子水68.67份配置)，羧基化碳纳米管(第一功能性纳米填料)4份，-10℃冷肼下预冷，加入8份纤维素棉短绒浆，5000rpm下搅拌2min，得到纤维素/纳米基元复合溶液；S1. 96.72 parts by mass of cellulose solvent (including 11.61 parts of sodium hydroxide, 16.44 parts of urea, and 68.67 parts of deionized water), 4 parts of carboxylated carbon nanotubes (the first functional nanofiller), -10°C Pre-cooling under cold hydrazine, adding 8 parts of cellulose cotton linter pulp, stirring at 5000 rpm for 2 min, to obtain a cellulose/nano-primitive composite solution;
S2.随后加入2份化学交联剂环氧氯丁烷，恒温-10℃，500rpm搅拌1h，得到化学交联后的粗产物；S2. Then add 2 parts of chemical cross-linking agent epichlorobutane, keep the temperature at -10°C, and stir at 500 rpm for 1 h to obtain the crude product after chemical cross-linking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在10℃下放置3h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, then poured into a mold gel and placed at 10°C for 3h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变180％)，然后置于2wt％植酸凝固浴10min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (the drawing strain is 180%), and then placed in a 2wt% phytic acid coagulation bath for 10 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.将20g复合纤维素水凝胶、90g去离子水、0.010g TEMPO(四甲基哌啶)、0.2g溴化钠、6.203g次氯酸钠混合，维持溶液PH＝10，氧化1h，洗净后二端夹持，25℃限域干燥，获得基元序构化纤维素基纳米流体离子导体材料。S5. Mix 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide, and 6.203g of sodium hypochlorite, maintain the solution pH=10, oxidize for 1h, and wash The two ends were clamped and dried at 25°C to obtain a fundamentally ordered cellulose-based nanofluidic ionic conductor material.
图4为本发明实施例2中纤维素基纳米流体离子导体材料的AFM图，其表明了功能性纤维素膜存在大量长程有序排列的纳米纤维，呈现高取向、高度致密化的结构，为离子在纳米尺度通道下产生更优异的运输性能。4 is an AFM image of the cellulose-based nanofluidic ionic conductor material in Example 2 of the present invention, which shows that there are a large number of long-range ordered nanofibers in the functional cellulose membrane, showing a highly oriented and highly densified structure, which is Ions produce better transport properties in nanoscale channels.
实施例3Example 3
一种基元序构化纤维素基纳米流体离子导体材料，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000004
Figure PCTCN2021089394-appb-000004
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经TEMPO氧化处理。Wherein, before the element-ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to undergo TEMPO oxidation treatment.
一种基元序构化纤维素纳米流体离子导体膜材料的制备方法，包括如下步骤：A preparation method of a cellulose nanofluid ionic conductor membrane material with a primitive order structure, comprising the following steps:
S1.按质量份数纤维素溶剂89.5份(其中氢氧化锂7.2份、尿素份13.4份、去离子水68.9份配置)，氧化石墨烯(第二功能性纳米填料)2份，-15℃冷肼下预冷，加入4份纤维素棉短绒浆，1000rpm下搅拌10min，得到纤维素/纳米基元复合溶液；S1. 89.5 parts by mass of cellulose solvent (including 7.2 parts of lithium hydroxide, 13.4 parts of urea, and 68.9 parts of deionized water), 2 parts of graphene oxide (second functional nanofiller), cooled at -15°C Pre-cooling under hydrazine, adding 4 parts of cellulose cotton linter pulp, stirring at 1000 rpm for 10 min, to obtain a cellulose/nano-primitive composite solution;
S2.随后加入0.5份化学交联剂聚乙二醇二缩水甘油醚，恒温-10℃，500rpm搅拌1.5h，得到化学交联后的粗产物；S2. Then add 0.5 part of chemical cross-linking agent polyethylene glycol diglycidyl ether, constant temperature -10 ° C, 500 rpm stirring for 1.5 h, to obtain a crude product after chemical cross-linking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在10℃下放置3h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, then poured into a mold gel and placed at 10°C for 3h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变200％)，然后置于凝固浴无水乙醇中20min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (drawing strain is 200%), and then placed in a coagulation bath of absolute ethanol for 20 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.将20g复合纤维素水凝胶、90g去离子水、0.010g TEMPO(四甲基哌啶)、 0.2g溴化钠、6.203g次氯酸钠混合，维持溶液PH＝10，氧化1h，洗净后二端夹持，25℃限域干燥，获得基元序构化纤维素基纳米流体离子导体材料。S5. Mix 20g composite cellulose hydrogel, 90g deionized water, 0.010g TEMPO (tetramethylpiperidine), 0.2g sodium bromide, 6.203g sodium hypochlorite, maintain solution pH=10, oxidize for 1h, and wash after The two ends were clamped and dried at 25°C to obtain a fundamentally ordered cellulose-based nanofluidic ionic conductor material.
图6说明了实施例3制备的功能性纤维素纳米流体膜在在10倍、100倍、100倍、1000倍盐浓度梯度下能产生的扩散电压和扩散电流。模拟验证了盐浓度梯度发电的可行性。Figure 6 illustrates the diffusion voltage and diffusion current that the functional cellulose nanofluidic film prepared in Example 3 can generate under 10-fold, 100-fold, 100-fold, and 1000-fold salt concentration gradients. Simulations verify the feasibility of salt concentration gradient power generation.
实施例4Example 4
一种基元序构化纤维素基纳米流体离子导体材料，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000005
Figure PCTCN2021089394-appb-000005
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经TEMPO氧化处理。Wherein, before the element-ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to undergo TEMPO oxidation treatment.
上述基元序构化纤维素纳米流体离子导体膜材料的制备方法，包括如下步骤：The preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
S1.按质量份数纤维素溶剂86.9份(其中氢氧化钠5.2份、尿素份8.7、去离子水73份配置)，MXene(第二功能性纳米填料)8份，-20℃冷肼下预冷，加入5份纤维素棉短绒浆料，6000rpm下搅拌5min，得到纤维素/纳米基元复合溶液；S1. 86.9 parts by mass of cellulose solvent (including 5.2 parts of sodium hydroxide, 8.7 parts of urea, and 73 parts of deionized water), 8 parts of MXene (second functional nano-filler), pre-treated under cold hydrazine at -20°C Cool, add 5 parts of cellulose cotton linter pulp, and stir at 6000 rpm for 5 min to obtain a cellulose/nano-primitive composite solution;
S2.随后加入0.1份化学交联剂聚乙二醇缩水甘油醚，恒温-5℃，350rpm搅拌3h，得到化学交联后的粗产物；S2. Then add 0.1 part of chemical cross-linking agent polyethylene glycol glycidyl ether, keep the temperature at -5°C, and stir at 350 rpm for 3 hours to obtain a crude product after chemical cross-linking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在-5℃下放置5h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, poured into the mold gel and placed at -5°C for 5h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变140％)，然后置于10wt％盐酸凝固浴1min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (drawing strain is 140%), and then placed in a 10wt% hydrochloric acid coagulation bath for 1 min to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.将20g复合纤维素水凝胶、90g去离子水、0.010g TEMPO(四甲基哌啶)、0.2g溴化钠、6.203g次氯酸钠混合，维持溶液PH＝10，氧化1h，洗净后二端夹持，25℃限域干燥，获得基元序构化纤维素纳米流体离子导体材料。S5. Mix 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide, and 6.203g of sodium hypochlorite, maintain the solution pH=10, oxidize for 1h, and wash The two ends were clamped and dried at 25°C to obtain the fundamentally ordered cellulose nanofluid ionic conductor material.
实施例5Example 5
一种基元序构化纤维素基纳米流体离子导体材料，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000006
Figure PCTCN2021089394-appb-000006
Figure PCTCN2021089394-appb-000007
Figure PCTCN2021089394-appb-000007
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经TEMPO氧化处理。Wherein, before the element-ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to undergo TEMPO oxidation treatment.
上述基元序构化纤维素纳米流体离子导体膜材料的制备方法，包括如下步骤：The preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
S1.按质量份数纤维素溶剂93.3份(其中氢氧化钠5.6份、尿素份9.3、去离子水78.4份配置)，氮化硼纳米片(第二功能性纳米填料)0.6份，-20℃冷肼下预冷，加入6份纤维素棉短绒浆料，4000rpm下搅拌4min，得到纤维素/纳米基元复合溶液；S1. 93.3 parts by mass of cellulose solvent (including 5.6 parts of sodium hydroxide, 9.3 parts of urea, and 78.4 parts of deionized water), 0.6 parts of boron nitride nanosheets (second functional nanofiller), -20°C Pre-cooling under cold hydrazine, adding 6 parts of cellulose cotton linter pulp, stirring at 4000 rpm for 4 min, to obtain a cellulose/nano-primitive composite solution;
S2.随后加入0.1份化学交联剂戊二醛，恒温-5℃，350rpm搅拌3h，得到化学交联后的粗产物；S2. Then add 0.1 part of chemical cross-linking agent glutaraldehyde, keep the temperature at -5°C, and stir at 350 rpm for 3 hours to obtain a crude product after chemical cross-linking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在-5℃下放置5h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, poured into the mold gel and placed at -5°C for 5h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变170％)，然后置于10wt％植酸凝固浴10min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (the drawing strain is 170%), and then placed in a 10 wt% phytic acid coagulation bath for 10 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.将20g复合纤维素水凝胶、90g去离子水、0.010g TEMPO(四甲基哌啶)、0.2g溴化钠、6.203g次氯酸钠混合，维持溶液PH＝10，氧化1h，洗净后二端夹持，25℃限域干燥，获得基元序构化纤维素纳米流体离子导体材料。S5. Mix 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide, and 6.203g of sodium hypochlorite, maintain the solution pH=10, oxidize for 1h, and wash The two ends were clamped and dried at 25°C to obtain the fundamentally ordered cellulose nanofluid ionic conductor material.
实施例6Example 6
一种基元序构化纤维素基纳米流体离子导体材料，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is prepared from the following raw materials in parts by mass:
Figure PCTCN2021089394-appb-000008
Figure PCTCN2021089394-appb-000008
其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经TEMPO氧化处理。Wherein, before the element-ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to undergo TEMPO oxidation treatment.
上述基元序构化纤维素纳米流体离子导体膜材料的制备方法，包括如下步骤：The preparation method of the above-mentioned elementary ordered cellulose nanofluidic ionic conductor membrane material comprises the following steps:
S1.按质量份数纤维素溶剂90.9份(其中氢氧化钠5.3份、尿素份9.1、去离子水76.5份配置)，羟基化氮化硼纳米片(第二功能性纳米填料)3份，-20℃冷肼下预冷，加入6份纤维素棉短绒浆料，4000rpm下搅拌4min，得到纤维素/纳米基元复合溶液；S1. 90.9 parts by mass of cellulose solvent (including 5.3 parts of sodium hydroxide, 9.1 parts of urea, and 76.5 parts of deionized water), 3 parts of hydroxylated boron nitride nanosheets (second functional nanofillers), - Pre-cooling under cold hydrazine at 20°C, adding 6 parts of cellulose cotton linter pulp, stirring at 4000 rpm for 4 min, to obtain a cellulose/nano-primitive composite solution;
S2.随后加入0.1份化学交联剂环氧氯丙烷，恒温-5℃，350rpm搅拌3h，得到 化学交联后的粗产物；S2. then add 0.1 part of chemical crosslinking agent epichlorohydrin, constant temperature -5 ° C, 350rpm stirring for 3h, to obtain the crude product after chemical crosslinking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在-5℃下放置5h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, poured into the mold gel and placed at -5°C for 5h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变160％)，然后置于10wt％柠檬酸凝固浴5min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (the drawing strain is 160%), and then placed in a 10wt% citric acid coagulation bath for 5 minutes to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.将20g复合纤维素水凝胶、90g去离子水、0.010g TEMPO(四甲基哌啶)、0.2g溴化钠、6.203g次氯酸钠混合，维持溶液PH＝10，氧化1h，洗净后二端夹持，25℃限域干燥，获得基元序构化纤维素纳米流体离子导体材料。S5. Mix 20g of composite cellulose hydrogel, 90g of deionized water, 0.010g of TEMPO (tetramethylpiperidine), 0.2g of sodium bromide, and 6.203g of sodium hypochlorite, maintain the solution pH=10, oxidize for 1h, and wash The two ends were clamped and dried at 25°C to obtain the fundamentally ordered cellulose nanofluid ionic conductor material.
对比实施例1Comparative Example 1
对比例实施例1与实施例1成分上的区别在于：对比例1是没有经过化学修饰的再生纤维素/功能基元复合膜，而实施例1是经过TEMPO氧化处理，纤维素分子链带负电的序构化纤维素/功能基元复合膜。The difference in composition between Example 1 and Example 1 is: Comparative Example 1 is a regenerated cellulose/functional element composite membrane without chemical modification, while Example 1 is TEMPO oxidized, and the cellulose molecular chain is negatively charged. Structured cellulose/functional motif composite membranes.
一种序构化纤维素/功能基元复合膜材料的制备方法，包括如下步骤：A preparation method of a structured cellulose/functional element composite membrane material, comprising the following steps:
S1.按质量份数纤维素溶剂82份(其中氢氧化钠4.92份、尿素份8.2、去离子水68.88份配置)，碳纳米管(第一功能性纳米填料)0.09份，-20℃冷肼下预冷，加入3份纤维素木浆，5000rpm下搅拌2min，得到纤维素/纳米基元复合溶液；S1. 82 parts by mass of cellulose solvent (including 4.92 parts of sodium hydroxide, 8.2 parts of urea, and 68.88 parts of deionized water), 0.09 parts of carbon nanotubes (the first functional nanofiller), and -20°C cold hydrazine Under pre-cooling, 3 parts of cellulose wood pulp were added, and stirred at 5000 rpm for 2 min to obtain a cellulose/nano-primitive composite solution;
S2.随后加入0.05份化学交联剂环氧氯丙烷，恒温-5℃，350rpm搅拌3h，得到化学交联后的粗产物；S2. Then add 0.05 part of chemical cross-linking agent epichlorohydrin, keep the temperature at -5°C, and stir at 350 rpm for 3 hours to obtain a crude product after chemical cross-linking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在-5℃下放置5h进行定型，得到复合碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, poured into the mold gel and placed at -5°C for 5h for shaping, to obtain a composite alkali gel;
S4.外力牵伸复合碱凝胶(牵伸应变160％)，然后置于10wt％硫酸凝固浴1min固定取向，获得高取向纤维素/纳米基元复合水凝胶；S4. The composite alkali gel is drawn by external force (the drawing strain is 160%), and then placed in a 10 wt% sulfuric acid coagulation bath for 1 min to fix the orientation to obtain a highly oriented cellulose/nano-element composite hydrogel;
S5.洗净后二端夹持，25℃限域干燥，获得序构化纤维素/功能基元复合膜材料。S5. After cleaning, the two ends are clamped, and dried at 25° C. to obtain a structured cellulose/functional unit composite membrane material.
对比实施例2Comparative Example 2
对比例实施例2与实施例1成分上的区别在于：对比实施例2中成分仅为再生纤维素，而实施例1中成分含再生纤维素和纳米功能基元。The difference between the components of Comparative Example 2 and Example 1 is that the components in Comparative Example 2 are only regenerated cellulose, while the components in Example 1 contain regenerated cellulose and nano-functional primitives.
一种序构化纤维素膜材料的制备方法，包括如下步骤：A preparation method of a sequenced cellulose membrane material, comprising the following steps:
S1.按质量份数纤维素溶剂82份(其中氢氧化钠4.92份、尿素份8.2、去离子水68.88份配置)，-20℃冷肼下预冷，加入3份纤维素木浆，5000rpm下搅拌2min，得到纤维素/纳米基元复合溶液；S1. 82 parts by mass of cellulose solvent (wherein 4.92 parts of sodium hydroxide, 8.2 parts of urea, and 68.88 parts of deionized water are configured), pre-cooled under cold hydrazine at -20°C, add 3 parts of cellulose wood pulp, under 5000rpm Stir for 2 min to obtain a cellulose/nano-element composite solution;
S2.随后加入0.05份化学交联剂环氧氯丙烷，恒温-5℃，350rpm搅拌3h，得 到化学交联后的粗产物；S2. add 0.05 part of chemical crosslinking agent epichlorohydrin subsequently, constant temperature-5 ℃, 350rpm stirs 3h, obtains the crude product after chemical crosslinking;
S3.0℃，6000rpm，离心5min，后倒入模具凝胶在-5℃下放置5h进行定型，得到碱凝胶；S3.0°C, 6000rpm, centrifuged for 5min, then poured into the mold gel and placed at -5°C for 5h for shaping, to obtain an alkaline gel;
S4.外力牵伸碱凝胶(牵伸应变160％)，然后置于10wt％硫酸凝固浴1min固定取向，获得高取向纤维素水凝胶；S4. The alkali gel is drawn by external force (drawing strain is 160%), and then placed in a 10wt% sulfuric acid coagulation bath for 1min to fix the orientation to obtain a highly oriented cellulose hydrogel;
S5.洗净后二端夹持，25℃限域干燥，获得序构化纤维素膜材料。S5. After washing, the two ends are clamped, and dried at 25° C. to obtain a sequenced cellulose membrane material.
测试例test case
(1)纳米基元序构化纤维素纳米流体离子导体膜(实施例1)的离子电导率测量(1) Measurement of ionic conductivity of nano-element-ordered cellulose nanofluidic ionic conductor membrane (Example 1)
测试方法：配制10 -6、10 -5、10 -4、10 -3、10 -2以及10 -1M六种浓度的氯化钾溶液，并分别测试六种浓度本体溶液的电导率数值。接着，测试分别浸泡在10 -6、10 -5、10 -4、10 -3、10 -2、10 -1M氯化钾溶液的纳米基元序构化纤维素纳米流体离子导体膜的电导率。在待测样品的两端放置上两条平行的测试探针，然后在探针的两端施加一定的电势，接着测量通过样品的电流。用得到的电流与电势做出I-V图像，再进行拟合，然后取斜率为电导率。电导率(λ)的计算方程如下： Test method: prepare six concentrations of potassium chloride solutions of 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 and 10 -1 M, and test the conductivity values of the bulk solutions of the six concentrations respectively. Next, the conductance of nano-element-structured cellulose nanofluidic ionic conductor membranes immersed in 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 , and 10 -1 M potassium chloride solution were tested. Rate. Two parallel test probes are placed at both ends of the sample to be tested, then a certain potential is applied to both ends of the probes, and then the current through the sample is measured. An IV image was made with the obtained current and potential, fitted, and the slope was taken as the conductivity. The formula for calculating conductivity (λ) is as follows:
λ＝G(l/hw)λ=G(l/hw)
其中G是测量电导(即，I-V曲线的斜率)，l为所测复合膜的长度，h为所测膜的高度、w为所测复合膜的宽度。where G is the measured conductance (ie, the slope of the I-V curve), l is the length of the measured composite film, h is the measured height of the film, and w is the measured width of the composite film.
(2)序构化纤维素/功能基元复合膜(对比实施例1)的离子电导率测量(2) Measurement of ionic conductivity of structured cellulose/functional unit composite membrane (Comparative Example 1)
测试方法：在待测样品的两端放置上两条平行的测试探针，样品内部分别浸渍10 -6、10 -5、10 -4、10 -3、10 -2、10 -1M氯化钾溶液然后在探针的两端施加一定的电势，接着测量通过序构化纤维素/功能基元复合膜的电流。用得到的电流与电势做出I-V图像，再进行拟合，然后取斜率为电导率。电导率(λ)的计算方程如下： Test method: Two parallel test probes are placed on both ends of the sample to be tested, and the inside of the sample is immersed in 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 , 10 -1 M chloride respectively The potassium solution then applies a certain potential across the probe, and the current through the ordered cellulose/functional motif composite membrane is then measured. An IV image was made with the obtained current and potential, fitted, and the slope was taken as the conductivity. The formula for calculating conductivity (λ) is as follows:
λ＝G(l/hw)λ=G(l/hw)
其中G是测量电导(即，I-V曲线的斜率)，l为所测序构化纤维素/功能基元复合膜的长度，h为所测序构化纤维素/功能基元复合膜的高度、w为所测序构化纤维素/功能基元复合膜的宽度。where G is the measured conductance (ie, the slope of the IV curve), l is the length of the sequenced structured cellulose/functional motif composite membrane, h is the height of the sequenced structured cellulose/functional motif composite membrane, and w is The width of the sequenced structured cellulose/functional motif composite membrane.
(3)序构化纤维素膜(对比实施例1)的离子电导率测量(3) Measurement of ionic conductivity of structured cellulose membrane (Comparative Example 1)
测试方法：在待测样品的两端放置上两条平行的测试探针，样品内部分别浸渍10 -6、10 -5、10 -4、10 -3、10 -2、10 -1M氯化钾溶液然后在探针的两端施加一定的电势，接着测量通过序构化纤维素膜的电流。用得到的电流与电势做出I-V图像，再进行拟 合，然后取斜率为电导率。电导率(λ)的计算方程如下： Test method: Two parallel test probes are placed on both ends of the sample to be tested, and the inside of the sample is immersed in 10 -6 , 10 -5 , 10 -4 , 10 -3 , 10 -2 , 10 -1 M chloride respectively The potassium solution then applies a potential across the probe and the current through the structured cellulose membrane is then measured. An IV image was made with the obtained current and potential, fitted, and the slope was taken as the conductivity. The formula for calculating conductivity (λ) is as follows:
λ＝G(l/hw)λ=G(l/hw)
其中G是测量电导(即，I-V曲线的斜率)，l为所测序构化纤维素膜的长度，h为所测序构化纤维素膜的高度、w为所测序构化纤维素膜的宽度。where G is the measured conductance (ie, the slope of the I-V curve), l is the length of the sequenced textured cellulose membrane, h is the height of the sequenced textured cellulose membrane, and w is the width of the sequenced textured cellulose membrane.
(4)纳米基元序构化纤维素纳米流体离子导体膜(实施例1)在梯度盐度下扩散电压和扩散电流测量(4) Measurement of diffusion voltage and diffusion current under gradient salinity of nanostructured cellulose nanofluidic ionic conductor membrane (Example 1)
设计一套混合海水(0.5M NaCl)和河水(0.01M NaCl)的***，两侧分别是海水和河水，中间是高取向功能性纤维素纳米流体材料，可获得一定电压和电流。首先，裁剪厚度为0.1mm、宽度为1mm功能性纤维素膜，并用胶封装，确保两端暴露；其次，将双槽电化学池左右槽分别加入0.5M、0.01M电解质溶液，硅胶封装好的上述功能膜置于两槽之间；最后，将数字源表的两测试电极分别浸入上述二个槽内，测试并记录功能性纤维素膜产生的扩散电压和扩散电流。A system of mixing seawater (0.5M NaCl) and river water (0.01M NaCl) is designed, with seawater and river water on both sides, and a highly oriented functional cellulose nanofluid material in the middle, which can obtain a certain voltage and current. First, cut a functional cellulose film with a thickness of 0.1mm and a width of 1mm, and encapsulate it with glue to ensure that both ends are exposed; secondly, add 0.5M and 0.01M electrolyte solutions to the left and right slots of the double-slot electrochemical cell, respectively, and seal the silica gel. The above-mentioned functional film is placed between the two grooves; finally, the two test electrodes of the digital source meter are immersed in the above-mentioned two grooves respectively to test and record the diffusion voltage and diffusion current generated by the functional cellulose film.
表1 不同样品在对应电解质溶液中离子电导率数据Table 1 Ionic conductivity data of different samples in corresponding electrolyte solutions
Figure PCTCN2021089394-appb-000009
Figure PCTCN2021089394-appb-000009
从表中可以看出，实施例1相比于对比例1-2，以及本体溶液，一般而言，在不同的溶液浓度下的电导率均有不同程度的优势。It can be seen from the table that, compared with Comparative Examples 1-2 and the bulk solution, in general, Example 1 has different degrees of advantages in electrical conductivity at different solution concentrations.
表2 实施例3中梯度浓度下纳米基元序构纤维素离子导体膜的扩散电流和扩散电势数据Table 2 Diffusion current and diffusion potential data of nano-element ordered cellulose ion conductor membrane under gradient concentration in Example 3
Figure PCTCN2021089394-appb-000010
Figure PCTCN2021089394-appb-000010
Figure PCTCN2021089394-appb-000011
Figure PCTCN2021089394-appb-000011

Claims (10)

  1. 一种基元序构化纤维素基纳米流体离子导体材料，其特征在于，由以下质量份数的原料制得：A fundamentally ordered cellulose-based nanofluid ionic conductor material is characterized in that, it is prepared from the following raw materials in parts by mass:
    Figure PCTCN2021089394-appb-100001
    Figure PCTCN2021089394-appb-100001
    其中，所述基元序构化纤维素基纳米流体离子导体材料制得前，需要经氧化处理；Wherein, before the elementary ordered cellulose-based nanofluid ionic conductor material is prepared, it needs to be oxidized;
    纤维素溶剂中包含碱、尿素和水；The cellulose solvent contains alkali, urea and water;
    第一功能性纳米填料包括碳纳米管或羧基化碳纳米管的一种或两种；The first functional nanofiller includes one or both of carbon nanotubes or carboxylated carbon nanotubes;
    第二功能性纳米填料包括石墨烯、氧化石墨烯、MXene、氮化硼纳米片或羟基化氮化硼纳米片的一种或多种。The second functional nanofiller includes one or more of graphene, graphene oxide, MXene, boron nitride nanosheets or hydroxylated boron nitride nanosheets.
  2. 根据权利要求1所述基元序构化纤维素基纳米流体离子导体材料，其特征在于，所述纤维素溶剂包括以下质量份数的成分：The element-ordered cellulose-based nanofluidic ionic conductor material according to claim 1, wherein the cellulose solvent comprises the following components in parts by mass:
    碱6-12份；尿素10-17份；水61-84份。Alkali 6-12 parts; urea 10-17 parts; water 61-84 parts.
  3. 根据权利要求1所述基元序构化纤维素基纳米流体离子导体材料，其特征在于，所述第一功能性纳米填料包括以下质量份数的成分：The element-ordered cellulose-based nanofluidic ionic conductor material according to claim 1, wherein the first functional nanofiller comprises the following components in parts by mass:
    碳纳米管0.09-4份；羧基化碳纳米管0.09-10份。0.09-4 parts of carbon nanotubes; 0.09-10 parts of carboxylated carbon nanotubes.
  4. 根据权利要求1所述基元序构化纤维素基纳米流体离子导体材料，其特征在于，所述第二功能性纳米填料包括以下质量份数的成分：The element-ordered cellulose-based nanofluidic ionic conductor material according to claim 1, wherein the second functional nanofiller comprises the following components in parts by mass:
    石墨烯0.09-6份；氧化石墨烯0.09-8份；MXene 0.09-8份；氮化硼纳米片0.09-8份；羟基化氮化硼纳米片0.09-10份。0.09-6 parts of graphene; 0.09-8 parts of graphene oxide; 0.09-8 parts of MXene; 0.09-8 parts of boron nitride nanosheets; 0.09-10 parts of hydroxylated boron nitride nanosheets.
  5. 根据权利要求1-4任一项所述基元序构化纤维素基纳米流体离子导体材料的制备方法，其特征在于，包括如下步骤：According to the preparation method of the element-ordered cellulose-based nanofluidic ionic conductor material according to any one of claims 1-4, it is characterized in that, comprises the following steps:
    S1.将纤维素原料溶解在纤维素溶剂中，并向其中掺杂第一或第二功能性纳米填料，搅拌形成纤维素/纳米基元复合溶液；S1. Dissolving the cellulose raw material in a cellulose solvent, doping it with the first or second functional nano-filler, and stirring to form a cellulose/nano-element composite solution;
    S2.将上述复合溶液离心后，加入化学交联剂反应，生成粗产物；S2. after the above-mentioned composite solution is centrifuged, a chemical cross-linking agent is added to react to generate a crude product;
    S3.将上述粗产物离心、定型，得到复合纳米基元的纤维素碱凝胶；S3. above-mentioned crude product is centrifuged and shaped to obtain the cellulose alkali gel of composite nano-element;
    S4.将上述碱凝胶牵伸取向、浸泡在凝固浴中进行取向固定；S4. The above-mentioned alkali gel is drawn and oriented and soaked in a coagulation bath for orientation fixation;
    S5.对上述取向复合水凝胶进行TEMPO氧化处理、水洗、干燥，得到基元序构化 纤维素基纳米流体离子导体材料。S5. TEMPO oxidation treatment, washing and drying are carried out on the above-mentioned oriented composite hydrogel to obtain a cellulose-based nanofluidic ionic conductor material of elementary ordered structure.
  6. 根据权利要求5所述基元序构化纤维素基纳米流体离子导体材料的制备方法，其特征在于，所述S1中，搅拌温度为-20--10℃，搅拌速度为1000-5000rpm，The method for preparing a cellulose-based nanofluidic ionic conductor material with a primitive order structure according to claim 5, wherein in the S1, the stirring temperature is -20--10°C, and the stirring speed is 1000-5000 rpm,
  7. 根据权利要求5所述基元序构化纤维素基纳米流体离子导体材料的制备方法，其特征在于，所述S1中，搅拌时间为2-10min。The method for preparing a cellulose-based nanofluidic ionic conductor material with elemental ordering according to claim 5, characterized in that, in the S1, the stirring time is 2-10 min.
  8. 根据权利要求5所述基元序构化纤维素基纳米流体离子导体材料的制备方法，其特征在于，所述化学交联剂选自环氧氯丙烷、环氧氯丁烷、戊二醛或聚乙二醇缩水甘油醚的一种或多种。The method for preparing a cellulose-based nanofluidic ionic conductor material with element ordering according to claim 5, wherein the chemical crosslinking agent is selected from epichlorohydrin, epichlorobutane, glutaraldehyde or One or more of polyethylene glycol glycidyl ethers.
  9. 根据权利要求5所述基元序构化纤维素基纳米流体离子导体材料的制备方法，其特征在于，所述凝固浴选自硫酸、盐酸、柠檬酸、植酸、醋酸、甲醇、乙醇或水的一种或多种。The method for preparing a cellulose-based nanofluidic ionic conductor material with elemental ordering according to claim 5, wherein the coagulation bath is selected from the group consisting of sulfuric acid, hydrochloric acid, citric acid, phytic acid, acetic acid, methanol, ethanol or water one or more of.
  10. 根据权利要求1-4任一项所述基元序构化纤维素基纳米流体离子导体材料在渗透能发电器中的应用。According to any one of claims 1-4, the application of the element-ordered cellulose-based nanofluid ionic conductor material in an osmotic energy generator.
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