WO2020119055A1 - 一种光-热能量转换和热能存储定形相变复合材料及其制备方法 - Google Patents

一种光-热能量转换和热能存储定形相变复合材料及其制备方法 Download PDF

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WO2020119055A1
WO2020119055A1 PCT/CN2019/091624 CN2019091624W WO2020119055A1 WO 2020119055 A1 WO2020119055 A1 WO 2020119055A1 CN 2019091624 W CN2019091624 W CN 2019091624W WO 2020119055 A1 WO2020119055 A1 WO 2020119055A1
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phase change
mxenes
alc
energy storage
nanosheet
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唐炳涛
樊晓乔
刘璐
张宇昂
张淑芬
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2255/00—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes
    • F28F2255/06—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes composite, e.g. polymers with fillers or fibres
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2255/00—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes
    • F28F2255/20—Heat exchanger elements made of materials having special features or resulting from particular manufacturing processes with nanostructures

Definitions

  • the invention belongs to the field of functional composite materials, and in particular relates to a light-heat energy conversion and thermal energy storage shaped phase change composite material and a preparation method thereof.
  • Organic solid-liquid phase change material can be used to store and release a large amount of energy within a small temperature range.
  • PCM can store heat energy from the surrounding environment, for example, waste heat generated by vehicles, electronic products, and the like.
  • PCM can convert sunlight into thermal energy and store it.
  • organic solid-liquid phase change materials also have certain problems, such as low thermal conductivity, easy leakage during use, and lack of energy conversion capabilities.
  • MXenes is a two-dimensional transition metal carbon/nitride with surface hydrophilicity, metal conductivity and excellent electrochemical performance, etc. It is expected to be used for energy storage, catalysis, adsorption, hydrogen storage, sensors and new polymer reinforcement Composite materials and many other fields. Because MXenes nanosheets have a local plasmon resonance effect (LSPR), which has strong absorption in the visible and near-infrared regions, MXenes nanosheets can be used in the field of energy storage.
  • LSPR local plasmon resonance effect
  • the object of the present invention is to provide a composite phase-change material for light-thermal energy conversion and thermal energy storage, which uses MXenes nanosheets as light-heat conversion functional materials and phase-change materials as energy storage materials to combine the two.
  • the new composite phase change material with high phase change enthalpy value, good shape stability and good thermal stability has broad prospects in the field of thermal energy storage and utilization.
  • the phase change components are evenly dispersed between the MXenes nanosheet layers to obtain a shaped phase change composite material that can realize light-heat energy conversion and heat energy storage.
  • This shaped phase change composite material has a high phase change enthalpy value and high thermal stability. It is still solid at 95°C, while the phase change material has partially melted at 65°C, indicating excellent shape stability.
  • a light-thermal energy conversion and thermal energy storage shaped phase change composite material is composed of a support material and an organic phase change material, and the mass ratio of the support material and the organic phase change material is 3:7 to 1:9 ;
  • the support material is in the form of a sheet, and the organic phase change material is evenly filled between the layers of the support material to form a layered stack structure;
  • the support material is Ti 2 C, Ti 3 C 2 , Ti 3 CN, V 2 C, Nb 2 C, TiNbC, Nb 4 C 3 , Ta 4 C 3 , (Ti 0.5 Nb 0.5 ) 2 C or (V 0.5 Cr 0.5 ) 3 C 2 nanosheet; the nanosheet is a single layer or several layers, and the nanosheet size is 0.5-2.2 ⁇ m;
  • the organic phase change material is paraffin, fatty acid, fatty acid ester or alcohol compound.
  • the stacked shape in the present invention refers to a shape similar to an accordion bellows portion.
  • the nanosheet in the present invention is a single layer or several layers, because the peeling generally cannot accurately control the number of layers of the nanosheet.
  • the thickness of the obtained nanosheet is a single layer or several layers, and the size of the nanosheet is 0.5-2.2 ⁇ m.
  • the shape of the cross-section can be a variety of shapes, when the shape of the cross-section is circular 0.5-2.2 ⁇ m refers to the diameter of the nanosheet.
  • the organic phase change material in the present invention is an organic solid-liquid phase change material.
  • the paraffin wax is a paraffin wax having a melting point of 20-60°C.
  • the fatty acid is dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid or stearic acid.
  • the alcohol compound is dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol or polyethylene glycol with a molecular weight of 2000-20,000.
  • Another object of the present invention is to provide a method for preparing light-heat energy conversion and thermal energy storage shaped phase change composite materials, the method including the following steps:
  • the precursors are Ti 2 AlC, Ti 3 AlC 2 , Ti 3 AlCN, V 2 AlC, Nb 2 AlC, TiNbAlC, Nb 4 AlC 3 , Ta 4 AlC 3 , (Ti 0.5 Nb 0.5 ) 2 AlC or (V 0.5 Cr 0.5 ) 3 AlC 2 ;
  • step 3 Mix the DMSO intercalated multilayer MXenes obtained in step 2 with deionized water at 1g:200mL ⁇ 1g:300mL, and ultrasonically peel for 5h (turn the multilayer MXenes nanosheets into MXenes nanosheets with fewer or single layers) After solid-liquid separation and ultrasonic cleaning, MXenes nanosheets are obtained, and the MXenes nanosheets are dissolved in a solvent to obtain a MXenes nanosheet dispersion with a mass fraction of 1% to 5%;
  • the mass ratio of the organic phase change material to MXenes nanosheet is 9:1-7:3, after ultrasonic mixing, dry to obtain light-heat energy conversion and thermal energy Storage of shaped phase change composite materials;
  • the organic phase change material is paraffin, fatty acid, fatty acid ester or alcohol compound.
  • the solvent is deionized water or ethanol.
  • the specific operation of the step 3 is as follows: after ultrasonic peeling, the solid-liquid separation is performed to obtain the target MXenes nanosheet, the precipitate is ultrasonically washed with deionized water 3 times, the supernatant is removed by centrifugation, and the lower target is deposited MXenes nanosheets are evenly dispersed in water or ethanol to obtain MXenes nanosheet dispersion.
  • step 4 ultrasonic mixing, adjust the pH of the solution to 8, and vacuum dry at 50°C.
  • the paraffin wax is a paraffin wax with a melting point of 20 to 60°C;
  • the fatty acid is dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid or stearic acid; and
  • the alcohol compound is dodecyl alcohol and decahydrate Tetralol, cetyl alcohol, stearyl alcohol or polyethylene glycol with a molecular weight of 2,000 to 20,000.
  • the polyethylene glycol of the present invention may also be abbreviated as PEG.
  • the organic solid-liquid phase change material is filled between the MXenes layers to obtain a composite shaped phase change energy storage material.
  • the phase change enthalpy value and phase change temperature of the composite shaped phase change energy storage material (PCM) are significantly lower than those of PEG, mainly because the crystallization of PEG in PCM is supported by the compounds that support the framework Limitations and interference.
  • the phase change enthalpy of the obtained composite phase change material reaches about 150J/g, indicating that the obtained shaped composite phase change energy storage material has excellent phase change heat storage performance.
  • the obtained nanosheet composite phase change energy storage material and PEG have similar crystallization characteristics.
  • the temperature of the composite phase change energy storage material rises rapidly, and the curve shows an inflection point near 59°C.
  • the phase change component in the surface material undergoes a phase change, and the light energy is stored in the form of latent heat.
  • the composite phase The temperature of the variable energy storage material drops rapidly. When the temperature drops to about 49°C, it no longer drops and rises slightly, and maintains at about 49°C for a period of time, indicating that the material has photothermal conversion and phase change heat storage characteristics.
  • PCM remains solid at 95°C, while PEG has partially melted at 65°C, indicating that the resulting composite phase change energy storage material has excellent shaped phase change characteristics.
  • the present invention is a light-heat energy conversion and heat energy storage composite phase change material, which uses MXenes nanosheets as light-heat conversion functional materials and phase change materials as energy storage materials. Compounding to obtain a new composite phase change material with high phase change enthalpy value (up to about 150J/g), excellent shape stability and thermal stability.
  • FIG. 3 is an XRD diagram of the PEG and the composite shaped phase change energy storage material described in Example 1;
  • Example 4 is a DSC curve diagram of the PEG and the composite shaped phase change energy storage material described in Example 1;
  • Example 5 is a photothermal conversion curve of the composite phase change energy storage material described in Example 1 (optical power density is 128.6mW/cm 2 );
  • Example 6 is a digital photo of the PEG and the composite phase change energy storage material described in Example 1 after being heated at 30°C, 65°C and 95°C for 20 minutes;
  • FIG. 7 is a TG curve diagram of the PEG and the composite shaped phase change energy storage material described in Example 1.
  • FIG. 7 is a TG curve diagram of the PEG and the composite shaped phase change energy storage material described in Example 1.
  • test methods in the following examples are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.
  • a light-heat energy conversion and heat energy storage shaped phase change composite material is prepared according to the following steps:
  • DMSO dimethyl sulfoxide
  • the quality score of the film is 1.4%;
  • the diameter of the Ti 3 C 2 nanosheets is about 0.5 to 2.2 ⁇ m, and the layer thickness is a single layer or a few layers.
  • the composite material is a layered stacked structure ( Figure 2). It can be seen from the XRD diagram of the material ( Figure 3) that the resulting nanosheet composite phase change energy storage material has similar crystalline characteristics as PEG, but the diffraction peak height of the composite phase change material is lower than that of PEG, which is due to the PEG Crystallization is caused by the limitation and interference of supporting materials.
  • phase change enthalpy and phase change temperature of the Ti 3 C 2 /PEG composite shaped phase change material can be seen from the DSC curve of the material ( Figure 4), the phase change of the Ti 3 C 2 nanosheet composite shaped phase change energy storage material
  • the enthalpy and phase transition temperature are significantly lower than those of PEG, mainly because the crystallization of PEG in Ti 3 C 2 /PEG is restricted and interfered by Ti 3 C 2 nanoplatelets that support the framework .
  • the phase change enthalpy value of the Ti 3 C 2 /PEG composite phase change material reaches about 167J/g, indicating that the obtained composite phase change energy storage material has excellent phase change heat storage performance.
  • the temperature change curve ( Figure 5) shows a temperature change platform at 59 ⁇ 63°C, indicating that the material undergoes a phase change here, and the light energy It is converted into heat energy and stored in the form of latent heat.
  • the temperature of the nanosheet composite phase change energy storage material drops rapidly. When the temperature drops to about 49°C, it does not drop and rises slightly, and maintains at about 49°C for a period of time. At time, latent heat is released, indicating that the material has photothermal conversion and phase change heat storage characteristics.
  • the mass ratio of polyethylene glycol 6000 to Ti 3 C 2 nanosheets was changed to 7:3, and the composite shaped phase change material of Ti 3 C 2 nanosheets was obtained by compounding.
  • the other conditions were the same as those in Example 1.
  • the phase change enthalpy value of the obtained composite shaped phase change material can still reach about 154J/g, and has the same high thermal stability as Example 1.
  • the mass ratio of polyethylene glycol 6000 to Ti 3 C 2 nanosheets was changed to 9:1, and the composite shaped phase change material of Ti 3 C 2 nanosheets was obtained by compounding. Other conditions were the same as those in Example 1.
  • the obtained composite shaped phase change material can still achieve a phase change enthalpy value of 177 J/g or more, and has the same high thermal stability as Example 1.
  • Example 1 Replace the precursor in Example 1 with Ti 2 AlC, Ti 3 AlCN, V 2 AlC, Nb 2 AlC, TiNbAlC, Nb 4 AlC 3 , Ta 4 AlC 3 , (Ti 0.5 Nb 0.5 ) 2 AlC or (V 0.5 Cr 0.5 ) 3 AlC 2 , other conditions are the same as in Example 1.
  • the obtained material can realize light-heat conversion and thermal energy storage, and the obtained material still has excellent shape stability, energy storage density and thermal stability.
  • Example 2 Replace the precursor in Example 2 with Ti 2 AlC, Ti 3 AlCN, V 2 AlC, Nb 2 AlC, TiNbAlC, Nb 4 AlC 3 , Ta 4 AlC 3 , (Ti 0.5 Nb 0.5 ) 2 AlC or (V 0.5 Cr 0.5 ) 3 AlC 2 , other conditions are the same as in Example 2.
  • the obtained material can realize light-heat conversion and thermal energy storage, and the obtained material still has excellent shape stability, energy storage density and thermal stability.
  • Example 3 Replace the precursor in Example 3 with Ti 2 AlC, Ti 3 AlCN, V 2 AlC, Nb 2 AlC, TiNbAlC, Nb 4 AlC 3 , Ta 4 AlC 3 , (Ti 0.5 Nb 0.5 ) 2 AlC or (V 0.5 Cr 0.5 ) 3 AlC 2 , other conditions are the same as in Example 2.
  • the obtained material can realize light-heat conversion and thermal energy storage, and the obtained material still has excellent shape stability, energy storage density and thermal stability.
  • the organic solid-liquid phase change material polyethylene glycol in Example 1-3 was replaced with dodecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, and stearic acid.
  • the solvent deionized water was replaced with ethanol
  • Ti 3 C 2 nanosheets are dispersed in ethanol, and other conditions are the same as those in Examples 1-3.
  • Ti 3 C 2 nanosheet composite shaped phase change materials are prepared.
  • the resulting materials can realize light-heat conversion and thermal energy storage. Has excellent shape stability, energy storage density and thermal stability.
  • the organic solid-liquid phase change material polyethylene glycol in Example 1-3 was replaced with dodecyl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol.
  • the solvent deionized water was replaced with ethanol, Ti 3 C 2 nanosheets are dispersed in ethanol.
  • Other conditions are the same as those in Examples 1-3.
  • Ti 3 C 2 nanosheets composite shaped phase change material is prepared.
  • the resulting material can realize light-heat conversion and thermal energy storage.
  • the resulting material still has excellent Shape stability, energy storage density and thermal stability.

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Abstract

一种光-热能量转换和热能存储定形相变复合材料，属于功能复合材料领域。一种光-热能量转换和热能存储定形相变复合材料，所述复合材料由支撑材料和有机相变材料组成，所述支撑材料与有机相变材料的质量比为3:7～1:9；所述支撑材料为片层状，有机相变材料均匀填充在支撑材料层间，构成层状堆叠结构；所述支撑材料为Ti2C、Ti3C2、Ti3CN、V2C、Nb2C、TiNbC、Nb4C3、Ta4C3、(Ti0.5Nb0.5)2C或(V0.5Cr0.5) 3C2的纳米片；所述有机相变材料为石蜡、脂肪酸、脂肪酸酯或醇类化合物。所述复合材料具有高相变焓值，优异的形状稳定性和热稳定性，在热能存储与利用领域具有广阔的前景。

Description

一种光-热能量转换和热能存储定形相变复合材料及其制备方法 技术领域
本发明属于功能复合材料领域，具体涉及一种光-热能量转换和热能存储定形相变复合材料及其制备方法。
背景技术
有机固液相变材料(PCM)，作为潜热存储材料，它的使用可以实现在温度变化很小的范围内储存和释放大量的能量。PCM可以储存来自周围环境的热能，例如，交通工具、电子产品等产生的废热。特别地，PCM可以将太阳光转换成热能进而储存起来。然而，有机固液相变材料也存在着一定的问题，如低的导热系数，使用过程中易泄漏，缺乏能量转换能力等。
MXenes是一种二维过渡金属碳/氮化物，具有表面亲水性、金属导电性及优良的电化学性能等，有望用于储能、催化、吸附、储氢、传感器以及新型聚合物增强基复合材料等诸多领域。由于MXenes纳米片具有局部等离子体共振效应(LSPR)，它在可见光区，近红外光区具有强的吸收，因此，MXenes纳米片可应用于能量存储领域。
发明内容
本发明的目的是提供一种光-热能量转换和热能存储复合相变材料，此种材料以MXenes纳米片为光-热转换功能材料，以相变材料为储能材料，将二者复合，得到具有相变焓值高，形状稳定好，热稳定性好的新型复合相变材料，在热能存储与利用领域具有广阔的前景。
本发明所述光-热能量转换和热能存储复合相变材料中，相变成分均匀得分散在MXenes纳米片层间，得到可实现光-热能量转换与热能储存的定形相变复合材料。此定形相变复合材料具有高的相变焓值和高的热稳定性。在95℃时仍然是固态，而相变材料在65℃时已经部分熔化，表明具有优异的形状稳定性。
一种光-热能量转换和热能存储定形相变复合材料，所述复合材料由支撑材料和有机相变材料组成，所述支撑材料与有机相变材料的质量比为3:7～1:9；
所述支撑材料为片层状，有机相变材料均匀填充在支撑材料层间，构成层状堆叠结构；
所述支撑材料为Ti 2C、Ti 3C 2、Ti 3CN、V 2C、Nb 2C、TiNbC、Nb 4C 3、Ta 4C 3、(Ti 0.5Nb 0.5) 2C或(V 0.5Cr 0.5) 3C 2的纳米片；所述纳米片为单层或几层，纳米片尺寸为0.5-2.2μm；
所述有机相变材料为石蜡、脂肪酸、脂肪酸酯或醇类化合物。
本发明所述堆叠状指的是一种类似手风琴风箱部分的形状。
本发明所述纳米片为单层或几层，是由于剥离一般都不能精确控制纳米片的层数，得到的纳米片厚度是单层或几层不等，纳米片尺寸为0.5-2.2μm指的是纳米片的横截面的尺寸，横截面的形状可以是多种形状，当横截面的形状是圆形时0.5-2.2μm指的是纳米片的直径尺寸。
本发明所述有机相变材料即为有机固液相变材料。
优选地，所述石蜡为熔点在20～60℃的石蜡。
优选地，所述脂肪酸为十二酸、十四酸、十五酸、棕榈酸或硬脂酸。
优选地，所述醇类化合物为十二醇、十四醇、十六醇、十八醇或分子量2000～20000的聚乙二醇。
本发明的另一目的是提供一种光-热能量转换和热能存储定形相变复合材料的制备方法，所述方法包括以下步骤：
①将前驱体与体积分数为40％的氢氟酸以1g:8mL～1g:10mL的比例混合放置1～3天，得堆叠状MXenes，所述前驱体为Ti 2AlC、Ti 3AlC 2、Ti 3AlCN、V 2AlC、Nb 2AlC、TiNbAlC、Nb 4AlC 3、Ta 4AlC 3、(Ti 0.5Nb 0.5) 2AlC或(V 0.5Cr 0.5) 3AlC 2；
②将所得堆叠状MXenes用去离子水离心洗涤至pH＝7，烘干，与二甲基亚砜以1g:10mL～1g:14mL的比例混合，室温下磁力搅拌18h，离心分离得沉淀物，为二甲基亚砜插层的MXenes，即DMSO插层的多层MXenes；
③将步骤②所得DMSO插层的多层MXenes与去离子水以1g:200mL～1g:300mL混合，超声剥离5h(将多层MXenes纳米片变成层数较少或者单层的MXenes纳米片)，固液分离超声清洗后得MXenes纳米片，将所述MXenes纳米片溶于溶剂，得质量分数为1％～5％的MXenes纳米片分散液；
④将有机相变材料加入MXenes纳米片分散液中，所述有机相变材料与MXenes纳米片的质量比为9：1～7：3，超声混合后，干燥即得光-热能量转换和热能存储定形相变复合材料；
所述有机相变材料为石蜡、脂肪酸、脂肪酸酯或醇类化合物。
进一步地，所述溶剂为去离子水或乙醇。
优选地，所述步骤③的具体操作如下：超声剥离后，固液分离得沉淀物目标MXenes纳米片，将沉淀物用去离子水超声清洗3次，离心除去上清液，将下沉淀物目标MXenes纳米片均匀分散在水或乙醇中得MXenes纳米片分散液。
优选地，所述步骤④超声混合后，调整溶液pH＝8，50℃真空干燥。
优选地，所述石蜡为熔点在20～60℃的石蜡；所述脂肪酸为十二酸、十四酸、十五酸、棕榈酸或硬脂酸；所述醇类化合物为十二醇、十四醇、十六醇、十八醇或分子量2000～20000的聚乙二醇。
本发明所述聚乙二醇也可简写为PEG。
本发明中有机固液相变材料填充在MXenes层间，得到复合定形相变储能材料。复合定形相变储能材料(PCM)的相变焓值及相变温度明显低于PEG的相变焓值及相变温度，主要是因为PCM中的PEG的结晶受到起骨架支撑作用的化合物的限制和干扰。所得复合相变材料的相变焓值达到150J/g左右，表明所得定形复合相变储能材料具有优良的相变储热性能。所得纳米片复合相变储能材料与PEG具有相似的结晶特性。
在太阳光照下，复合相变储能材料温度迅速升高，曲线在59℃附近出现拐点，表面材料中的相变成分发生相变，光能以潜热的形式存储起来，停止光照后，复合相变储能材料温度迅速下降，当温度降至49℃左右时不再下降且略微升高，并在49℃左右维持一段时间，表明材料具有光热转换与相变储热特性。
PCM在95℃时仍保持固态，而PEG在65℃时已发生部分熔化，表明所得复合相变储能材料具有优异的定形相变特性。
本发明的有益效果：本发明一种光-热能量转换和热能存储复合相变材料，此种材料以MXenes纳米片为光-热转换功能材料，以相变材料为储能材料，将二者复合，得到具有相变焓值高(达到150J/g左右)，具有优异形状稳定性，热稳定性的新型复合相变材料。
附图说明
图1(a)和(b)为实施例1所述MXenes纳米片的扫描电镜(SEM)及透射电镜(TEM)图；
图2(a)和(b)为实施例1中所述PCM的扫描电镜(SEM)图；
图3为实施例1中所述PEG及复合定形相变储能材料的XRD图；
图4为实施例1中所述PEG及复合定形相变储能材料的DSC曲线图；
图5为实施例1中所述复合相变储能材料的光热转换曲线图(光功率密度为128.6mW/cm 2)；
图6为实施例1中所述PEG及复合相变储能材料在30℃，65℃及95℃条件下加热20min后的数码照片；
图7为实施例1中所述PEG及复合定形相变储能材料的TG曲线图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
一种光-热能量转换和热能存储定形相变复合材料，按照下述步骤制备：
①将1gTi 3AlC 2溶于8mL水中得前驱体溶液，将1g氢氟酸溶于10mL水中得氢氟酸溶液，将前驱体溶液与氢氟酸溶液混合放置3天，得堆叠状Ti 3C 2；
②将处理后得到的堆叠状Ti 3C 2用去离子水离心洗涤至pH＝7，烘干，与二甲基亚砜(以下简称DMSO)混合，混合比例为1g:12mL，室温下磁力搅拌18h，离心倒去上清液，得DMSO插层的多层Ti 3C 2沉淀；
③将DMSO插层的多层Ti 3C 2沉淀物与去离子水以1g:300mL的比例混合，超声5h，离心倒掉上清液，沉淀用去离子超声清洗3次，得Ti 3C 2纳米片，以去离子水为溶剂，将所述Ti 3C 2纳米片均匀分散在去离子水中得Ti 3C 2纳米片分散液，在Ti 3C 2纳米片分散液中Ti 3C 2纳米片的质量分数为1.4％；
④将聚乙二醇6000加入Ti 3C 2纳米片分散液，聚乙二醇与Ti 3C 2纳米片的质量比为4：1，超声30min，调节pH＝8，50℃真空干燥，得Ti 3C 2纳米片复合定形相变材料。
从材料的SEM图和TEM图(附图1)可以看出，Ti 3C 2纳米片的直径尺寸约为0.5～2.2μm，层厚为单层或几层，与聚乙二醇复合后，复合材料为层状堆叠结构(附图2)。从材料的XRD图(附图3)可以看出，所得纳米片复合相变储能材料与PEG具有相似的结晶特性，但复合相变材料的衍射峰高度较PEG的低，这是由于PEG的结晶受到支撑材料的限制和干扰所致。Ti 3C 2/PEG复合定形相变材料的相变焓值及相变温度从材料的DSC曲线(附图4)可以看出，Ti 3C 2纳米片复合定形相变储能材料的相变焓值及相变温度明显低于PEG的相变焓值及相变温度，主要是因为中的Ti 3C 2/PEG中PEG的结晶受到起骨架支撑作用的Ti 3C 2纳米片限制和干扰。DSC曲线图中，Ti 3C 2/PEG复合相变材料的相变焓值达到167J/g左右，表明所得复合相变储能材料具有优良的相变储热性能。在光照下，Ti 3C 2/PEG复合定形相变储能材料温度迅速升高，温度变化曲线(附图5)在59～63℃出现温度变化平台，表明材料在此发生相变，光能转换成热能，以潜热的形式存储起来，停止光照后，纳米片复合相变储能材料温度迅速下降，当温度降至49℃左右时不再下降且略微升高，并在49℃左右维持一段时间， 潜热释放出来，表明材料具有光热转换与相变储热特性。从材料在不同温度下的定型效果图(附图6)可以看出，材料在95℃时仍保持固态，而聚乙二醇在65℃时已发生部分熔化，表明所得Ti 3C 2纳米片复合相变储能材料具有优异的定形相变特性。从材料的TG曲线(附图7)可以看出，材料的分解发生在350℃，远高于相转变温度，说明所得材料具有高的热稳定性。
实施例2
将聚乙二醇6000与Ti 3C 2纳米片的质量比换为7：3，复合得到Ti 3C 2纳米片复合定形相变材料，其他条件和实施例1一致。所得复合定形相变材料的相变焓值仍能达到154J/g左右，且具有与实施例1同样高的热稳定性。
实施例3
将聚乙二醇6000与Ti 3C 2纳米片的质量比换为9：1，复合得到Ti 3C 2纳米片复合定形相变材料，其他条件和实施例1一致。所得复合定形相变材料的相变焓值仍能达到177J/g以上，且具有与实施例1同样高的热稳定性。
实施例4-12
将实施例1中的前驱体换为Ti 2AlC、Ti 3AlCN、V 2AlC、Nb 2AlC、TiNbAlC、Nb 4AlC 3、Ta 4AlC 3、(Ti 0.5Nb 0.5) 2AlC或(V 0.5Cr 0.5) 3AlC 2，其他条件和实施例1一致。所得材料可实现光-热转换与热能存储，所得材料仍具有优异的形状稳定性、储能密度以及热稳定性。
实施例13-21
将实施例2中的前驱体换为Ti 2AlC、Ti 3AlCN、V 2AlC、Nb 2AlC、TiNbAlC、Nb 4AlC 3、Ta 4AlC 3、(Ti 0.5Nb 0.5) 2AlC或(V 0.5Cr 0.5) 3AlC 2，其他条件和实施例2一致。所得材料可实现光-热转换与热能存储，所得材料仍具有优异的形状稳定性、储能密度以及热稳定性。
实施例22-30
将实施例3中的前驱体换为Ti 2AlC、Ti 3AlCN、V 2AlC、Nb 2AlC、TiNbAlC、Nb 4AlC 3、Ta 4AlC 3、(Ti 0.5Nb 0.5) 2AlC或(V 0.5Cr 0.5) 3AlC 2，其他条件和实施例2一致。所得材料可实现光-热转换与热能存储，所得材料仍具有优异的形状稳定性、储能密度以及热稳定性。
实施例31-45
将实施例1-3中的有机固液相变材料聚乙二醇换为十二酸、十四酸、十五酸、棕榈酸、硬脂酸，步骤③中将溶剂去离子水换为乙醇，Ti 3C 2纳米片分散在乙醇中，其他条件与实施例1-3一致，制备Ti 3C 2纳米片复合定形相变材料，所得材料可实现光-热转换与热能存储，所得材料仍具有优异的形状稳定性、储能密度以及热稳定性。
实施例46-57
将实施例1-3中的有机固液相变材料聚乙二醇换为十二醇、十四醇、十六醇、十八醇，步骤③中将溶剂去离子水换为乙醇，Ti 3C 2纳米片分散在乙醇中，其他条件与实施例1-3一致，制备Ti 3C 2纳米片复合定形相变材料，所得材料可实现光-热转换与热能存储，所得材料仍具有优异的形状稳定性、储能密度以及热稳定性。

Claims (8)

  1. 一种光-热能量转换和热能存储定形相变复合材料，其特征在于，所述复合材料由支撑材料和有机相变材料组成，所述支撑材料与有机相变材料的质量比为3:7～1:9；
    所述支撑材料为片层状，有机相变材料均匀填充在支撑材料层间，构成层状堆叠结构；
    所述支撑材料为Ti 2C、Ti 3C 2、Ti 3CN、V 2C、Nb 2C、TiNbC、Nb 4C 3、Ta 4C 3、(Ti 0.5Nb 0.5) 2C或(V 0.5Cr 0.5) 3C 2的纳米片；所述纳米片为单层或多层，纳米片尺寸为0.5-2.2μm；
    所述有机相变材料为石蜡、脂肪酸、脂肪酸酯或醇类化合物。
  2. 根据权利要求1所述材料，其特征在于，所述石蜡为熔点在20～60℃的石蜡。
  3. 根据权利要求1所述材料，其特征在于，所述脂肪酸为十二酸、十四酸、十五酸、棕榈酸或硬脂酸。
  4. 根据权利要求1所述材料，其特征在于，所述醇类化合物为十二醇、十四醇、十六醇、十八醇或分子量2000～20000的聚乙二醇。
  5. 权利要求1所述的光-热能量转换和热能存储定形相变复合材料的制备方法，其特征在于，所述方法包括以下步骤：
    ①将前驱体与体积分数为40％的氢氟酸以1g:8mL～1g:10mL的比例混合放置1～3天，得堆叠状MXenes，所述前驱体为Ti 2AlC、Ti 3AlC 2、Ti 3AlCN、V 2AlC、Nb 2AlC、TiNbAlC、Nb 4AlC 3、Ta 4AlC 3、(Ti 0.5Nb 0.5) 2AlC或(V 0.5Cr 0.5) 3AlC 2；
    ②将所得堆叠状MXenes用去离子水离心洗涤至pH＝7，烘干，与二甲基亚砜以1g:10mL～1g:14mL的比例混合，室温下磁力搅拌18h，离心分离得沉淀物；
    ③将步骤②所得沉淀物与去离子水以1g:200mL～1g:300mL混合，超声剥离5h，固液分离超声清洗后得MXenes纳米片，将所述MXenes纳米片溶于溶剂，得质量分数为1％～5％的MXenes纳米片分散液；
    ④将有机相变材料加入MXenes纳米片分散液中，所述有机相变材料与MXenes纳米片的质量比为9：1～7：3，超声混合后，干燥即得光-热能量转换和热能存储定形相变复合材料；
    所述有机相变材料为石蜡、脂肪酸、脂肪酸酯或醇类化合物。
  6. 根据权利要求5所述方法，其特征在于，所述步骤③的具体操作如下：超声剥离后，固液分离得沉淀物MXenes纳米片，将该沉淀物用去离子水超声清洗3次，固液分离除去上清液，再将沉淀物MXenes纳米片均匀分散在水或乙醇中得MXenes纳 米片分散液；所述固液分离为离心分离。
  7. 根据权利要求5所述方法，其特征在于，所述步骤④超声混合后，调整溶液pH＝8，50℃真空干燥。
  8. 根据权利要求5所述方法，其特征在于，所述石蜡为熔点在20～60℃的石蜡；所述脂肪酸为十二酸、十四酸、十五酸、棕榈酸或硬脂酸；所述醇类化合物为十二醇、十四醇、十六醇、十八醇或分子量2000～20000的聚乙二醇。
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