CN103289655B - Expanded graphite composite heat storage material and its preparation method and application - Google Patents
Expanded graphite composite heat storage material and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 44
- 239000010439 graphite Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000005338 heat storage Methods 0.000 title abstract description 14
- 239000011232 storage material Substances 0.000 title abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 17
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 12
- 238000004146 energy storage Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 8
- -1 M is Co Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002114 nanocomposite Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000008602 contraction Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000007431 microscopic evaluation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910004860 CaZn Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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Abstract
本发明公开了一种膨胀石墨复合蓄热材料及其制备方法，其分子式为CaxMy(OH)[2(x+y)-z]Clz·2H2O/C，其中M为Co、Ni或Zn，x/y为0.25～2，C表示石墨，CaxMy(OH)[2(x+y)-z]Clz·2H2O与C的重量比为0.25～0.5。本发明把氢氧化钙与过渡金属氧化物制成纳米复合材料，并储放在多孔膨胀石墨基体中避免这些微粒在吸热放热反应中再次聚合在一起，多孔膨胀石墨基体的存在可以有效地提高蒸汽的传热性能以及减少反应过程中固相的膨胀和收缩对反应的影响。The invention discloses an expanded graphite composite heat storage material and a preparation method thereof, the molecular formula of which is Ca x M y (OH) [2(x+y)-z] Cl z 2H 2 O/C, wherein M is Co , Ni or Zn, x/y is 0.25-2, C represents graphite, and the weight ratio of Ca x M y (OH) [2(x+y)-z] Cl z ·2H 2 O to C is 0.25-0.5. In the present invention, calcium hydroxide and transition metal oxides are made into nanocomposites, and stored in a porous expanded graphite matrix to avoid re-aggregation of these particles in endothermic and exothermic reactions. The presence of porous expanded graphite matrix can effectively Improve the heat transfer performance of steam and reduce the influence of the expansion and contraction of the solid phase on the reaction during the reaction.
Description
技术领域 technical field
本发明涉及一种膨胀石墨复合蓄热材料及其制备方法。 The invention relates to an expanded graphite composite heat storage material and a preparation method thereof.
背景技术 Background technique
目前，化学蓄热是一种高效的蓄热技术，具有非常好的发展前景，其储能密度比相变蓄热要大一个数量级。氢氧化钙化学蓄热材料具有稳定性好、储能密度高、循环性好、空隙率合适等特点，是一种非常好的太阳能化学反应蓄热方式。但脱水动力学速度过慢严重制约这种材料的规模化应用，开发复合材料是提高其脱水动力学性能的主要手段，其中降低热分解反应的温度和提高复合材料内部传质传热性能是提高其脱水动力学的关键。 At present, chemical heat storage is an efficient heat storage technology with very good development prospects, and its energy storage density is an order of magnitude larger than that of phase change heat storage. Calcium hydroxide chemical heat storage material has the characteristics of good stability, high energy storage density, good cycle performance, and appropriate porosity. It is a very good solar energy chemical reaction heat storage method. However, the slow dehydration kinetics seriously restricts the large-scale application of this material. The development of composite materials is the main means to improve its dehydration kinetics. Among them, reducing the temperature of thermal decomposition reaction and improving the internal mass and heat transfer performance of composite materials are the key to improving the dehydration kinetics. key to its dehydration kinetics.
发明内容 Contents of the invention
本发明的目的是提供一种膨胀石墨复合材料CaxMy(OH)[2(x+y)-z]Clz·2H2O/C，以降低反应所需的温度，解决太阳能化学蓄热材料的脱水动力学问题。 The purpose of the present invention is to provide an expanded graphite composite material Ca x M y (OH) [2(x+y)-z] Cl z · 2H 2 O/C, to reduce the temperature required for the reaction and solve the problem of solar energy chemical storage Dehydration kinetics of thermal materials.
本发明另一目的是提供上述膨胀石墨复合材料的制备方法。 Another object of the present invention is to provide a preparation method of the above-mentioned expanded graphite composite material.
本发明实现过程如下： The realization process of the present invention is as follows:
分子式CaxMy(OH)[2(x+y)-z]Clz·2H2O/C表示的膨胀石墨复合材料，其中M为Co、Ni或Zn，x/y为0.25～2，C表示石墨，CaxMy(OH)[2(x+y)-z]Clz·2H2O与C的重量比为0.25～0.5。 An expanded graphite composite material represented by the molecular formula Ca x M y (OH) [2(x+y)-z] Cl z 2H 2 O/C, wherein M is Co, Ni or Zn, and x/y is 0.25 to 2, C represents graphite, and the weight ratio of Ca x M y (OH) [2(x+y)-z] Cl z ·2H 2 O to C is 0.25-0.5.
x、y和z合理取值，[2(x+y)-z]不等于零，通常情况下，4z＞[2(x+y)-z]＞0.5z。 The values of x, y and z are reasonable, and [2(x+y)-z] is not equal to zero. Usually, 4z>[2(x+y)-z]>0.5z.
上述膨胀石墨复合材料的制备方法，包括以下步骤： The preparation method of above-mentioned expanded graphite composite material, comprises the following steps:
（1）将氢氧化钙和M(OH)2加至饱和氯化铵溶液中搅拌反应得到悬浮液，M为Co、Ni或Zn； (1) Add calcium hydroxide and M(OH) 2 to saturated ammonium chloride solution and stir to obtain a suspension, M is Co, Ni or Zn;
（2）加入可膨胀石墨充分超声振动； (2) Add expandable graphite to fully ultrasonic vibration;
（3）静置陈化生长； (3) static aging growth;
（4）加热蒸干水分。 (4) Heat and evaporate to dryness.
上述膨胀石墨复合材料可应用于化学储能中。 The above-mentioned expanded graphite composite material can be applied to chemical energy storage.
本发明依据的化学原理如下： The chemical principle of the present invention basis is as follows:
本发明的优点与积极效果：本发明提出了一种膨胀石墨复合材料，把氢氧化钙与过渡金属氧化物制成纳米复合材料，并储放在多孔膨胀石墨基体中避免这些微粒在吸热放热反应中再次聚合在一起，多孔膨胀石墨基体的存在可以有效地提高蒸汽的传热性能以及减少反应过程中固相的膨胀和收缩对反应的影响。 Advantages and positive effects of the present invention: the present invention proposes a kind of expanded graphite composite material, and calcium hydroxide and transition metal oxide are made nano-composite material, and are stored in the porous expanded graphite matrix to avoid these particles from absorbing heat and releasing heat. Polymerized together again in the thermal reaction, the presence of the porous expanded graphite matrix can effectively improve the heat transfer performance of the steam and reduce the influence of the expansion and contraction of the solid phase on the reaction during the reaction.
附图说明 Description of drawings
图1为复合材料的微观组织； Fig. 1 is the microstructure of composite material;
图2为复合材料的在对应点的能谱图； Fig. 2 is the energy spectrum diagram at corresponding point of composite material;
图3为复合材料热重图。 Figure 3 is the thermogravimetric diagram of the composite material.
具体实施方式 detailed description
为进一步了解本发明的发明内容和特点，用以下实施例作进一步的详细说明，但本发明要求保护的范围并不局限于实施例表示的范围。 In order to further understand the content and characteristics of the present invention, the following examples are used for further detailed description, but the scope of protection of the present invention is not limited to the scope indicated by the examples.
实施例1 Example 1
向烧杯中加入1000mL蒸馏水并加热至293K，然后将足量的氯化铵加入到烧杯中，充分搅拌，过滤得到饱和氯化铵溶液，称量144mg氢氧化钙加入到烧杯中，搅拌使其充分溶解；称量162mg氧化锌加入到氢氧化钙溶液中，不断搅拌，连续反应12h，得到乳白色的悬浮液;将200mg粉末状膨胀石墨加至烧杯中，在293K的温度下超声振动24h；然后将该溶液在293K的温度下静置约12h后，将烧杯放置在353K的温度下约10h排氨气和水，烘干后取出膨胀石墨用蒸馏水洗涤，加热至353K的温度下干燥10h，循环水洗、干燥重复2-3次即可得到最终膨胀石墨基钙系纳米复合太阳能蓄热材料。微观分析表明该材料的化学式为CaZn0.97(OH)2.8Cl1.14·2H2O/C，具有无定型的晶体结构，能够实现纳米级的复合。其常压下的平均脱水分解温度约为370℃，与单纯的氢氧化钙相比降低了约130℃，循环稳定性较好，储能密度约为97.3kJ/kg。对应的微观组织见图1所示，对应点的能谱分析见图2所示，该复合材料热重分析见图3所示。 Add 1000mL of distilled water to the beaker and heat to 293K, then add enough ammonium chloride into the beaker, stir well, filter to obtain a saturated ammonium chloride solution, weigh 144mg of calcium hydroxide and add it to the beaker, stir to make it fully Dissolve; weigh 162mg of zinc oxide and add it to the calcium hydroxide solution, stir continuously, and react continuously for 12 hours to obtain a milky white suspension; add 200mg of powdered expanded graphite to the beaker, and ultrasonically vibrate for 24 hours at a temperature of 293K; then After the solution was left to stand for about 12 hours at a temperature of 293K, the beaker was placed at a temperature of 353K for about 10 hours to discharge ammonia and water, and after drying, the expanded graphite was taken out and washed with distilled water, heated to 353K, dried for 10 hours, and washed with circulating water and drying repeated 2-3 times to obtain the final expanded graphite-based calcium-based nanocomposite solar heat storage material. Microscopic analysis shows that the chemical formula of the material is CaZn 0.97 (OH) 2.8 Cl 1.14 ·2H 2 O/C, which has an amorphous crystal structure and can realize nanoscale compounding. Its average dehydration decomposition temperature under normal pressure is about 370°C, which is about 130°C lower than that of pure calcium hydroxide. The cycle stability is better, and the energy storage density is about 97.3kJ/kg. The corresponding microstructure is shown in Figure 1, the energy spectrum analysis of the corresponding points is shown in Figure 2, and the thermogravimetric analysis of the composite material is shown in Figure 3.
实施例2 Example 2
向烧杯中加入1000mL蒸馏水并加热至293K，然后将足量的氯化铵加入到烧杯中，充分搅拌，过滤得到饱和氯化铵溶液，称量74mg氢氧化钙并加入到烧杯中，并搅拌使其充分溶解；称量162mg氧化锌加入到配置的氢氧化钙溶液中，不断搅拌，连续反应12h,得到乳白色的悬浮液;将200mg粉末状膨胀石墨放置在烧杯中，在293K的温度下超声振动24h；然后将该溶液在293K的温度下静置约12h后，将烧杯放置在353K的温度下约10h排氨气和水，烘干后取出膨胀石墨并对表面进行清理；将取出的膨胀石墨冷却至室温，并用蒸馏水洗涤；将样品加热至353K的温度下约10h,使样品干燥。循环水洗、干燥步骤2-3次即可得到最终膨胀石墨基CaxZny(OH)2(x+y)-zClz·2H2O纳米复合太阳能蓄热材料。微观分析表明该材料的化学式为CaZn1.73(OH)3.12Cl2.34·2H2O/C，具有无定型的晶体结构，能够实现纳米级的复合。其常压下的平均脱水分解温度约为300℃，与单纯的氢氧化钙相比降低了约200℃，循环稳定性很好，储能密度约为78.3kJ/kg。 Add 1000mL of distilled water to the beaker and heat to 293K, then add enough ammonium chloride to the beaker, stir well, filter to obtain a saturated ammonium chloride solution, weigh 74mg of calcium hydroxide and add it to the beaker, and stir to make It is fully dissolved; weigh 162mg of zinc oxide and add it to the prepared calcium hydroxide solution, stir continuously, and react continuously for 12 hours to obtain a milky white suspension; place 200mg of powdered expanded graphite in a beaker and vibrate ultrasonically at a temperature of 293K 24h; then put the solution at a temperature of 293K for about 12h, place the beaker at a temperature of 353K for about 10h to discharge ammonia and water, take out the expanded graphite after drying and clean the surface; the taken out expanded graphite Cool to room temperature and wash with distilled water; heat the sample to a temperature of 353K for about 10h to dry the sample. The final expanded graphite-based Ca x Zn y (OH) 2(x+y)-z Cl z · 2H 2 O nanocomposite solar heat storage material can be obtained by circulating water washing and drying steps for 2-3 times. Microscopic analysis shows that the material has a chemical formula of CaZn 1.73 (OH) 3.12 Cl 2.34 ·2H 2 O/C, has an amorphous crystal structure, and can realize nanoscale recombination. Its average dehydration decomposition temperature under normal pressure is about 300°C, which is about 200°C lower than that of pure calcium hydroxide. The cycle stability is very good, and the energy storage density is about 78.3kJ/kg.
实施例3 Example 3
向烧杯中加入1000mL蒸馏水并加热至293K，然后将足量的氯化铵加入到烧杯中，充分搅拌，过滤得到饱和氯化铵溶液，称量74mg氢氧化钙并加入到烧杯中，并搅拌使其充分溶解；称量150mg氧化镍加入到配置的氢氧化钙溶液中，不断搅拌，连续反应12h,得到乳白色的悬浮液;将粉末状膨胀石墨放置在烧杯中，在293K的温度下超声振动24h；然后将该溶液在293K的温度下静置约12h后，将烧杯放置在353K的温度下约10h排氨气和水，烘干后取出膨胀石墨并对表面进行清理；将取出的膨胀石墨冷却至室温，并用蒸馏水洗涤；将样品加热至353K的温度下约10h,使样品干燥。循环水洗、干燥步骤2-3次即可得到最终膨胀石墨基CaxNiy(OH)2(x+y)-zClz·2H2O纳米复合太阳能蓄热材料。微观分析表明该材料的化学式为CaNi2.32(OH)4.34Cl2.30·2H2O/C，具有无定型的晶体结构，能够实现纳米级的复合。其常压下的平均脱水分解温度约为310℃，与单纯的氢氧化钙相比降低了约190℃，循环稳定性很好，储能密度约为74.6kJ/kg。 Add 1000mL of distilled water to the beaker and heat to 293K, then add enough ammonium chloride to the beaker, stir well, filter to obtain a saturated ammonium chloride solution, weigh 74mg of calcium hydroxide and add it to the beaker, and stir to make It is fully dissolved; weigh 150 mg of nickel oxide and add it to the prepared calcium hydroxide solution, stir continuously, and react continuously for 12 hours to obtain a milky white suspension; place powdered expanded graphite in a beaker, and ultrasonically vibrate at a temperature of 293K for 24 hours Then the solution was left to stand at a temperature of 293K for about 12h, and the beaker was placed at a temperature of 353K for about 10h to exhaust ammonia and water, and after drying, the expanded graphite was taken out and the surface was cleaned; the expanded graphite taken out was cooled to room temperature, and washed with distilled water; the sample was heated to a temperature of 353K for about 10h, and the sample was dried. The final expanded graphite-based Ca x Ni y (OH) 2(x+y)-z Cl z · 2H 2 O nanocomposite solar heat storage material can be obtained by circulating water washing and drying steps for 2-3 times. Microscopic analysis shows that the material has a chemical formula of CaNi 2.32 (OH) 4.34 Cl 2.30 ·2H 2 O/C, has an amorphous crystal structure, and can realize nanoscale compounding. The average dehydration decomposition temperature under normal pressure is about 310°C, which is about 190°C lower than that of pure calcium hydroxide. The cycle stability is very good, and the energy storage density is about 74.6kJ/kg.
实施例4 Example 4
向烧杯中加入1000mL蒸馏水并加热至293K，然后将足量的氯化铵加入到烧杯中，充分搅拌，过滤得到饱和氯化铵溶液，称量144mg氢氧化钙并加入到烧杯中，并搅拌使其充分溶解；称量162mg氧化镍加入到配置的氢氧化钙溶液中，不断搅拌，连续反应12h,得到乳白色的悬浮液;将200mg粉末状膨胀石墨放置在烧杯中，在293K的温度下超声振动24h；然后将该溶液在293K的温度下静置约12h后，将烧杯放置在353K的温度下约10h排氨气和水，烘干后取出膨胀石墨并对表面进行清理；将取出的膨胀石墨冷却至室温，并用蒸馏水洗涤；将样品加热至353K的温度下约10h,使样品干燥。循环水洗、干燥步骤2-3次即可得到最终膨胀石墨基钙系纳米复合太阳能蓄热材料。微观分析表明该材料的化学式为CaNi1.33(OH)2.3Cl2.36·2H2O/C，具有无定型的晶体结构，能够实现纳米级的复合。其常压下的平均脱水分解温度约为370℃，与单纯的氢氧化钙相比降低了约130℃，循环稳定性较好，储能密度约为104.2kJ/kg。 Add 1000mL of distilled water to the beaker and heat to 293K, then add enough ammonium chloride to the beaker, stir well, filter to obtain a saturated ammonium chloride solution, weigh 144mg of calcium hydroxide and add it to the beaker, and stir to make It is fully dissolved; weigh 162mg of nickel oxide and add it to the prepared calcium hydroxide solution, stir continuously, and react continuously for 12 hours to obtain a milky white suspension; place 200mg of powdered expanded graphite in a beaker and vibrate ultrasonically at a temperature of 293K 24h; then put the solution at a temperature of 293K for about 12h, place the beaker at a temperature of 353K for about 10h to discharge ammonia and water, take out the expanded graphite after drying and clean the surface; the taken out expanded graphite Cool to room temperature and wash with distilled water; heat the sample to a temperature of 353K for about 10h to dry the sample. The final expanded graphite-based calcium-based nano-composite solar heat storage material can be obtained by circulating water washing and drying steps for 2-3 times. Microscopic analysis shows that the chemical formula of the material is CaNi 1.33 (OH) 2.3 Cl 2.36 ·2H 2 O/C, which has an amorphous crystal structure and can realize nanoscale compounding. Its average dehydration decomposition temperature under normal pressure is about 370°C, which is about 130°C lower than that of pure calcium hydroxide. The cycle stability is better, and the energy storage density is about 104.2kJ/kg.
实施例5 Example 5
向烧杯中加入1000mL蒸馏水并加热至293K，然后将足量的氯化铵加入到烧杯中，充分搅拌，过滤得到饱和氯化铵溶液，称量74mg氢氧化钙并加入到烧杯中，并搅拌使其充分溶解；称量150mg氧化钴加入到配置的氢氧化钙溶液中，不断搅拌，连续反应12h,得到乳白色的悬浮液;将200mg粉末状膨胀石墨放置在烧杯中，在293K的温度下超声振动24h；然后将该溶液在293K的温度下静置约12h后，将烧杯放置在353K的温度下约10h排氨气和水，烘干后取出膨胀石墨并对表面进行清理；将取出的膨胀石墨冷却至室温，并用蒸馏水洗涤；将样品加热至353K的温度下约10h,使样品干燥。循环水洗、干燥步骤2-3次即可得到最终膨胀石墨基CaxCoy(OH)2(x+y)-zClz·2H2O纳米复合太阳能蓄热材料。微观分析表明该材料的化学式为CaCo1.94(OH)3.05Cl2.83·2H2O/C，具有无定型的晶体结构，能够实现纳米级的复合。其常压下的平均脱水分解温度约为340℃，与单纯的氢氧化钙相比降低了约160℃，循环稳定性很好，储能密度约为67.8kJ/kg。 Add 1000mL of distilled water to the beaker and heat to 293K, then add enough ammonium chloride to the beaker, stir well, filter to obtain a saturated ammonium chloride solution, weigh 74mg of calcium hydroxide and add it to the beaker, and stir to make It is fully dissolved; weigh 150mg of cobalt oxide and add it to the prepared calcium hydroxide solution, stir continuously, and react continuously for 12 hours to obtain a milky white suspension; place 200mg of powdered expanded graphite in a beaker and vibrate ultrasonically at a temperature of 293K 24h; then put the solution at a temperature of 293K for about 12h, place the beaker at a temperature of 353K for about 10h to discharge ammonia and water, take out the expanded graphite after drying and clean the surface; the taken out expanded graphite Cool to room temperature and wash with distilled water; heat the sample to a temperature of 353K for about 10h to dry the sample. The final expanded graphite-based Ca x Co y (OH) 2(x+y)-z Cl z · 2H 2 O nanocomposite solar heat storage material can be obtained by circulating water washing and drying steps for 2-3 times. Microscopic analysis shows that the material has a chemical formula of CaCo 1.94 (OH) 3.05 Cl 2.83 ·2H 2 O/C, has an amorphous crystal structure, and can realize nanoscale recombination. The average dehydration decomposition temperature under normal pressure is about 340°C, which is about 160°C lower than that of pure calcium hydroxide. The cycle stability is very good, and the energy storage density is about 67.8kJ/kg.
实施例6 Example 6
向烧杯中加入1000mL蒸馏水并加热至293K，然后将足量的氯化铵加入到烧杯中，充分搅拌，过滤得到饱和氯化铵溶液，称量74mg氢氧化钙并加入到烧杯中，并搅拌使其充分溶解；称量75mg氧化钴加入到配置的氢氧化钙溶液中，不断搅拌，连续反应12h,得到乳白色的悬浮液;将200mg粉末状膨胀石墨放置在烧杯中，在293K的温度下超声振动24h；然后将该溶液在293K的温度下静置约12h后，将烧杯放置在353K的温度下约10h排氨气和水，烘干后取出膨胀石墨并对表面进行清理；将取出的膨胀石墨冷却至室温，并用蒸馏水洗涤；将样品加热至353K的温度下约10h,使样品干燥。循环水洗、干燥步骤2-3次即可得到最终膨胀石墨基钙系纳米复合太阳能蓄热材料。微观分析表明该材料的化学式为CaCo0.73(OH)2.28Cl1.18·2H2O/C，具有无定型的晶体结构，能够实现纳米级的复合。其常压下的平均脱水分解温度约为410℃，与单纯的氢氧化钙相比降低了约90℃，循环稳定性较好，储能密度约为108.5kJ/kg。 Add 1000mL of distilled water to the beaker and heat to 293K, then add enough ammonium chloride to the beaker, stir well, filter to obtain a saturated ammonium chloride solution, weigh 74mg of calcium hydroxide and add it to the beaker, and stir to make It is fully dissolved; weigh 75 mg of cobalt oxide and add it to the prepared calcium hydroxide solution, stir continuously, and react continuously for 12 hours to obtain a milky white suspension; place 200 mg of powdered expanded graphite in a beaker and vibrate ultrasonically at a temperature of 293K 24h; then put the solution at a temperature of 293K for about 12h, place the beaker at a temperature of 353K for about 10h to discharge ammonia and water, take out the expanded graphite after drying and clean the surface; the taken out expanded graphite Cool to room temperature and wash with distilled water; heat the sample to a temperature of 353K for about 10h to dry the sample. The final expanded graphite-based calcium-based nano-composite solar heat storage material can be obtained by circulating water washing and drying steps for 2-3 times. Microscopic analysis shows that the chemical formula of the material is CaCo 0.73 (OH) 2.28 Cl 1.18 ·2H 2 O/C, which has an amorphous crystal structure and can realize nanoscale recombination. Its average dehydration decomposition temperature under normal pressure is about 410°C, which is about 90°C lower than that of pure calcium hydroxide. The cycle stability is better, and the energy storage density is about 108.5kJ/kg.
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