CN103289654B - Expanded graphite composite heat storage material, as well as preparation method and application thereof - Google Patents
Expanded graphite composite heat storage material, as well as preparation method and application thereof Download PDFInfo
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- CN103289654B CN103289654B CN201310274286.8A CN201310274286A CN103289654B CN 103289654 B CN103289654 B CN 103289654B CN 201310274286 A CN201310274286 A CN 201310274286A CN 103289654 B CN103289654 B CN 103289654B
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- expanded graphite
- graphite composite
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- exfoliated
- graphite
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Abstract
The invention discloses an expanded graphite composite material, namely CaxMy(OH)2(x+y).2H2O/C, and a preparation method thereof, wherein M is Co, Ni or Zn, x/y is 0.25-4, C represents expanded graphite, and the weight ratio of CaxMy(OH)2(x+y).2H2O to C is 0.25-0.5. According to the expanded graphite composite material disclosed by the invention, calcium hydroxide and a transition metal oxide are prepared into a nano-composite material and stored in a porous expanded graphite substrate, particles can be prevented from being re-gathered together during heat absorption and heat release reactions, and the existence of the porous expanded graphite substrate can effectively improve the heat transfer performance of steam and reduce the influence of expansion and shrinkage of a solid phase during the reaction processes on reactions.
Description
Technical field
The present invention relates to a kind of exfoliated-graphite composite Ca
xm
y(OH)
2 (x+y)2H
2o/C and its preparation method and application.
Background technology
At present, chemical heat accumulation is a kind of heat storage technology efficiently, has extraordinary development prospect, its energy storage density order of magnitude larger than phase-transition heat-storage.Calcium hydroxide chemical heat-accumulating material has the features such as good stability, energy storage density is high, cyclicity good, voidage is suitable, is a kind of extraordinary sun power chemical reaction heat storage type.But its Dehydration Kinetics speed crosses the mass-producing application of this material of slow serious restriction; exploitation matrix material is the Main Means improving its Dehydration Kinetics performance, wherein reduces the temperature of pyrolysis and improves the key that composite inner mass-and heat-transfer performance is its Dehydration Kinetics of raising.
Summary of the invention
An object of the present invention is to provide a kind of exfoliated-graphite composite Ca
xm
y(OH)
2 (x+y)2H
2o/C, to reduce the temperature needed for reaction accumulation of heat, solves the Dehydration Kinetics problem of sun power chemical heat-accumulating material;
Another object of the present invention is to provide the preparation method of above-mentioned exfoliated-graphite composite.
Implementation procedure of the present invention is as follows:
Molecular formula Ca
xm
y(OH)
2 (x+y)2H
2the exfoliated-graphite composite that O/C represents, wherein M is Co, Ni or Zn, and x/y is that 0.25 ~ 4, C represents expanded graphite, Ca
xm
y(OH)
2 (x+y)2H
2the weight ratio of O and C is 0.25 ~ 0.5.
The preparation method of above-mentioned exfoliated-graphite composite, comprises the following steps:
(1) calcium hydroxide is dissolved in 40 ~ 90 DEG C of water;
(2) add MO fully to stir, M is Co, Ni or Zn;
(3) expanded graphite ultrasonic vibration is added;
(4) still aging;
(5) heat evaporating water and namely obtain exfoliated-graphite composite.
Above-mentioned exfoliated-graphite composite can be applicable in chemical energy storage.
Below with Ca
xzn
y(OH)
2 (x+y)2H
2the equation of preparing of O/C is that example illustrates preparation principle of the present invention.
Advantage of the present invention and positively effect: the present invention proposes a kind of exfoliated-graphite composite, calcium hydroxide and transition metal oxide are made nano composite material, and store in porous expanded graphite matrix, avoid these particulates again to condense together in heat absorption thermopositive reaction, the existence of porous expanded graphite matrix can improve the heat transfer property of steam and the expansion reducing solid phase in reaction process and the impact of shrinking reaction effectively.
Accompanying drawing explanation
Fig. 1 is the microtexture of matrix material;
Fig. 2 is the energy spectrogram in corresponding points of matrix material;
Fig. 3 is matrix material thermal multigraph.
Embodiment
For understanding summary of the invention of the present invention and feature further, be described in further detail by following examples, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
In beaker, add 1000 mL distilled water and be heated to 330 K, adding 74 mg calcium hydroxides, stirring and make it fully dissolve, 81 mg zinc oxide are joined in aqua calcis, constantly stirring lower successive reaction 12 h, obtain milky suspension.Be 200mg by quality, the cylinder shape cellular expansion graphite of radius to be 2.5 cm length be 5 cm adds in suspension, ultrasonic vibration 24 h at the temperature of 330 K, leave standstill about 12 h at the temperature of 293 K after, dry at the temperature of 373 K, take out expanded graphite rinsing 1-2 time, then in the baking oven of 323 k, namely dry 5 h can be made into expanded graphite-based CaZn
1.03(OH)
4.062H
2o/C composite solar chemical heat-accumulating material.Microanalysis shows that this material has unformed crystalline structure, can realize nano level compound, and the average dehydration decomposition temperature under its normal pressure is about 350 DEG C, reduces about 150 DEG C compared with simple calcium hydroxide.Energy storage density is about 95.7 kJ/kg.As shown in Figure 1, as shown in Figure 2, this matrix material thermogravimetric analysis as shown in Figure 3 in the energy spectrum analysis of corresponding points for corresponding microtexture.
Embodiment 2
In beaker, add 1000 mL distilled water and be heated to 330 K, then weigh 74 mg calcium hydroxides and join in beaker, and stirring makes it fully dissolve; Weighing 162 mg zinc oxide joins in the aqua calcis of configuration, constantly stirs, and successive reaction 12 h, obtains milky suspension; Be 200mg by quality, the cylinder shape cellular expansion graphite of radius to be 2.5 cm length be 5 cm is placed in beaker, ultrasonic vibration 24 h at the temperature of 330 K; Then this solution is left standstill after about 12 h at the temperature of 293 K, dry under beaker being placed on the temperature of 373 K, take out expanded graphite and effects on surface is cleared up.Last rinsing 1-2 time, is then placed on dry 5 h in the baking oven of 323 k and namely can be made into expanded graphite-based CaZn
1.92(OH)
5.842H
2o/C composite solar chemical heat-accumulating material, microanalysis shows that this material has unformed crystalline structure, can realize nano level compound.Average dehydration decomposition temperature under its normal pressure is about 300 DEG C, reduces about 200 DEG C compared with simple calcium hydroxide.Energy storage density is about 72.3 kJ/kg.
Embodiment 3
In beaker, add 1000 mL distilled water and be heated to 330K, then weigh 74 mg calcium hydroxides and join in beaker, and stirring makes it fully dissolve; Weighing 150 mg nickel oxide joins in the aqua calcis of configuration, constantly stirs, and successive reaction 12 h, obtains milky suspension; Be that the Powdered expanded graphite of 200mg is placed in beaker by quality, ultrasonic vibration 24 h at the temperature of 330 K; Then this solution is left standstill after about 12 h at the temperature of 293 K, dry under beaker being placed on the temperature of 373 K, take out expanded graphite and effects on surface is cleared up.Last rinsing 1-2 time, is then placed on dry 5 h in the baking oven of 323 k and namely can be made into expanded graphite-based CaNi
2.12(OH)
4.242H
2o/C composite solar chemical heat-accumulating material, microanalysis shows that this material has unformed crystalline structure, can realize nano level compound.Average dehydration decomposition temperature under its normal pressure is about 320 DEG C, reduces about 180 DEG C compared with simple calcium hydroxide.Energy storage density is about 83.3 kJ/kg.
Embodiment 4
In beaker, add 1000 mL distilled water and be heated to 330 K, then weigh 74 mg calcium hydroxides and join in beaker, and stirring makes it fully dissolve; Weighing 75 mg nickel oxide joins in the aqua calcis of configuration, constantly stirs, and successive reaction 12 h, obtains milky suspension; Be that the Powdered expanded graphite of 200mg is placed in beaker by quality, ultrasonic vibration 24 h at the temperature of 330 K; Then this solution is left standstill after about 12 h at the temperature of 293 K, dry under beaker being placed on the temperature of 373 K, take out expanded graphite and effects on surface is cleared up.Last rinsing 1-2 time, is then placed on dry 5 h in the baking oven of 323 k and namely can be made into expanded graphite-based CaNi
1.08(OH)
4.162H
2o/C composite solar chemical heat-accumulating material, microanalysis shows that this material has unformed crystalline structure, can realize nano level compound.Average dehydration decomposition temperature under its normal pressure is about 350 DEG C, reduces about 130 DEG C compared with simple calcium hydroxide.Energy storage density is about 99.6 kJ/kg.
Embodiment 5
In beaker, add 1000 mL distilled water and be heated to 330 K, then weigh 74 mg calcium hydroxides and join in beaker, and stirring makes it fully dissolve; Weighing 94 mg cobalt oxides joins in the aqua calcis of configuration, constantly stirs, and successive reaction 12 h, obtains milky suspension; Be that the Powdered expanded graphite of 200mg is placed in beaker by quality, ultrasonic vibration 24 h at the temperature of 330 K; Then this solution is left standstill after about 12 h at the temperature of 293 K, dry under beaker being placed on the temperature of 373 K, take out expanded graphite and effects on surface is cleared up.Last rinsing 1-2 time, is then placed on dry 5 h in the baking oven of 323 k and namely can be made into expanded graphite-based CaCo
0.98(OH)
3.962H
2o/C composite solar chemical heat-accumulating material, microanalysis shows that this material has unformed crystalline structure, can realize nano level compound.Average dehydration decomposition temperature under its normal pressure is about 342 DEG C, reduces about 138 DEG C compared with simple calcium hydroxide.Energy storage density is about 94.6 kJ/kg.
Claims (3)
1. molecular formula Ca
xm
y(OH)
2 (x+y)2H
2the exfoliated-graphite composite that O/C represents, wherein M is Co, Ni or Zn, and x/y is that 0.25 ~ 4, C represents expanded graphite, Ca
xm
y(OH)
2 (x+y)2H
2the weight ratio of O and C is 0.25 ~ 0.5.
2. the preparation method of exfoliated-graphite composite according to claim 1, is characterized in that comprising the following steps:
(1) calcium hydroxide is dissolved in 40 ~ 90 DEG C of water;
(2) add MO fully to stir, M is Co, Ni or Zn;
(3) expanded graphite ultrasonic vibration is added;
(4) still aging;
(5) heat evaporating water and namely obtain exfoliated-graphite composite.
3. the application of exfoliated-graphite composite described in claim 1 in chemical energy storage.
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| CN104650821A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Solid particle blocks for chemical heat storage |
| CN104650820A (en) * | 2013-11-17 | 2015-05-27 | 成都奥能普科技有限公司 | Formula of chemical heat storage material for heat transfer |
| JP6642247B2 (en) * | 2016-04-28 | 2020-02-05 | 株式会社デンソー | Refrigeration cycle device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732231A (en) * | 2012-07-12 | 2012-10-17 | 中国科学院广州能源研究所 | Metal-matrix composite chemical heat-storage material and method for preparing same |
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