CN109370542A

CN109370542A - Compound carbon-based chemical heat-accumulating material of one kind and preparation method thereof

Info

Publication number: CN109370542A
Application number: CN201811560036.XA
Authority: CN
Inventors: 赵建国; 李世杰; 邢宝岩; 张进; 李经纬; 李新宇; 邢国强
Original assignee: Shanxi Datong University
Current assignee: Shanxi Datong University
Priority date: 2018-12-19
Filing date: 2018-12-19
Publication date: 2019-02-22

Abstract

The invention discloses a kind of compound carbon-based chemical heat-accumulating materials, it is made of inorganic salt hydrate and carbon material.Preferred inorganic salt hydrate is CaSO₄·2H₂O、CaCl₂·2H₂O、MgSO₄·7H₂O、CuSO₄·5H₂O or Al₂(SO₄)₃·18H₂O, carbon material is graphene and/or expanded graphite or the compound carbon materials of expanded graphite-graphene, and discloses preparation method.The chemical heat accumulation active material that the present invention selects has the characteristics that wide regenerator temperature range, exothermic reaction mild condition, thermal storage density are high, can make full use of low grade heat energy；High-ratio surface carbon material makes chemical heat accumulation active component realize nano-dispersion as carrier, and accumulation of heat particle size is small, agglomeration not easy to reunite, stores exothermic reaction ability and is substantially improved；High thermal conductivity complex carbon material effectively improves heat-storing material overall thermal conductivity energy as carrier, is conducive to store thermal energy transmitting in exothermic process.

Description

Compound carbon-based chemical heat-accumulating material of one kind and preparation method thereof

Technical field

The present invention relates to a kind of compound carbon-based chemical heat-accumulating materials and preparation method thereof, belong to heat storage technology field.

Background technique

With the development of the social economy, fossil energy constantly consumes.Therefore renewable energy development and utilization, to reduce it is normal Energy energy consumption is advised, guarantees that energy resource supply has a very important significance.Chemical heat accumulation technology is as a kind of raising energy utilization rate And solve the effective means of energy supply and demand matching problem, it has also become one of the research hotspot in heat energy utilization field at present.Chemistry stores The storage and release that hot material passes through reversible chemical reaction realization thermal energy as the core composition of chemical heat accumulation technology.For being lower than 200 DEG C of low temperature heat energy, which is usually selected, reacts inorganic salt hydrate mild, that thermal storage density is high as heat-storing material；But such Material there are still hydration rates at present it is slow, heating conduction is bad, easy to reunite, cyclical stability is poor the problems such as.It generally can be by multiple It closes that high thermal conductivity is hydrophilic and porous material realizes the optimization of integral material heat storage performance.Patent CN1224747 is by multicomponent inorganic salts Hydrate progress is compound to be used for low-temperature heat accumulating, and heat storage performance is optimized, but thermal storage density is still lower.Patent CN103542752 provides a kind of for inhibiting chemical heat-accumulating material to agglomerate cured chemical heat storage device, but the device knot Structure is complicated and does not improve material heat storage performance inherently, and heat-storing material needs to regenerate.

High-ratio surface and surface-functionalized porous carbon materials are because its good physicochemical properties is as carrier and auxiliary agent Has wide application in fields such as catalysis, electronic devices.Such material is equally also suitable for the dispersion of accumulation of heat active material and bears It carries.For promoting material entirety heat storage performance significance.Patent CN104194735 provides a kind of graphene oxide-loaded change Heat-storing material preparation method is learned, effectively increases heat-storing material reactivity worth, but there are biggish corrosivity and equipment for the material Compatibility is bad.

Summary of the invention

The purpose of the invention is to provide compound carbon-based chemical heat-accumulating material of one kind and preparation method thereof, can be used for low The utilization of temperature solar thermal energy and industrial exhaust heat waste heat, while this method can also be used for the preparation of other types heat-storing material.

In order to achieve the above objectives, the present invention adopts the following technical scheme that:

A kind of compound carbon-based chemical heat-accumulating material, it is the nothing made of inorganic salt hydrate and carbon material The mass ratio of machine salt hydrate and carbon material are as follows: inorganic salt hydrate/carbon material=30%~95%.

Preferably, in compound carbon-based chemical heat-accumulating material above-mentioned, the inorganic salt hydrate is CaSO₄·2H₂O、 CaCl₂·2H₂O、MgSO₄·7H₂O、CuSO₄·5H₂O or Al₂(SO₄)₃·18H₂O, the carbon material be graphene and/or Expanded graphite or the compound carbon materials of expanded graphite-graphene.

Preferably, in compound carbon-based chemical heat-accumulating material above-mentioned, the graphene uses oxidation-reduction method step by step Preparation, expanded graphite are prepared using chemical oxidization method, and the compound carbon materials of expanded graphite-graphene are prepared using hydro-thermal method.

Preferably, in compound carbon-based chemical heat-accumulating material above-mentioned, prepared by the oxidation-reduction method step by step of the graphene Specific step is as follows: it is mixed to be slowly stirred in 98% concentrated sulfuric acid and in ice-water bath that 100mL mass concentration is added in 10g sodium nitrate It closes, 20g natural flake graphite is added in the solution later, while taking 60g potassium permanganate, be added in above-mentioned solution and being warming up to 100mL distilled water is added after 40 DEG C, 1 hour and dilutes and react 30min, is warming up to 80 DEG C after reaction, while 100mL is added Mass concentration is 30% hydrogen peroxide, is finally cooled to room temperature and obtains graphite oxide；Gained graphite oxide is washed with 5% HCl For several times, it then is washed to neutrality with distillation, gained graphite oxide is added in bag filter and is dialysed 1 week, in the process every 6h Primary distilled water is changed, ultrasonic removing, ultrasonic power 100W, ultrasound are carried out to graphite oxide in ultrasonic cleaner after dialysis Time is 8 hours；It is dry in freeze drier after gained liquid after ultrasound is centrifuged, obtain graphene oxide powder End adds graphene oxide into tube furnace, 10min is heated at 900 DEG C, graphene powder is made.

Preferably, in compound carbon-based chemical heat-accumulating material above-mentioned, the chemical oxidization method of the expanded graphite prepares tool Steps are as follows for body: the concentrated nitric acid of the 90mL mass concentration sulfuric acid for being 70% and 75mL mass concentration 65% is added in beaker, it will The two is added 3.5g potassium permanganate after being sufficiently mixed and stirs evenly, and is eventually adding 15g natural flake graphite and carries out oxidation reaction, instead It is filtered after answering 1h, enough 30% hydrogen peroxide is added in suction filtration gained solid mixt and completely remove the manganese dioxide of generation；It will Gained mixture filters after being washed till neutrality, and filter cake dry 1h at 120 DEG C finally obtains expansible graphite, by expansible graphite It is placed in high temperature process furnances at 900 DEG C of nitrogen protection and reacts the obtained expanded graphite of 5min.

Preferably, in compound carbon-based chemical heat-accumulating material above-mentioned, the water of the compound carbon materials of expanded graphite-graphene Specific step is as follows for thermal method preparation: taking 1g graphene oxide ultrasonic disperse in 200mL deionized water, it is molten that graphene oxide is made Liquid, then 1g expanded graphite is taken to be scattered in graphene oxide solution, it is subsequently transferred in 250mL hydrothermal reaction kettle, it is anti-at 150 DEG C Answer 12 hours, after hydro-thermal reaction cooled to room temperature to get arrive the compound carbon materials of graphene-expanded graphite.

The preparation method of compound carbon-based chemical heat-accumulating material above-mentioned, include the following steps: (6.1) using hydro-thermal method or Infusion process, and carbon material and inorganic salt hydrate are assembled using deionized water as solvent；(6.2) it is dried.Infusion process The preferred ultrasonic power of the parameter of ultrasonic disperse is 100W, and ultrasonic time is 8 hours.

Preferably, in the preparation method of compound carbon-based chemical heat-accumulating material above-mentioned, hydro-thermal method in the step (6.1) Specific steps are as follows: take 1g graphene oxide to be scattered in 100mL deionized water, graphene oxide solution is made, then 1g is taken to expand Graphite is added after graphene oxide solution is thoroughly mixed and is transferred in 250mL hydrothermal reaction kettle, then weighs 1g inorganic salts Hydrate crystal, which is dissolved in 10mL deionized water, stirs 10min under the conditions of 20 DEG C, the solution is transferred to hydrothermal reaction kettle later In with 200r/min revolving speed continue stir 1h, after stirring by hydrothermal reaction kettle heat carry out hydro-thermal reaction, hydro-thermal reaction temperature Degree is 110 DEG C~180 DEG C, and the reaction time is 10~20 hours, after reaction takes out mixture, i.e. assembling finishes.

Preferably, in the preparation method of compound carbon-based chemical heat-accumulating material above-mentioned, infusion process in the step (6.1) It using unsaturated maceration extract, at the uniform velocity stirring, mixing time 1-6 hours, 25-50 DEG C of whipping temp, the rate of stirring is 100~ 300r/min。

Preferably, in the preparation method of compound carbon-based chemical heat-accumulating material above-mentioned, using low in the step (6.2) Composite chemical heat storage material is dried in warm boulton process, and dry vacuum degree is 10~100 pas, and drying temperature is- 20 DEG C~-50 DEG C, drying time is 24~72 hours.

The beneficial effects of the present invention are:

1. the chemical heat accumulation active material that the present invention selects has wide regenerator temperature range, exothermic reaction mild condition, stores The features such as heat density is high can make full use of low grade heat energy.

2. the present invention uses high-ratio surface carbon material as carrier, chemical heat accumulation active component is made to realize nano-dispersion, Accumulation of heat particle size is small, agglomeration not easy to reunite, stores exothermic reaction ability and is substantially improved.

3. the present invention uses high thermal conductivity complex carbon material to effectively improve heat-storing material overall thermal conductivity energy as carrier, favorably It is transmitted in storing thermal energy in exothermic process.

4. the present invention can effectively improve chemical heat-accumulating material dispersion degree, prevent material from reuniting, improve material thermal storage density, Reaction stability is improved, Waste Heat Reuse more than the storage of low-temperature solar energy thermal energy and industry can be preferably applied to.

Detailed description of the invention

Fig. 1 is graphene/MgSO in embodiment 1₄·7H₂O Composite chemical heat storage material stores heat release cyclical stability test knot Fruit.

Fig. 2 is graphene/MgSO in embodiment 1₄·7H₂O Composite chemical heat storage material heating conduction test result.

Specific embodiment

Invention is further explained combined with specific embodiments below.

Embodiment 1

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂Made of O and graphene, wherein MgSO₄· 7H₂The mass ratio of O and graphene is 50%.

Above-mentioned compound carbon-based chemical heat-accumulating material is prepared as follows using infusion process:

1g Graphene powder powder material is weighed, while weighing 0.5g MgSO₄·7H₂O crystal is dissolved in 15mL deionized water, with Graphene is impregnated in Adlerika afterwards.Ultrasonic disperse is carried out to mixed liquor, while being existed with the stirring rate of 300r/min It is stirred 4 hours under the conditions of 25 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying 48 at -20 DEG C Hour, obtain required graphene/MgSO₄·7H₂O Composite chemical heat storage material.

The composite material is placed in high temperature process furnances heat resolve under 150 DEG C of nitrogen protections, is then cooled to 30 DEG C simultaneously Composite material thermal storage density is measured up to 740kJ/kg after being passed through vapor reaction, and thermal conductivity reaches 5W/mK.Fig. 1 is graphite Alkene/MgSO₄·7H₂O Composite chemical heat storage material stores heat release cyclical stability test result.Fig. 2 is that thermal conductivity is surveyed under corresponding conditions Test result.By Fig. 1 and Fig. 2 it is found that composite material thermal storage density and heating conduction after 20 circular responses do not occur to show Write decaying.

Embodiment 2

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂Made of O and expanded graphite, wherein MgSO₄· 7H₂The mass ratio of O and expanded graphite is 50%.

Weigh 0.5g MgSO₄·7H₂O crystal is dissolved in 10mL deionized water, then weighs 1g expanded graphite, will expand stone Ink is impregnated in Adlerika.Ultrasonic disperse, ultrasonic power 100W are carried out to mixed liquor, ultrasonic time is 8 hours, simultaneously It is stirred 2 hours under the conditions of 25 DEG C with the stirring rate of 200r/min and obtains uniform solidliquid mixture.Mixture is taken out ,- 50 pa vacuum freeze drying 24 hours at 20 DEG C, obtain required expanded graphite/MgSO₄·7H₂O Composite chemical heat storage material.

The composite material is placed in high temperature process furnances heat resolve under 150 DEG C of nitrogen protections, is then cooled to 30 DEG C simultaneously Composite material thermal storage density is measured up to 710kJ/kg after being passed through vapor reaction, and thermal conductivity reaches 10W/mK.

Embodiment 3

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂O, made of graphene and expanded graphite, wherein MgSO₄·7H₂The mass ratio of O and carbon material is 50%.

Above-mentioned compound carbon-based chemical heat-accumulating material is prepared as follows using hydro-thermal method:

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1g MgSO₄·7H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, the Adlerika is transferred in hydrothermal reaction kettle with 200r/ later Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 180 DEG C, the reaction time Being 10 hours, after reaction takes out mixture, i.e. assembling finishes, 100 pa vacuum freeze drying 24 hours at -20 DEG C, Obtain required expanded graphite-graphene/MgSO₄·7H₂O Composite chemical heat storage material.

The composite material is placed in high temperature process furnances heat resolve under 150 DEG C of nitrogen protections, is then cooled to 30 DEG C simultaneously Composite material thermal storage density is measured up to 760kJ/kg after being passed through vapor reaction, and thermal conductivity reaches 7.5W/mK.

Embodiment 4

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂Made of O and graphene, wherein CaSO₄· 2H₂The mass ratio of O and graphene is 50%.

1g expanded graphite is weighed, while weighing 0.5g CaSO₄·2H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CaSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min in 35 DEG C of items It is stirred 4 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 24 hours at -50 DEG C, Obtain required graphene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 5

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂Made of O and graphene, wherein CaCl₂· 2H₂The mass ratio of O and graphene is 50%.

1g Graphene powder powder material is weighed, while weighing 0.5g CaCl₂·2H₂O crystal is dissolved in 15mL deionized water, with Graphene is impregnated in CaCl afterwards₂In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min 50 It is stirred 1 hour under the conditions of DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze dryings 24 are small at -50 DEG C When, obtain required graphene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 6

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂Made of O and graphene, wherein CuSO₄· 5H₂The mass ratio of O and graphene is 50%.

1g Graphene powder powder material is weighed, while weighing 0.5g CuSO₄·5H₂O crystal is dissolved in 15mL deionized water, with Graphene is impregnated in CuSO afterwards₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min 40 It is stirred 4 hours under the conditions of DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze dryings 72 are small at -30 DEG C When, obtain required graphene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 7

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂Made of O and graphene, wherein Al₂ (SO₄)₃·18H₂The mass ratio of O and graphene is 50%.

1g Graphene powder powder material is weighed, while weighing 0.5g Al₂(SO₄)₃·18H₂O crystal is dissolved in 15mL deionized water In, graphene is then impregnated in Al₂(SO₄)₃In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring of 300r/min Rate stirs 6 hours under the conditions of 25 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 50 pa vacuum refrigeration at -20 DEG C It is 48 hours dry, obtain required graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 8

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂Made of O and expanded graphite, wherein CaSO₄· 2H₂The mass ratio of O and expanded graphite is 50%.

1g expanded graphite is weighed, while weighing 0.5g CaSO₄·2H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CaSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min in 45 DEG C of items It is stirred 4 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 24 hours at -50 DEG C, Obtain required expanded graphite/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 9

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂Made of O and expanded graphite, wherein CaCl₂· 2H₂The mass ratio of O and expanded graphite is 50%.

1g expanded graphite is weighed, while weighing 0.5g CaCl₂·2H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CaCl₂In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min in 35 DEG C of items It is stirred 3 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 36 hours at -50 DEG C, Obtain required expanded graphite/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 10

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂Made of O and expanded graphite, wherein CuSO₄· 5H₂The mass ratio of O and expanded graphite is 50%.

1g expanded graphite is weighed, while weighing 0.5g CuSO₄·5H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CuSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min in 50 DEG C of items It is stirred 2 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying 72 hours, obtain at -30 DEG C To required expanded graphite/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 11

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂Made of O and expanded graphite, wherein Al₂ (SO₄)₃·18H₂The mass ratio of O and expanded graphite is 50%.

1g expanded graphite is weighed, while weighing 0.5g Al₂(SO₄)₃·18H₂O crystal is dissolved in 15mL deionized water, with Expanded graphite is impregnated in Al afterwards₂(SO₄)₃In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring of 300r/min speed Rate stirs 5 hours under the conditions of 30 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 50 pa vacuum refrigerations are dry at -20 DEG C Dry 60 hours, obtain required expanded graphite/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 12

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂O, made of graphene and expanded graphite, wherein CaSO₄·2H₂The mass ratio of O and carbon material is 50%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1g CaSO₄·2H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CaSO₄Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 110 DEG C, the reaction time It is 20 hours, after reaction takes out mixture, is i.e. assembling finishes, and 10 pa vacuum freeze drying 24 hours, obtain at -20 DEG C To required expanded graphite-graphene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 13

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂O, made of graphene and expanded graphite, wherein CaCl₂·2H₂The mass ratio of O and carbon material is 50%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1g CaCl₂·2H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CaCl₂Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, after reaction takes mixture Out, i.e., assembling finishes, and 50 pa vacuum freeze drying 24 hours at -20 DEG C obtain required expanded graphite-graphene/CaCl₂· 2H₂O Composite chemical heat storage material.

Embodiment 14

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂O, made of graphene and expanded graphite, wherein CuSO₄·5H₂The mass ratio of O and carbon material is 50%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1g CuSO₄·5H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CuSO₄Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 150 DEG C, the reaction time It is 15 hours, after reaction takes out mixture, is i.e. assembling finishes, and 50 pa vacuum freeze drying 48 hours, obtain at -40 DEG C To required expanded graphite-graphene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 15

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂O, graphene and expanded graphite are made , wherein Al₂(SO₄)₃·18H₂The mass ratio of O and carbon material is 50%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1g Al₂(SO₄)₃·18H₂O crystal It is dissolved in 10mL deionized water and stirs 10min under the conditions of 20 DEG C, later by the Al₂(SO₄)₃Solution is transferred in hydrothermal reaction kettle Continuing to stir 1h with 200r/min revolving speed, hydrothermal reaction kettle is heated after stirring and carries out hydro-thermal reaction, temperature is 120 DEG C, Reaction time is 10 hours, after reaction takes out mixture, i.e. assembling finishes, the 100 pa vacuum freeze drying at -50 DEG C 24 hours, obtain required expanded graphite-graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 16

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂Made of O and graphene, wherein MgSO₄· 7H₂The mass ratio of O and graphene is 30%.

1g Graphene powder powder material is weighed, while weighing 0.3g MgSO₄·7H₂O crystal is dissolved in 15mL deionized water, with Graphene is impregnated in Adlerika afterwards.Ultrasonic disperse is carried out to mixed liquor, while being existed with the stirring rate of 300r/min It is stirred 4 hours under the conditions of 45 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying 48 at -20 DEG C Hour, obtain required graphene/MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 17

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂Made of O and expanded graphite, wherein MgSO₄· 7H₂The mass ratio of O and expanded graphite is 30%.

Weigh 0.3g MgSO₄·7H₂O crystal is dissolved in 10mL deionized water, then weighs 1g expanded graphite, will expand stone Ink is impregnated in Adlerika.It is stirred and is obtained within 2 hours uniformly admittedly under the conditions of 50 DEG C with the stirring rate of 200r/min simultaneously Liquid mixture.Mixture is taken out, 50 pa vacuum freeze drying 24 hours at -20 DEG C, obtain required expanded graphite/ MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 18

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂O, made of graphene and expanded graphite, wherein MgSO₄·7H₂The mass ratio of O and carbon material is 30%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 0.6g MgSO₄·7H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, the Adlerika is transferred in hydrothermal reaction kettle with 200r/ later Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 170 DEG C, the reaction time It is 18 hours, after reaction takes out mixture, is i.e. assembling finishes, and 50 pa vacuum freeze drying 24 hours, obtain at -40 DEG C To required expanded graphite-graphene/MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 19

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂Made of O and graphene, wherein CaSO₄· 2H₂The mass ratio of O and graphene is 30%.

1g expanded graphite is weighed, while weighing 0.3g CaSO₄·2H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CaSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min in 30 DEG C of items It is stirred 4 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 24 hours at -50 DEG C, Obtain required graphene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 20

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂Made of O and graphene, wherein CaCl₂· 2H₂The mass ratio of O and graphene is 30%.

1g Graphene powder powder material is weighed, while weighing 0.3g CaCl₂·2H₂O crystal is dissolved in 15mL deionized water, with Graphene is impregnated in CaCl afterwards₂In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min 40 It is stirred 3 hours under the conditions of DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze dryings 24 are small at -50 DEG C When, obtain required graphene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 21

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂Made of O and graphene, wherein CuSO₄· 5H₂The mass ratio of O and graphene is 30%.

1g Graphene powder powder material is weighed, while weighing 0.3g CuSO₄·5H₂O crystal is dissolved in 15mL deionized water, with Graphene is impregnated in CuSO afterwards₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min 50 It is stirred 2 hours under the conditions of DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze dryings 72 are small at -30 DEG C When, obtain required graphene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 22

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂Made of O and graphene, wherein Al₂ (SO₄)₃·18H₂The mass ratio of O and graphene is 30%.

1g Graphene powder powder material is weighed, while weighing 0.3g Al₂(SO₄)₃·18H₂O crystal is dissolved in 15mL deionized water In, graphene is then impregnated in Al₂(SO₄)₃In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring of 300r/min Rate stirs 3 hours under the conditions of 45 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 50 pa vacuum refrigeration at -20 DEG C It is 48 hours dry, obtain required graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 23

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂Made of O and expanded graphite, wherein CaSO₄· 2H₂The mass ratio of O and expanded graphite is 30%.

1g expanded graphite is weighed, while weighing 0.3g CaSO₄·2H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CaSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min in 35 DEG C of items It is stirred 5 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 36 hours at -50 DEG C, Obtain required expanded graphite/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 24

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂Made of O and expanded graphite, wherein CaCl₂· 2H₂The mass ratio of O and expanded graphite is 30%.

1g expanded graphite is weighed, while weighing 0.3g CaCl₂·2H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CaCl₂In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min in 50 DEG C of items It is stirred 1 hour under part and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 72 hours at -50 DEG C, Obtain required expanded graphite/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 25

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂Made of O and expanded graphite, wherein CuSO₄· 5H₂The mass ratio of O and expanded graphite is 30%.

1g expanded graphite is weighed, while weighing 0.3g CuSO₄·5H₂O crystal is dissolved in 15mL deionized water, then will be swollen Swollen graphite impregnation is in CuSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min in 45 DEG C of items It is stirred 4 hours under part and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying 72 hours, obtain at -30 DEG C To required expanded graphite/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 26

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂Made of O and expanded graphite, wherein Al₂ (SO₄)₃·18H₂The mass ratio of O and expanded graphite is 30%.

1g expanded graphite is weighed, while weighing 0.3g Al₂(SO₄)₃·18H₂O crystal is dissolved in 15mL deionized water, with Expanded graphite is impregnated in Al afterwards₂(SO₄)₃In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring of 300r/min speed Rate stirs 6 hours under the conditions of 35 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 50 pa vacuum refrigerations are dry at -20 DEG C Dry 48 hours, obtain required expanded graphite/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 27

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂O, made of graphene and expanded graphite, wherein CaSO₄·2H₂The mass ratio of O and carbon material is 30%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 0.6g CaSO₄·2H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CaSO₄Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 130 DEG C, the reaction time It is 15 hours, after reaction takes out mixture, is i.e. assembling finishes, and 50 pa vacuum freeze drying 24 hours, obtain at -40 DEG C To required expanded graphite-graphene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 28

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂O, made of graphene and expanded graphite, wherein CaCl₂·2H₂The mass ratio of O and carbon material is 30%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 0.6g CaCl₂·2H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CaCl₂Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 160 DEG C, the reaction time Being 16 hours, after reaction takes out mixture, i.e. assembling finishes, 100 pa vacuum freeze drying 72 hours at -20 DEG C, Obtain required expanded graphite-graphene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 29

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂O, made of graphene and expanded graphite, wherein CuSO₄·5H₂The mass ratio of O and carbon material is 30%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 0.6g CuSO₄·5H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CuSO₄Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 170 DEG C, the reaction time It is 11 hours, after reaction takes out mixture, is i.e. assembling finishes, and 10 pa vacuum freeze drying 24 hours, obtain at -30 DEG C To required expanded graphite-graphene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 30

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂O, graphene and expanded graphite are made , wherein Al₂(SO₄)₃·18H₂The mass ratio of O and carbon material is 30%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 0.6g Al₂(SO₄)₃·18H₂O is brilliant Body, which is dissolved in 10mL deionized water, stirs 10min under the conditions of 20 DEG C, later by the Al₂(SO₄)₃Solution is transferred to hydrothermal reaction kettle In with 200r/min revolving speed continue stir 1h, after stirring by hydrothermal reaction kettle heat carry out hydro-thermal reaction, temperature 110 DEG C, the reaction time is 20 hours, after reaction takes out mixture, i.e. assembling finishes, the 100 pa vacuum refrigeration at -50 DEG C It is 24 hours dry, obtain required expanded graphite-graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 31

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂Made of O and graphene, wherein MgSO₄· 7H₂The mass ratio of O and graphene is 95%.

1g Graphene powder powder material is weighed, while weighing 0.95g MgSO₄·7H₂O crystal is dissolved in 15mL deionized water, Then graphene is impregnated in Adlerika.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 300r/min It is stirred 5 hours under the conditions of 25 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying at -20 DEG C 48 hours, obtain required graphene/MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 32

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂Made of O and expanded graphite, wherein MgSO₄· 7H₂The mass ratio of O and expanded graphite is 95%.

Weigh 0.95g MgSO₄·7H₂O crystal is dissolved in 10mL deionized water, then weighs 1g expanded graphite, will be expanded Graphite impregnation is in Adlerika.It is stirred and is obtained within 4 hours uniformly under the conditions of 25 DEG C with the stirring rate of 200r/min simultaneously Solidliquid mixture.Mixture is taken out, 50 pa vacuum freeze drying 24 hours at -20 DEG C, obtain required expanded graphite/ MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 33

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂O, made of graphene and expanded graphite, wherein MgSO₄·7H₂The mass ratio of O and carbon material is 95%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1.9g MgSO₄·7H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, the Adlerika is transferred in hydrothermal reaction kettle with 200r/ later Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 180 DEG C, the reaction time It is 15 hours, after reaction takes out mixture, is i.e. assembling finishes, and 10 pa vacuum freeze drying 24 hours, obtain at -20 DEG C To required expanded graphite-graphene/MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 34

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂Made of O and graphene, wherein CaSO₄· 2H₂The mass ratio of O and graphene is 95%.

1g expanded graphite is weighed, while weighing 0.95g CaSO₄·2H₂O crystal is dissolved in 15mL deionized water, then will Expanded graphite is impregnated in CaSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min at 40 DEG C Under the conditions of stir 5 hours and obtain uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze dryings 24 are small at -50 DEG C When, obtain required graphene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 35

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂Made of O and graphene, wherein CaCl₂· 2H₂The mass ratio of O and graphene is 95%.

1g Graphene powder powder material is weighed, while weighing 0.95g CaCl₂·2H₂O crystal is dissolved in 15mL deionized water, Graphene is then impregnated in CaCl₂In solution.Ultrasonic disperse is carried out to mixed liquor, while being existed with the stirring rate of 200r/min It is stirred 2 hours under the conditions of 50 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze drying 24 at -50 DEG C Hour, obtain required graphene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 36

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂Made of O and graphene, wherein CuSO₄· 5H₂The mass ratio of O and graphene is 95%.

1g Graphene powder powder material is weighed, while weighing 0.95g CuSO₄·5H₂O crystal is dissolved in 15mL deionized water, Graphene is then impregnated in CuSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while being existed with the stirring rate of 100r/min It is stirred 6 hours under the conditions of 25 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying 72 at -30 DEG C Hour, obtain required graphene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 37

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂Made of O and graphene, wherein Al₂ (SO₄)₃·18H₂The mass ratio of O and graphene is 95%.

1g Graphene powder powder material is weighed, while weighing 0.95g Al₂(SO₄)₃·18H₂O crystal is dissolved in 15mL deionization In water, graphene is then impregnated in Al₂(SO₄)₃In solution.Ultrasonic disperse, while stirring with 300r/min are carried out to mixed liquor It mixes rate and is stirred 4 hours under the conditions of 35 DEG C and obtain uniform solidliquid mixture.Mixture is taken out, 50 pa vacuum are cold at -20 DEG C It is lyophilized dry 72 hours, obtains required graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 38

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂Made of O and expanded graphite, wherein CaSO₄· 2H₂The mass ratio of O and expanded graphite is 95%.

1g expanded graphite is weighed, while weighing 0.95g CaSO₄·2H₂O crystal is dissolved in 15mL deionized water, then will Expanded graphite is impregnated in CaSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min at 50 DEG C Under the conditions of stir 1 hour and obtain uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze dryings 24 are small at -50 DEG C When, obtain required expanded graphite/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 39

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂Made of O and expanded graphite, wherein CaCl₂· 2H₂The mass ratio of O and expanded graphite is 95%.

1g expanded graphite is weighed, while weighing 0.95g CaCl₂·2H₂O crystal is dissolved in 15mL deionized water, then will Expanded graphite is impregnated in CaCl₂In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 200r/min at 50 DEG C Under the conditions of stir 1 hour and obtain uniform solidliquid mixture.Mixture is taken out, 100 pa vacuum freeze dryings 24 are small at -50 DEG C When, obtain required expanded graphite/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 40

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂Made of O and expanded graphite, wherein CuSO₄· 5H₂The mass ratio of O and expanded graphite is 95%.

1g expanded graphite is weighed, while weighing 0.95g CuSO₄·5H₂O crystal is dissolved in 15mL deionized water, then will Expanded graphite is impregnated in CuSO₄In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring rate of 100r/min at 25 DEG C Under the conditions of stir 6 hours and obtain uniform solidliquid mixture.Mixture is taken out, 10 pa vacuum freeze drying 72 hours at -30 DEG C, Obtain required expanded graphite/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 41

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂Made of O and expanded graphite, wherein Al₂ (SO₄)₃·18H₂The mass ratio of O and expanded graphite is 95%.

1g expanded graphite is weighed, while weighing 0.95g Al₂(SO₄)₃·18H₂O crystal is dissolved in 15mL deionized water, with Expanded graphite is impregnated in Al afterwards₂(SO₄)₃In solution.Ultrasonic disperse is carried out to mixed liquor, while with the stirring of 300r/min speed Rate stirs 1 hour under the conditions of 50 DEG C and obtains uniform solidliquid mixture.Mixture is taken out, 50 pa vacuum refrigerations are dry at -20 DEG C Dry 48 hours, obtain required expanded graphite/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 42

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂O, made of graphene and expanded graphite, wherein CaSO₄·2H₂The mass ratio of O and carbon material is 95%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1.9g CaSO₄·2H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CaSO₄Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 160 DEG C, the reaction time It is 13 hours, after reaction takes out mixture, is i.e. assembling finishes, and 10 pa vacuum freeze drying 24 hours, obtain at -50 DEG C To required expanded graphite-graphene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 43

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂O, made of graphene and expanded graphite, wherein CaCl₂·2H₂The mass ratio of O and carbon material is 95%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1.9g CaCl₂·2H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CaCl₂Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 120 DEG C, the reaction time It is 18 hours, after reaction takes out mixture, is i.e. assembling finishes, and 10 pa vacuum freeze drying 24 hours, obtain at -20 DEG C To required expanded graphite-graphene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 44

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂O, made of graphene and expanded graphite, wherein CuSO₄·5H₂The mass ratio of O and carbon material is 95%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1.9g CuSO₄·5H₂O crystal is dissolved in 10min is stirred in 10mL deionized water under the conditions of 20 DEG C, later by the CuSO₄Solution is transferred in hydrothermal reaction kettle with 200r/ Min revolving speed continues to stir 1h, heats hydrothermal reaction kettle after stirring and carries out hydro-thermal reaction, and temperature is 170 DEG C, the reaction time It is 11 hours, after reaction takes out mixture, is i.e. assembling finishes, and vacuum freeze drying 24 hours at -20 DEG C obtain institute Need expanded graphite-graphene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 45

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂O, graphene and expanded graphite are made , wherein Al₂(SO₄)₃·18H₂The mass ratio of O and carbon material is 95%.

1g graphene dispersion is weighed in 100mL deionized water, graphene solution is made, then takes 1g expanded graphite that stone is added Black alkene solution is transferred in 250mL hydrothermal reaction kettle after being thoroughly mixed, and then weighs 1.9g Al₂(SO₄)₃·18H₂O is brilliant Body, which is dissolved in 10mL deionized water, stirs 10min under the conditions of 20 DEG C, later by the Al₂(SO₄)₃Solution is transferred to hydrothermal reaction kettle In with 200r/min revolving speed continue stir 1h, after stirring by hydrothermal reaction kettle heat carry out hydro-thermal reaction, temperature 180 DEG C, the reaction time is 10 hours, after reaction takes out mixture, i.e. assembling finishes, the 100 pa vacuum refrigeration at -50 DEG C It is 72 hours dry, obtain required expanded graphite-graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 46

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CaSO₄·2H₂The mass ratio of O and carbon material is 50%.

Weigh 1g CaSO₄·2H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 25 DEG C, obtains CaSO₄ 2g graphene-compound carbon materials of expanded graphite are impregnated in the solution and are continued at 25 DEG C with 300r/min revolving speed later by solution Stir 6h, after stirring, mixture is taken out, 10 pa vacuum freeze drying 72 hours at -20 DEG C, obtain required graphene/ CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 47

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CaCl₂·2H₂The mass ratio of O and carbon material is 50%.

Weigh 1g CaCl₂·2H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 35 DEG C, obtains CaCl₂ 2g graphene-compound carbon materials of expanded graphite are impregnated in the solution and are continued at 35 DEG C with 200r/min revolving speed later by solution Stir 4h, after stirring, mixture is taken out, 50 pa vacuum freeze drying 48 hours at -35 DEG C, obtain required graphene/ CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 48

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein MgSO₄·7H₂The mass ratio of O and carbon material is 50%.

Weigh 1g MgSO₄·7H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 50 DEG C, obtains MgSO₄ 2g graphene-compound carbon materials of expanded graphite are impregnated in the solution and are continued at 50 DEG C with 100r/min revolving speed later by solution Stir 1h, after stirring, mixture is taken out, 100 pa vacuum freeze drying 24 hours at -50 DEG C, obtain required graphene/ MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 49

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CuSO₄·5H₂The mass ratio of O and carbon material is 50%.

Weigh 1g CuSO₄·5H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 30 DEG C, obtains CuSO₄ 2g graphene-compound carbon materials of expanded graphite are impregnated in the solution and are continued at 30 DEG C with 100r/min revolving speed later by solution Stir 4h, after stirring, mixture is taken out, 30 pa vacuum freeze drying 60 hours at -30 DEG C, obtain required graphene/ CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 50

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂O, expanded graphite-graphene composite carbon Made of material, wherein Al₂(SO₄)₃·18H₂The mass ratio of O and carbon material is 50%.

Weigh 1g Al₂(SO₄)₃·18H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 40 DEG C, obtains Al₂(SO₄)₃2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 200r/min revolving speed 40 by solution later Continue to stir 2h at DEG C, after stirring, mixture be taken out, 60 pa vacuum freeze drying 36 hours at -40 DEG C, needed for obtaining Graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 51

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CaSO₄·2H₂The mass ratio of O and carbon material is 30%.

Weigh 0.6g CaSO₄·2H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 25 DEG C, obtains CaSO₄2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 300r/min revolving speed at 25 DEG C by solution later Continue to stir 6h, after stirring, mixture be taken out, 10 pa vacuum freeze drying 72 hours, obtain required graphite at -20 DEG C Alkene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 52

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CaCl₂·2H₂The mass ratio of O and carbon material is 30%.

Weigh 0.6g CaCl₂·2H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 35 DEG C, obtains CaCl₂2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 200r/min revolving speed at 35 DEG C by solution later Continue to stir 4h, after stirring, mixture be taken out, 50 pa vacuum freeze drying 48 hours, obtain required graphite at -35 DEG C Alkene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 53

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein MgSO₄·7H₂The mass ratio of O and carbon material is 30%.

Weigh 0.6g MgSO₄·7H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 50 DEG C, obtains MgSO₄2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 100r/min revolving speed at 50 DEG C by solution later Continue to stir 1h, after stirring, mixture be taken out, 100 pa vacuum freeze drying 24 hours, obtain required stone at -50 DEG C Black alkene/MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 54

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CuSO₄·5H₂The mass ratio of O and carbon material is 30%.

Weigh 0.6g CuSO₄·5H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 30 DEG C, obtains CuSO₄2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 100r/min revolving speed at 30 DEG C by solution later Continue to stir 4h, after stirring, mixture be taken out, 30 pa vacuum freeze drying 60 hours, obtain required graphite at -30 DEG C Alkene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 55

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂O, expanded graphite-graphene composite carbon Made of material, wherein Al₂(SO₄)₃·18H₂The mass ratio of O and carbon material is 30%.

Weigh 0.6g Al₂(SO₄)₃·18H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 40 DEG C, obtains To Al₂(SO₄)₃2g graphene-compound carbon materials of expanded graphite are impregnated in the solution and are existed with 200r/min revolving speed later by solution Continue to stir 2h at 40 DEG C, after stirring, mixture be taken out, 60 pa vacuum freeze drying 36 hours, obtain institute at -40 DEG C Need graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

Embodiment 56

A kind of compound carbon-based chemical heat-accumulating material, is by CaSO₄·2H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CaSO₄·2H₂The mass ratio of O and carbon material is 95%.

Weigh 1.9g CaSO₄·2H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 25 DEG C, obtains CaSO₄2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 300r/min revolving speed at 25 DEG C by solution later Continue to stir 6h, after stirring, mixture be taken out, 10 pa vacuum freeze drying 72 hours, obtain required graphite at -20 DEG C Alkene/CaSO₄·2H₂O Composite chemical heat storage material.

Embodiment 57

A kind of compound carbon-based chemical heat-accumulating material, is by CaCl₂·2H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CaCl₂·2H₂The mass ratio of O and carbon material is 95%.

Weigh 1.9g CaCl₂·2H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 35 DEG C, obtains CaCl₂2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 200r/min revolving speed at 35 DEG C by solution later Continue to stir 4h, after stirring, mixture be taken out, 50 pa vacuum freeze drying 48 hours, obtain required graphite at -35 DEG C Alkene/CaCl₂·2H₂O Composite chemical heat storage material.

Embodiment 58

A kind of compound carbon-based chemical heat-accumulating material, is by MgSO₄·7H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein MgSO₄·7H₂The mass ratio of O and carbon material is 95%.

Weigh 1.9g MgSO₄·7H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 50 DEG C, obtains MgSO₄2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 100r/min revolving speed at 50 DEG C by solution later Continue to stir 1h, after stirring, mixture be taken out, 100 pa vacuum freeze drying 24 hours, obtain required stone at -50 DEG C Black alkene/MgSO₄·7H₂O Composite chemical heat storage material.

Embodiment 59

A kind of compound carbon-based chemical heat-accumulating material, is by CuSO₄·5H₂O, the compound carbon materials of expanded graphite-graphene are made , wherein CuSO₄·5H₂The mass ratio of O and carbon material is 95%.

Weigh 1.9g CuSO₄·5H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 30 DEG C, obtains CuSO₄2g graphene-compound carbon materials of expanded graphite are impregnated in the solution with 100r/min revolving speed at 30 DEG C by solution later Continue to stir 4h, after stirring, mixture be taken out, 30 pa vacuum freeze drying 60 hours, obtain required graphite at -30 DEG C Alkene/CuSO₄·5H₂O Composite chemical heat storage material.

Embodiment 60

A kind of compound carbon-based chemical heat-accumulating material, is by Al₂(SO₄)₃·18H₂O, expanded graphite-graphene composite carbon Made of material, wherein Al₂(SO₄)₃·18H₂The mass ratio of O and carbon material is 95%.

Weigh 1.9g Al₂(SO₄)₃·18H₂O crystal, which is dissolved in 15mL deionized water, stirs 10min under the conditions of 40 DEG C, obtains To Al₂(SO₄)₃2g graphene-compound carbon materials of expanded graphite are impregnated in the solution and are existed with 200r/min revolving speed later by solution Continue to stir 2h at 40 DEG C, after stirring, mixture be taken out, 60 pa vacuum freeze drying 36 hours, obtain institute at -40 DEG C Need graphene/Al₂(SO₄)₃·18H₂O Composite chemical heat storage material.

In above-described embodiment 1,3,4~7,12~15,16,18,19~22,27~30,31,33,34~37,42~45 The following preparation of oxidation-reduction method step by step can be used in graphene, the specific steps are as follows:

By 10g sodium nitrate addition 100mL mass concentration to be slowly stirred mixing in 98% concentrated sulfuric acid and in ice-water bath, it 20g natural flake graphite is added in the solution afterwards, while taking 60g potassium permanganate, be added in above-mentioned solution and is warming up to 40 DEG C, 100mL distilled water is added after 1 hour and dilutes and react 30min, is warming up to 80 DEG C after reaction, while 100mL mass is added Concentration is 30% hydrogen peroxide, is finally cooled to room temperature and obtains graphite oxide；Gained graphite oxide is washed for several times with 5% HCl, Then it is washed to neutrality with distillation, gained graphite oxide is added in bag filter and is dialysed 1 week, is changed once every 6h in the process Distilled water, carries out ultrasonic removing, ultrasonic power 100W to graphite oxide in ultrasonic cleaner after dialysis, and ultrasonic time is 8 hours；It is dry in freeze drier after gained liquid after ultrasound is centrifuged, graphene oxide powder is obtained, it will Graphene oxide is added in tube furnace, 10min is heated at 900 DEG C, graphene powder is made.

Following chemical oxidation can be used in expanded graphite in above-described embodiment 2,8~11,17,23~26,32,38~41 Method preparation, the specific steps are as follows:

The concentrated nitric acid of the 90mL mass concentration sulfuric acid for being 70% and 75mL mass concentration 65% is added in beaker, by the two 3.5g potassium permanganate is added after being sufficiently mixed to stir evenly, is eventually adding 15g natural flake graphite and carries out oxidation reaction, react 1h After filter, filter and enough 30% hydrogen peroxide are added completely remove the manganese dioxide of generation in gained solid mixt；By gained Mixture filters after being washed till neutrality, and filter cake dry 1h at 120 DEG C finally obtains expansible graphite, expansible graphite is placed in 5min is reacted in high temperature process furnances at 900 DEG C of nitrogen protection, expanded graphite is made.

Following hydro-thermal method preparation, tool can be used in the compound carbon materials of expanded graphite-graphene in above-described embodiment 46~60 Steps are as follows for body:

It takes 1g graphene oxide ultrasonic disperse in 200mL deionized water, graphene oxide solution is made, then 1g is taken to expand Graphite dispersion is subsequently transferred in 250mL hydrothermal reaction kettle in graphene oxide solution, is reacted 12 hours at 150 DEG C, hydro-thermal Cooled to room temperature after reaction obtains the compound carbon materials of graphene-expanded graphite.

Wherein used graphene oxide powder can using foregoing graphites alkene oxidation-reduction method step by step in be prepared into The graphene oxide powder arrived.

Claims

1. a kind of compound carbon-based chemical heat-accumulating material, which is characterized in that it be made of inorganic salt hydrate and carbon material, The mass ratio of the inorganic salt hydrate and carbon material are as follows: inorganic salt hydrate/carbon material=30%~95%.

2. compound carbon-based chemical heat-accumulating material according to claim 1, which is characterized in that the inorganic salt hydrate For CaSO₄·2H₂O、CaCl₂·2H₂O、MgSO₄·7H₂O、CuSO₄·5H₂O or Al₂(SO₄)₃·18H₂O, the carbon material For graphene and/or expanded graphite or the compound carbon materials of expanded graphite-graphene.

3. compound carbon-based chemical heat-accumulating material according to claim 2, which is characterized in that the graphene use by Grade oxidation-reduction method preparation, expanded graphite are prepared using chemical oxidization method, and the compound carbon materials of expanded graphite-graphene use hydro-thermal method Preparation.

4. compound carbon-based chemical heat-accumulating material according to claim 3, which is characterized in that the oxygen step by step of the graphene Changing reduction method preparation, specific step is as follows: it is in 98% concentrated sulfuric acid and in ice-water bath that 100mL mass concentration, which is added, in 10g sodium nitrate In be slowly stirred mixing, 20g natural flake graphite is added in the solution later, while taking 60g potassium permanganate, be added it is above-mentioned molten 100mL distilled water is added in liquid and after being warming up to 40 DEG C, 1 hour and dilutes and react 30min, is warming up to 80 DEG C after reaction, It is 30% hydrogen peroxide that 100mL mass concentration is added simultaneously, is finally cooled to room temperature and obtains graphite oxide；Gained graphite oxide is used 5% HCl washing for several times, is then washed to neutrality with distillation, gained graphite oxide is added in bag filter and is dialysed 1 week, herein Primary distilled water is changed every 6h in the process, ultrasonic removing, ultrasonic function are carried out to graphite oxide in ultrasonic cleaner after dialysis Rate is 100W, and ultrasonic time is 8 hours；It is dry in freeze drier after gained liquid after ultrasound is centrifuged, it obtains It to graphene oxide powder, adds graphene oxide into tube furnace, 10min is heated at 900 DEG C, graphene powder is made.

5. compound carbon-based chemical heat-accumulating material according to claim 3, which is characterized in that the chemistry of the expanded graphite Specific step is as follows for oxidizing process preparation: sulfuric acid and the 75mL mass concentration 65% that 90mL mass concentration is 70% being added in beaker Concentrated nitric acid, after the two is sufficiently mixed be added 3.5g potassium permanganate stir evenly, be eventually adding 15g natural flake graphite progress Oxidation reaction filters after reacting 1h, filters in gained solid mixt and enough 30% hydrogen peroxide are added by the manganese dioxide of generation It completely removes；It is filtered after gained mixture is washed till neutrality, filter cake dry 1h at 120 DEG C finally obtains expansible graphite, will Expansible graphite, which is placed in high temperature process furnances at 900 DEG C of nitrogen protection, reacts the obtained expanded graphite of 5min.

6. compound carbon-based chemical heat-accumulating material according to claim 3, which is characterized in that the expanded graphite-graphite Specific step is as follows for the hydro-thermal method preparation of the compound carbon materials of alkene: taking 1g graphene oxide ultrasonic disperse in 200mL deionized water, makes At graphene oxide solution, then 1g expanded graphite is taken to be scattered in graphene oxide solution, is subsequently transferred to 250mL hydro-thermal reaction It in kettle, is reacted 12 hours at 150 DEG C, cooled to room temperature is after hydro-thermal reaction to get compound to graphene-expanded graphite Carbon materials.

7. the preparation method of any compound carbon-based chemical heat-accumulating material of claim 1~6, which is characterized in that including Following steps: (6.1) use hydro-thermal method or infusion process, and carry out using deionized water as solvent to carbon material and inorganic salt hydrate Assembling；(6.2) it is dried.

8. the preparation method of compound carbon-based chemical heat-accumulating material according to claim 7, which is characterized in that the step (6.1) hydro-thermal method specific steps in are as follows: take 1g graphene oxide to be scattered in 100mL deionized water, it is molten that graphene oxide is made Liquid, then take 1g expanded graphite to be added after graphene oxide solution is thoroughly mixed and be transferred in 250mL hydrothermal reaction kettle, then It weighs 1g inorganic salt hydrate crystal and is dissolved in 10mL deionized water and stir 10min under the conditions of 20 DEG C, later shift the solution Continue to stir 1h with 200r/min revolving speed into hydrothermal reaction kettle, it is after stirring that hydrothermal reaction kettle heating progress hydro-thermal is anti- It answers, hydrothermal temperature is 110 DEG C~180 DEG C, and the reaction time is 10~20 hours, is after reaction taken out mixture, i.e., Assembling finishes.

9. the preparation method of compound carbon-based chemical heat-accumulating material according to claim 7, which is characterized in that the step (6.1) infusion process is at the uniform velocity stirred, mixing time 1-6 hours, 25-50 DEG C of whipping temp using unsaturated maceration extract in, stirring Rate is 100~300r/min.

10. the preparation method of compound carbon-based chemical heat-accumulating material according to claim 7, which is characterized in that the step Suddenly Composite chemical heat storage material is dried using low temperature vacuum drying method in (6.2), dry vacuum degree is 10~100 Pa, drying temperature are -20 DEG C~-50 DEG C, and drying time is 24~72 hours.