WO2015025175A1 - Strontium bromide phase change material - Google Patents

Strontium bromide phase change material Download PDF

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Publication number
WO2015025175A1
WO2015025175A1 PCT/GB2014/052580 GB2014052580W WO2015025175A1 WO 2015025175 A1 WO2015025175 A1 WO 2015025175A1 GB 2014052580 W GB2014052580 W GB 2014052580W WO 2015025175 A1 WO2015025175 A1 WO 2015025175A1
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Prior art keywords
phase change
pcm
bromide
temperature
change material
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PCT/GB2014/052580
Other languages
French (fr)
Inventor
Andrew John Bissell
Oliver PULHAM
David Oliver
Original Assignee
Sunamp Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sunamp Limited filed Critical Sunamp Limited
Priority to CN201480045945.3A priority Critical patent/CN105492567A/en
Priority to US14/913,398 priority patent/US10184075B2/en
Priority to RU2016106136A priority patent/RU2656464C2/en
Priority to EP14756121.1A priority patent/EP3036300B1/en
Priority to AU2014310415A priority patent/AU2014310415B2/en
Priority to KR1020167007010A priority patent/KR102394085B1/en
Priority to JP2016535533A priority patent/JP6389891B2/en
Priority to CA2921280A priority patent/CA2921280C/en
Publication of WO2015025175A1 publication Critical patent/WO2015025175A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • phase change materials There exists a problem in the field of phase change materials of providing a phase change material that has a phase change in about the 75°C to 80°C temperature range. This is because there exists at this temperature range mild incongruent melting of compositions such as magnesium bromide hexahydrate.
  • the PCM of the present invention is therefore based on a mixture of Strontium Bromide and a Metal Halide such as Magnesium Bromide or its hydrate.
  • a Metal Halide such as Magnesium Bromide or its hydrate.
  • Alternatives to Magnesium Bromide may be any one of or combination of the following Bromides or their hydrates:
  • Strontium Bromide Anhydrous (CAS: 100476-81 -0) and Magnesium Bromide Anhydrous (CAS: 7789-48-2) may be used instead as initial components instead of the hexahydrate forms. In this case, water must be added to reach the final PCM.
  • compositions of about 30 - 35 wt.% Magnesium Bromide Hexahydrate and about 65 - 70 wt.% Strontium Bromide there exists a phase change at 75°C - 80°C. This temperature is important for phase change material applications such as found in energy storage systems.
  • PCM has a phase change in the region of about 76°C to 88°C temperature range.
  • the Strontium Bromide and Metal Halide may be mixed together in a mixing vessel or heat battery enclosure if the PCM is made directly in a final heat battery.
  • the present invention resides in the provision of phase change material that is optimal to storing heat in about the 76°C to 88°C temperature range.
  • Example 3 Addition of trimethylolethane (TME) to strontium bromide hexahydrate to depress melting point

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

There is herein described a phase change material (PCM) for use in energy storage systems. More particularly, there is described a phase change material comprising Strontium Bromide and a Metal Halide that is optimal to storing heat in about the 76ºC to 88ºC temperature range.

Description

STRONTIUM BROMIDE PHASE CHANGE MATERIAL
FIELD OF THE INVENTION
The present invention relates to a phase change material (PCM) for use in energy storage systems. More particularly, the present invention relates to a phase change material comprising Strontium Bromide and a Metal Halide that is optimal to storing heat in about the 76°C to 88°C temperature range.
BACKGROUND OF THE INVENTION
There exists a problem in the field of phase change materials of providing a phase change material that has a phase change in about the 75°C to 80°C temperature range. This is because there exists at this temperature range mild incongruent melting of compositions such as magnesium bromide hexahydrate.
Strontium bromide hexahydrate has a congruent melting point of 88°C and has rarely, if ever, been used as a PCM before. The only previous mention in the literature is having been discounted by Lane who is a leading expert in the field [ Lane G.A.: Solar Heat Storage: Latent Heat Material - Volume I: Background and Scientific Principles, CRC Press, Florida (1983)] for being too expensive. There is also reference to Strontium bromide hexahydrate in US4003426 which although mentioning the strontium bromide hexahydrate as being used as a phase change material it makes no disclosure of this being used in combination with a Metal Halide.
There has therefore been much effort in the field of phase change materials to find a phase change material that has a phase change in about the 76°C to 88°C temperature range and is capable of operating efficiently. Such a temperature change for a phase change is extremely useful for energy storage systems capable of being used in the domestic heating market. It is an object of at least one aspect of the present invention to obviate or mitigate at least one or more of the aforementioned problems.
It is a further object of at least one aspect of the present invention to provide a phase change material with a phase change in about the 76°C to 88°C temperature range.
SUMMARY OF THE INVENTION
According to a first aspect of the present invention there is provided a phase change material (PCM) comprising:
Strontium Bromide; and
at least one Metal Halide;
wherein the PCM has a phase change in the region of about 76°C to 88°C temperature range.
Generally speaking, the present invention therefore resides in the provision of a PCM with a phase change in the region of about 76°C to 88°C. This makes the PCM highly suitable for energy storage systems such as described in WO2009/138771 and WO201 1/058383 which are incorporated herein by reference.
The PCM of the present invention is therefore based on a mixture of Strontium Bromide and a Metal Halide such as Magnesium Bromide or its hydrate. Alternatives to Magnesium Bromide may be any one of or combination of the following Bromides or their hydrates:
Zinc Bromide;
Cobalt Bromide;
Lithium Bromide;
Sodium Bromide;
Potassium Bromide; Calcium Bromide;
Iron Bromide;
Copper Bromide; and
Aluminium Bromide.
Alternatives to Magnesium Bromide may be any miscible organic compound.
In addition Strontium salts of Chloride may also be used.
Typically, the Strontium Bromide and the at least one Metal Halide may be in the hydrated form.
Strontium Bromide Anhydrous (CAS: 100476-81 -0) and Magnesium Bromide Anhydrous (CAS: 7789-48-2) may be used instead as initial components instead of the hexahydrate forms. In this case, water must be added to reach the final PCM.
The Strontium Bromide may be present in an amount from about 20 - 50 wt.% and preferably about 30 - 35 wt.%.
The Metal Halide may be present in an amount from about 50 - 85 wt.% and preferably about 65 - 70 wt.%.
For example, a preferred embodiment may be about 25 - 35 wt.% or preferably 32 wt.% MgBr2.H20; about 55 - 75 wt.% or preferably about 65 wt.% SrBr2.H20; and about 1 - 5 wt.% or preferably about 3wt.% water. A PCM comprising 32 wt.% MgBr2.H20, 65 wt.% SrBr2.H20 and 3 wt.% water was found to have a phase change of about 77°C.
At compositions of about 30 - 35 wt.% Magnesium Bromide Hexahydrate and about 65 - 70 wt.% Strontium Bromide there exists a phase change at 75°C - 80°C. This temperature is important for phase change material applications such as found in energy storage systems.
A minimum melting point at 32 wt.% MgBr2.H20, 65 wt.% SrBr2.H20 and 3wt.% water was found at about 77°C. According to a second aspect of the present invention there is provided a process for forming a PCM comprising:
providing Strontium Bromide; and
providing at least one Metal Halide;
mixing said Strontium Bromide and at least one Metal Halide together;
wherein the PCM has a phase change in the region of about 76°C to 88°C temperature range.
The Strontium Bromide and Metal Halide may be mixed together in a mixing vessel or heat battery enclosure if the PCM is made directly in a final heat battery.
During the mixing the temperature of the mixing vessel or heat battery enclosure may be increased to a temperature higher than the phase change temperature by about 2°C - 5°C (e.g. 3°C) and kept it at this temperature to melt the materials.
The resulting mixture may be stirred/mixed mixture until it is liquid and homogenous.
Alternatively, starting from the anhydrous forms the following process may be followed:
1) Mix the correct ratio of Strontium Bromide Anhydrous and Metal Halide Anhydrous (e.g. Magnesium Bromide Anhydrous) with optionally another phase change temperature depressing substance according to the required phase change temperature.
2) Add hot water in the correct ratio to obtain the required phase change material at a temperature above the required final phase change temperature to melt the two components. Alternatively, add water in the right ratio to obtain the required phase change material at a temperature below the required final phase change and increase the temperature of the mixing vessel or heat battery enclosure (if the PCM is made directly in the final heat battery) to a temperature higher than the phase change temperature by about
2°C - 5°C (e.g. 3°C) and keep it at this temperature to melt the materials.
3) Stir the mixture until it is liquid and homogenous.
The PCM may be as defined in the first aspect.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings in which:
Figure 1 is a representation of the relationship between the percentage of Strontium Bromide Hexahydrate against the phase change temperature.
BRIEF DESCRIPTION
Generally speaking, the present invention resides in the provision of phase change material that is optimal to storing heat in about the 76°C to 88°C temperature range.
The phase change material (PCM) of the present invention is based on a mixture of Strontium Bromide and a metal halide such as Magnesium Bromide. Alternatives to Magnesium Bromide may be any one of or combination of the following Bromides or their hydrates:
Zinc Bromide;
Cobalt Bromide;
Lithium Bromide;
Sodium Bromide;
Potassium Bromide; Calcium Bromide;
Iron Bromide;
Copper Bromide; and
Aluminium Bromide.
In addition Strontium salts of Chloride may also be used.
EXAMPLE 1
Below is a non-limiting example of preparing a PCM according to the present invention.
a) Starting from the Hexahydrate forms:
1) Mix the correct ratio of the two components according to the required phase change temperature.
2) Increase the temperature of the mixing vessel or heat battery enclosure (if the PCM is made directly in the final heat battery) to a temperature higher than the phase change temperature by about 2°C - 5°C (e.g. 3°C) and keep it at this temperature to melt the materials.
3) Stir the mixture till it is liquid and homogenous,
b) Starting from the anhydrous forms:
1) Mix the correct ratio of Strontium Bromide Anhydrous and Magnesium Bromide Anhydrous (or other phase change temperature depressing substance) according to the required phase change temperature.
2) Add hot water in the correct ratio to obtain the required phase change material at a temperature above the required final phase change temperature to melt the two components. Alternatively, add water in the right ratio to obtain the required phase change material at temperature below the required final phase change and increase the temperature of the mixing vessel or heat battery enclosure (if the PCM is made directly in the final heat battery) to a temperature higher than the phase change temperature by about 2°C - 5°C (e.g. 3°C) and keep it at this temperature to melt the materials.
3) Stir the mixture till it is liquid and homogenous.
At compositions of about 30 - 35 wt.% Magnesium Bromide Hexahydrate and about 65-70 wt.% Strontium Bromide there exists a phase change at 75°C - 80°C. This temperature is important for phase change material applications.
A minimum melting point at 32 wt.% MgBr2.H20, 65 wt.% SrBr2.H20 and 3 wt.% water was found at about 77°C.
FURTHER EXAMPLES
The following non-limiting examples provided in the Experimental results are representative of the PCM composition MX.nH20 with varying amounts of miscible organic compound, as are the processes for their preparation.
SrBr2.6H20:
Example 2: Addition of glycerol to strontium bromide hexahydrate to depress melting point
Test samples of strontium bromide hexahydrate (Sunamp supplied) and glycerol
(available from VWR CAS 56-81-5) were prepared, from 100% strontium bromide hexahydrate composition to 1 :1 molar ratio using the masses listed below. The samples were then heated to 95 °C whilst stirring, to ensure a homogenous mixture. Upon cooling and solidifying, the samples remained as a single phase. Mass (g)
Molar
strontium bromide
Ratio Glycerol
hexahydrate
9: 1 19.4405 0.5595
8:2 18.7837 1.2163
7:3 18.0018 1.9982
6:4 17.0551 2.9449
5:5 15.8855 4.1 145
Upon observing the melting and freezing of the materials (heating to 95°C in a water bath, allowing the materials to fully melt, and then cooling to room temperature in air, recording temperature of material using thermocouple) it was seen that the melting point was progressively depressed, with increasing amounts of glycerol. Repeated cycling confirmed that the melting and freezing point of strontium bromide was decreased with the addition of glycerol. The extent of depression, with the corresponding molar and weight % of glycerol, is listed below.
The effect of increasing the
amount of glycerol on the freezing
temperature of the samples
Molar Temp/ °C Mass
0% 88 0%
10% 84 2.8%
20% 78 6.1 % 30% 71 10%
40% 66 14.7%
50% 55 20.6%
Example 3: Addition of trimethylolethane (TME) to strontium bromide hexahydrate to depress melting point
Test samples of strontium bromide hexahydrate and TME (available from Fischer Scientific Ltd. CAS 77-85-0) were prepared using the ratios listed below and using the same method as in Example 1.
Figure imgf000010_0001
Temperatures during the melting and freezing of the materials were recorded using the same method as listed in Example 2. As seen in Example 2, increased melting and freezing point depression was observed with increasing amounts of TME. The effect of increasing the
amount of TME on the freezing
temperature of the samples
Molar Temp/ °C Mass
0% 88 0%
10% 84 3.6%
20% 79 7.8%
30% 76 12.7%
40% 75 18.4%
50% 68 25.3%
Example 4: Addition of acetamide to strontium bromide hexahydrate to depress melting point
Test samples of strontium bromide and acetamide (available from Alfa Aesar
CAS 77-85-0) were prepared using the ratios listed below and using the same method as in Example 2.
Mass (g)
Molar
strontium bromide
Ratio acetamide
hexahydrate
9:1 19.6375 0.3625
8:2 19.2024 0.7976
7:3 18.6706 1.3294
6:4 18.0057 1.9943
5:5 17.1506 2.8494 The effect of increasing the
amount of acetamide on
the freezing temperature of
the samples
Molar Temp/ °C Mass
0% 88 0%
10% 86 1.8%
20% 84 4.0%
30% 73 6.6%
40% 68 10.0%
50% 64 14.2%
Whilst specific embodiments of the present invention have been described above, it will be appreciated that departures from the described embodiments may still fall within the scope of the present invention. For example, any suitable type of mixture of Strontium Bromide and metal halide may be used along with additional components where necessary. The amount of each component may be varied to adjust for the required phase change temperature.

Claims

1. A phase change material (PCM) comprising:
Strontium Bromide; and
at least one Metal Halide;
wherein the PCM has a phase change in the region of about 76°C to 88°C temperature range.
2. A phase change material (PCM) according to claim 1 , wherein the PCM is capable of being used in an energy storage system.
3. A phase change material (PCM) according to any of claims 1 or 2, wherein the Metal Halide is Magnesium Bromide or its hydrate form.
4. A phase change material (PCM) according to any of claims 1 or 2, wherein the Metal Halide is any one of or combination of the following Bromides or their hydrates:
Magnesium Bromide;
Zinc Bromide;
Cobalt Bromide;
Lithium Bromide;
Sodium Bromide;
Potassium Bromide;
Calcium Bromide;
Iron Bromide;
Copper Bromide; and
Aluminium Bromide.
5. A phase change material (PCM) according to any preceding claim, wherein the PCM also comprises Strontium salts of Chloride.
6. A phase change material (PCM) according to any preceding claim, wherein the Strontium Bromide is present in an amount from about 20 - 50 wt.% or about 30 - 35 wt.%.
7. A phase change material (PCM) according to any preceding claim, wherein the Metal Halide is present in an amount from about 50 - 85 wt.% or about 65 - 70 wt.%.
8. A phase change material (PCM) according to any preceding claim, wherein the PCM is about 25 - 35 wt.% or 32 wt.% MgBr2.H20, about 55 - 75 wt.% or about 65 wt.% SrBr2.H20 and about 1 - 5 wt.% or about 3 wt.% water.
9. A phase change material (PCM) according to any preceding claim, wherein the PCM comprises 32 wt.% MgBr2.H20, 65 wt.% SrBr2.H20 and 3 wt.% water which has a phase change of about 77°C.
10. A method for forming a PCM comprising:
providing Strontium Bromide; and
providing at least one Metal Halide;
mixing said Strontium Bromide and at least one Metal Halide together;
wherein the PCM has a phase change in the region of about 76°C to 88°C temperature range.
11. A method for forming a PCM according to claim 10, wherein the Strontium Bromide and Metal Halide are mixed together in a mixing vessel or heat battery enclosure (if the PCM is made directly in the final heat battery).
12. A method for forming a PCM according to any of claim1 1 , wherein during the mixing the temperature of the mixing vessel or heat battery enclosure are increased to a temperature higher than the phase change temperature by about 2°C - 5°C (e.g. 3°C) and kept it at this temperature to melt the materials.
13. A method for forming a PCM according to any of claim 12, wherein the resulting mixture is stirred/mixed mixture until it is liquid and homogenous.
14. A method for forming a PCM according to any of claims 10 to 13, wherein starting from the anhydrous forms the process comprises:
1) Mixing the correct ratio of Strontium Bromide Anhydrous and Metal Halide
Anhydrous (e.g. Magnesium Bromide Anhydrous) with optionally another phase change temperature depressing substance according to the required phase change temperature.
2) Adding hot water in the correct ratio to obtain the required phase change material at a temperature above the required final phase change temperature to melt the two components or alternatively, adding water in the right ratio to obtain the required phase change material at temperature below the required final phase change and increase the temperature of the mixing vessel or heat battery enclosure (if the PCM is made directly in the final heat battery) to a temperature higher than the phase change temperature by about 2°C - (e.g. 3°C) and keep it at this temperature to melt the materials and 3) Stirring the mixture until it is liquid and homogenous.
PCT/GB2014/052580 2013-08-23 2014-08-22 Strontium bromide phase change material WO2015025175A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CN201480045945.3A CN105492567A (en) 2013-08-23 2014-08-22 Strontium bromide phase change material
US14/913,398 US10184075B2 (en) 2013-08-23 2014-08-22 Strontium bromide phase change material
RU2016106136A RU2656464C2 (en) 2013-08-23 2014-08-22 Strontium bromide phase change material
EP14756121.1A EP3036300B1 (en) 2013-08-23 2014-08-22 Strontium bromide phase change material
AU2014310415A AU2014310415B2 (en) 2013-08-23 2014-08-22 Strontium Bromide phase change material
KR1020167007010A KR102394085B1 (en) 2013-08-23 2014-08-22 Strontium bromide phase change material
JP2016535533A JP6389891B2 (en) 2013-08-23 2014-08-22 Strontium bromide phase change material
CA2921280A CA2921280C (en) 2013-08-23 2014-08-22 Strontium bromide phase change material

Applications Claiming Priority (2)

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GBGB1315098.2A GB201315098D0 (en) 2013-08-23 2013-08-23 Strontium Bromide Phase Change Material
GB1315098.2 2013-08-23

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GB201901761D0 (en) * 2019-02-08 2019-03-27 Sunamp Ltd Phase change materials (PCMs) with solid to solid transitions
IT202000006259A1 (en) * 2020-03-25 2021-09-25 Groppalli S R L INERT MIX AND ITS USE AS A PHASE CHANGE MATERIAL FOR HIGH TEMPERATURE APPLICATIONS
US11631565B2 (en) 2020-11-10 2023-04-18 Science Applications International Corporation Thermal fuse
CN112421077B (en) * 2020-11-23 2022-05-24 浙江大学 Fuel cell low-temperature starting heating and waste heat recovery system based on heat storage of strontium chloride ammoniated

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KR20160045780A (en) 2016-04-27
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RU2016106136A3 (en) 2018-03-29
KR102394085B1 (en) 2022-05-03
CN105492567A (en) 2016-04-13
US20160200956A1 (en) 2016-07-14
AU2014310415A1 (en) 2016-03-03
RU2016106136A (en) 2017-09-26
RU2656464C2 (en) 2018-06-05
GB201315098D0 (en) 2013-10-09
EP3036300A1 (en) 2016-06-29
AU2014310415B2 (en) 2018-03-01
JP2016535148A (en) 2016-11-10
EP3036300B1 (en) 2019-02-27
CA2921280C (en) 2022-05-31
US10184075B2 (en) 2019-01-22

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