WO2011147701A1 - Système de stockage d'énergie thermoélectrique et procédé pour stocker de l'énergie thermoélectrique - Google Patents
Système de stockage d'énergie thermoélectrique et procédé pour stocker de l'énergie thermoélectrique Download PDFInfo
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- WO2011147701A1 WO2011147701A1 PCT/EP2011/057799 EP2011057799W WO2011147701A1 WO 2011147701 A1 WO2011147701 A1 WO 2011147701A1 EP 2011057799 W EP2011057799 W EP 2011057799W WO 2011147701 A1 WO2011147701 A1 WO 2011147701A1
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- working fluid
- heat
- pressure
- intermediate pressure
- cycle
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D17/00—Regenerative heat-exchange apparatus in which a stationary intermediate heat-transfer medium or body is contacted successively by each heat-exchange medium, e.g. using granular particles
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K3/00—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein
- F01K3/12—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein having two or more accumulators
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
- F01K25/08—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours
- F01K25/10—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using special vapours the vapours being cold, e.g. ammonia, carbon dioxide, ether
Definitions
- the present invention relates generally to the storage of electric energy. It relates in particular to a system and a method for storing electric energy in the form of thermal energy in a thermal energy storage.
- Base load generators such as nuclear power plants and generators with stochastic, intermittent energy sources such as wind turbines and solar panels, generate excess electrical power during times of low power demand.
- Large-scale electrical energy storage systems are a means of diverting this excess energy to times of peak demand and balance the overall electricity generation and consumption.
- thermoelectric energy storage converts excess electricity to heat in a charging cycle, stores the heat, and converts the heat back to electricity in a discharging cycle, when necessary.
- TEES thermoelectric energy storage
- Such an energy storage system may be robust, compact, site independent and may be suited to the storage of electrical energy in large amounts.
- Thermal energy may be stored in the form of sensible heat via a change in temperature or in the form of latent heat via a change of phase or a combination of both.
- the storage medium for the sensible heat may be a solid, liquid, or a gas.
- the storage medium for the latent heat occurs via a change of phase and may involve any of these phases or a combination of them in series or in parallel.
- the round-trip efficiency of an electrical energy storage system may be defined as the percentage of electrical energy that can be discharged from the storage in comparison to the electrical energy used to charge the storage, provided that the state of the energy storage system after discharging returns to its initial condition before charging of the storage.
- the roundtrip efficiency of the thermoelectric energy storage system is limited for various reasons rooted in the second law of thermodynamics. The first reason relates to the coefficient of performance of the system. When the system is in the charging mode, its ideal efficiency may be governed by the coefficient of performance (COP) of a heat pump.
- the COP depends on the temperatures of the cold side (7 C ) and the hot side (T h ) as given by
- thermoelectric energy storage systems because they are not concerned with heat for the exclusive purpose of storing electricity.
- thermoelectric energy storage having a high round- trip efficiency, whilst minimising the system costs involved.
- An aspect of the invention relates to a thermoelectric energy storage system for storing electrical energy by transferring thermal energy to a thermal storage in a charging cycle, and for generating electricity by retrieving the thermal energy from the thermal storage in a discharging cycle.
- the thermoelectric energy storage system comprises a working fluid circuit circulating a working fluid; a first compressor, in the charging cycle, compressing the working fluid from a low pressure to an intermediate pressure (such that the temperature of the working fluid is rising), an intercooler, in the charging cycle, cooling the working fluid at the intermediate pressure (for lowering the temperature of the working fluid), a second compressor, in the charging cycle, compressing the working fluid from the intermediate pressure to a high pressure, a first heat exchanger, in the charging cycle, transferring heat from the working fluid at the high pressure to the thermal storage and, in the discharging cycle, transferring heat from the thermal storage to the working fluid at the high pressure.
- the working fluid may be compressed in two stages: from the low pressure to the intermediate pressure in a first stage and from the intermediate pressure to the high pressure in a second stage.
- the intercooler comprises a flash intercooler and/or a second heat exchanger.
- the intercooling may be carried out by (a) flashing a portion of the working fluid (taken from the output of a expander) in the flash intercooler and/or by (b) heating a secondary thermal storage with the second heat exchanger.
- This may have the advantage of (a) reducing the compressor energy of the first stage without compromising the thermal energy delivered to the main thermal storage and/or of (b) carrying out a reheat in the discharging cycle by using the secondary thermal storage to increase the power output.
- second heat exchanger in the charging cycle, transfers heat from the working fluid at the intermediate pressure to a second thermal storage and, in the discharging cycle, transfers heat from the second thermal storage to the working fluid at intermediate pressure.
- thermoelectric energy storage system may be referred to as a heat pump cycle and the discharging cycle of a thermoelectric energy storage system may be referred to as a heat engine cycle.
- thermoelectric energy storage concept heat needs to be transferred from a hot working fluid to a thermal storage medium during the charging cycle and back from the thermal storage medium to the working fluid during the discharging cycle.
- a heat pump requires work to move thermal energy from a cold source to a warmer heat sink. Since the amount of energy deposited at the hot side, i.e. the thermal storage medium part of a thermoelectric energy storage, is greater than the compression work by an amount equal to the energy taken from the cold side, i.e. the heat absorbed by the working fluid at the low pressure, a heat pump deposits more heat per work input to the hot storage than resistive heating.
- the ratio of heat output to work input is called coefficient of performance, and it is a value larger than one.
- thermoelectric energy storage system may comprise a work recovering expander, an evaporator, a compressor and a heat exchanger, all connected in series by a working fluid circuit. Further, a cold storage tank and a hot storage tank, for example, containing a fluid thermal storage medium may be coupled together via the heat exchanger. Whilst the working fluid passes through the evaporator, it absorbs heat from the ambient or from a thermal bath and evaporates.
- the discharging cycle of a thermoelectric energy storage system may comprise a pump, a condenser, a turbine and a heat exchanger, all connected in series by a working fluid circuit.
- a cold storage tank and a hot storage tank for example, containing a fluid thermal storage medium may be coupled together via the heat exchanger. Whilst the working fluid passes through the condenser, it exchanges heat energy with the am bient or the thermal bath and condenses.
- the same thermal bath such as a river, a lake or a water-ice mixture pool, may be used in both the charging and discharging cycles.
- the present invention overcomes the problem of an excessive temperature rise in the working fluid during compression in the charging cycle.
- This problem occurs where the ratio of the highest operating pressure of a transcritical thermoelectric energy storage system to the evaporator pressure of the charging cycle is relatively great.
- this excessive temperature rise is detrimental to the completion of the compression process in a single stage unless the working fluid is heated to an acceptably high temperature.
- thermoelectric energy storage system where the charging and discharging cycles are designed to have corresponding compressor intercooling and reheat sections, respectively, with matching heat loads and temperature levels, and where an intercooler may be used for cooling each of the additional compression stages of the charging cycle.
- intercoolers are located at the corresponding compressor discharges and are fed with partially expanded working fluid from the condenser exit, such that the heat of compression is absorbed by the process of vaporizing the liquid part of the working fluid.
- the present invention provides a multi-stage compression system in which the working fluid is cooled close to its saturation temperature as it is output from each intermediate compression stage.
- the heat released from the working fluid during said cooling is recovered and utilised to improve roundtrip efficiency of the thermoelectric energy storage system.
- a further aspect of the invention relates to a method for storing electrical energy in a charging cycle and retrieving electrical energy in a discharging cycle.
- the charging cycle comprises the steps: compressing the working fluid from a low pressure to an intermediate pressure for storing electrical energy (particularly for converting electrical energy into heat energy); cooling the working fluid at the intermediate pressure; compressing the working fluid from the intermediate pressure to a high pressure for storing electrical energy; transferring heat from the working fluid at the high pressure to the thermal storage.
- the discharging cycle comprises the steps: transferring heat from the thermal storage to the working fluid at the high pressure; expanding the working fluid from the high pressure for generating electrical energy.
- FIG. 1 a shows a simplified schematic diagram of a charging cycle of a thermoelectric energy storage system according an embodiment of the invention.
- Figure 1 b shows a simplified schematic diagram of a discharging cycle of a thermoelectric energy storage system according an embodiment of the invention.
- Figure 2a shows an enthalpy-pressure diagram of the heat transfer in the charging cycle of a transcritical thermoelectric energy storage system according to an embodiment of the invention.
- Figure 2b shows an enthalpy-pressure diagram of the heat transfer in the discharging cycle of a transcritical thermoelectric energy storage system according to an embodiment of the invention.
- Figure 3a shows an enthalpy-pressure diagram of the heat transfer in the charging cycle of a thermoelectric energy storage system according to an embodiment of the invention.
- Figure 3b shows an enthalpy-pressure diagram of the heat transfer in the discharging cycle of a thermoelectric energy storage system according to an embodiment of the invention.
- FIGs 1 a and 1 b show a simplified schematic diagram of a thermoelectric energy storage system 10 according to an embodiment of the invention.
- the charging cycle system 12 shown in Figure 1 a comprises a first compression stage with a compressor 14, a second compression stage with a compressor 16 and a third compression stage with a compressor 18.
- the charging cycle system 12 comprises further a first expansion stage with an expander 20 and a second expansion stage with an expansion valve 22.
- a working fluid circulates through all components of a working fluid circuit 24 as indicated by the solid line with arrows.
- the charging cycle system 12 comprises a stream splitter 26 between the expander 20 and the expansion valve 22, a flash intercooler 28 between the compressor 14 and the compressor 16 and a heat exchanger 30 between the compressor 16 and the compressor 18.
- the charging cycle system 12 comprises a heat exchanger 34, and at the low pressure side 36, the charging cycle system 12 comprises a heat exchanger 38.
- the charging cycle system 12 performs a transcritical cycle and the working fluid flows around the thermoelectric energy storage system 10 in the following manner.
- the working fluid enters the expander 20 where the working fluid is expanded from a high pressure to a lower (intermediate) pressure.
- the working fluid stream is split in two streams by the stream splitter 26, with a first portion of the working fluid flowing to the second expansion stage with expansion valve 22 and a second portion passing directly to the flash intercooler 28.
- the working fluid passes to the heat exchanger 38 where the working fluid absorbs heat from the ambient or from a cold storage 40 and evaporates.
- the heat exchanger 38 is a counter flow heat exchanger 38 and a cold storage medium circulates from a first cold storage tank 42 to a second cold storage tank 44 for exchanging heat with the working fluid.
- the vaporised working fluid is circulated to a first compression stage in which surplus electrical energy is utilized to compress and heat the working fluid in a compressor 14 from the low pressure to the intermediate pressure. On exiting the compressor 14, this first portion of working fluid is mixed with the relatively cooler, second portion of working fluid in the flash intercooler 28.
- the mixed working fluids pass to a second compression stage which comprises the compressor 16.
- a second compression stage which comprises the compressor 16.
- further surplus electrical energy is utilized to compress the working fluid from the intermediate pressure to a higher second intermediate pressure.
- the working fluid mass flow through the second compression stage is greater than the working fluid mass flow through the first compression stage.
- the working fluid passes through the heat exchanger 30 where it is cooled as heat energy is transferred from the working fluid to a thermal storage medium from a further heat storage 46.
- the heat exchanger 30 is a counter flow heat exchanger 30 and the storage medium circulates from a first storage tank 48 to a second storage tank 50 for exchanging heat with the working fluid.
- the working fluid is then directed to a third compression stage where it passes through the compressor 18 before entering the heat exchanger 34.
- the third compression stage again surplus electrical energy is driving the compressor 18 for compressing the working fluid from the second intermediate pressure to the (higher) high pressure.
- heat energy is transferred from the working fluid into a thermal storage medium from a hot storage 52.
- the heat exchanger 34 is a counter flow heat exchanger 34 and the storage medium circulates from a first hot storage tank 54 to a second hot storage tank 56 for exchanging heat with the working fluid.
- the flash intercooler 28 is a spray intercooler 28. In alternative embodiments, other types of flash intercoolers 28 may be used.
- intercooler 28, 30 is required in the charging cycle 12 in order to achieve improved efficiency of the system 10.
- each compression stage may be equipped with a flash intercooler 28, when reheat options are not considered in the discharging cycle.
- a flash intercooler 28 when reheat options are not considered in the discharging cycle.
- different working fluids may be used for the different cycles, as long as the temperature levels for the heat load of the heat pump, the heat storage and the heat engine are chosen appropriately.
- the charging cycle may operate in the temperature range of 5°C and 120°C. The intercooling occurs at a temperature levels well distributed within this range.
- the system 10 comprises a first expander 20, in the charging cycle, expanding the working fluid after the first heat exchanger 34 to the intermediate pressure; wherein, in the charging cycle, a first portion of the working fluid at the intermediate pressure is input directly into the flash intercooler 28.
- the system 10 comprises a second expander 22, in the charging cycle, expanding a second portion of the working fluid at the intermediate pressure to the low pressure.
- the system 10 comprises a third heat exchanger 38, in the charging cycle, transferring heat from a third thermal storage 40 to the working fluid at low pressure and, in the discharging cycle, transferring heat from the working fluid at low pressure to the third thermal storage.
- the intercooler comprises a flash intercooler 28 and a third heat exchanger 30, wherein, in the charging cycle, the working fluid between the flash intercooler and the third heat exchanger is compressed from a first intermediate pressure to a second intermediate pressure by a further compressor 16.
- the heat stored in the heat storages 40, 46 and 52 is subsequently utilised in the discharging cycle system 56 shown in Fig. 1 b.
- the working fluid in the discharging cycle system 58 coming from the heat exchanger 38 is pumped from the low pressure to the high pressure by pump 60. After that the working fluid is heated in the heat exchanger 34 and enters a first turbine 62 for converting the heat into mechanical and subsequently into electrical energy.
- the working fluid is reheated again in heat exchanger 30 and enters a second turbine 64 for generating further electrical energy.
- the working fluid is expanded from the high pressure to the intermediate pressure and in the second turbine 64 to the low pressure. After that the working fluid is cooled in the heat exchanger 38.
- the system 10 comprises a first turbine 62, in the discharging cycle, expanding the working fluid from the high pressure to the intermediate pressure for generating electrical energy and/or a second turbine 64, in the discharging cycle, expanding the working fluid from the intermediate pressure to the low pressure for generating electrical energy.
- the system 10 comprises a pump 60, in the discharging cycle, pumping the working fluid from the low pressure to the high pressure during the discharging cycle.
- FIGs 2a and 3a show a charging cycle 12a, 12b, and Figures 2b and 3b a discharging cycle 58a, 58b of a transcritical thermoelectric energy storage system 10.
- the cycles are depicted in pressure-enthalpy diagrams.
- a vapor dome 66 is indicated.
- the critical point 68 of the working fluid is shown on top of the vapor dome.
- the working fluid is in liquid phase
- right of the vapor dome 66 the working fluid is in gas phase (wet steam phase).
- the working fluid Under the vapor dome 66, the working fluid is in a mixed liquid and gas phase.
- a phase change of the working fluid only occurs, when a state change passes the limiting line of the vapor dome 66.
- FIG. 2a illustrates the charging cycle 12 of a storage system 10 which may comprise two heat exchangers 30 for intercooling the working fluid.
- the charging cycle 12a follows a counter-clockwise direction as indicated by the arrows.
- the charging cycle 12a starts at point A where the working fluid is first evaporated at a low pressure 70 by utilizing, for example a low grade heat source such as ambient air or by a heat exchanger 38. This transition is indicated in Figure 2a with the line from point A to point B1 .
- the resultant vapor is compressed utilizing electrical energy in three stages from point B1 to C1 to a first intermediate pressure 72, from B2 to C2 to a second intermediate pressure 74, and from B3 to C3 to a high pressure 76.
- Such compression occurring in three stages is a consequence of the thermoelectric energy storage 10 having a compressor train comprising three individual units, for example the compressors 14, 16, 18.
- the working fluid is cooled from point C1 to B2 and point C2 to B3.
- the working fluid may be cooled by two heat exchangers 30.
- the hot compressed working fluid exiting the compression train at point C3 is cooled down at constant pressure 76 to point D, for example in a heat exchanger 34. Since the cycle 12a is supercritical between the points C3 and D, no condensation of the working fluid takes place. The heat rejected between point C1 to B2, C2 to B3, and C3 and D is transferred to a thermal storage medium via heat exchangers 30, 34, thereby storing the heat energy. After reaching point D, the cooled working fluid is returned to its initial low pressure state 70 at point A via a thermostatic expansion valve 22 or alternatively with an energy recovering expander.
- FIG. 2b illustrates the discharging cycle of a thermoelectric energy storage system 10 with one turbine 62 that follows a clockwise direction as indicated by the arrows.
- the discharging cycle 58a starts with the compression of the working fluid as it is pumped from point E to point F from low pressure 70 to high pressure 76, for example by pump 60. From point F to point G, the working fluid is in contact with the thermal storage medium in a direct or indirect manner, wherein stored heat is transferred from the thermal storage medium to the working fluid. For example, this may be done with a heat exchanger 34. The working fluid is in a supercritical state between point F and point G, hence no evaporation takes place.
- the subsequent expansion of the working fluid in a turbine 62 from pressure 76 to pressure 70 in order to generate electricity is represented between point G and point H.
- the working fluid is condensed to its initial state by exchanging heat, for example with a cooling medium such as ambient air or with a cold storage 40 via a heat exchanger 38. This is represented from point H to point E on Figure 2b.
- thermodynamic cycles 12a, 58a shown in Figures 2a and 2b would use the same working fluid, it is noted that the total heat energy generated in the charging cycle 12a is greater than the heat energy requirement of the discharging cycle 58a.
- the total heat energy required for functioning of the discharging cycle 58a which is equal to the enthalpy difference from point F to point G in Figure 1 b, can be provided solely by the heat energy released during the charging cycle between point C3 and point D in Figure 1 a. Therefore, it would be beneficial to efficiently utilize the excess heat resulting from compressor intercooling.
- a storage system 10 with a charging cycle 12a comprises a discharging cycle, wherein the heat stored during intercooling is used for reheating the working fluid between the expansions in turbines 62, 64.
- a storage system 10 with a discharging cycle 58a comprises a discharging cycle, wherein a flash intercooler 28 is used for cooling the working fluid between two compression stages.
- Figure 3a and Figure 3b depict a charging cycle 12b and a discharging cycle 58b, respectively, on a pressure-enthalpy diagram, which may be performed by an embodiment of the transcritical thermoelectric energy storage system 10 shown in Figures 1 a and 1 b. Referring first to Figure 3a, the charging cycle 12b follows a counter-clockwise direction as indicated by the arrows.
- the charging cycle 12b starts with the expansion of the working fluid which occurs in two stages, between point D and point A1 from pressure 76 to pressure 72 (expander 20), and between point A1 and point A2 from pressure 72 to pressure 70 (expansion valve 22).
- the working fluid stream is divided at point A1 (stream splitter 26), where a first portion is diverted to point B2 and the remaining portion is expanded further to point A2 (expansion valve 22).
- the third compression stage from pressure 74 to pressure 76 occurs between points B3 and C3 (compressor 18).
- thermoelectric energy storage 10 having a compressor train comprising three individual units 14, 16, 18. In between each of these compression stages the working fluid is cooled from point C1 to B2 and point C2 to B3 at constant pressure.
- the hot compressed working fluid exiting the compression train at point C3 is cooled down at constant pressure 76 to point D (heat exchanger 34). Since the cycle 12b is supercritical between the points C3 and D, no condensation of the working fluid takes place. The rejected heat energy between points C3 and D is stored in a thermal storage medium (hot storage 52). After reaching point D, the cooled working fluid is returned to its initial low pressure state 70 at point A1 via a work recovering expander 20 / thermostatic expansion valve 22.
- the flash intercooler 28 utilized in the charging cycle 12b may be a direct-contact heat exchanger, where the liquid working fluid from point A1 to be evaporated is injected or sprayed into the compressed working fluid vapour flow at C1.
- Such a direct-contact heat exchanger comprises a shell filled with a packing of a high specific surface area in order to increase the wetted heat transfer area.
- FIG 3b illustrates the discharging cycle 58b of the thermoelectric energy storage system 10 that follows a clockwise direction as indicated by the arrows.
- the discharging cycle starts with the compression (pump 60) of the working fluid from low pressure 70 to high pressure 76 and this transition is indicated in Figure 3b with the line from point E to point F.
- the working fluid is in contact with the thermal storage medium in a direct or indirect manner, wherein stored heat is transferred from the thermal storage medium to the working fluid at constant pressure (heat exchanger 34).
- the working fluid is in a supercritical state between point F and point G1 , hence no evaporation takes place.
- the subsequent expansion of the working fluid in a turbine 62 in order to generate electricity is represented between point G1 and point H1 .
- a reheat stage at pressure 74 where the reheat energy is provided from the thermal storage 46.
- said thermal storage 46 is coupled to the heat exchanger 30 corresponding to the second intercooling stage in the charging cycle 12b.
- different working fluids may be utilized in the charging and discharging cycles.
- the temperature levels for the charging cycle, the heat storage and the discharging cycle must be adjusted to ensure transfer of heat in the desired direction.
- water is used as the working fluid in the charging cycle.
- another fluid with a high boiling point may be utilised instead of water.
- the intercooling heat load is at a suitably high temperature to be stored and used to drive a secondary discharging cycle having a low boiling point working fluid (such as hydrocarbon).
- thermal energy stored during intercooling can be efficiently recovered without utilising a flash intercooler.
- thermoelectric energy storage system may be replaced with a multi-purpose heat exchange device that can assume both roles, since the use of the evaporator in the charging cycle and the use of the condenser in the discharging cycle will be carried out in different periods.
- turbine and the compressor roles can be carried out by the same machinery, referred to herein as a thermodynamic machine, capable of achieving both tasks.
- temperatures, the pressures and the amount of working fluid exiting the stream splitter 26 may be measured and these values may be controlled by valves situated in the working fluid circuit.
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Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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CN2011800368821A CN103003531A (zh) | 2010-05-28 | 2011-05-13 | 用于储存热电能的热电能量储存系统和方法 |
US13/687,235 US20130087301A1 (en) | 2010-05-28 | 2012-11-28 | Thermoelectric energy storage system and method for storing thermoelectric energy |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP10164288.2 | 2010-05-28 | ||
EP10164288A EP2390473A1 (fr) | 2010-05-28 | 2010-05-28 | Système de stockage d'énergie thermoélectrique et procédé de stockage d'énergie thermoélectrique |
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US13/687,235 Continuation US20130087301A1 (en) | 2010-05-28 | 2012-11-28 | Thermoelectric energy storage system and method for storing thermoelectric energy |
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WO2011147701A1 true WO2011147701A1 (fr) | 2011-12-01 |
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US (1) | US20130087301A1 (fr) |
EP (1) | EP2390473A1 (fr) |
CN (1) | CN103003531A (fr) |
WO (1) | WO2011147701A1 (fr) |
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CN103003531A (zh) | 2013-03-27 |
EP2390473A1 (fr) | 2011-11-30 |
US20130087301A1 (en) | 2013-04-11 |
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