CN103534536A

CN103534536A - Articles and devices for thermal energy storage and methods thereof

Info

Publication number: CN103534536A
Application number: CN201180038984.7A
Authority: CN
Inventors: J·M·图多尔; A·N·索克霍雅克; D·H·班克; K·塞哈诺比施; P·瓦利亚
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2010-08-12
Filing date: 2011-08-11
Publication date: 2014-01-22
Also published as: CA2806469A1; JP2014508908A; US20120037148A1; WO2012021673A3; KR20130143007A; MX2013001797A; BR112013003042A2; EP2603745A2; WO2012021673A2

Abstract

The present invention relates to articles 2 and heat storage devices 80 for storage of thermal energy. The articles 2 include a metal base sheet 12 and a metal cover sheet 14, wherein the metal base sheet and the metal cover sheet are sealingly joined to form one or more sealed spaces 18, The articles 2 include a thermal energy storage material 16 that is contained within the sealed spaces 18. The sealed spaces preferably are substantially free of wafer or includes liquid water at a concentration of about 1 percent by volume or less at a temperature of about 25 DEG C, based on the total volume of the sealed spaces 18. The articles include one or more of the following features: a) the pressure 36 in a sealed space is about 700 Torr or less, when the temperature of the thermal energy storage material is about 25 DEG C; b) the metal cover- sheet 14 includes one or more stiffening features 34, wherein the stiffening features Include indents into the sealed space, protrusions out of the sealed space, or both, that are sufficient in size and number to reduce the maximum von Mises stress in the cover sheet during thermal cycling; c) the metal cover sheet 14 and/or the metal base sheet 12 includes one or more volume expansion features 62; or d) the metal cover sheet has a thickness, tc, and the metal base sheet has a thickness, tb, wherein tc is greater than tb; so that the article is durable.; For example, the article does not leak after thermal cycling between about 25 DEG C and about 240 DEG C, for 1,000 cycles.

Description

Goods and devices and methods therefor for thermal energy storage

Invention field

The present invention relates to use the thermal energy storage of thermal energy storage material, and relate to the packing of described thermal energy storage material, to allow effective heat accumulation and effectively to conduct heat both.

the rights and interests requirement of the applying date

The present invention requires U.S. Provisional Patent Application 61/373,008 (submission on August 12nd, 2010) and U.S. Patent application 13/207, the rights and interests of the applying date of 607 (submissions on August 11st, 2011), the content of described two applications is incorporated to herein by reference with its full content.

Background technology

Generally speaking, industrial quarters is actively sought effectively to catch and is stored used heat to can use in the moment preferably its new method.In addition the demand that, realizes energy storage in tight space requires exploitation can in Unit Weight and unit volume, store the new material of high energy content.The potential application of disruptive technology comprises transportation, solar energy, industrial manufacture process and municipal administration and/or commercial establishment heating.

For transportation industry, well-known, the operational efficiency of internal combustion engine is low.The source of this poor efficiency comprises by exhaust, the heat leakage that cooling, radiant heat causes and comes from the mechanical loss of system.According to estimates, more than 30% exhaust by engine to the fuel energy of internal combustion engine supply is lost in environment.

As everyone knows, during " cold start-up ", internal combustion engine moves with significantly lower efficiency, produces more discharges, or both, this is because burning is carried out under non-optimum temperature, and internal combustion engine need to be done the friction that extra merit is caused by the high viscosity of cold lubricant with antagonism.Thereby for internal combustion engine intermittent running, extend cold start and/or within the period of single operational vehicle, cause repeatedly occurring the hybrid-power electric vehicle of cold start, this problem is even even more important.In order to help to address this problem, the solution that can effectively store and discharge used heat is being found by creative equipment manufacturers.Basic idea is to reclaim and store used heat at vehicle normal operation period, then more late time, controls the release of this heat, thereby reduces or minimize duration and the frequency of cold start, finally improves the efficiency of internal combustion engine, reduces and discharge or both.

Become actual solution, the energy density of thermal energy storage system and thermal power density requirements are high.The applicant had submitted 1 in the past) the U.S. Patent Application Publication No. 2009-0211726 of Soukhojak etc., be entitled as " thermal energy storage material " (Thermal Energe Storage Materials), on August 27th, 2009, announce; 2) the U.S. Patent Publication No. 2009-0250189 of Bank etc., is entitled as " heat storage devices " (Heat Storage Devices), on October 8th, 2009, announces; 3) PCT publication number PCT/US09/67823, is entitled as " heat transfer system that utilizes thermal energy storage material " (Heat Transfer Systems Utilizing Thermal Energe Storage Materials), on December 14th, 2009, submits to; And 4) U.S. Provisional Application number 61/299,565, is entitled as " thermal energy storage " (Thermal Energe Storage), on January 29th, 2010, submits to.Application before these is incorporated to herein in full by reference with it.

In prior art, there is known heat storage devices and waste heat recovery plant.Yet for example, for the thermmal storage ability of long-term (being greater than approximately 6 hours) is provided, they generally occupy large volume, need pumping large volume heat-transfer fluid, need relatively large pump to overcome fluid resistance etc.Therefore, the heat storage system for the combination beyond example of high-energy-density, high power density, long heat accumulation time, lightweight, the low fluid resistance that heat-transfer fluid is flowed or its any combination can be provided, exists demand.

For example, for needing lightweight system, application in transit, the packaging Problems of thermal energy storage material requires firm packing material and lightweight package thing.For example, packing material should be durable, makes it can hold high concentration thermal energy storage material, holds thermal energy storage material (after this it may experience large Volume Changes) in wide temperature range, in a plurality of cells that seal each other or capsule, hold thermal energy storage material, or its any combination.To the demand of lightweight thermal energy storage system, may need to reduce packing material weight.

For example, for being encapsulated in lightweight, have in high-energy-density or high power density and durable capsule and (for example to make capsule after the temperature of approximately 400 ℃, not leak being heated to; Capsule is not leaked to approximately 1,000 of Repeat-heating between the temperature of approximately 240 ℃ or more circulation the temperature of approximately 25 ℃; Or both) thermal energy storage material, exist demand.

summary of the invention

One aspect of the present invention is a kind of goods, and it comprises: bottom sheet (being preferably metal bottom sheet material); Be tightly connected to form the cover sheets (being preferably metal cover sheets) of cystic structures with described bottom sheet, wherein said cystic structures comprises one, two or more seal cavities; Thermal energy storage material, wherein said thermal energy storage material is included in described seal cavity, and wherein said thermal energy storage material has approximately 150 ℃ or higher liquidus temperature; Wherein said seal cavity is substantially free of water, or comprises the cumulative volume based on described seal cavity at the temperature of approximately 25 ℃, and concentration is by volume approximately 1% or lower aqueous water; And wherein said goods comprise following one or more feature: a) when the temperature of described thermal energy storage material is about 25 ℃, the pressure in seal cavity is about 700Torr or lower; B) described cover sheets comprises one or more than one or more reinforcement feature, wherein said reinforcement feature comprises that protuberance outside recess in recessed described seal cavity, outstanding described seal cavity or both, its size and quantity are enough to reduce maximum Feng meter Si (von Mises) stress in described cover sheets during thermal cycle; C) described bottom sheet and/or described cover sheets comprise one or more volumetric expansion parts; Or d) described cover sheets has thickness t _c, described bottom sheet has thickness t _b, t wherein _cbe greater than t _b; Described goods are not being leaked after approximately 1,000 circulation of thermal cycle between approximately 25 ℃ to approximately 240 ℃.Described reinforcement feature can be the stress that can redistribute in described bottom sheet and described cover sheets, for example, while increasing (fusing by thermal expansion or described thermal energy storage material causes) with pressure in the described seal cavity of box lunch, maximum Feng meter Si stress compares with the bottom sheet and/or the cover sheets that do not have described reinforcement feature and stand same pressure any parts (for example recess or protuberance) that are lowered.The limiting examples of the reinforcement feature that can use in described metal cover sheets comprises dimple (dimple), chevron (chevron), rib (rib) or its any combination.

Of the present invention particularly preferred aspect in, described cystic structures has one or more fluid passages, it is large must be enough to allow heat-transfer fluid to flow through described one or more fluid passage; And when described cystic structures contacts with heat-transfer fluid, described thermal energy storage material and described heat-transfer fluid are isolated.

Another aspect of the present invention is a kind of device, the group heap that it comprises two or more goods in container and described container.For example, described device can comprise a plurality of goods described herein.Under preferable case, each goods comprises fluid passage and contains described thermal energy storage material.Under preferable case, described in there is fluid passage goods be stacked so that the preferably roughly alignment in the axial direction of their fluid passage.

Another aspect of the present invention is that for example, described method comprises the following steps: to form one, two or more grooves in bottom sheet for the preparation of goods, the method for goods described herein; Ii) with one of the filling at least partly of thermal energy storage material, groove described in two or more; And the first metal forming (for example described bottom sheet) for example, is connected to (being for example tightly connected) to form seal cavity at least partly with the second metal forming (described cover sheets); Wherein said thermal energy storage material comprises slaine, and wherein said slaine during Connection Step in molten condition.

Another aspect of the present invention relates to the method for heat accumulation, and described method comprises the following steps: the thermal energy transfer of q.s to goods of the present invention, so that the thermal energy storage material in described goods is heated to approximately 200 ℃ or higher temperature.

Under vantage, goods of the present invention, device, system and method can hold high concentration thermal energy storage material so that can store a large amount of heat energy (for example having high-energy-density), can between described heat-transfer fluid and the goods that contain described thermal energy storage material, there is high surface area, make heat can be delivered to fast in described thermal energy storage material and/or for example, from wherein transmitting and out (there is high power density, preferably higher than about 8kW/L), can there are a plurality of flow paths with similar or equal fluid resistance, so that heat is evenly delivered to zones of different and/or transmits out from zones of different, they there is Rotational Symmetry so that can easily be arranged, there is robust structure, having high heat storage density needs compact design, light components or both application so that they can be used in, heat-transfer fluid is flowed and has lower fluid resistance (for example the heat-transfer fluid pump rate at approximately 10 liters/min bends down the Pressure Drop in about 1.5kPa) to reduce the pumping requirement to described heat-transfer fluid, enough firm so that after the cystic structures that comprises described thermal energy storage material being heated to the temperature of approximately 400 ℃, described thermal energy storage material does not leak from seal cavity, enough durable so that will there is cystic structures Repeat-heating approximately 1 between approximately 25 ℃ to approximately 240 ℃ of described thermal energy storage material, after 000 or more circulation, described thermal energy storage material does not leak from seal cavity, or its combination.

accompanying drawing summary

In the following detailed description, limiting examples by embodiment of the present invention the present invention is described further with reference to a plurality of figure that propose, reference number same in described figure represents same parts in several views of figure, and in described figure:

Fig. 1 is the figure with the exemplary article of sealing compartment.

Fig. 2 A is the cross-sectional view of the exemplary article that comprises a plurality of seal cavities.

Fig. 2 B is the exemplary cross-sectional with the single capsule of the seal cavity that can use in goods.

Fig. 3 is the figure of the exemplary base sheet material that can use in goods.

Fig. 4 A is the figure of the exemplary cover sheets with chevron that can use in goods.

Fig. 4 B is the figure of the exemplary capsule that comprises the cover sheets with dimple, and described dimple can be used in having the goods of one or more capsules.

Fig. 4 C is the figure of one section of exemplary cover sheets comprising the dimple that can use in goods.

Fig. 4 D has a plurality of reinforcement features that can use in goods, the figure of the exemplary cover sheets of a plurality of protuberances and/or recess for example.

Fig. 5 A is the exemplary cross-sectional of sealing compartment at the sealed temperature of described compartment.

Fig. 5 B is the exemplary cross-sectional of sealing compartment at the temperature lower than seal temperature.

Fig. 5 C is the exemplary cross-sectional of sealing compartment at the temperature higher than seal temperature.

Fig. 6 A, 6B and 6C are the figure that has been formed into the ribbed exemplary sheet material of tool.

Fig. 7 A and 7B are the figure that explanation has the sheet material of volumetric expansion parts, and described volumetric expansion parts allow to increase the volume (to be for example adapted to the expansion of its volume when heat energy material is heated and/or melts) of seal cavity.

Fig. 8 is exemplary diagram, and it shows when cover sheets being used in the goods that containing thermal energy storage material and to described thermal energy storage material heating, the relation between the maximum Feng meter Si stress in the thickness of cover sheets and cover sheets.

Fig. 9 is exemplary diagram, and it shows for smooth cover sheets and the cover sheets that comprises rib, the relation between the thickness of cover sheets and the greatest expected Feng meter Si stress in cover sheets.

Figure 10 is exemplary diagram, it shows for smooth cover sheets, the cover sheets that comprises dimple, the cover sheets that comprises chevron and the cover sheets that comprises rib, the relation between the thickness of cover sheets and the greatest expected Feng meter Si stress in cover sheets.

Figure 11 is the figure of a part for the instrument that can use in the manufacture of the sheet material that comprises rib.

Figure 12 shows the exemplary group heap of goods.

Figure 13 shows the bottom sheet surface of the goods that comprise one or more sealing compartments.Figure 13 has shown that sealing compartment can have the first sealing (primary seal) and one or more the second sealing (secondary seal).

Figure 14 is the figure of exemplary hot storage device.

Figure 15 is for impressing the figure of the exemplary tool of bottom sheet.

Figure 16 shows the bottom sheet surface of the goods that comprise one or more spaces of using nozzle to be filled with thermal energy storage material.

detailed description of the present invention

In the following detailed description, in conjunction with preferred embodiment, specific embodiment of the invention scheme is described.Yet for the particular of the technology of the present invention or the degree of application-specific, its object is only illustrative, and just provides simple and clear description to exemplary for description below.Therefore, the invention is not restricted to described specific embodiments below, on the contrary, present invention resides in all alternative schemes, modification and equivalent in the true scope of the claims of enclosing.

As by what see the instruction from herein, the invention provides for heat energy storage and/or by the thermal energy transfer storing unique goods, device, the system and method to fluid.For example, the goods for heat energy storage of the present invention and device when heat energy storage more effectively, allow Transmit evenly heat energy more, allow to use the less Pressure Drop transferring heat energy of heat-transfer fluid, or its any combination.

Various aspects of the present invention are based on a kind of goods, it comprises one or more thermal energy storage materials in the one or more seal cavities that have the cystic structures (being capsule) of one or more seal cavities and be encapsulated in cystic structures, described in seal and make thermal energy storage material can not flow out cystic structures or remove from cystic structures by alternate manner.When run duration heats thermal energy storage material, volume may increase due to thermal expansion, the liquid phase of thermal energy storage material and the density contrast of solid phase or both.The increase of thermal energy storage material volume can be approximately 5% or more, approximately 10% or more, approximately 15% or more or even approximately 20% or more.For example, slaine is as lithium nitrate, and when being heated to approximately 300 ℃ from approximately 23 ℃, volume may increase over 20%.Should be realized that, when thermal energy storage material is heated, the pressure in seal cavity may increase.Cystic structures should be enough durable, makes when thermal energy storage material expands during use, and it does not leak or otherwise breaks down.Cystic structures preferably has the heat-transfer fluid of permission and from thermal energy storage material, effectively removes the geometry of heat.The limiting examples of preferred cystic structures comprises that Soukhojak equals disclosed the U.S. Patent Application Publication No. 2009/0250189 and U.S. Provisional Patent Application submitted on January 29th, 2010 number 61/299 on October 8th, 2009, described in 565, described patent application is incorporated to herein by reference.For example, cystic structures can have the geometry that comprises one or more fluid passages, and described fluid passage is large must be enough to make cystic structures can allow fluid (for example heat-transfer fluid) to flow through fluid passage.Thermal energy storage material can be fully encapsulated in one or more seal cavities, makes when heat-transfer fluid contacts with cystic structures thermal energy storage material and fluid-phase isolation.

Determined the whole bag of tricks of the durability of advantageously improving cystic structures, described method comprises when the temperature of thermal energy storage material is about 25 ℃, the metal bottom sheet material that use comprises one or more reinforcement features (for example one or more ribs), the metal cover sheets that use comprises one or more reinforcement features (for example one or more ribs, one or more dimple, one or more chevron or its any combination), used thickness surpasses cover sheets or its any combination of bottom sheet thickness, and making the pressure in seal cavity is about 700Torr or lower vacuum.

By reducing the pressure of seal cavity at the temperature of approximately 25 ℃, also can reduce the pressure of seal cavity when thermal energy storage material is heated.Can use any applicable means by seal cavity the pressure decreased at approximately 25 ℃ of temperature to about 700Torr or lower.For example, can be at thermal energy storage material in sufficiently high connection temperature T _jwhen lower, cover sheets is connected to form seal cavity with bottom sheet, when thermal energy storage material in seal cavity is cooled, thermal energy storage Material shrinkage, and the pressure drop in seal cavity is to lower than about 700Torr.Connecting temperature can be higher than the liquidus temperature T of thermal energy storage material _{l, TESM}.Under preferable case, connect temperature T _jbe about T _{l, TESM}+ 10 ℃ or higher, be more preferably T _{l, TESM}+ 20 ℃ or higher, be even more preferably about T _{l, TESM}+ 30 ℃ or higher, be even more preferably about T _{l, TESM}+ 40 ℃ or higher, be even more preferably about T _{l, TESM}+ 50 ℃ or higher, be most preferably T _{l, TESM}+ 60 ℃ or higher.For example, T _jcan for approximately 200 ℃ or higher, preferably approximately 230 ℃ or higher, more preferably from about 250 ℃ or higher, even more preferably from about 270 ℃ or higher and most preferably from about 290 ℃ or higher.When bottom sheet is connected with cover sheets, the temperature of thermal energy storage material can for approximately 700 ℃ or lower, preferably approximately 500 ℃ or lower, more preferably from about 400 ℃ or lower.

In another example, cover sheets is connected with bottom sheet when can apply vacuum in the region to becoming seal cavity.If used, vacuum should have enough low pressure, makes after bottom sheet and cover sheets are tightly connected, and seal cavity is vacuum.For example, can exert pressure as about 700Torr or lower, about 660Torr or lower, about 600Torr or lower, about 550Torr or lower, about 500Torr or lower, about 400Torr or lower or about 300Torr or lower vacuum.Therefore, whole connection procedure can carry out in vacuum environment.Can the pressure in becoming the region of seal cavity be about 0.1Torr or higher, preferred about 1.0Torr or higher, 10Torr or when higher more preferably from about, cover sheets is connected with bottom sheet.Also can use lower pressure.Under preferable case, thermal energy storage material is under predetermined seal temperature, namely under the high temperature when bottom sheet and cover sheets are tightly connected, to after goods being cooled to approximately 25 ℃, form vacuum in seal cavity.Predetermined seal temperature can be any temperature, if at described temperature the density of thermal energy storage material lower than it density at 25 ℃.Under preferable case, predetermined seal temperature higher than the liquidus temperature of thermal energy storage material (for example than liquidus temperature high approximately 10 ℃ or more, approximately 30 ℃ or more or approximately 60 ℃ or more).Predetermined seal temperature can for approximately 50 ℃ or higher, approximately 100 ℃ or higher, approximately 150 ℃ or higher, approximately 200 ℃ or higher, approximately 250 ℃ or higher or approximately 300 ℃ or higher.Predetermined seal temperature is preferably enough low, so that thermal energy storage material is not degraded in seal process.Predetermined seal temperature can for approximately 500 ℃ or lower, approximately 400 ℃ or lower or approximately 350 ℃ or lower.

Thermal energy storage material in seal cavity is in the lower time of temperature of approximately 25 ℃, and seal cavity is preferably about 600Torr or lower, more preferably from about 500Torr or lower, even more preferably from about 400Torr or lower, most preferably from about 300Torr or lower vacuum.When thermal energy storage material is during in 25 ℃, the lower limit of seal cavity internal pressure depends on manufacturability, and is preferably about 0.1Torr or higher, more preferably from about 1Torr, 10Torr or higher most preferably from about.

By adding one or more reinforcement features to bottom sheet, cover sheets or both, can increase the durability of cystic structures.Reinforcement feature can be the stress of redistributing in bottom sheet and cover sheets, for example, while increasing (fusing by thermal expansion or described thermal energy storage material causes) with pressure in convenient seal cavity, maximum Feng meter Si stress compares with the bottom sheet and/or the cover sheets that do not have reinforcement feature and stand same pressure any parts that are lowered.Reinforcement feature can be recess or the protuberance forming in sheet material.Therefore, reinforcement feature can be the section variation of sheet material.Reinforcement feature can for example, work to reduce maximum Feng meter Si stress by redistributing stress in seal cavity (stress obtaining when the heated sealant space).Reinforcement feature can be described by its degree of depth (for example with compare the amount of section variation away from the region of described reinforcement feature), its length, its width or its any combination.Reinforcement feature preferably have about 0.1mm or more greatly, more preferably from about 0.2mm or more greatly, even more preferably from about 0.3mm or more greatly, even more preferably from about 0.4mm or more greatly, even more preferably from about 0.5mm or larger and most preferably from about 0.6mm or the larger degree of depth.Reinforcement feature preferably has the enough little degree of depth, to pile up as described herein or the effect of stacking a plurality of cystic structures is not subject to large impact.Therefore, reinforcement feature preferably has about 10mm or less, more preferably from about 5mm or less, even more preferably from about 3mm or less, most preferably from about 2mm or the less degree of depth.The limiting examples of operable reinforcement feature comprises rib, dimple, chevron etc.Reinforcement feature can comprise length-width ratio be greater than approximately 1, preferably approximately 2 or more greatly, even more preferably from about 4 or more greatly, most preferably from about 10 or larger protuberance or recess, for example rib.If used, two ribs in seal cavity region in bottom sheet or cover sheets can be parallel, vertical or acutangulate.Reinforcement feature can have the cross section of unitary circular, for example dimple.Reinforcement feature can be with the arranged in patterns repeating, and described pattern comprises a plurality of reinforcement features of alignment in one direction and a plurality of reinforcement features that align in different directions, for example chevron pattern.Reinforcement feature is preferably placed on the region of containing seal cavity of sheet material.Sheet material containing also not placing reinforcement feature in the region of seal cavity.

Reinforcement feature (for example reinforcement feature in cover sheets) can have enough sizes and quantity, make to contain thermal energy storage material and be heated to the maximum Feng meter Si stress of the cystic structures of 250 ℃, lower than except not containing reinforcement feature (for example sheet material have smooth generally surface, generally smooth or both, smooth, smooth cover sheets generally for example) outside other Feng meter Si stress of identical cystic structures all.Reinforcement feature preferably exists with enough sizes and quantity, Feng meter Si stress in the cystic structures that makes to contain thermal energy storage material at 250 ℃ with except reinforcement feature, be removed (for example sheet material have smooth generally surface, generally smooth or both) other all the Feng meter Si stress of identical cystic structures compare, reduce approximately 5% or more, more preferably from about 10% or more, even more preferably from about 15% or more, even more preferably from about 20% or more, even more preferably from about 30% or more, most preferably from about 40% or more.

Reinforcement feature (optionally together with one or more miscellaneous parts disclosed herein) can be used for reducing the maximum Feng meter Si stress in the seal cavity that contains thermal energy storage material, makes the maximum Feng meter Si stress S in 250 ℃ of temperature lower bottom part sheet materials and cover sheets _{max, 250}yield stress with metal at 250 ℃ (for example junior in the metal of cover sheets or bottom sheet and cover sheets) S _{y, 250}ratio, be preferably approximately 0.95 or lower, more preferably from about 0.90 or lower, even more preferably from about 0.85 or lower, even more preferably from about 0.80 or lower, most preferably from about 0.70 or lower.

By adding one or more ribs to bottom sheet, cover sheets or both, can increase the durability of cystic structures.Under preferable case, bottom sheet, cover sheets comprise rib structure (for example rib of sufficient amount and/or the rib of sufficient size), it provides enough rigidity to cystic structures, so that cystic structures can not be bent to, is not enough to surrender and is not otherwise deformed into be enough to surrender.

According to instruction herein, should be realized that bottom sheet can have more more rigid than cover sheets generally structure, for example, comprise the structure of one or more grooves.Under vantage, the thickness of bottom sheet can fully be reduced, and makes the rigidity of bottom sheet more closely be matched with the rigidity of cover sheets.By reducing the thickness of bottom sheet, can reduce the volume of bottom sheet and/or packaging material, can reduce the weight of bottom sheet and/or packaging material, or both.Therefore, the more high percent of cystic structures weight can be the weight of thermal energy storage material.Therefore, bottom sheet can have t _bthickness (for example average thickness), cover sheets can have about t _cthickness (for example average thickness), t wherein _cbe greater than t _b.T _c/ t _bratio be preferably approximately 1.05 or more greatly, more preferably from about 1.10 or more greatly, even more preferably from about 1.15 or more greatly, even more preferably from about 1.20 or more greatly, even more preferably from about 1.25 or more greatly, even more preferably from about 1.30 or more greatly, most preferably from about 1.35 or larger.T _cwith t _bdifference be preferably about 0.01mm or more greatly, more preferably from about 0.02mm or more greatly, even more preferably from about 0.03mm or more greatly, even more preferably from about 0.035mm or more greatly, even more preferably from about 0.04mm or more greatly, 0.05mm or larger most preferably from about.T _cwith t _bdifference be preferably about 1mm or less, more preferably from about 0.5mm or less, 0.25mm or less most preferably from about.For example, i) t _c/ t _bratio can for approximately 1.05 or larger, approximately 1.10 or larger, approximately 1.20 or larger or approximately 1.30 or larger; Ii) t _c/ t _bdifference can be about 0.01mm or larger, about 0.02mm or larger, about 0.03mm or larger or about 0.05mm or larger; Or meet simultaneously (i) and (ii) both.

Bottom sheet, cover sheets or both can have one or more volumetric expansion parts, make when thermal energy storage material expands between heating and/or melting stage, and the volume of seal cavity can reversibly increase.The example of volumetric expansion parts comprises gauffer, pleat, curling, folding, vibration etc.For example, volumetric expansion parts can comprise one, two or more curling, folding or pleat.Preferred volumetric expansion parts can have the shape (although typically not having aperture) of bellows generally or accordion.Reinforcement feature for example one or more dimples, one or more chevron or one or more rib also can play the effect of volumetric expansion parts.Should be realized that the amount that the quantity of the size of volumetric expansion parts, shape and volumetric expansion parts can expand the volume that affects seal cavity.If used, volumetric expansion parts may be enough to the volume of seal cavity to increase approximately 5% or more, preferably approximately 10% or more, more preferably from about 13% or more, most preferably from about 15% or more.Volumetric expansion parts can allow seal cavity fully to expand, for example, so that when thermal energy storage material is heated to thermal energy storage material and becomes the temperature of liquid (to approximately 200 ℃, to approximately 240 ℃ or to approximately 250 ℃) from approximately 25 ℃, the internal pressure in seal cavity changes increases about 35kPa or still less (preferred about 20kPa or still less, 10kPa or still less more preferably from about).

Other aspects of the present invention comprise the new arrangement mode that comprises a plurality of goods, the new equipment that comprises one or more goods, for the manufacture of the new method of goods and the new method of using one or more goods.By using new product can fill allotting device, described device can store a large amount of heat energy, heat energy can be delivered to fast in thermal energy storage material or from wherein transmitting out, compactness, lightweight, the low pressure drop with heat-transfer fluid or its any combination.

Cystic structures in general dimension (being thickness) is in one direction less than the dimension in other directions.The limiting examples of cystic structures, be included in the U.S. Patent Application No. 12/389 that is entitled as " heat storage devices " (Heat Storage Devices) of submitting on February 20th, 2009, the U.S. Provisional Application that is entitled as " thermal energy storage " (Thermal Energe Storage) of submitting on January 29th, 598 and 2010 number 61/299, disclosed in 565, the two is incorporated to herein by reference.

The shape of cystic structures and/or goods can determine by packaging space, and can be by moulding oddly.Goods can comprise having the cover sheets (being cover sheets) of top surface and the contrary bottom sheet with basal surface roughly.Cover sheets (for example top surface of cover sheets), bottom sheet (for example basal surface of bottom sheet) or both can some be (may be maybe) general planar (for example having generally flat surface), roughly arc or its any combination.Under preferable case, the basal surface of bottom sheet and/or bottom sheet comprises roughly arc part or roughly arc, and the top surface of goods is generally flat (for example, cover sheets is general planar), or both.In various embodiments of the present invention, generally flat cover sheets can comprise one or more reinforcement features (example is one or more ribs, dimple, chevron or other protuberances or recess as described in this article) and/or one or more volumetric expansion parts.Just as described herein, cover sheets also can replace by the second bottom sheet.Therefore, cystic structures can be defined by two identical or different bottom sheet.

Cystic structures can comprise one or more openings, for example fluid passage.For example, cystic structures can comprise one or more fluid passages, make fluid for example heat-transfer fluid can flow through goods and not contact with thermal energy storage material.Without limitation, cystic structures can comprise having the U.S. Provisional Application that is entitled as " thermal energy storage " (Thermal Energe Storage) submitted on January 29th, 2010 number 61/299, the fluid passage of the one or more features described in 565 7-12,28-43 and 54-67 section and Fig. 1,2,3,4,5,6 and 7, described application is incorporated to herein by reference.

Cover sheets and bottom sheet both comprise one or more openings.Cover sheets and bottom sheet can be aligned to and make at least one opening of cover sheets and at least one superposition of end gap of bottom sheet.Thus, cover sheets and bottom sheet can have one or more corresponding openings.Cover sheets has periphery in the most remote areas from cover sheets center.Cover sheets can also have one or more edge of opening in the region of the opening that approaches cover sheets (preferably approaching center) of cover sheets.Bottom sheet has periphery in the region away from bottom sheet center, and locates to have edge of opening approaching the opening of bottom sheet (preferably approaching center).Each cover sheets and bottom sheet can along sheet material periphery separately each other or with one or more other optional minor structures (for example outer shroud) seal attached, for form one or more seal cavities between it.Each cover sheets and bottom sheet can along sheet material edge of opening separately each other or with one or more other optional minor structures (for example, in ring) seal attached, for form one or more seal cavities between it.Under preferable case, cover sheets and bottom sheet along their peripheries separately, along at least one their corresponding edge of opening or both separately, seal each other attached.Under most preferred case, cover sheets and bottom sheet along their peripheries separately and along at least one their corresponding edge of opening separately, seal each other attached.Should be appreciated that, cover sheets and bottom sheet also can be along one or more other regions (region outside their edge) each other or attached with one or more other optional minor structures sealings, to form a plurality of seal cavities.

Cystic structures can optionally comprise one or more minor structures, and it is when sealing and form one or more seal cavities when attached with bottom sheet and cover sheets.Without limitation, if you are using, minor structure can comprise one of feature described in the U.S. Provisional Application that is entitled as " thermal energy storage " (Thermal Energe Storage) submitted on January 29th, 2010 number or its any combination, and described application is incorporated to herein by reference.For example, bottom sheet, cover sheets or both can attach to one or more rings, for example one or more interior rings, one or more outer shroud or both.If you are using, minor structure can comprise cellular or other open-celled structures, and such as described in the 83rd section of U.S. Patent Application Publication No. 2009-0250189 of disclosed Bank on the 8th etc. October in 2009, described application is incorporated to herein by reference.

The thickness of cystic structures for example, for example, is decided by the equispaced between the top surface (top surface of cover sheets) of goods and the basal surface (basal surface of bottom sheet) of goods.Goods can have enough thin geometry, so that heat can be fed to thermal energy storage material and/or remove to fast fluid from thermal energy storage material from fluid Quick.Goods can have and are less than the length of goods or the thickness of diameter.

For example, the ratio of the thickness of the length of goods or diameter and goods can for approximately 2 or larger, approximately 5 or larger, approximately 10 or larger or approximately 20 or larger.Without limitation, the ratio of the thickness of the length of goods or diameter and goods can for approximately 1,000 or less, preferably approximately 300 or less, more preferably from about 150 or less.Under preferable case, the thickness of goods is 80mm or less, more preferably from about 20mm or less, even more preferably from about 10mm or less, 8mm or less most preferably from about.The thickness of goods is preferably greater than about 0.5mm, more preferably greater than about 1mm.

The longest dimension of goods (for example length of goods or diameter), in typical case much larger than the thickness of goods, makes goods can have large volume (for example thermal energy storage material for comprising large volume) and high surface area (for example, for quick transferring heat energy) simultaneously.The longest dimension of goods is preferably greater than approximately 30, more preferably greater than about 50mm, be most preferably greater than about 100mm.The longest dimension is by applying decision, and can be in application-specific, meet thermmal storage, heat is transmitted or any length of both needs.The longest dimension of goods be typically less than about 2m (2,000mm), yet also can use the longest dimension to be greater than the goods of about 2m.

Goods can have one or more side surfaces.For example, goods can have one or more nonplanar side surfaces.Goods can have roughly arc, on-plane surface, roughly continuously or the single side surface of its any combination roughly.Under preferable case, one or more side surfaces are roughly equidistant apart from the center of goods, and goods can be placed in the container with substantial cylindrical cavity, and the diameter of described cavity is only greater than the average diameter of goods slightly.When the ratio of cavity diameter and goods average diameter is low, a large amount of cavitys are occupied by goods.For example, the ratio of the maximum gauge of goods and goods average diameter can be less than approximately 1.8, is preferably less than approximately 1.2, is more preferably less than approximately 1.1, is most preferably less than approximately 1.05.Should be realized that, the maximum gauge of goods and the ratio of average diameter are approximately 1.0 or larger (for example approximately 1.001 or larger).

Most of volume of cystic structures is the volume (being the volume of one or more seal cavities) of sealing, and makes goods can comprise relatively a large amount of thermal energy storage materials.The total measurement (volume) of one or more seal cavities of goods, in the total measurement (volume) of goods be preferably at least about 50vol.%, more preferably at least about 80vol.%, more preferably at least about 85vol.%, 90vol.% most preferably from about.The total measurement (volume) of one or more seal cavities of goods, in the total measurement (volume) of goods, is typically less than about 99.9vol.%.The residual volume not occupied by thermal energy storage material, can comprise cystic structures, void space (for example comprising one or more gases), one or more for improving structure or its any combination of the heat transfer between thermal energy storage material and cystic structures, or substantially by them, be formed completely.For improving the structure of the heat transfer between thermal energy storage material and cystic structures, comprise being formed by the material with relative high-termal conductivity (for example, with respect to thermal energy storage material), can increase any structure of the flow rate of heat from thermal energy storage material to heat-transfer fluid.For improving the preferred structure of heat flow speed, comprise fan, silk screen, enter the protuberance of seal cavity etc.

Goods are preferably easy to the goods identical with other shapes or have other goods on approximate match surface stacking.For example, treat that stacking goods can have relative surface for two, they are surfaces of approximate match, and two goods when stacking are nested together.Should be realized that, so that a kind of method that they are easy to nest together, be to select to have the rotational symmetric shape of high-order (for example the shape of arcuate surfaces is, the shape of seal cavity or both) for stacking goods.Rotational Symmetry can for example, around the axle on stacking direction (axle of the fluid passage by cystic structures).Rotational symmetric exponent number has typically been described the quantity that makes its different rotary nesting together between two surfaces to be stacked.Goods, bottom sheet (for example arcuate surfaces of bottom sheet) or both rotational symmetric exponent numbers are preferably at least 2, more preferably at least 3, more preferably at least 5, most preferably at least 7.

Goods preferably have the cystic structures that is difficult to bending.For example, cystic structures can be not containing cover sheets wherein and bottom sheet for example, at the cross section that spreads all over the major part of cross section or even contact on all length (diameter of cystic structures).There are various distinct methods to can be used for guaranteeing that cystic structures is difficult to bending, comprise and for example select the arrangement mode of capsule, so that rotational symmetric exponent number is not even number, the arrangement mode of selecting capsule makes there is not Rotational Symmetry, select to comprise two or more the arrangement mode of capsule of capsule ring (concentric ring) of rotation relative to each other, make each radial segment comprise at least one seal cavity, or its any combination.Should be realized that, can manufacture by other geometries and other means the cryptomere goods of bend resistance.For example, for the material of cystic structures, can be selected to overall stiffness, structure can comprise one or more reinforcing ribs (such as in tangential direction) etc.

All thermal energy storage materials of goods can be in single seal cavity.The thermal energy storage material of goods can be optionally between a plurality of seal cavities separately, if seal cavity is pierced or because other reasons leaks, no matter the improvement of describing in this article, only some thermal energy storage material can be removed.Therefore, the quantity of seal cavity in goods (seal cavity that for example contains thermal energy storage material) can be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more.The upper limit of seal cavity quantity depends on actual conditions, for application-specific, by the needs of applying, is decided.Yet the quantity of seal cavity is typically less than 1,000 in goods.But, should be realized that, very large goods can have 1,000 or above seal cavity.By the same token, be present in the volume fraction of the thermal energy storage material in any single sealing compartment, take the cumulative volume of thermal energy storage material in goods can be as approximately 100%, be less than approximately 55%, be less than approximately 38%, be less than approximately 29% or be less than approximately 21%.In typical case, seal cavity comprises at least 0.1vol.% of thermal energy storage material in goods.Yet should be realized that, it is substantially one or more or even completely not containing the seal cavity of thermal energy storage material that goods can comprise.

Seal cavity can be optionally to promote stacking goods of the present invention effectively and effectively transfer its energy to capsule and/or arrange from the mode that capsule spreads out of energy, as a plurality of concentric rings, comprise innermost ring (for example approaching most the ring of edge of opening) and outer shroud (for example approaching most the ring of periphery), its each contain one or more seal cavities.Seal cavity in a ring can have the pattern roughly repeating.For example, each seal cavity in ring or 2,3,4 every group or more seal cavity can have roughly the same shape and size.The quantity of the seal cavity in each ring can be identical or different.Under preferable case, outer shroud has than the more seal cavity of innermost ring, the average length of the seal cavity of outer shroud is less than the average length (wherein average length is in the measurement in the radial direction from outward opening week) of the seal cavity of innermost ring or meets both simultaneously, to reduce the volume variation between outer shroud and the seal cavity of innermost ring.

As what discussed hereinafter, goods can be placed in to container, for example there is the container of overall cylindrical cavity.Preferably, can be only bigger than the longest dimension of goods in the dimension of cavity.For example, the diameter of container cavity can only be greater than the diameter of the cystic structures of goods slightly.The diameter of cavity should be enough large, and goods can be inserted in cavity.When goods (or the group of goods heap) are placed in container, may need fluid between the periphery of goods and the inwall of container, to flow.This can realize by the relevance design of internal tank and article shape is produced and maintains fluid flow path.Can use any means that produce such fluid flow path.Therefore, goods can optionally have one or more recesses along its edge (for example, cover sheets and bottom sheet can have one or more corresponding recesses along they peripheries separately), to be formed for the mobile space of heat-transfer fluid.Optional or in addition, the cavity of container can have the surface with one or more grooves, described groove flows between article periphery and vessel surface for fluid.As another example, the diameter of goods can be enough little with respect to the inside diameter of cavity, so that fluid can flow along the whole periphery of goods.For example, goods can have one or more recesses or container can have one or more grooves, for each seal cavity of the outer shroud of seal cavity.Recess or groove can have any shape, and such as polygon, arc, wedge shape etc., as long as it has sufficient size to allow heat-transfer fluid to flow.If you are using, the smallest dimension of recess and/or groove is typically at least about 0.1mm.Should be realized that, can use two or more to produce the combination of the means of fluid flow path.For example, goods can have the one or more recesses along its periphery, and goods can have enough little diameter, and fluid when being placed in cavity can be flowed along its whole periphery.

For the goods that comprise thermal energy storage material, comprise a kind of bottom sheet, described bottom sheet is formed into and makes it comprise the one or more grooves that are suitable for receiving fluids.Described bottom sheet can be used therein thermal energy storage materials filling for one or more grooves, by the cover sheets of general planar, covers, and is then connected with cover sheets in the method for (preferably thermal energy storage material at least partly in molten condition time).Bottom sheet can optionally have one or more protuberances, make when goods with there are another surperficial goods with bottom sheet approximate match when stacking, only part is nested for two goods.Therefore, one or more protuberances can play the work of spacer in order to separate the surface of approximate match, and fluid (for example heat-transfer fluid) can be flowed between the surface of coupling.If used, protuberance preferably only covers the sub-fraction of the surface area of bottom sheet, so that one or more protuberance does not significantly disturb flowing of fluid.The height that can select protuberance for example, to limit the height (average height) of the flow path between the surface of two approximate match.

Bottom sheet can comprise in addition one or more volumetric expansion parts and/or play one or more reinforcement features of strengthening bottom sheet effect, for example one or more ribs, one or more dimple, one or more chevron or its any combination.Observe surprisingly, when the goods that contain thermal energy storage material are heated, the groove of bottom sheet, reinforcement feature, volumetric expansion parts or its any combination can reduce the maximum stress in bottom sheet.For example, when the thermal energy storage material in seal cavity is heated, the maximum stress in bottom sheet for example maximum Feng meter Si stress can be lower than for example, being made by same material (same metal) and having the maximum Feng meter Si stress with the smooth cover sheets of bottom sheet same thickness.Relatively low stress in bottom sheet, can have by use the bottom sheet of lower thickness (being for example less than the thickness of cover sheets thickness), for the amount that reduces the weight of goods and/or increase thermal energy storage material in goods offers an opportunity.

Also observe surprisingly, can, by add optional reinforcement feature for example rib, dimple or chevron to bottom sheet, further reduce bottom sheet, cover sheets or both thickness.If you are using, reinforcement feature preferably has enough sizes, shape and quantity so that the maximum Feng meter Si stress of described sheet material (for example bottom sheet or cover sheets) reduce preferably approximately 2% or above, more preferably from about 5% or above, most preferably from about 10% or more than.Reinforcement feature can comprise protuberance parts (from the outside parts of seal cavity), recess parts (entering the parts of seal cavity) or both.The depth/height of preferred reinforcement feature protuberance or recess be about 0.2mm or more greatly, more preferably from about 0.4mm or more greatly, 0.6mm or larger most preferably from about.The depth/height of preferred reinforcement feature protuberance or recess is about 5mm or less, more preferably from about 3mm or less, 1mm or less most preferably from about.

When stacking goods, they can be arranged in the cover sheets that comes from two adjacent article is contacted each other at least partly.Two cover sheets have large contact area so that they,, in good thermal communication, and/or exist very little space or interval so that wasting space not may conform with expectation between two cover sheets.Therefore, cover sheets can only include recess.Good contact between two cover sheets also can obtain by the cover sheets by surperficial approximate match.For example, the first cover sheets can have one or more recesses that the one or more protuberances with the second cover sheets match, and/or in contrast.

Bottom sheet and cover sheets is attached so that form the seal cavity that comprises thermal energy storage material.Bottom sheet and cover sheets attached for example can comprise, around the first sealing around of one or more (all) seal cavities, so that by seal cavity and any other seal cavity and/or open with the zone isolation of goods outside.Bottom sheet and cover sheets attached can comprise one or more the second sealings, for example in the situation of the first seal failure by the region of seal cavity and goods outside and/or the sealing kept apart with other seal cavities.

Without limitation, for the preferred thermal energy storage material of heat storage devices, comprise the material that can show relatively high heat density, described heat energy as sensible heat, latent heat or preferably both.Compatible with the temperature range of operation of heat storage devices under thermal energy storage material preferable case.For example, thermal energy storage material is preferably solid heat storage devices compared with under low-running-temperature, and under the maximum operating temperature of heat storage devices, be liquid (being for example entirely liquid) at least partly, not significantly degraded or decomposition under the maximum operating temperature of device, or its any combination.Thermal energy storage material is preferably being heated to maximum operating temperature approximately 1,000 hour or longer or even approximately 10,000 hours or the not significantly degraded or decompose when longer of device.

Thermal energy storage material can be the phase-change material with solid liquid phase transition temperature.The solid liquid phase transition temperature of thermal energy storage material can be liquidus temperature, fusion temperature or low consolute temperature.Solid liquid phase transition temperature is should be enough high, makes to store enough energy when thermal energy storage material is at least partly or even substantially complete during in liquid state, so that one or more heated material are heated to temperature required.Solid liquid phase transition temperature should be enough low, makes heat-transfer fluid, one or more heated material or both not be heated to its degradable temperature.Therefore, the temperature required of solid liquid phase transition temperature may be depended on object to be heated and transmit hot method.For example, in the application of using glycol/water heat-transfer fluid that the heat storing for example, is transmitted to engine (internal combustion engine), the highest solid liquid phase transition temperature can be the temperature of heat-transfer fluid degraded.As another example, can use heat-transfer fluid the heat of storage to be delivered to the electrochemical cell of battery pack, wherein heat-transfer fluid has high degradation temperature, and the highest solid liquid phase transition temperature can be degraded or the temperature that lost efficacy in other respects decides by electrochemical cell.Solid liquid phase transition temperature can higher than approximately 30 ℃, preferably higher than approximately 35 ℃, more preferably higher than approximately 40 ℃, even more preferably higher than approximately 45 ℃, most preferably higher than approximately 50 ℃.Thermal energy storage material can have lower than approximately 400 ℃, preferably lower than approximately 350 ℃, more preferably less than approximately 290 ℃, more preferably less than approximately 250 ℃, most preferably lower than the solid liquid phase transition temperature of approximately 200 ℃.Should be realized that, depend on application, solid liquid phase transition temperature can be approximately 30 ℃ to approximately 100 ℃, approximately 50 ℃ to approximately 150 ℃, approximately 100 ℃ to approximately 200 ℃, approximately 150 ℃ to approximately 250 ℃, approximately 175 ℃ to approximately 400 ℃, approximately 200 ℃ to approximately 375 ℃, approximately 225 ℃ to approximately 400 ℃ or approximately 200 ℃ to approximately 300 ℃.

For some application examples, as transportation related application, in little space, effectively the heat energy material of storage power may be desirable.Therefore, thermal energy storage material can have high heat of fusion density (being often upgraded to unit representation with megajoule), it is defined as the long-pending of heat of fusion (take megajoule every kilogram be unit representation) and density (measure at approximately 25 ℃, and kilogram to be often upgraded to unit representation).Thermal energy storage material can have be greater than about 0.1MJ/ liter, be preferably greater than about 0.2MJ/ liter, more preferably greater than about 0.4MJ/ liter, be most preferably greater than the heat of fusion density that about 0.6MJ/ rises.In typical case, thermal energy storage material has the heat of fusion density that is less than about 5MJ/ liter.Yet, also can use the thermal energy storage material with higher heat of fusion density.

For some application examples, as transportation related application, the thermal energy storage material of lightweight may be desirable.For example, thermal energy storage material can have and is less than about 5g/cm ³, be preferably less than about 4g/cm ³, be more preferably less than about 3.5g/cm ³, be most preferably less than about 3g/cm ³density (at approximately 25 ℃ measure).The lower limit of density depends on actual conditions.Thermal energy storage material can have and is greater than about 0.6g/cm ³, be preferably greater than about 1.2g/cm ³, more preferably greater than about 1.7g/cm ³density (at approximately 25 ℃ measure).

Seal cavity can contain any known thermal energy storage material of the art.The example that can be used for the thermal energy storage material in thermal energy storage material compartment is included in the material of describing in following document: Atul Sharma, V.V.Tyagi.C.R.Chen, D.Buddhi, " use thermal energy storage and the application summary of phase-change material " (Review on thermal energy stroage with phase change materials and applications), Renewable and Sustainable Energy Reviews 13 (2009) 318-345, and Belen Zalba, Jose Ma Mann, Luisa F.Cabeza, Harald Mehling, " the summary with the thermal energy storage of phase transformation: material, analysis of Heat Transfer and application " (Review on thermal energy stroage with phase change:materials, heat transfer analysis and applications), Applied Thermal Engineering 23 (2003) 251-283, the two is incorporated by reference in its entirety at this.Other examples of the applicable thermal energy storage material that can use in heat-transfer arrangement, be included in the U.S. Patent Application No. 12/389 that is entitled as " thermal energy storage material " (Thermal Energe Storage Materials) of submitting on February 20th, 2009, the thermal energy storage material of describing in the U.S. Patent Application No. 12/389,598 that is entitled as " heat storage devices " (Heat Storage Devices) of submitting on February 20th, 416 and 2009.Other examples of the preferred thermal energy storage material that can use in heat-transfer arrangement, be included in U.S. Patent Application Publication No. 2009/0211726 (being entitled as " thermal energy storage material " (Thermal Energe Storage Materials) open on August 27th, 2009) and 2009/0250189 (be entitled as " heat storage devices " (Heat Storage Devices) and disclose on October 8th, 2009) and U.S. Provisional Patent Application number 61/299, the thermal energy storage material of describing in the 54-63 section of 565 (are entitled as " thermal energy storage " (Thermal Energe Storage) and submit on January 29th, 2010).

Thermal energy storage material can comprise the mixture that shows above described solid liquid phase transition temperature, heat of fusion density or both organic materials, inorganic material or organic and inorganic material.Operable organic compound comprises that alkane and non-alkane belong to for example aliphatic acid of organic material.Operable inorganic material comprises hydrated salt and metallics.Thermal energy storage material can be that compound or the mixture (for example eutectic mixture) that solid liquid phase changes generally occurs at single temperature.Thermal energy storage material can be that compound or the mixture that solid liquid phase changes occurs at the temperature of certain limit (for example, higher than approximately 3 ℃ or higher than approximately 5 ℃ of scopes).

Without limitation, thermal energy storage material can comprise one or more inorganic salts, and it is selected from nitrate, nitrite, bromide, chloride, other halide, sulfate, sulfide, phosphate, phosphite, hydroxide, carbonyl compound, bromate, its mixture and combination thereof.

Thermal energy storage material can comprise at least one first metal-containing material, the more preferably combination (or even can substantially consist of them or consist of them) of at least one first metal-containing material and at least one the second metal-containing material.The first metal-containing material, the second metal-containing material or both can be substantially pure metal, the alloy alloy that for example comprises substantially pure metal and one or more other alloying components (for example one or more other metals), interphase, metallic compound (for example salt, oxide or other) or its any combination.A kind of method for optimizing is to utilize one or more metal-containing material as a part for metallic compound; Preferred method is to utilize the mixture of at least two kinds of metallic compounds.For example, preferred metallic compound can be selected from oxide, hydroxide, the compound that comprises nitrogen and oxygen (for example nitrate, nitrite or both), halide or its any combination.May also can use ternary, quaternary or other multicomponent mixture material systems.Thermal energy storage material herein can be the mixture that shows eutectic two or more materials.

The volume of the thermal energy storage material of one or more seal cavities of goods is enough high, makes goods can store a large amount of heat energy.The volume of thermal energy storage material comprising in goods and the ratio of the total measurement (volume) of one or more seal cavities, the volume of thermal energy storage material and the ratio of goods cumulative volume or both (volume is measured at the temperature during in liquid at the temperature of approximately 25 ℃ or thermal energy storage material), be preferably greater than approximately 0.5, more preferably greater than approximately 0.7, be most preferably greater than approximately 0.9.The volume of thermal energy storage material comprising in goods and the ratio of the total measurement (volume) of one or more seal cavities, the volume of thermal energy storage material and the ratio of goods cumulative volume or both (volume is measured at the temperature during in liquid at the temperature of approximately 25 ℃ or thermal energy storage material), typically be less than approximately 1.0, be more typically less than approximately 0.995.

Seal cavity can comprise and contains gas for example air, N ₂or the volume of inert gas such as He, Ar etc., thermal energy storage material can be expanded when heating.For example, seal cavity can have the region that does not contain thermal energy storage material at approximately 25 ℃, make thermal energy storage material be heated above after its liquidus temperature, thermal energy storage material can expand and can in cover sheets or bottom sheet, not form hole or cause one or more sheet material delaminations.At 25 ℃, for example, containing the volume (volume that contains the seal cavity of gas) of the seal cavity of the thermal energy storage material inside total measurement (volume) in seal cavity not, can be at least about 0.5%, preferably at least about 1%, most preferably at least about 1.5%.

Thermal energy storage material, seal cavity or both can be substantially free of or completely containing the material of experience evaporation or distillation when goods are used to store heat, so that greatly increase of the pressure in seal cavity.For example, thermal energy storage material, seal cavity or both can be substantially free of approximately 25 ℃ to approximately 100 ℃, preferably approximately 25 ℃ to approximately 150 ℃, more preferably from about 25 ℃ to approximately 200 ℃, most preferably from about at the temperature of 25 ℃ to approximately 300 ℃, experience the material that evaporates or distil.Therefore, thermal energy storage material, seal cavity or both can be substantially free of water.Utilizing approximately 100 ℃ or higher temperature to come in the application of heat energy storage, seal cavity is substantially free of or is even completely not moisture may be desired.If present, the water concentration in seal cavity can be about 5wt.% or lower, more preferably from about 1wt.% or lower, even more preferably from about 0.2wt.% or lower, 0.1wt.% or lower most preferably from about.

Fig. 1 is the figure that a part for the goods 2 with cystic structures is described.The a part of outer surface (basal surface) that has shown the bottom sheet 12 of goods in Fig. 1.Goods comprise a plurality of capsules 10.As shown in fig. 1, capsule 10 can be with periodic arrangement 11 location.Bottom sheet can have one or more grooves 8, be for example used in by bottom sheet and cover sheets attached before and/or during hold the groove of thermal energy storage material.Bottom sheet also comprises lip district 6.Lip district can be used for bottom sheet to attach to cover sheets.Therefore ，Chun district can be the region not covered by thermal energy storage material when attached when bottom sheet and cover sheets.

Fig. 2 A is the cross-sectional view of the exemplary cystic structures 2 that comprises one or more seal cavities 18.Fig. 2 B is single capsule, for example, has the cystic structures of a capsule 10 or have the cross-sectional view of a part of cystic structures 2 of a plurality of capsules 10.As shown in Figure 2A and 2B, capsule 10 can be seal cavity 18, and it contains thermal energy storage material 16 and optional general gap 20 or other spaces that does not contain thermal energy storage material.Goods can comprise one or more the first sealings 22, for example by the region 24 of seal cavity 18 and goods outside, the sealing kept apart with other seal cavities or both.Goods can comprise one or more the second sealings 22 ', isolating seal space in its situation that can lose efficacy in the first sealing 22.As shown in Figure 2A and 2B, can for example,, by bottom sheet 12Chun district 6 is attached to cover sheets 14 (cover sheets of general planar) around, form seal cavity 18.Bottom sheet can also comprise groove district 8.Because bottom sheet is strengthened by groove 8 ', the thickness 13 of bottom sheet can reduce the thickness 15 of cover sheets (for example with respect to).Sealing (for example first sealing 11, second sealing 22 ' or both) can by bottom sheet and cover sheets are welded, for example, by Laser Welding, fetch formation.

One or more seal cavities can be by preparing with one, two or more weld part connection metal cover sheets and metal bottom sheet material, and wherein said weld part surrounds one or more seal cavities completely.Single seal cavity can be prepared with single continuous welding portion or a plurality of weld part.A plurality of weld parts can form continuous periphery.A plurality of weld parts can be discontinuous.For example, single seal cavity can have along weld part of outer periphery with along the second weld part of interior periphery.

Fig. 3 is the schematic diagram of a part for the formed sheet 40 (for example bottom sheet 12) that can use in having the goods 2 of a plurality of seal cavities.Formed sheet can have the opening 46 (for example opening of circular) at close sheet material center.Fig. 3 has only shown approximately 1/4 of formed sheet, has therefore only shown 1/4 of opening 46.Fig. 3 has shown the basal surface 41 of formed sheet 40.Formed sheet has a plurality of grooves district 8 and a plurality of lips district 6.Groove district preferably provides the groove 55 that can hold thermal energy storage material.Groove district 8 can be arranged in a plurality of grooved rings 50,50 ', 50 ".As illustrated, formed sheet can have interior grooved ring 50 and outermost grooved ring 50 '.Formed sheet also can have one or more other grooved rings 50 between interior and outermost grooved ring 50,50 ' ".As shown in Figure 3, the some or all of groove in the some or all of groove in ring or even different rings, can have approximately identical shape, approximately identical volume, substantially congruence or its any combination.Should be realized that, the quantity of interior grooved ring middle slot can be greater than, be less than or equal to the quantity of outermost grooved ring middle slot.Under preferable case, the quantity of the interior grooved ring middle slot of formed sheet 40 is less than the quantity of outermost grooved ring middle slot, as shown in Figure 6.Some or preferred all grooves district 8 have around Chun district, groove district 6.Therefore ，Cao district 8 can be distinguished and separate with other grooves by lip district 6.Formed sheet 40 can have outer periphery 45, interior periphery 47 or both.As shown in Figure 3, formed sheet externally has one or more recesses 51 near periphery 45.One or more recesses can be used for along the flow channel of outer periphery 45 or flow path.Under preferable case, the outer periphery of the basal surface of formed sheet 40 has the shape of circular (except optional one or more recesses 51).As shown in Figure 3, outer periphery 45, interior periphery 47 and preferably both, can Shi Chun district 6.

Fig. 4 A shows a part for the cover sheets 14 with chevron 30.Dimension in Fig. 4 A (for example x, y, z or its any combination) can YimmWei unit.Chevron 30 can have about 3mm or above periodicity (in one or more directions), about 50mm or following periodicity or both.The periodicity of chevron can be enough little, makes the part of cover sheets on single seal cavity have a plurality of chevrons 30.For example, the quantity of the chevron 30 on the region of cover sheets 14 on single seal cavity can be approximately 2 or more, approximately 5 or more, approximately 10 or more, approximately 20 or more or approximately 30 or more.Chevron 30 can have the periodicity of about 5mm.Chevron 30 can have about 0.2mm or the above degree of depth, about 4mm or the following degree of depth or both.For example, chevron 30 can have the degree of depth of about 1mm.Should be realized that, also can use the chevron with higher or lower periodicity and/or the greater or lesser degree of depth.Dimension in Fig. 4 A (for example x, y, z or its any combination) can be taked identical or different any arbitrary unit, or can YimmWei unit.Chevron can the section of cover sheets in covering seal cavity in, away from the region of the cover sheets of seal cavity or both.Should be realized that, chevron can be used in bottom sheet, cover sheets or both.

Fig. 4 B is the schematic diagram with the exemplary capsule 10 of the cover sheets 14 that comprises dimple 32.Fig. 4 C is the top view of the part of cover sheets 14 on the capsule shown in single capsule, for example Fig. 4 B.As shown in Fig. 4 Ba and 4C, cover sheets 14 can comprise the dimple 33 of one or more dimple 32, particularly one or more recesses.Dimple 32 can be taked any arrangement mode.For example, dimple can have brick wall pattern, makes the adjacent lines displacement of dimple.Dimple preferably has about 1mm or above, more preferably from about 2mm or above, most preferably from about 3mm or above periodicity (periodicity).The periodicity of dimple is preferably about 30mm or following, more preferably from about 15mm or following, 10mm or following most preferably from about.The periodicity of dimple can be enough little, makes the part of cover sheets on single seal cavity have a plurality of dimples 32.For example, the quantity of the dimple 32 on the region of cover sheets 14 on single seal cavity can be approximately 2 or more, approximately 5 or more, approximately 10 or more, approximately 20 or more or approximately 30 or more.Dimple preferably have about 0.1mm or more greatly, more preferably from about 0.2mm or more greatly, even more preferably from about 0.3mm or more greatly, even more preferably from about 0.5mm or more greatly, most preferably from about 0.5mm or the larger degree of depth.Dimple preferably has about 3mm or less, more preferably from about 2mm or less, most preferably from about 1mm or the less degree of depth.Should be realized that, also can use the dimple with higher or lower periodicity and/or the greater or lesser degree of depth.In the section of covering seal cavity that dimple 32 can be in cover sheets, cover sheets away from the region of seal cavity in or both.Should be realized that, dimple can be used in bottom sheet, cover sheets or both.

Fig. 4 D shows the schematic diagram of a part for the sheet material (for example cover sheets 14) that comprises reinforcement feature.Reinforcement feature 34 can be with overall random arranged in patterns.As shown in Fig. 4 D, reinforcement feature 34 can have difformity, different size or both.The periodicity of reinforcement feature can be enough little, makes the part of cover sheets 14 on single seal cavity have a plurality of reinforcement features 34.For example, the quantity of the reinforcement feature 34 on the region of cover sheets 14 on single seal cavity can be approximately 2 or more, approximately 5 or more, approximately 10 or more, approximately 20 or more or approximately 30 or more.

Fig. 5 A, 5B and 5C shown under different temperatures and at the seal cavity 18 ', 18 of different sealing temperature lower seal " ' in

pressure

36,36 ', 36 ".As shown in Figure 5 A, under seal temperature, seal cavity 18 ', 18 " internal pressure 36 and external pressure 38 can be roughly the same.As shown in Figure 5 B, when seal cavity 18 ' seals at low temperatures and goods 2 are heated to higher temperature, the internal pressure 36 ' of seal cavity 18 ' can be higher than external pressure 38.As shown in Figure 5 B, when described temperature is during higher than seal temperature, in cover sheets 14, may there is the clean outside power 35 being caused by pressure differential.Fig. 5 C has shown when at high temperature sealing while then reducing temperature, seal cavity 18 " internal pressure 36 " can be lower than external pressure 38.As shown in Figure 5 B, when described temperature is during lower than seal temperature, in cover sheets 14, may there is the clean inside power 35 being caused by pressure differential.

Fig. 6 A, 6B and 6C show the illustrative examples of the sheet material (for example cover sheets) that comprises rib structure 39, and described rib structure comprises protuberance and recess.Fig. 6 A is the surface topography map for the region of the sheet material of single capsule.Fig. 6 B is the photo of part of sheet material that comprises a plurality of features of Fig. 6 A.Fig. 6 C has shown when the seal cavity that comprises sheet material is heated, the impact of design feature on the power on sheet material.As shown in Figure 6, rib can be confined to top-sheet in the region of seal cavity.For example, in cover sheets and the attached region of bottom sheet, cover sheets can have the rib of not conforming to or other reinforcement features Chun district.

Fig. 7 A and 7B show the sheet material 60 (for example bottom sheet 12) that comprises volumetric expansion parts 62, and while making the thermal energy storage material expansion in seal cavity, the volume of described seal cavity increases, and when thermal energy storage Material shrinkage, reduces volume.Fig. 8 A is one section of schematic diagram with the bottom sheet 12 of volumetric expansion parts 62.As shown in Figure 7A, volumetric expansion parts 62 can comprise one or more gauffers, for example one or more curling 64.Volumetric expansion parts can comprise bellows.Fig. 7 A shows the volumetric expansion parts 62 in bottom sheet 12.Yet, should be realized that, bottom sheet 12, cover sheets 14 or both can comprise one or more volumetric expansion parts 62.Volumetric expansion parts can be by making sheet material reversibly be contracted in seal cavity and work.Fig. 7 B is the exemplary cross section of a part that comprises the capsule 10 of sheet material 60, and described capsule has volumetric expansion parts 62, cover sheets 14 and thermal energy storage material 16.Thermal energy storage material 16 can be in seal cavity 18, and it is by the first sealing 22 and preferably the second sealing 22 ' sealing.

Fig. 8 shown when capsule 10 is heated to approximately 250 ℃, the exemplary relation that the prospective peak value Feng meter Si stress in cover sheets changes with the thickness of cover sheets 15.Fig. 8 has also shown the yield stress of the metal using in forming cover sheets.Under low thickness, peak value Feng meter Si stress is higher than the yield stress of metal, and cover sheets may be surrendered or ftracture.Under higher caliper, peak value Feng meter Si stress is lower than the yield stress of metal, and cover sheets is unyielding or damage.Fig. 9 has shown the cover sheets and the cover sheets with the rib structure shown in Fig. 6 for general planar, when capsule being heated to approximately 250 ℃, the exemplary relation that the prospective peak value Feng meter Si stress in cover sheets changes with the thickness of cover sheets 15.When using rib structure, can reduce and prevent that cover sheets from surrendering required cover sheets thickness.Therefore, the rib structure of Fig. 6 can allow goods and heat storage devices lightweight, contain greater amount thermal energy storage material or both.

Figure 10 has shown for the cover sheets of general planar and has had the chevron structure of the rib structure shown in Fig. 6, Fig. 4 A and the cover sheets of the dimple pattern of Fig. 4 B, when capsule being heated to approximately 250 ℃, the exemplary relation that the prospective peak value Feng meter Si stress in cover sheets changes with the thickness of cover sheets.When using different reinforcement structures, can reduce and prevent that cover sheets from surrendering required cover sheets thickness.Therefore, Fig. 4 A, 4B and 6 structure can allow goods and heat storage devices lightweight, contain greater amount thermal energy storage material or both.

Figure 11 shows and can have one or more reinforcement features, a part for the instrument 61 for example for example, using in the preparation of the sheet material of one or more ribs (cover sheets 14).Such instrument can be used in moulding process.Should be realized that, moulding process can be continuous process or batch process.

The goods that contain thermal energy storage material goods that preferably can be identical with other or for example, with second goods on surface (bottom sheet of approximate match) with approximate match stacking.Goods can be stacked in axial layer, at adjacent shaft to thering is interval between layer so that heat-transfer fluid can axially between layer, flow.Axially layer generally contains one, two or more goods.Axially layer (for example each axial layer) preferably contains one or two goods.For example, axially layer can have two goods that for example contact on bottom surface or coverage rate on surface, and fluid generally can not be flowed between two goods.Therefore, some goods (for example each goods except the goods of group heap end) can have the first surface (for example bottom surface) generally contacting completely with the surface of the first adjacent article, fluid can not be flowed along first surface, and (for example there is relative surface with the second adjacent article, it is the surface with second surface approximate match) second surface that separates, make fluid can be along some, great majority or even all second surfaces flow.Two adjacent shafts can be caused by any isolating means known in the art to the isolation between layer.For example, preferred isolating means comprises one or more protuberances at least one product surface, the isolated material between two-layer, the capillary structure between two-layer, or its any combination.Under preferable case, the second surface of goods has roughly arc shape, and goods are nested with the second adjacent article part.The preferred constant in interval between the nested goods of two parts (except protuberance or cause other spacers that adjacent article separates).Should be realized that, the stacking of goods can comprise axial rotary layer (for example rotating goods) or otherwise it be arranged so that axially layer with adjacent shaft at least part of nested step of layer.Fluid is generally taked radial direction at two adjacent shafts to flowing between two apparent surfaces of layer, and can be described to roughly Radial Flow.The every pair of axial layer being spaced all will have radial flow path.Goods group heap typically has a plurality of radial flow path (for example 2,3 or more).Two or more (for example each) radial flow path can have identical length of flow, identical thickness, identical shape of cross section or its any combination.For example, two or more (for example all) radial flow path can be identical.Should be realized that, if opening (being fluid passage) is positioned at article center, radial flow path can be roughly symmetrical, no matter flow direction how.

When stacking (for example, in the group heap that contains 3,4 or more goods), goods preferably have at least one opening separately, it is corresponding to the opening from each other goods (may except the goods at group heap end), a part of fluid can be flowed and between adjacent article, do not flow (not overall radially flow) by being inserted in the respective openings of the goods between first goods and last goods, and first goods from group heap flow to last goods in group heap.By flowing of opening, generally take axial direction, and can be described to flowing of overall axial.

As mentioned above, goods group heap can define central axial flow path (axis for example forming by the opening by goods) and roughly vertical with central axial flow path one or more radial flow path.

Goods group heap is tightly packed (for example, except radial flow path) generally, makes goods group heap compactness and contains a large amount of thermal energy storage materials.Therefore, radial flow path generally has little height (in the direction between adjacent article), for example average height.The height of radial flow path is preferably less than about 15mm, is more preferably less than about 5mm, is more preferably less than about 2mm, is more preferably less than about 1mm, is most preferably less than about 0.5mm.The height of radial flow path is enough large in typical case, so that fluid can flow through path.In typical case, radial flow path height (for example average height) is greater than about 0.001mm (being for example greater than about 0.01mm).

Figure 12 has shown one aspect of the present invention, and it comprises a plurality of goods 2, and each goods has for comprising one or more seal cavities 18 of thermal energy storage material 16, and described goods are arranged and form goods group heap 70.Goods 2 can comprise the formed sheet with roughly arc surface 41, and for example bottom sheet 12.The surface 41 of goods can with the surperficial approximate match of the second goods.Goods can be aligned to adjacent article is partly nested together.Goods shown in Figure 12 have the interior ring of 9 roughly the same capsules and the outer shroud of 17 roughly the same capsules.Therefore only the Rotational Symmetry exponent number of the goods shown in Figure 12 is 1, and in a position, two goods of facing are can part nested.Stacking for the ease of goods, each goods can have one or more positioning elements.Should be realized that, can use the goods with higher symmetrical exponent number.For example, goods can have single capsule ring (or even single capsule), or goods can have the first capsule ring, and it for example has, with respect to the capsule of each capsule integral multiple of the second capsule ring (1,2,3 times or more times).As shown in Figure 12, goods 2 can have the cross section (for example, in the direction vertical with stacking direction) of circular.The periphery of each goods can have a plurality of recesses 51, and it is large must be enough to allow fluid to flow.Goods 2 can have seal cavity 74, and it is arranged in one or more concentric rings of seal cavity.Each goods 2 can have fluid passage 46.Fluid passage 46 can be roughly near the center of goods 2, make for example, to form when goods stacking (stacking with axial direction) axial flow path 84.Axial flow path 84 preferably includes the fluid passage 46 of each goods 2.

Figure 13 shows the goods 2 of the capsule 10 that comprises odd number.Goods can have odd number rotational symmetry, and it can not be easily out of shape around diameter.Goods 2 can have the cross section of circular, in article center, have one or more openings 46.Opening 46 can be circular.As shown in Figure 13, one or more or even each capsule or seal cavity can have the first sealing 22 that the external isolation of seal cavity and goods is opened.Goods can also have one or more the second sealings 22 '.The second sealing can comprise near the sealing of the interior periphery 47 (being open circumferential) of goods, near the sealing of the outer periphery 45 of goods or both.The second sealing 22 ' was enough to prevent that thermal energy storage material 16 from leaking from seal cavity 18 when the first sealing 22 is lost efficacy.

Goods described herein (for example goods group heap) can be used in heat storage devices.Heat storage devices can comprise container or other shells, and it has one or more for making heat-transfer fluid enter the hole of container and one or more for making heat-transfer fluid leave the hole of container.Heat storage devices has one or more heat-transfer fluid compartments.Under preferable case, heat storage devices comprises single heat-transfer fluid compartment.Heat-transfer fluid compartment can comprise the connected space that heat-transfer fluid can flow therein by the container between entrance and exit, or substantially it, consists of.Container is preferably heat insulation at least partly, to can reduce or minimize the heat loss from container to environment.

Heat storage devices can be designed to make it to contain high concentration thermal energy storage material, so that it can be between heat-transfer fluid and thermal energy storage material fast and/or Transmit evenly heat energy, so that it is compact generally, so that its heat accumulation for a long time, or its any combination.

The internal tank of heat storage devices can have any shape that can hold goods group heap.Under preferable case, the interior shape of container makes goods group heap occupy most of internal capacity of container.The ratio of the cumulative volume of the thermal energy storage material comprising in the seal cavity of products in containers (for example at approximately 25 ℃ measure) and total internal capacity (for example, at the temperature of approximately 25 ℃) of container, can be greater than approximately 0.3, is preferably greater than approximately 0.5, more preferably greater than approximately 0.6, more preferably greater than approximately 0.7, be most preferably greater than approximately 0.8.The upper limit of the volume of thermal energy storage material in container is the space requirement contacting with goods for the heat-transfer fluid of transferring heat energy.The ratio of total internal capacity (for example, at the temperature of approximately 25 ℃) of the cumulative volume of the thermal energy storage material comprising in the seal cavity of products in containers (for example measuring at approximately 25 ℃) and container, can be less than approximately 0.99, preferably be less than approximately 0.95.

Heat storage devices has for mobile heat-transfer fluid compartment, and it can comprise heat-transfer fluid when heat-transfer fluid circulates by device.Heat-transfer fluid compartment preferably with for example, for heat transmission being flow to one or more holes (one or more entrances) of heat-transfer fluid compartment is connected.Heat-transfer fluid compartment preferably for example, is connected with the one or more holes (one or more outlets) for heat-transfer fluid compartment that heat transmission is flowed.Heat-transfer fluid compartment can be at least part of space being limited by the wall of one or more heat-transfer fluid compartments, the space being limited by one or more goods at least partly, at least part of space being limited by shell or the container of heat storage devices, or its any combination.

Heat-transfer fluid compartment defines heat-transfer fluid by the flow path of heat storage devices.Heat-transfer fluid compartment comprises the roughly axial flow path of the opening piled by goods group.Heat-transfer fluid compartment comprises the roughly flow path radially between two adjacent article.Should be realized that, Radial Flow can be the inwardly mobile of circumferential openings from goods, or flows from the outside of outward opening week of goods.Heat-transfer fluid compartment is included in has the flow path of axial component (with optional tangential component) generally between article periphery and chamber wall.Under preferable case, the radial flow path of merging has relatively high fluid resistance.For example, the fluid resistance that the radial flow path of merging has is greater than (more preferably greatly at least 2 times) central axial flow path, outside axial flow path or both fluid resistances.

Heat-transfer fluid compartment preferably has enough thermal communications with the seal cavity that contains thermal energy storage material, makes it can remove heat or provides heat to heat energy storage material.Heat-transfer fluid compartment is preferably communicated with one or more (or more preferably all) seal cavity direct heat.It can be that seal cavity and heat-transfer fluid compartment do not contain the path of any beeline between the part of low thermal conductivity material that direct heat is communicated with.Low thermal conductivity material comprises that thermal conductivity is less than about 100W/ (mK), is preferably less than about 10W/ (mK), is more preferably less than the material of about 3W/ (mK).For example, heat-transfer fluid or heat-transfer fluid compartment can contact with the wall of one or more (or preferably all) seal cavity, or for example, separate with the material that seal cavity is had high thermal conductivity (be greater than about 5W/ (mK), be greater than about 12W/ (mK) or be greater than about 110W/ (mK)) substantially or completely.

Heat-transfer fluid compartment is preferably communicated with one or more (or more preferably all) the seal cavity direct heat in heat storage devices.It can be that thermal energy storage compartment and heat-transfer fluid compartment do not contain the path of any beeline between the part of low thermal conductivity material that direct heat is communicated with.For example, heat-transfer fluid or heat-transfer fluid compartment can for example, contact with the wall (bottom sheet or cover sheets) of one or more (or preferably all) seal cavity, or for example, separate with the material that seal cavity is had high thermal conductivity (be greater than about 5W/ (mK), be greater than about 12W/ (mK) or be greater than about 110W/ (mK)) substantially or completely.Should be realized that, the very thin layer of low thermal conductivity material (be for example less than about 0.1mm, be preferably less than about 0.01mm, be more preferably less than about 0.001mm) can be between heat-transfer fluid compartment and thermal energy storage material compartment, and significantly impact conduct heat.

Can select the size and dimension of seal cavity and/or goods, to maximize heat to being contained in the phase-change material transmission in capsule and spreading out of from phase-change material.The average thickness of goods can be relatively short, makes the heat can the quick dissipation from the center of seal cavity.Goods, seal cavity or both average thickness can be less than about 100mm, are preferably less than about 30mm, are more preferably less than about 10mm, are more preferably less than about 5mm, are most preferably less than about 3mm.Goods, seal cavity or both average thickness can be greater than about 0.1mm, be preferably greater than about 0.5mm, more preferably greater than about 0.8mm, be most preferably greater than 1.0mm.

Goods preferably have relatively high surface-to-volume ratio, make relative high with the contact area of heat-transfer fluid.For example, goods can have the surface contacting maximizing with heat-transfer fluid compartment, and goods can have the geometry of the heat transmission maximizing between capsule and heat-transfer fluid compartment, or have both simultaneously.The ratio of the cumulative volume of thermal energy storage material in the total surface area at the interface in heat storage devices between heat-transfer fluid compartment and goods and heat storage devices, can be greater than about 0.02mm ^-1, be preferably greater than about 0.05mm ^-1, more preferably greater than about 0.1mm ^-1, even more preferably greater than about 0.2mm ^-1, be most preferably greater than about 0.3mm ^-1.

Heat storage devices has for comprising the container of goods group heap.Goods group heap can be included in one or more cavitys of container.The limiting examples of operable container, be included in U.S. Patent Application Publication No. 2009-0211726 (on August 27th, 2009 is open), container described in PCT application number PCT/US09/67823 (submission on December 14th, 2009) and U.S. Provisional Application number 61/299,565 (January 29 in 2010 submits to).Preferred container for example has, for making heat-transfer fluid flow into one or more apertures (one or more entrances) of container cavity and for example, for making heat-transfer fluid flow out one or more apertures (one or more outlets) of container cavity.Entrance and exit can for example, in the same side of heat storage devices or not on homonymy (opposition side).Except aperture, container preferably fluid sealed or that be configured to make flow through container does not leak out container, makes the fluid that flows through container can have the pressure higher than environmental pressure, or both.

Heat storage devices can be used for the long-time store heat of requirement, for example, in overall cold environment (temperature is lower than approximately 0 ℃ or even lower than the environment of approximately-30 ℃) in store heat or both application.Under preferable case, the heat being stored in heat storage devices is slowly lost to environment.Therefore preferably use in the present invention some form of thermal insulation.System heat insulation better, the storage time is longer.

Can utilize any known form of thermal insulation of the rate of heat dispation that reduces heat storage devices.For example, can use at U.S. Patent number 6,889, disclosed any form of thermal insulation in 751, described patent is incorporated by reference in its entirety at this.Heat storage devices is preferably (heat) isolated container, so that it is isolated on one or more surfaces.Under preferable case, the some or all of surfaces that are exposed to environment or outside will have the insulator of adjacency.Heat-barrier material can play a role by reducing heat loss through convection, minimizing heat loss through radiation, minimizing heat loss through conduction or any combination.Under preferable case, heat insulation insulator material or the structure can preferably by using with relative low-heat conduction obtains.Heat insulation can acquisition by the gap between the wall separating with relative.Gap can by gaseous medium for example air space occupy, or may can be even the space of finding time (for example, by using Dewar type container), there is material or the structure of low heat conductivity, the material with low heat emission or structure, the material with low convection current or structure or its any combination.Without limitation, heat insulationly can comprise ceramic insulation (for example quartz or glass heat-proof), polymer heat insulation or its any combination.Heat insulationly can take fibers form, form of foam, density layer, coating or its any combination.The heat insulation form that can take to work out material, woven materials, non-woven material or its combination.Heat transfer unit (HTU) can come with Dewar type container heat insulation, is more specifically to comprise being configured to limit the roughly relative wall of internal reservoir cavity and the container of the wall cavity between relative wall, and its mesospore cavity is pumped down to lower than atmospheric pressure.Wall can further utilize reflective surface will coating (for example minute surface) to minimize heat loss through radiation.

Under preferable case, at heat storage devices and/or heat storage system, provide vacuum heat-insulation around.More preferably in situation, provide disclosed vacuum heat-insulation in the U.S. Patent number 6,889,751 being incorporated by reference in its entirety at this.

Heat storage devices can optionally comprise one or more compactors for goods group heap, so that the interval generally between sustaining layer.Compactor can be any instrument that can exert pressure to goods group heap.Pressure should be enough high, makes two goods relative to each other not rotate, relative to each other not move axially, or both.Pressure can be enough low, makes goods not permanent deformation, cracking or both occur simultaneously.Preferred compactor is the variation between solid phase and liquid phase or both and become by the variation that allows the thickness of goods along with thermal energy storage material temperature, thermal energy storage material.For example, one or more compactors can comprise one or more springs on goods group heap, the one or more springs under goods group heap or both.Without limitation, for example, in the time of can utilizing compactor for example spring reduce or minimizes thermal energy storage material and be heated, experience phase transformation (solid liquid phase transformation) or both, the variation of the radial flow path thickness between two adjacent article.

Heat storage devices can have a plurality of flow paths, the flowing by device for heat-transfer fluid.Each flow path can comprise at least one Radial Flow between two adjacent article.Under preferable case, two or more (for example each) flow paths by heat storage devices have similar total length, similar total fluid resistance or both.Without limitation, heat storage devices can comprise the one or more seals for heat-transfer fluid, one or more plate, one or more connector or one or more flow path, described in U.S. Patent Application Publication No. 2009-0211726 (announcement on August 27th, 2009), PCT application number PCT/US09/67823 (submission on December 14th, 2009) and U.S. Provisional Application number 61/299,565 (on January 29th, 2010).

The cystic structures that contains thermal energy storage material and goods can be with provide any method of sealing to form for thermal energy storage material.Nonrestrictive, method can be utilized one of the following or any combination: cut out or go out the opening (for example hole) by cover sheets, for example cut out or go out, for example, by the opening (hole) of bottom sheet (fine sheet for example paillon foil), for example, to bottom sheet moulding (thermoforming, punching press, impression or other modes of texturing) to define the pattern that comprises at least one depression or groove region in sheet material, bottom sheet moulding is comprised to the pattern in one or more lips district and one or more grooves district with definition in sheet material, in bottom sheet, cut out or go out periphery (for example periphery of circular), in cover sheets, cut out or go out periphery (for example periphery of circular), for example, with thermal energy storage material filling slot (groove forming from bottom sheet), by cover sheets, cover groove (groove of for example filling), cover sheets is sealed to attached (for example, to bottom sheet) to form the one or more seal cavities that contain thermal energy storage material, bottom sheet is attached along periphery sealing, bottom sheet is attached along edge of opening sealing, cover sheets is sealed to attached (for example arriving bottom sheet) along edge of opening, or cover sheets is sealed to attached (for example arriving bottom sheet) along periphery.The method that forms goods preferably includes the step of bottom sheet punching press, impression or thermoforming.The method of formation goods can be utilized one or more method steps of the generation capsule described in the U.S. Patent Application No. 12/389,598 that is entitled as " heat storage devices " (Heat Storage Devices) of submitting on February 20th, 2009.The method that is used to form goods optionally comprises one of following method or any combination: by bottom sheet sealing be attached to one or more minor structures for example in ring, outer shroud or both; By cover sheets sealing be attached to one or more minor structures for example in ring, outer shroud or both; Or along the periphery of bottom sheet and/or cover sheets cut out, punching press or go out one or more recesses.Figure 15 is the photo that can be used for the exemplary tool of embossed web material (for example bottom sheet).Figure 15 shows the sheet material 5 that was placed in instrument 61 before sheet material 5 is shaped to bottom sheet 12.

For the preparation of cover sheets, bottom sheet or both methods, can comprise one or more steps that sheet material is impressed or is otherwise shaped, so that sheet material comprises one or more reinforcement features for example one or more dimples, one or more rib, one or more chevron or its any combination.

The method of preparing goods can comprise the step of filling bottom sheet with thermal energy storage material.Can to bottom sheet, fill during in solid state or molten condition at thermal energy storage material.Under preferable case, at thermal energy storage material, bottom sheet is filled during in molten condition.Therefore, method can comprise the step of heating and/or melting heat energy storage material.

The method of preparing goods can comprise and top-sheet is connected to form the step of one or more seal cavities with bottom sheet.Connection Step can comprise the step that forms the first sealing.Under preferable case, Connection Step comprises the step that forms the first sealing and the step that forms the second sealing.Connection Step preferably carries out during in molten condition at thermal energy storage material.For example, Connection Step can carry out at thermal energy storage material at approximately 100 ℃ or higher, approximately 150 ℃ or higher, approximately 200 ℃ or higher, approximately 250 ℃ or higher or approximately 300 ℃ or higher temperature.

The method of preparing goods can comprise the step that bottom sheet is partly connected with cover sheets, with form when bottom sheet and cover sheets are not approximate horizontal orientation can receiving fluids part seal cavity.Space between bottom sheet and cover sheets can be filled by proceeding to as follows small part: nozzle one end is inserted in space to be filled, and thermal energy storage material (preferably under molten condition) pumping is passed through to nozzle entering part seal cavity.Therefore,, when bottom sheet is roughly vertical, the space between bottom sheet and cover sheets can be filled at least partly, can fill the sheet material in the groove in bottom sheet simultaneously.Should be realized that, the method for such use thermal energy storage material packing space can produce the thermal energy storage material of higher volume.For example, the percentage by volume that seal cavity is occupied by air or other gas can for approximately 8% or lower, approximately 6% or lower, approximately 5% or lower, approximately 4% or lower, approximately 3% or lower, approximately 2% or lower or approximately 1% or lower.This method for packing space also can be for filling two spaces between bottom sheet.Therefore, cover sheets can be the second bottom sheet.With after thermal energy storage material packing space, can form remaining the first sealing so that packing space becomes seal cavity.For the second sealing, if existed, at least a portion the second sealing (for example, in inserting the region of nozzle) is until the just formation after being inserted in space of thermal energy storage material.The goods with a plurality of seal cavities can be by comprising that the method for one or more following steps fills: by forming a part the first sealing, come part to seal one or more spaces (for example by bottom sheet is connected with cover sheets or by two bottom sheet are connected), thermal energy storage material is inserted to described one or more spaces, form remaining the first sealing (for example to make space sealed), rotate goods to be filled, thermal energy storage material is inserted in the one or more other space with a part the first sealing, and form one or more other spaces remaining first sealing.

Figure 16 shows the example of goods 2, and described goods have and are filled with one or more (for example 4) capsules 10 of thermal energy storage material and one or more spaces to be filled (for example the 5th space).Space to be filled can have part the first sealing 74.Space to be filled can optionally comprise part the second sealing 75.Space to be filled preferably has fill area 76, and it does not have the first sealing 22 completely and does not have the second sealing 22 ' completely.Seal cavity can be filled with the nozzle 77 that inserts or be otherwise placed in fill area 76.Should be realized that, can be before forming section first sealing 74, during or afterwards nozzle is placed in to fill area.As shown in Figure 16, nozzle 77 can be inserted into the top in space to be filled, make thermal energy storage material 16 not leak out fill area 76.After in thermal energy storage material 16 is inserted into space to be filled, method can comprise following one or more step: remove nozzle (preferably before rotating goods), form remaining the first sealing (preferably before rotating goods), or form the second sealing or remaining the second sealing.Therefore, goods can be prepared with carrying out following machine: 1) forming section the first sealing (for example, by two sheet materials are carried out to laser weld) between two and half sheet materials, 2) thermal energy storage material (for example, under molten condition) is injected to two spaces between sheet material, 3) complete the first sealing.If expect a plurality of seal cavities, method can comprise rotates sheet material so that can fill one or more steps in another space between sheet material.

The sheet material that is applicable to seal thermal energy storage material comprises durable, corrosion-resistant or both any foil material (for example metal forming), makes sheet material can comprise thermal energy storage material and preferably not leak.Metal sheet may surpass 1 year, plays a role in preferably surpassing the vehicle environmental of repeated thermal cycles of 5 years having.In addition, metal sheet can have the outer surface of inertia substantially, and it is in operation and contacts with thermal energy storage material.The outer surface of the metal sheet contacting with thermal energy storage material should be included in while contacting with thermal energy storage material significantly do not react with it, corrosion or both one or more materials, or substantially by described material, formed.Without limitation, operable illustrative metal sheet material comprises having at least metal sheet of one deck brass, copper, aluminium, nickel-ferro alloy, bronze, titanium, stainless steel etc.Sheet material can be totally noble metal, or it can be the sheet material that comprises and have oxide skin(coating) the metal of (for example native oxide layer or the oxide skin(coating) that can form from the teeth outwards).A kind of illustrative metal sheet material be comprise aluminium or aluminium-containing alloy (for example contain be greater than 50wt.% aluminium, be preferably greater than the aluminium alloy of the aluminium of 90wt.%) aluminium foil of layer.Another kind of illustrative metal sheet material is stainless steel.Preferred stainless steel comprises austenitic stainless steel, ferritic stainless steel or martensitic stain less steel.Without limitation, stainless steel can comprise concentration be greater than about 10wt.%, be preferably greater than about 13wt.%, more preferably greater than about 15wt.%, be most preferably greater than the chromium of about 17wt.%.Stainless steel can comprise concentration and be less than about 0.30wt.%, is preferably less than about 0.15wt.%, is more preferably less than about 0.12wt.%, is most preferably less than the carbon of about 0.10wt.%.The stainless steel 304 (SAE title) that for example contains 19wt.% chromium and about 0.08wt.% carbon.Preferred stainless steel also comprises containing molybdenum stainless steel 316 (SAE titles) for example.Metal sheet can have the coating any known in the art that possibility reduces or eliminate the corrosion of metal sheet.

Metal sheet has sufficiently high thickness, to do not form hole or crack between the operating period when die pressing, when filling capsule with thermal energy storage material, at capsule or during its any combination.For application examples, as transportation, the preferred relative thin of metal sheet, is not greatly increased the weight of heat storage devices by metal sheet.The thickness of metal sheet can be greater than approximately 10 μ m, is preferably greater than approximately 20 μ m, more preferably greater than approximately 50 μ m.Metal forming can have be less than about 3mm, be preferably less than 1mm, the be more preferably less than 0.5mm thickness of (being for example less than about 0.25mm).

Figure 14 shows has a plurality of goods 2 " and 2 " ' the cross section of exemplary hot storage device 80, described in each, goods have the thermal energy storage material 16 being encapsulated in a plurality of seal cavities 18.Goods are arranged in heat-insulated container 82, and it can have substantial cylindrical shape.Device comprises having the first adjacent article 2 " ' (a) He the second adjacent article 2 " ' goods 2 (b) ".Goods 2 " and the first adjacent article 2 " ' (a) can be arranged in the top surface (being outer surface) of their corresponding smooth cover sheets is roughly contacted.Goods 2 " and the second adjacent article 2 " ' (b) can there is the surface (for example the outer surface of their corresponding bottom sheet can be the surface of approximate match) of approximate match, and can be aligned to they are partly nested together.Spacer (not shown) can be used for keeping goods 2 " and its second adjacent article 2 " ' distance between (b), make heat-transfer fluid can pass through two goods 2 " and 2 " ' radial flow path 83 between (b) flows with general radial direction.Goods 2 " and the second adjacent article 2 " ' space between (b) can form from a sheet material of goods 2.As shown in Figure 14, each goods can have the surface (for example surface of bottom sheet) that can contact with heat-transfer fluid, make heat-transfer fluid can with each goods and preferably each seal cavity directly contact.As shown in Figure 14, each radial flow path 83 can have equal length, identical cross-section or even can congruence.Each goods 2 can have opening near the heart therein.Opening can be to make heat-transfer fluid flow through a part for the compartment of device.Goods 2 " and 2 " ' can be aligned to and make its opening form central axial flow path 84.Goods 2 " and 2 " ' periphery and the space between the inner surface of container 85 be also a part for heat-transfer fluid compartment, and form outside axial flow path 86.Heat storage devices can have the first aperture 87, and it is communicated with central axial flow path 84 fluids.Heat storage devices 80 can have the first seal or plate 88, and it separates the first aperture 87 with outside axial flow path 86.Container 82 can have the second aperture 89, and it can be positioned in a side identical with the first aperture 87 of container, or on the not homonymy of container, as shown in Figure 14.Heat storage devices can have the second seal 90, and it separates the second aperture 89 with central axial flow path.The first seal, the second seal or both can prevent that fluid from flowing between two axial flow path 84 and 86, and do not flow through radial flow path 83.Container 82 is preferably heat insulation.For example, container can have inwall 91 and outer wall 92.Space 93 between two walls can be evacuated or fill with the heat-barrier material with low heat conductivity.Device also can have for example one or more Compress Springs 94 of one or more springs, and it is exerted pressure to goods group heap.

Figure 14 shows the heat storage devices 80 in a side of container with two apertures 87 and 89.Such device can utilize the pipe 95 being connected with the first aperture 87, for fluid is flowed in the first aperture and apart between the region 96 of the first aperture central axial flow path 84 farthest.With reference to Figure 14, the first seal 88 and the second seal 90 can be used for preventing that fluid from flowing to the second aperture 89 from the first aperture 87, and first do not flow through radial flow path 83.By selecting the size of two

axial flow path

84 and 86, heat storage devices 80 can be take Tichelmann system as feature.

When temperature is approximately 25 ℃, the pressure in one or more or even all seal cavities can for example, lower than atmospheric pressure, under vacuum.For example, at 25 ℃, the pressure in seal cavity can be preferably about 600Torr or lower, about 500Torr or lower, about 400Torr or lower, about 300Torr or lower or about 100Torr or lower.Vacuum in seal cavity can be when cover sheets and bottom sheet are tightly connected, to apply the result of vacuum, the result when thermal energy storage material is under high temperature, cover sheets and bottom sheet being tightly connected, or both.For example, method bottom sheet and cover sheets being tightly connected can comprise the step that applies about 600Torr or lower, about 500Torr or lower, about 400Torr or lower, about 300Torr or lower, about 200Torr or lower, about 100Torr or lower or about 50Torr or lower vacuum to bottom sheet Cao district.

Heat storage devices can be used in heat storage system, and described system utilizes one or more heat-transfer fluids to transfer heat in heat storage devices, and heat is passed out to heat storage devices, or both.

For transferring heat to and/or pass out the heat-transfer fluid of thermal energy storage material, can be any liquid or gas, for example, for example, so that the miscellaneous part (providing hot parts, one or more tube connector or line, heat to remove parts or its any combination) of (not fixed) heat storage devices or the process that circulates when it turns cold is provided fluid.Heat-transfer fluid can be known in the art any heat-transfer fluid or the cooling agent conducting heat at the temperature that can use at heat storage devices.Heat-transfer fluid can be liquid or gas.Under preferable case, the minimum operating temperature that heat-transfer fluid can may expose during use at it (for example lowest desired environment temperature) current downflow.For example, heat-transfer fluid approximately 1 atmospheric pressure and approximately 25 ℃, preferably can be liquid or gas at approximately 0 ℃, more preferably-20 ℃, most preferably from about-40 ℃.Without limitation, for heating and/or the preferred heat-transfer fluid of cooling one or more electrochemical cells is liquid at approximately 40 ℃.

Heat-transfer fluid should be able to transport a large amount of heat energy, is typically sensible heat.Heat-transfer fluid can have at least about 1J/gK, preferably at least about 2J/gK, more preferably at least about 2.5J/gK, most preferably at least about the specific heat of 3J/gK (for example measuring at approximately 25 ℃).Under preferable case, heat-transfer fluid is liquid.

Operable heat-transfer fluid and working fluid are included in described in U.S. Patent Application Publication 2009-0250189 (announcement on October 8th, 2009) and PCT application number PCT/US09/67823 (submission on December 14th, 2009).For example, any engine coolant known in the art can be used as heat-transfer fluid.System is preferably utilized single heat-transfer fluid that heat is delivered to the thermal energy storage material from heat storage devices in the thermal energy storage material in heat storage devices and by heat and is removed.Alternatively, system can utilize the first heat-transfer fluid that heat is delivered to thermal energy storage material, and utilizes the second heat-transfer fluid to remove heat from thermal energy storage material.

Without limitation, the heat-transfer fluid of can be separately or using as mixture comprises the known heat-transfer fluid of professional of the art, and preferably includes the fluid that contains water, one or more aklylene glycols, one or more PAGs, one or more oils, one or more cold-producing mediums, one or more alcohols, one or more betaines or its any combination.

Heat storage system can optionally comprise one or more heaters.Heater can be the temperature of thermal energy storage material in heat storage devices can be increased to any heater over the temperature of its transition temperature.Heater can be energy (for example electric energy, mechanical energy, chemical energy or its any combination) to be transformed into any heater of heat (being heat energy).One or more heaters can be one or more electric heaters.One or more heaters can be used to the some or all of thermal energy storage materials in heat hot storage device.Under preferable case, system comprises the one or more heaters with heat storage devices thermal communication.For example, system can comprise the one or more heaters in heat storage devices thermal insulation layer.Electric heater can utilize come from one or more electrochemical cells, from external source or both electric power.For example, when medium is pulled in the outlet being connected with fixed target, can use the electric power that comes from external source that heat storage devices is maintained to the temperature higher than the liquidus temperature of thermal energy storage material in heat storage devices.When medium is not switched in the outlet being connected with fixed target, can use the electric power producing from electrochemical cell that heat storage devices is maintained to the temperature higher than the liquidus temperature of thermal energy storage material heat storage devices.

Heat storage devices can be used to heat in the method for one or more parts.Method can comprise makes heat transfer fluid flow heat transfer device.The step that makes heat transfer fluid flow cross heat storage devices can comprise that the heat-transfer fluid that makes to have initial temperature flows through the entrance of device; Make heat transfer fluid flow through axial flow path to heat-transfer fluid can be separated in a plurality of radial flow path; Make heat-transfer fluid flow through radial flow path so that it can remove heat from thermal energy storage material, wherein thermal energy storage material has the temperature higher than the initial temperature of heat-transfer fluid; Make heat-transfer fluid flow through disalignment to flow path to a plurality of radial flow path can be reconsolidated; The heat-transfer fluid that makes to have outlet temperature flows through the outlet of device; Or its any combination.Under preferable case, the outlet temperature of heat-transfer fluid is higher than the initial temperature of heat-transfer fluid.For the method that heats one or more parts, can utilize flow path by heat storage devices, comprise a selected radial flow path and two axial flow path, described flow path has certain total length of flow, and wherein total length of flow is constants for different radial flow path.

The feature of heat storage devices and/or heat storage system can be to have relative high power (for example measuring between 30 or 60 second initial period of heating), for example, so that it can Fast Heating assembly, internal combustion engine.The feature of heat storage devices and/or heat storage system can be mean power be greater than approximately 5 watts, be preferably greater than approximately 10 watts, more preferably greater than approximately 15 watts, be most preferably greater than approximately 20 watts.

The feature of heat storage devices and/or heat storage system can be to have relative high power density, so that it can hold a large amount of heat energy in relatively little compartment.For example, the feature of heat storage devices and/or heat storage system can be have be greater than about 4kW/L, be preferably greater than about 8kW/L, more preferably greater than about 10kW/L, be most preferably greater than the power density of about 12kW/L.

The feature of heat storage devices and/or heat storage system can be to have relatively low heat-transfer fluid Pressure Drop (measuring under the heat-transfer fluid flow velocity of about 10L/min).For example, the feature of heat storage devices and/or heat storage system can be to have to be less than about 2.0kPa, to be preferably less than about 1.5kPa, to be more preferably less than about 1.2kPa, to be most preferably less than the heat-transfer fluid Pressure Drop of about 1.0kPa.

For example, thermal energy storage system can for example, for storing the energy that comes from engine exhaust in haulage vehicle (automobile).When engine produces waste gas, bypass valve can guide gas communication cross heat storage devices in case heat storage devices filled can, or by by-pass line to prevent heat storage devices superheated.When tail-off, for example, during vehicle parking, the most of heat storing in heat storage devices can retain for a long time (for example, due to heat storage devices vacuum heat-insulating layer around).Under preferable case, vehicle is being berthed under the environment temperature of approximately-40 ℃ after 16 hours, in heat storage devices, at least 50% thermal energy storage material remains on liquid condition.If vehicle is enough to make engine significantly cooling (for example make temperature difference lower than approximately 20 ℃) between engine and environment by berthing long-time (for example, at least 2 or 3 hours), can for example,, by making heat-transfer fluid (engine coolant) flow through the heat exchanger comprising for the condenser of working fluid, the heat being stored in heat storage devices be discharged in cold engine or other heat acceptors indirectly.The capillary structure that uses heat storage devices inside circulates working fluid in capillary pump loop, and working fluid is vaporized therein.The heat that comes from working fluid is passed to the engine coolant in heat exchanger.By using heat storage devices, otherwise will can be hunted down at the front heat being once wasted during travel, to alleviate cold start-up and/or to provide driving cabin immediately to heat.

Use working fluid transferring heat to start by opening working fluid valve (being drain valve).The working fluid holder of the sealing being connected with loop by other liquid line, does not cause that for the variation of regulating loop internal work fluid body volume significant pressure changes.At enough or all available heats, from heat storage devices transmits out, can close drain valve.In heat storage devices remaining working fluid can evaporate (for example from heat storage devices remaining heat or when heat storage devices start to fill can time), then condensation in condenser.When heat storage devices is drained working fluid, the fluid level of working fluid liquid level may change (for example raising).

Heat storage devices can be optionally cross-current type heat exchanger (flow direction with working fluid with perpendicular flow direction) for exhaust-gas flow.For example, at run duration, heat storage devices can comprise three bins, and it is by 1) waste gas, 2) phase-change material (for example inner at capsule, for example blister package) and 3 stagnated) working fluid occupies.All three bins by being applicable to material, be preferably the thin-walled that stainless steel makes and keep separating.Waste gas can for example, flow between the surface (curved surface) of the phase-change material capsule of bubble-cap inside, working fluid can for example,, between the different surfaces (plane surface) of the phase-change material capsule of bubble-cap inside, flow with the direction substantially vertical with exhaust gas flow direction.The liquid working fluid that enters its bin preferably soaks capillary structure (for example metal-cored), and by the capillary force acting on the inner working fluid meniscus forming of capillary, the combining ability of antigravity and vapour pressure is upwards transported.This flowing by using the heat continuous evaporation liquid of extracting out from the phase-change material in bubble-cap to maintain.The steam of working fluid leaves capillary structure, and is emitted to device top by steam channel, for example, between the surface (plane surface) of the phase-change material capsule that described passage can be in bubble-cap, between the post of the capillary structure of extruding, mutually intersects.The steam of working fluid flows into condenser, it arrives cold cooling agent by its heat of vaporization and sensible heat transfer there, become liquid and again return to heat storage devices and continue its circulation in loop, it for example, by the inner capillary force pumping existing of the capillary structure (metal-cored) that is partly impregnated with liquid working fluid.All posts of capillary structure can be connected with common porous matrix.Such porous matrix can be used for the liquid working fluid entering from bottom of device to be distributed to different posts.

In addition, the present invention can be used in combination with other elements/components/steps.For example, for the absorption of air-conditioning or absorption type cycle refrigeration system, can be used as replacing or the heat acceptor except cold cooling agent (for example, condenser also can be used as the evaporimeter of the cold-producing medium that circulates in the fluid circuit of air-conditioning).In Another application, can build the stable state WHRS rankine cycle for example of using thermo-motor, so that it uses identical or different capillary pump loop working fluid, and add mechanical power generation turbine (for example, to overcome the high vapour pressure of turbine upstream) to the vapor line between heat storage devices and condenser, and/or add liquor pump to the liquid line between condenser and heat storage devices.Above-mentioned turbine can be transformed into useful machinery or electric power merit by a part of heat of catching from waste gas used heat, thereby improves the overall fuel efficiency of vehicle.

Embodiment

Embodiment 1 is the goods that comprise 7 seal cavities that contain thermal energy storage material and be applicable to heat accumulation.Device has 7 grooves bottom sheet by filling with thermal energy storage material forms.Each groove can hold about 7cm ³liquid.Bottom sheet is covered by smooth cover sheets.Bottom sheet and cover sheets are made by stainless steel 304, and have the thickness of about 0.102mm.Thermal energy storage material is slaine, and has the liquidus temperature of approximately 195 ℃.Thermal energy storage material is anhydrous or has about 0.01wt.% or following moisture concentration.When thermal energy storage material connects two blocks of sheet materials when solid-state (approximately 23 ℃).By the periphery around each seal cavity by bottom sheet together with cover sheets laser weld, the first sealing is provided.When being heated to the temperature of approximately 250 ℃, seal cavity has the internal pressure of about 69kPa (about 10psi).

Thermal cycling test

By the stacking juxtaposition of goods of approximately 10 embodiment 1 in thering is the container of entrance and exit.The cold heat-transfer fluid reservoir of approximately 15 ℃ of the hot heat-transfer fluid reservoir of approximately 250 ℃ of entrance and temperature and temperature is connected.Make heat-transfer fluid flow through container until the temperature of thermal energy storage material is approximately 240 ℃, then make cold heat-transfer fluid flow through container until the temperature of thermal energy storage material is approximately 25 ℃.By approximately 1,000 circulation of the temperature of thermal energy storage material circulation in approximately every 5 minutes.

During thermal cycling test, before reaching 1,000 circulation, the seal cavity of one or more embodiment 1 breaks and/or leaks in the first sealing.Thermal energy storage material leaks out from one or more seal cavities, and embodiment 1 fails to pass through thermal cycling test.

Heat test

The goods of embodiment 1 in being about the baking box of 400 ℃, temperature are placed approximately 30 minutes.Then goods evaluation being determined whether to exist makes thermal energy storage material leak out any leakage of goods or break.Observe one or more leakages and/or break, and embodiment 1 fails by heat test.

Embodiment 2 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is by carrying out laser weld, preparing the second sealing near the periphery of bottom sheet and cover sheets and near its corresponding open circumferential.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is higher than the yield stress of paper tinsel.During thermal cycle, the first seal failure around of one or more seal cavities.After 1,000 thermal cycle, the second sealing was not lost efficacy, and thermal energy storage material does not leak out goods.

By being heated to 400 ℃ of goods to another embodiment 2, test.At 400 ℃, one or more the first seal failures.Yet the second sealing was not lost efficacy, and thermal energy storage material does not leak.

Embodiment 3 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is to be about at bottom sheet and cover sheets used thickness the paper tinsel of 0.204mm.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is lower than the yield stress of paper tinsel.After 1,000 thermal cycle, the first sealing was not lost efficacy, and thermal energy storage material does not leak out goods.

By being heated to 400 ℃, the goods of another embodiment 3 were tested in 20 minutes.At 400 ℃, all sealings were not all lost efficacy, and thermal energy storage material does not leak.

Embodiment 4 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is that cover sheets used thickness is the paper tinsel of about 0.204mm.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress drop is low to moderate about 180MPa, lower than the yield stress of paper tinsel.After 1,000 thermal cycle, the first sealing was not lost efficacy, and thermal energy storage material does not leak out goods.

By being heated to 400 ℃, the goods of another embodiment 4 were tested in 20 minutes.At 400 ℃, all sealings were not all lost efficacy, and thermal energy storage material does not leak.

Embodiment 5 is the goods that comprise 7 seal cavities, it uses the method preparation of embodiment 1, difference is that cover sheets is stamped the cover sheets making on each seal cavity that contains thermal energy storage material and has approximately 15 ribs, and it comprises recess and the protuberance separately with 0.1 to the 0.5mm degree of depth.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is about 233MPa, lower than the yield stress of paper tinsel.After 1,000 thermal cycle, the first sealing was not lost efficacy, and thermal energy storage material does not leak out goods.Should be realized that, can use one, two or more ribs, and rib can be recess, protuberance or both.

By being heated to 400 ℃, the goods of another embodiment 5 were tested in 20 minutes.At 400 ℃, all sealings were not all lost efficacy, and thermal energy storage material does not leak.

Embodiment 6 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is that cover sheets is stamped so that the seal cavity that comprises thermal energy storage material has approximately 34 dimples that are recessed into about 0.6mm in seal cavity.Dimple in cover sheets is taked the brick wall pattern that in Fig. 4 B, signal shows.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is about 590MPa, higher than the yield stress of paper tinsel.The first seal failure during thermal cycle, thermal energy storage material leaks out goods.Should be realized that, can use still less or more dimple, and dimple can be darker or more shallow.

By being heated to 400 ℃, the goods of another embodiment 6 were tested in 20 minutes.At 400 ℃, seal failure and thermal energy storage material leak.

Embodiment 7 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 6, and difference is that the paper tinsel that cover sheets is about 0.153mm by thickness makes.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is about 282MPa, lower than the yield stress of paper tinsel.During thermal cycle, the first sealing was not lost efficacy, and heat energy storage material does not leak out goods after 1,000 thermal cycle.

By being heated to 400 ℃, the goods of another embodiment 7 were tested in 20 minutes.At 400 ℃, sealing was not lost efficacy and thermal energy storage material does not leak.

Embodiment 8 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is that cover sheets has been stamped a plurality of chevrons, and it comprises recess and the protuberance of about 0.5mm.Chevron in cover sheets is taked the repeat patterns that in Fig. 4 A, signal shows.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is about 600MPa, higher than the yield stress of paper tinsel.

Embodiment 9 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is, applies the vacuum of about 200Torr when cover sheets and bottom sheet weld together.When thermal energy storage material is during in the temperature of approximately 25 ℃, the pressure in seal cavity is lower than about 400Torr.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is lower than the yield stress of paper tinsel.During thermal cycle, the first sealing was not lost efficacy, and heat energy storage material does not leak out goods after 1,000 thermal cycle.

By being heated to 400 ℃, the goods of another embodiment 9 were tested in 20 minutes.At 400 ℃, seal failure and thermal energy storage material leak.

Embodiment 10 is the goods that comprise 7 seal cavities, and it uses the method preparation of embodiment 1, and difference is cover sheets and bottom sheet to be welded together during in the temperature of approximately 250 ℃ when thermal energy storage material.When thermal energy storage material is during in the temperature of approximately 25 ℃, the pressure in seal cavity is lower than about 400Torr.Use and with method identical described in embodiment 1, goods are tested.Maximum Feng meter Si stress is lower than the yield stress of paper tinsel.During thermal cycle, the first sealing was not lost efficacy, and heat energy storage material does not leak out goods after 1,000 thermal cycle.

By being heated to 400 ℃, the goods of another embodiment 10 were tested in 20 minutes.At 400 ℃, seal failure and thermal energy storage material leak.

The preferred embodiments of the invention are disclosed.Yet, it will be recognized by those of ordinary skills, some modification will be within instruction of the present invention.Therefore, should determine true scope of the present invention and content to claims research below.

Any numerical value of enumerating in above-mentioned application comprises that the increment from lower limit to higher limit is all values of 1 unit, as long as be separated by least Liang Ge unit between any lower limit and any higher limit.For example, if the value of the statement amount of component or method variable such as temperature, pressure, time etc. is for example 1 to 90, preferably 20 to 80, more preferably 30 to 70, mean clearly to be enumerated in this manual such as 15 to 85,22 to 68,43 to 51,30 to 32 etc. value.For the value that is less than 1,1 unit is considered to 0.0001,0.001,0.01 or 0.1, depends on the circumstances.These are only the examples of the value that specifically means, and all possible combination of the numerical value between the lower limit of enumerating and higher limit is all considered to clearly be stated in this application in a similar manner.Unless otherwise stated, otherwise all scopes comprise all numerals between end points and end points.When coverage, the use of " approximately " or " being similar to " is applicable to the two ends of described scope.Therefore, " approximately 20 to 30 " are intended to cover " approximately 20 to approximately 30 ", at least comprise the end points of appointment.When using in this article, parts by weight refer to and contain the composition of 100 parts by weight.All articles and list of references, comprise the disclosure of patent application and announcement, for all objects are incorporated to by reference.For describe combination term " substantially by ... form " should comprise key element, composition, parts or the step of appointment and other key elements, composition, parts or the step that the fundamental sum new feature of described combination be there is no to substantial effect.For describing, the term of the combination of key element, composition, parts or step herein " comprises " or the use of " comprising ", has also considered the embodiment substantially consisting of described key element, composition, parts or step.A plurality of key elements, composition, parts or step can be provided by single integrated key element, composition, parts or step.Alternatively, single integrated key element, composition, parts or step can be divided into independently a plurality of key elements, composition, parts or step.For what describe key element, composition, parts or step, without concrete quantity (" a ") or " one " open, be not intended to get rid of other key elements, composition, parts or step.

Claims

1. goods, it comprises:

Metal bottom sheet material;

Metal cover sheets, wherein said metal bottom sheet material and described metal cover sheets are tightly connected, and form one or more seal cavities;

Thermal energy storage material, wherein said thermal energy storage material is included in described seal cavity;

Wherein said seal cavity is substantially free of water, or comprises the cumulative volume based on described seal cavity at the temperature of approximately 25 ℃, and concentration is by volume approximately 1% or aqueous water still less; And

Wherein said goods comprise one or more following features:

A) when the temperature of described thermal energy storage material is approximately 25 ℃, the pressure in seal cavity is about 700Torr or lower;

B) described metal cover sheets comprises one or more reinforcement features, wherein said reinforcement feature comprises that the recess of recessed described seal cavity is, the protuberance of outstanding described seal cavity or both, and its size and quantity are enough to reduce the maximum Feng meter Si stress in described cover sheets during thermal cycle;

C) described metal cover sheets and/or described metal bottom sheet material comprise one or more volumetric expansion parts; Or

D) described metal cover sheets has thickness t _c, described metal bottom sheet material has thickness t _b, t wherein _cbe greater than t _b;

Described goods are not being leaked after 1,000 circulation of thermal cycle between approximately 25 ℃ to approximately 240 ℃.

2. the goods of claim 1, wherein the pressure in seal cavity is about 600Torr or lower vacuum at the temperature of approximately 25 ℃.

3. claim 1 or 2 goods, wherein said goods are prepared by the method comprising the steps: as the liquidus temperature (T of described thermal energy storage material at least described thermal energy storage material _{l, TESM}) connection temperature (T _j) time, described metal bottom sheet material is connected with described metal cover sheets.

4. the goods of claims 1 to 3 any one, wherein:

I) the ratio t of the thickness of the thickness of described metal cover sheets and described metal bottom sheet material _c/ t _b, be approximately 1.05 or larger;

Ii) the difference t of the thickness of the thickness of described metal cover sheets and described metal bottom sheet material _c-t _b, be about 0.02mm or larger; Or

Iii) meet i simultaneously) and ii) both.

5. the goods of claim 1 to 4 any one, wherein said goods comprise the one or more weld parts that connect described metal cover sheets and described metal bottom sheet material, wherein said one or more weld parts surround described seal cavity completely; Described goods have opening near the center of described goods, so that heat-transfer fluid can flow through described opening; And described goods are sealed around the periphery of described opening, make described heat-transfer fluid not contact the thermal energy storage material in described seal cavity.

6. the goods of claim 1 to 5 any one, wherein said metal cover sheets comprises one or more reinforcement features.

7. the goods of claim 1 to 6 any one, wherein said metal cover sheets, metal bottom sheet material or both comprise one or more volumetric expansion parts.

8. the goods of claim 7, wherein said one or more volumetric expansion parts comprise dimple, chevron, gauffer, folding, curling or its any combination.

9. the goods of claim 1 to 8 any one, wherein said metal cover sheets is stamped, make described goods and metal cover sheets wherein substantially smooth goods compare, the Feng meter Si stress at approximately 250 ℃ of temperature reduces approximately 10% or more.

10. the goods of claim 1 to 9 any one, wherein during the repeated thermal cycles between approximately 30 ℃ to approximately 250 ℃, the described metal bottom sheet material being caused by the thermal expansion of described thermal energy storage material and the Feng meter Si stress in metal cover sheets, be less than the yield stress of the metal of described cover sheets.

The goods of 11. claim 1 to 10 any one, the described seal cavity of wherein said goods does not leak after approximately 4 hours being heated to approximately 400 ℃.

The goods of 12. claim 1 to 11 any one, wherein said thermal energy storage material has approximately 25 ℃ or higher liquidus temperature.

The goods of 13. claim 1 to 12 any one, wherein said thermal energy storage material has approximately 150 ℃ or higher liquidus temperature, and described thermal energy storage material is substantially anhydrous.

14. 1 kinds of methods that are used to form the goods of claim 1 to 13 any one, wherein said metal bottom sheet material comprises one or more grooves that can receiving fluids, and described method comprises with described thermal energy storage material and fills at least partly the step of one or more grooves.

The method of 15. claims 14, wherein when described bottom sheet and cover sheets are tightly connected, under the predetermined temperature of the liquidus temperature of described thermal energy storage material at least described thermal energy storage material, make, described goods are cooled to after approximately 25 ℃, in described seal cavity, to form vacuum.

The method of 16. claims 14 or 15, the step of wherein said be tightly connected described bottom sheet and cover sheets started before the step of filling described groove with described thermal energy storage material, and completed after the step of filling described groove with described thermal energy storage material.

The method of 17. claim 14 to 16 any one, wherein said goods are prepared to form the method for the step of described seal cavity by comprising the described metal bottom sheet material of connection and described metal cover sheets, and wherein said Connection Step applies the step of vacuum before being included in and connecting described sheet material to the region of described seal cavity.

18. 1 kinds of devices, it comprises the group heap of goods of two or more claim 1 to 13 any one.

The device of 19. claims 18, wherein each goods comprises opening separately, and wherein said goods are aligned to and make generally alignment in the axial direction of opening, and described goods group heap is comprised in thermally insulated container.

20. 1 kinds of methods for store heat, described method comprises the steps:

To the goods of claim 1 to 15 any one, transmit the heat energy of q.s, the thermal energy storage material in described goods is heated to approximately 200 ℃ or higher temperature.