201240173 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種熱電產生器，其包含至少一個傳導熱 介質之管道及至少一個熱電模組。 【先前技術】 廢氣熱量（例如來自發電廠或機動車輛）常常未經利用便 釋放到環境中。然而’有效使用此熱量將產生更高效率。 利用此廢氣熱！的一種裝置為熱電產生器（teg)，由於 西白克效應（Seebeck effect)(有時亦稱為熱電效應），若發 生沿導體之溫差，則其在彼此連接的兩個導體之開路端產 生電壓。利用廢氣熱量產生能量之裝置已知且已揭示於例 如 DE 10 2008 005 334 A1 中。 根據所用之方法，廢氣具有2〇0〇c與1〇〇〇〇c之間的溫 度。迄今為止用於熱電產生器之材料（例如鉍、碲化物或 碲化鉛)並不耐受此等高溫’且因此任-者均須隔熱，需 要供給旁路（一旦廢氣溫度對於所用材料而言變得過高， 則該旁路轉移廢氣)。兩者均意謂成本因併入閥門、旁路 s C等而升同功率消耗因額外元件及量測與調控裝置而 增大，及裝配時間延長。201240173 VI. Description of the Invention: [Technical Field] The present invention relates to a thermoelectric generator comprising at least one conduit for conducting a heat medium and at least one thermoelectric module. [Prior Art] Exhaust heat (e.g., from a power plant or motor vehicle) is often released into the environment without being utilized. However, 'effective use of this heat will result in higher efficiency. Use this exhaust heat! One type of device is a thermoelectric generator (teg). Due to the Seebeck effect (sometimes referred to as the thermoelectric effect), if a temperature difference along the conductor occurs, it is generated at the open ends of the two conductors connected to each other. Voltage. Devices for generating energy using exhaust heat are known and are disclosed, for example, in DE 10 2008 005 334 A1. The exhaust gas has a temperature between 2 〇 0 〇 c and 1 〇〇〇〇 c, depending on the method used. Materials used to date for thermoelectric generators (such as antimony, telluride or lead telluride) are not tolerant of such high temperatures' and therefore all must be insulated and need to be supplied to the bypass (once the exhaust gas temperature is for the materials used) If the words become too high, the bypass will transfer the exhaust gas). Both mean that the cost is increased due to the incorporation of valves, bypass s C, etc., due to the additional components and measurement and control devices, and the assembly time is extended.
境中而無利用的可能性。 【發明内容】 梯度愈大’則其效率愈高。隔熱 亦即相當大部分之熱量釋放到環 ，其包含至 因此本發明之目標為提供一種熱電產生器 158887.doc 201240173 少一個傳導熱介質之管道及至少一個甚至在高溫下仍可充 分起作用且仍然具有較高效率的熱電模組。 該目標係利用包含至少一個傳導熱介質之管道且包含至 少一個熱電模組的熱電產生器來達成，其中熱電產生器包 含至少一層相變材料（PCM)。在本發明之情形下，相變材 料層意"胃一層單獨的至少一種相變材料或包含至少一種相 變材料之合金。 此層較佳安裝在管道（例如傳導熱廢氣流之廢氣管道）與 熱電模組之間。同樣地，在本發明之情形下，該層可組態 成圍繞熱電產生器的外殼，例如封裝。 本發明所提出之另一可能的組態方法為將熱電產生器之 至乂個熱電模組埋置於一層或若干層相變材料中。 相變材料具有能夠利用儲存熱量來調節其環境溫度之特 性。材料自利用生產方法可調節之溫度Τχ開始熔融且由於 其熔化熱高而吸收大量熱量。若整個相變材料未熔融，則 相變材料之環境溫度不升高。 如下文所述，過剩熱量qe表示超過溫度極限TL時之熱介 質熱量(熱介質溫度=Tactual)。若無相變材料層或無包含相 變材料之合金存在以吸收此過剩熱量，則 該至少一個熱電模組將無保護地暴露於此過剩熱量q E中。 若熱介質之溫度升高超過溫度值Τχ(其較佳餘溫度極 限TL且對熱電模組之運轉㈣鍵作用），則發生相變且此 意謂相變材料熔融且因此吸收過剩熱量QE。由此保護熱電 模組免受過高溫度影響且同時確保過剩熱量以儲存於相變 i588S7.doc 201240173 材料中。 相變材料層在過高溫度下儲存過剩熱量Qe，且以此方式 保護熱電模組免受過熱影響。一旦熱介質之溫度再次下 降，則相變材料將熱量釋放回熱電模組中，且此過程對由 其製成之熱電產生器之效率具有積極的作用。同時，可省 卻高成本及材料密集型改造β 相變材料的熔化潛熱、溶解熱或吸收熱遠大於其在無相 變效應情況下基於標準比熱容可儲存的熱量。 充當熱量儲存介質之相變材料係藉由吸收極大量熱之熔 融進行「充電」。因為此操作可逆，所以熱量儲存介質在 自液相變為固相時（亦即在凝固時）再次精確地釋放此量之 熱量。此熱量儲存技術之優勢係基於在利用所用儲存材料 之溶融溫度精確確定的溫度範圍内以最小質量儲存最大量 之熱。 亦可利用相同原理來保護熱電產生器。舉例而言，存在 南溫相變材料或合金。可調節此等高溫相變材料或合金以 使其在200°c與lOOOt：之間的規定溫度τχ下熔融及再次凝 固，且因此儲存或釋放熱量。 相變材料層配置於例如傳導熱介質之管道與至少一個熱 電模組之間’從而構成熱電產生器之基本單元。此熱電產 生器可設計為單獨系統或整體式組件。 相變材料層可以單片或以至少一個薄層形式形成。其亦 可已引入熱電模組與管道之間的全部區域或區段中，平行 或垂直於管道長度。 158887.doc 201240173 相變材料層較佳為直接或間接配置於熱源與熱電模組的 熱端之間，此又有效保護熱電模組之熱端，防止出現否則 會發生的過熱現象。 另外，相變材料層可整合至熱電模組或熱電產生器中、 或施加在管道内側上、或以獨立層形式分別配置在管道與 熱電模組之間。 一旦熱介質之溫度再次下降，則相變材料將其中之熱量 釋放回熱電模組中。此確保熱電模組可在較高能量下操作 更長時間’因此產生更好的效能且提高效率，而且同時排 除過熱。 熱電模組之熱電材料包含方鈷礦（skutterudite)、半豪斯 勒合金（Semi-Heusler)、籠形物 '氧化物、矽化物、硼化 物、碲化鉍及其衍生物、碲化鉛及其衍生物、銻化物（諸 如銻化鋅）及津特耳相（Zintl phase)。 相變材料層不僅可與管道及熱電模組直接接觸，還亦可 組態為圍繞管道及/或熱電模組的封裝。封裝之材料包含 至少一種純金屬’例如鎳H、銀或鐵，及/或至少 種基於鎳、鉻、鐵、锆或鈦之金屬合金。 該層之相變材料包含熔點在250oc與i 700t之間的所有 無機金屬鹽。適合的金屬鹽包含例如氟離子、氯離子、溴 離子、破離子、硫酸根、石肖酸根、碳酸根、鉻酸根、翻酸 根、飢酸根或鎢酸根作為陰離子，以及鐘、納、卸、修、 絶、鎂ϋ或鋇作為陽離子。此等材料可同樣地包含 以二元、三元、四元或五元共晶形成無機金属鹽之所有鹽 158887.doc 201240173 處合物。 ^才目變材料層組態為合金時，相變材料合金包含如上所 述之相變材料及至少一種具有200°C與1800°C之間之熔點 土於辞鎮、紹、銅、弼、碎、鱗或録的金屬合金。 本發明之實施例顯示於圖中且在隨後描述中詳細說明。 機動車輛之熱回收備受關注，因為其所產生之排氣熱量 枢·據模型可雨達35%。有效利用此熱量可大大改良内燃機 之效率。 舉例而言’相變材料層可已裝配在以下任一者中之至少 一個位置：排氣管中、排氣歧管上或排氣歧管中、排氣再 循裱皆道上或排氣再循環管道中、排氣管道上或排氣管道 中、中間消聲器上或中間消聲器中及/或後消聲器上或後 消聲器中。 本發明所提出之熱電產生器亦可在發電廠中用於熱量回 收’例如整合在煙道之内側。 另外，本發明之熱電產生器亦可設想用於其他領域，例 如利用微電子組件、地熱發電、家庭與工業廢熱之周圍熱 量或結合光電設備作為混合系統使用。 【實施方式】 下文舉例詳細說明機動車輛之冑氣管冑或排4再擴環管 中包含相變材料之熱電產生器。 實施例 為了保護熱電模經’迄今為止已通常將熱電模組隔执以 防過熱1已在廢氣系統中併入旁路，且—旦廢氣溫度變 158887.doc 201240173 得過高則轉移廢氣。 為了更好地說明本發明，圖i顯示用於保護熱電模組免 受過高溫度影響之具有現存旁路之廢氣系統的示意結構。 在具有永久溫度量測之廢氣管道10中，熱氣體以溫度The possibility of not using in the environment. SUMMARY OF THE INVENTION The greater the gradient, the higher the efficiency. Insulation, i.e., a substantial portion of the heat released to the ring, is included so that the object of the present invention is to provide a thermoelectric generator 158887.doc 201240173 one less conductive medium conduit and at least one that is fully functional even at high temperatures And still have a higher efficiency thermoelectric module. The object is achieved by a thermoelectric generator comprising at least one conduit for conducting a heat medium comprising at least one thermoelectric module, wherein the thermoelectric generator comprises at least one layer of phase change material (PCM). In the context of the present invention, a phase change material layer is intended to mean at least one phase change material alone or an alloy comprising at least one phase change material. This layer is preferably installed between the pipe (e.g., the exhaust pipe that conducts the hot exhaust gas stream) and the thermoelectric module. Likewise, in the context of the present invention, the layer can be configured to surround the outer casing of the thermoelectric generator, such as a package. Another possible configuration method proposed by the present invention is to embed one thermoelectric generator into one or several layers of phase change material. Phase change materials have the property of being able to utilize stored heat to regulate their ambient temperature. The material begins to melt from the temperature tunable by the production method and absorbs a large amount of heat due to its high heat of fusion. If the entire phase change material is not melted, the ambient temperature of the phase change material does not increase. As described below, the excess heat qe represents the heat of the heat medium (heat medium temperature = Tactual) when the temperature limit TL is exceeded. If no phase change material layer or alloy containing no phase change material is present to absorb the excess heat, the at least one thermoelectric module will be unprotected exposed to the excess heat q E . If the temperature of the heat medium rises above the temperature value 其 (the preferred residual temperature limit TL and the operation of the thermoelectric module (4) key), a phase change occurs and this means that the phase change material melts and thus absorbs excess heat QE. This protects the thermoelectric module from excessive temperature and ensures excess heat for storage in the phase change i588S7.doc 201240173 material. The phase change material layer stores excess heat Qe at an excessively high temperature, and in this way protects the thermoelectric module from overheating. Once the temperature of the heat medium drops again, the phase change material releases heat back into the thermoelectric module, and this process has a positive effect on the efficiency of the thermoelectric generator made therefrom. At the same time, the latent heat of fusion, heat of dissolution or heat absorption of the β-phase-change material, which is cost-effective and material-intensive, can be saved much larger than the heat that can be stored based on the standard specific heat capacity without a phase change effect. The phase change material that acts as a heat storage medium is "charged" by absorbing a very large amount of heat. Since this operation is reversible, the heat storage medium releases this amount of heat again accurately from the liquid phase to the solid phase (i.e., upon solidification). The advantage of this heat storage technique is based on the maximum amount of heat stored at a minimum mass over a temperature range that is accurately determined using the melting temperature of the storage material used. The same principle can also be used to protect the thermoelectric generator. For example, there are south temperature phase change materials or alloys. These high temperature phase change materials or alloys may be adjusted to melt and re-solidify at a specified temperature between 200 ° C and 1000 °: and thus store or release heat. The phase change material layer is disposed between, for example, a conduit for conducting a heat medium and at least one thermoelectric module to constitute a basic unit of the thermoelectric generator. This thermoelectric generator can be designed as a separate system or as a unitary component. The phase change material layer may be formed in a single piece or in at least one thin layer. It may also have been introduced into all areas or sections between the thermoelectric module and the pipe, parallel or perpendicular to the length of the pipe. 158887.doc 201240173 The phase change material layer is preferably disposed directly or indirectly between the heat source and the hot end of the thermoelectric module, which effectively protects the hot end of the thermoelectric module from overheating that would otherwise occur. Alternatively, the phase change material layer may be integrated into the thermoelectric module or the thermoelectric generator, or applied to the inside of the pipe, or disposed as a separate layer between the pipe and the thermoelectric module. Once the temperature of the heat medium drops again, the phase change material releases the heat back into the thermoelectric module. This ensures that the thermoelectric module can operate for a longer period of time at higher energies' thus resulting in better performance and improved efficiency, while at the same time eliminating overheating. The thermoelectric material of the thermoelectric module comprises skutterudite, semi-Heusler, clathrate 'oxide, telluride, boride, antimony telluride and its derivatives, lead telluride and Its derivatives, tellurides (such as zinc telluride) and Zintl phase. The phase change material layer can be directly contacted not only with the pipe and the thermoelectric module, but also with the package surrounding the pipe and/or the thermoelectric module. The encapsulating material comprises at least one pure metal 'e.g., nickel H, silver or iron, and/or at least a metal alloy based on nickel, chromium, iron, zirconium or titanium. The phase change material of this layer comprises all inorganic metal salts having a melting point between 250 oc and i 700 t. Suitable metal salts include, for example, fluoride, chloride, bromide, sulphate, sulphate, sulphate, carbonate, chromate, acidate, sulphate or tungstate as anions, as well as clock, nano, unloading, repairing , 绝, magnesium strontium or strontium as a cation. These materials may likewise comprise all salts of inorganic metal salts formed by binary, ternary, quaternary or pentad eutectic 158887.doc 201240173. When the material layer is configured as an alloy, the phase change material alloy comprises the phase change material as described above and at least one kind of melting point between 200 ° C and 1800 ° C in the town, Shao, copper, bismuth, Broken, scaled or recorded metal alloy. Embodiments of the invention are shown in the drawings and are described in detail in the following description. The heat recovery of motor vehicles has received much attention because of the 35% of the exhaust heat generated by the model. Effective use of this heat can greatly improve the efficiency of the internal combustion engine. For example, the phase change material layer may have been assembled in at least one of the following: in the exhaust pipe, on the exhaust manifold, or in the exhaust manifold, exhaust gas is circulated or exhausted. In the circulating pipe, on the exhaust pipe or in the exhaust pipe, on the intermediate muffler or in the intermediate muffler and/or in the rear muffler or in the rear muffler. The thermoelectric generator proposed by the present invention can also be used in power plants for heat recovery, e.g., integrated inside the flue. In addition, the thermoelectric generator of the present invention can also be envisaged for use in other fields, such as the use of microelectronic components, geothermal power generation, ambient heat of household and industrial waste heat, or in combination with photovoltaic devices as a hybrid system. [Embodiment] Hereinafter, a thermoelectric generator including a phase change material in a helium gas pipe 胄 or a row 4 re-expansion pipe of a motor vehicle will be described in detail. EXAMPLES In order to protect the thermoelectric mold, the thermoelectric module has been conventionally blocked to prevent overheating1, which has been bypassed in the exhaust system, and the exhaust gas has been transferred if the temperature of the exhaust gas becomes 158887.doc 201240173 is too high. To better illustrate the invention, Figure i shows a schematic structure of an exhaust system with an existing bypass for protecting the thermoelectric module from excessive temperature. In the exhaust gas pipe 10 having a permanent temperature measurement, the hot gas is at a temperature
Tactual存在。為了再循環一部分氣體之熱能，將此氣體藉 助於第二廢氣管道12經由一個或眾多熱電產生器14傳遞。 在此過程中，氣體釋放一些其熱量且隨後在較低溫度下饋 回廢氣管道10中。 當氣體溫度Taetual超過溫度極限TL(對應於熱電產生器之 穩定性及運轉處於危險之溫度）時，氣體藉助於旁路管道 16經由閥門18轉移，且隨後饋回至廢氣管道1〇中。由於氣 體之此轉移，氣體將未經利用之熱量釋放到環境中，且此 熱量不再可用於發電。 整合至傳導廢氣流之管道32内之本發明熱電產生器3〇的 結構顯示於圖2中。 管道32之一種橫截面34較佳為圓形，但亦可想像所有其 他一維邊何形式。管道32之一種長度36例如至少等於管道 32之一種直徑38。在機動車輛或發電廠中，管道32為廢氣 管道或廢氣再循環管道。 眾多熱電模組40可已與冷卻管46之上端連接。熱電模組 40及冷卻管46可埋置於熱交換器中或分別存在。 熱電模組40之熱電材料包含方鈷礦、半豪斯勒合金、範 形物、氧化物、石夕化物、硼化物、締化叙及其衍生物、碌 化錯及其衍生物、録化物（諸如録化鋅）及津特耳相。 158887.doc 201240173 舉例而言’所用氧化物可為Nax、Ca〇2、CaCo、09、Tactual exists. In order to recycle the thermal energy of a portion of the gas, the gas is delivered via the one or more thermoelectric generators 14 via the second exhaust gas conduit 12. During this process, the gas releases some of its heat and is then fed back into the exhaust gas conduit 10 at a lower temperature. When the gas temperature Taetual exceeds the temperature limit TL (corresponding to the stability of the thermoelectric generator and the temperature at which the operation is at risk), the gas is transferred via the bypass pipe 16 via the valve 18 and then fed back into the exhaust gas pipe 1〇. Due to this transfer of gas, the gas releases unutilized heat into the environment and this heat is no longer available for power generation. The structure of the thermoelectric generator 3A of the present invention integrated into the conduit 32 for conducting exhaust gas flow is shown in FIG. A cross section 34 of the conduit 32 is preferably circular, but it is also conceivable for all other one dimensional sides. A length 36 of the conduit 32 is, for example, at least equal to a diameter 38 of the conduit 32. In a motor vehicle or power plant, the conduit 32 is an exhaust conduit or an exhaust gas recirculation conduit. A plurality of thermoelectric modules 40 may have been coupled to the upper end of the cooling tube 46. The thermoelectric module 40 and the cooling tube 46 may be embedded in the heat exchanger or separately. The thermoelectric material of the thermoelectric module 40 comprises skutterudite, semi-Hausler alloy, paradigm, oxide, asheti, boride, association and its derivatives, muddy and its derivatives, and recorded materials. (such as recorded zinc) and Jinte ear phase. 158887.doc 201240173 For example, the oxide used may be Nax, Ca〇2, CaCo, 09,
Bi2Sr2、Ca2Oy、Sr2Ti04、Sr3Ti207、Sr4Ti301()、RikHkCoOs (R=稀土金屬’ H=鹼土金屬）、Srn+1Tim03n+i(其中n=整 數）、YBa2Cu307.K ;矽化物可為FeSi2、Mg2Si、Mn15Si26 ; 棚化物可為B4C、CaB6 ;方鈷礦可為c〇Sb3 ; RuPdSb6、Bi2Sr2, Ca2Oy, Sr2Ti04, Sr3Ti207, Sr4Ti301(), RikHkCoOs (R=rare earth metal 'H=alkaline earth metal), Srn+1Tim03n+i (where n=integer), YBa2Cu307.K; telluride can be FeSi2, Mg2Si, Mn15Si26 The shed can be B4C, CaB6; the skutter deposit can be c〇Sb3; RuPdSb6,
Tx6(T=Co、Rh、Ir ; X=p、As、Sb)、□ΛΥν 其中 X=Co、Rh、Ir ; Y=P、As、Sb ’ 口=鑭系元素、婀系元 素、鹼土金屬、鹼金屬、鉈、1¥族元素；半豪斯勒合金， 例如Ti、Ni、Sn ; HfPdSn及金屬間相；籠形物可為Tx6 (T=Co, Rh, Ir; X=p, As, Sb), □ΛΥν where X=Co, Rh, Ir; Y=P, As, Sb 'mouth = lanthanide, actinide, alkaline earth metal , alkali metal, lanthanum, 1 ¥ group element; semi-Hosler alloy, such as Ti, Ni, Sn; HfPdSn and intermetallic phase; clathrate can be
Zn4Sb3、Si8Go16Ge3〇 ; C58Sn44、Cu4TeSbn ;及津特耳相Zn4Sb3, Si8Go16Ge3〇; C58Sn44, Cu4TeSbn; and Jinte ear phase
Ybi4MnSbn 〇 熱電模組40具有特定最大使用溫度tg〇若廢氣之溫度升 高超過此溫度’則熱電模組可被損壞且失去其運轉能力。 若已在管道32之内側48與熱電模組40之熱端之間引入包 含相變材料之層’則此層可藉由儲存過剩熱量仏來保護熱 電模組40免受過高溫度影響。 選擇相變材料以使相變材料在熱電模組達到最大使用溫 度TG之前開始熔融。此首先能夠補償過高溫度及保護熱電 模組40 ’且其次將熱電產生器保持在怪溫。由此產生更好 的效能且提高熱電模組4〇之效率。 另外’儲存於相變材料中之過剩熱量qe在熱電產生器3〇 冷卻之後再次釋放，且可利用熱電模組40轉化為電力。在 迄今用於廢氣熱量回收之方法中，此過剩熱量^未經利用 便釋放到環境中且不能用於發電。 158887.doc 201240173 , ' 相變材料層可以單片或以至少一個薄層形式形成。其亦 可已引人熱電模組40與管道32之間的全部區域或區段中， 平行或垂直於管道32之長度。 相變材料層可已整合至熱電模組4〇或熱電產生器3〇中， 施加在官道32之内側上或以獨立層形式分別引入管道32與 熱電模組40之間。 相變材料層可已直接或間接配置於熱源與熱電模組4〇之 熱端之間。 在相變材料直接配置之情況下’其與熱氣流直接接觸， 而在相變材料間接配置之情況下，廢氣管道1 〇之管道壁介 於熱廢氣流與相變材料之間。 在相變材料直接配置之情況下，其直接暴露於熱氣流 (亦即廢氣流20)，而在相變材料層間接配置之情況下，管 道壁介於廢氣流20(亦即熱氣流）與相變材料之間。 相變材料層不僅可與管道32及熱電模組40直接接觸，還 亦可組態成圍繞管道32及/或熱電模組40的封囊^封囊之 材料包含至少一種純金屬，諸如鎳、錯、欽、銀或鐵，及/ 或至少一種基於鎳、鉻、鐵、锆或鈦之金屬合金。 相變材料層可已裝配於以下任何所需位置：廢氣管中、 廢氣歧管上或廢氣歧管中、廢氣再循環管道上或廢氣再循 環管道中、廢氣管道上或廢氣管道中、中間消聲器上或中 間消聲器中及/或後消聲器上或後消聲器中。 該層之可能的相變材料包含熔點在250°c與17〇〇°C之間 的所有無機金屬鹽。適合的金屬鹽包含例如IL離子、氣離 158887.doc 201240173 子、溴離子、碘離子、硫酸根、硝酸根、碳酸根、鉻酸 根、鉬酸根、釩酸根或鎢酸根作為陰離子，以及鋰、納、 鉀、铷、鉋、鎂、鈣、锶或鋇作為陽離子。此等材料可同 樣地包含以二元、三元、四元或五元共晶形成無機金屬鹽 之所有鹽混合物。 當該層組態成相變材料合金時，相變材料合金包含至少 一種具有200°C與1800°C之間熔點之基於鋅、鎂、銘、 銅、鈣、矽、磷或銻的金屬合金。 圖3顯示在傳導熱介質之廢氣管道與熱電模組之間配置 相變材料的第一實施例。 根據圖3之圖可推斷’廢氣流20在此圖示意性所示之排 氧管道10内沿箭頭方向流動。此導致廢氣管道1〇的外表面 變熱，此外表面上已施加呈繞線66之形式的相變材料6〇。 可在封裝62中組態成薄相變材料6〇層之形式的相變材料6〇 將至少一個熱電模組40之内側與熱端分隔（在本發明之情 況下，亦即與傳導廢氣流2〇之廢氣管道1〇的外表面以分 隔）。如圖3中之圖明顯所示，至少一個熱電模組4〇之内側 可直接毗鄰封裝62之外側70，且此產生至少一個熱電模組 40及相變材料60之第一可能配置72。另一方面，至少一個 熱電模組40亦可已部分埋置於由相變材料仙組成之封裝62 中，且利用相變材料6〇之封裝62完全或部分包裹至少一個 熱電模組40之末端，以使至少-個熱電模組40僅外壁表面 保持裸露（亦即無包裹）。 元件符號68係指封裝62的外表面，該表面與至少一個熱 158887.doc 201240173 • 電材料40之内側接觸。廢氣管道10之外表面料與至少—個 熱電模組40之内側之間的封裝62之中間位置排除其不允許 的過熱。 由相變材料60組成之封裝62充當熱量存儲器，其在達到 特定溫度時開始熔融且由於其熔化熱容量而吸收大量熱。 除非相變材料60已在封裝62内完全熔融，否則溫度不升 高；該至少一個熱電模組4〇可在較高能量下操作。另一方 面，確保該至少一個熱電模組40被永久保護免受溫度影 響。雖然提供旁路之現存解決方法存在熱量損失，但本發 明所提出之涉及由相變材料組成之封裝62的解決方法提供 其中熱量的完全轉化。一旦熱廢氣流2〇之溫度回落至低於 相變材料60或相變材料合金之熔融溫度時，則相變材料 自固相變為液相時以熔化熱形式結合的熱量再次釋放。此 相變材料60可適應廢氣管道1〇之任何幾何形式；例如其可 呈圓形、角形、扁平或圓柱形。根據圖3之圖，相變材料 60在封裝62内可呈任何幾何形式，例如依層順序形成的圓 柱體形式、環狀形式及/或類似形式。. 圖4之圖中顯示用於保護至少一個熱電模組免受過高溫 度影響之相變材料之配置的另一實施例。 /、圖3之實施例對比，在圖4之實施例中，至少一個熱電 模組40在一側外部利用封裝^内之相變材料6〇封裝。元件 符號76指不封裝厚度。如圖4中之圖明顯所示，至少一個 熱電模組40之上端與下端之封裝厚度％基本相同；然而， 此並非絕對必要，且因此亦可根據熱應力，尤其封裝^之 158887.doc •12· 201240173 内側(亦即緊鄰外表面64)與至少一個熱電模組40之相關内 側之間出現之熱應力，提高所選擇之封裝厚度76，以使得 相^材料60尤其在此較高熱受壓點下具有足夠的分隔與足 夠的體積。圖4中之圖顯示至少一個熱電模組4〇基本上完 王被封裝62内的相變材料6〇圍繞。圖4所示之至少一個熱 電模組40之第二種可能配置同樣地產生本發明所提出之解 決方法的有利效果，如上文已結合圖3中之封裝實施例所 描述。 圖4所不之至少一個熱電模組40(其為熱電產生器30之一 4 /刀）之第二種可能配置78之可能組態亦達成以下效果’ 亦即相變材料6 〇由於其熱儲存容量高而使經由廢氣管道i 〇 之外表面64的熱廢氣流2〇所產生之高溫與至少一個熱電模 、且4〇隔離。首先，可保護此模組免受過熱影響；其次，從 長遠觀點來看，至少一個熱電模組4〇可在更高能量下操 作。根據封裝62之相變材料60之選擇，可使用例如熔點在 250°C與170(TC之間的無機金屬鹽，諸如使用氟化物、氣 化物、溴化物、碘化物、硫酸鹽、硝酸鹽、碳酸鹽、絡酸 鹽、鉬酸鹽、釩酸鹽及鎢酸鹽作為鋰、鈉、鉀、铷、绝、 鎂、鈣、锶及鋇之鹽。相變材料60為例如形成二元與三元 共明之上述無機金屬鹽的鹽組合物，或相變材料可組熊 成例如形成四元或五元共晶之上述無機金屬鹽之鹽組: 物。 另外’作為相變材料60，可使用形成二亓、一_ 〜 二7C、四元 或五元共晶之金屬合金及其組合，例如以下金屬：諸如 158887.doc •13· 201240173 鋅、鎂、鋁、銅、鈣、矽、磷及銻。此參屬合金之熔點在 200°C 與 1800°C 之間。 選擇相變材料60高度取決於在廢氣管道10之自由橫截面 内流動之廢氣流2〇之溫度。舉例而言，自燃内燃機之排氣 流與火花點燃内燃機之排氣流或可作為製程熱用於至少 一個熱電模組40之氣流可具有不同溫度。 【圖式簡單說明】 圖1用於保護熱電模組免受過离、、w许&細 皿度影響之具有現存旁 路之廢氣系統的示意結構； 圖2排氣管道或排氣再循環管道 ^遏内之熱電產生器之結 構； —個熱電模組之 圖3相變材料之第一實施例；及 圖4由相變材料組成之其中已y入至 封裝的另一實施例。 【主要元件符號說明】 10 排氣管道 12 用於TEG之排氣管道 14 熱電產生器（TEG) 16 旁路管道 18 閥門 20 廢氣流 22 第一廢氣流 24 第二廢氣流 30 熱電產生器（TEG) 158887.doc 管道 管道32之橫截面 熱電模組（TEM) 冷卻管 管道之内側 相變材料（PCM) 封裝 廢氣管道之外表面 圍繞10之PCM繞線 封裝之外表面 封裝之外側 第一 TEM配置 封裝厚度 第二TEM配置 •15-The Ybi4MnSbn® thermoelectric module 40 has a specific maximum operating temperature tg. If the temperature of the exhaust gas rises above this temperature, the thermoelectric module can be damaged and lose its operational capability. If a layer containing phase change material has been introduced between the inner side 48 of the conduit 32 and the hot end of the thermoelectric module 40, the layer can protect the thermoelectric module 40 from excessive temperature by storing excess heat. The phase change material is selected such that the phase change material begins to melt before the thermoelectric module reaches the maximum service temperature TG. This first compensates for the excessive temperature and protects the thermoelectric module 40' and secondly keeps the thermoelectric generator at a strange temperature. This results in better performance and improved efficiency of the thermoelectric module. Further, the excess heat qe stored in the phase change material is released again after the thermoelectric generator 3 is cooled, and can be converted into electric power by the thermoelectric module 40. In the method for heat recovery of exhaust gas hitherto, this excess heat is released into the environment without being used and cannot be used for power generation. 158887.doc 201240173 , ' The phase change material layer may be formed in a single piece or in at least one thin layer. It may also have been introduced into the entire area or section between the thermoelectric module 40 and the conduit 32, either parallel or perpendicular to the length of the conduit 32. The phase change material layer may have been integrated into the thermoelectric module 4 or the thermoelectric generator 3, applied to the inside of the official track 32 or separately introduced between the pipe 32 and the thermoelectric module 40 in the form of a separate layer. The phase change material layer may be disposed directly or indirectly between the heat source and the hot end of the thermoelectric module 4〇. In the case where the phase change material is directly disposed, it is in direct contact with the hot gas stream, and in the case of indirect configuration of the phase change material, the pipe wall of the exhaust gas pipe 1 is interposed between the hot exhaust gas stream and the phase change material. In the case where the phase change material is directly disposed, it is directly exposed to the hot gas stream (ie, the exhaust gas stream 20), and in the case where the phase change material layer is indirectly disposed, the pipe wall is interposed between the exhaust gas stream 20 (ie, the hot gas stream) and Phase change between materials. The phase change material layer may not only be in direct contact with the pipe 32 and the thermoelectric module 40, but may also be configured to surround at least one pure metal such as nickel, the material surrounding the pipe 32 and/or the sealing of the thermoelectric module 40. Wrong, chin, silver or iron, and / or at least one metal alloy based on nickel, chromium, iron, zirconium or titanium. The phase change material layer can be assembled in any of the following required locations: in the exhaust pipe, on the exhaust manifold or in the exhaust manifold, on the exhaust gas recirculation pipe or in the exhaust gas recirculation pipe, on the exhaust gas pipe or in the exhaust gas pipe, in the middle muffler In the upper or middle muffler and/or in the rear muffler or in the rear muffler. Possible phase change materials for this layer comprise all inorganic metal salts having a melting point between 250 ° C and 17 ° C. Suitable metal salts include, for example, IL ions, gas 158887.doc 201240173, bromide, iodide, sulfate, nitrate, carbonate, chromate, molybdate, vanadate or tungstate as anions, and lithium, sodium , potassium, strontium, planing, magnesium, calcium, strontium or barium as a cation. These materials may likewise comprise all salt mixtures of binary, ternary, quaternary or pentad eutectic to form inorganic metal salts. When the layer is configured as a phase change material alloy, the phase change material alloy comprises at least one metal alloy based on zinc, magnesium, indium, copper, calcium, strontium, phosphorus or bismuth having a melting point between 200 ° C and 1800 ° C. . Figure 3 shows a first embodiment of a phase change material disposed between an exhaust gas conduit that conducts a heat medium and a thermoelectric module. It can be inferred from the diagram of Figure 3 that the exhaust gas stream 20 flows in the direction of the arrow within the oxygen venting conduit 10 shown schematically in this Figure. This causes the outer surface of the exhaust gas conduit 1 to heat up, and in addition the phase change material 6〇 in the form of a winding 66 has been applied to the surface. The phase change material 6 in the form of a thin phase change material 6 〇 layer in the package 62 can separate the inner side of the at least one thermoelectric module 40 from the hot end (in the case of the present invention, ie, the conductive exhaust gas flow) 2) The outer surface of the exhaust pipe is separated by 1). As is apparent from the diagram of FIG. 3, the inner side of at least one thermoelectric module 4 can be directly adjacent to the outer side 70 of the package 62, and this produces at least one thermoelectric module 40 and a first possible configuration 72 of phase change material 60. On the other hand, at least one thermoelectric module 40 may also be partially embedded in the package 62 composed of the phase change material, and the end of the at least one thermoelectric module 40 may be completely or partially wrapped by the package 62 of the phase change material 6〇. So that at least one of the thermoelectric modules 40 is only exposed to the outer wall surface (ie, no package). Component symbol 68 refers to the outer surface of package 62 that is in contact with at least one of the inner sides of the heat 158887.doc 201240173 • electrical material 40. The intermediate position of the outer surface of the exhaust gas pipe 10 and the inner side of at least one of the thermoelectric modules 40 excludes the unacceptable overheating. The package 62, comprised of phase change material 60, acts as a thermal store that begins to melt upon reaching a particular temperature and absorbs a significant amount of heat due to its heat of fusion capacity. Unless the phase change material 60 has completely melted within the package 62, the temperature does not rise; the at least one thermoelectric module 4 can operate at higher energies. On the other hand, it is ensured that the at least one thermoelectric module 40 is permanently protected from temperature. While there are heat losses in existing solutions that provide bypass, the solution proposed by the present invention involving a package 62 comprised of a phase change material provides for complete conversion of heat therein. Once the temperature of the hot exhaust gas stream falls back below the melting temperature of the phase change material 60 or the phase change material alloy, the heat coupled in the form of heat of fusion is again released when the phase change material changes from the solid phase to the liquid phase. The phase change material 60 can accommodate any geometric form of the exhaust gas conduit 1; for example, it can be circular, angular, flat or cylindrical. According to the diagram of Fig. 3, the phase change material 60 can be in any geometric form within the package 62, such as in the form of a cylinder formed in a layer sequence, in the form of a ring, and/or the like. Another embodiment of a configuration of phase change material for protecting at least one thermoelectric module from excessive temperature is shown in the diagram of FIG. / In contrast to the embodiment of Fig. 3, in the embodiment of Fig. 4, at least one of the thermoelectric modules 40 is externally packaged on one side with a phase change material 6 内 in the package. Component Symbol 76 refers to the thickness of the package. As is apparent from the diagram in FIG. 4, the package thickness % of the upper end and the lower end of the at least one thermoelectric module 40 are substantially the same; however, this is not absolutely necessary, and thus may also be based on thermal stress, especially the package 158887.doc • 12· 201240173 Thermal stress occurring between the inner side (ie, immediately adjacent the outer surface 64) and the associated inner side of the at least one thermoelectric module 40 increases the selected package thickness 76 such that the material 60 is particularly hot pressed here. There is enough separation under the point and enough volume. The diagram in Figure 4 shows that at least one thermoelectric module 4 is substantially surrounded by a phase change material 6 内 in the package 62. The second possible configuration of the at least one thermoelectric module 40 shown in Figure 4 likewise produces the advantageous effects of the solution proposed by the present invention, as described above in connection with the package embodiment of Figure 3. The possible configuration of the second possible configuration 78 of at least one thermoelectric module 40 (which is one of the thermoelectric generators 30 / knives) of Figure 4 also achieves the following effect - that is, the phase change material 6 〇 due to its heat The storage capacity is high such that the high temperature generated by the hot exhaust gas stream 2〇 via the outer surface 64 of the exhaust gas conduit is isolated from at least one thermoelectric mold and 4〇. First, the module can be protected from overheating; secondly, at least one thermoelectric module 4 can operate at higher energies from a long-term perspective. Depending on the choice of phase change material 60 of package 62, for example, an inorganic metal salt having a melting point between 250 ° C and 170 (TC, such as fluoride, vapor, bromide, iodide, sulfate, nitrate, Carbonates, complexes, molybdates, vanadates, and tungstates are salts of lithium, sodium, potassium, rubidium, magnesium, calcium, strontium, and barium. Phase change materials 60 are, for example, binary and tertiary. The salt composition of the above inorganic metal salt, or the phase change material, may be formed into a salt group of the above-mentioned inorganic metal salt, for example, forming a quaternary or pentad eutectic: In addition, as the phase change material 60, it may be used. Metal alloys and combinations thereof forming a bismuth, a _~2, a 7C, a quaternary or a pentad eutectic, such as the following metals: such as 158887.doc • 13· 201240173 zinc, magnesium, aluminum, copper, calcium, strontium, phosphorus and The melting point of the reference alloy is between 200 ° C and 1800 ° C. The phase change material 60 is selected to be highly dependent on the temperature of the exhaust gas stream flowing in the free cross section of the exhaust gas conduit 10 . For example, spontaneous combustion The exhaust flow of an internal combustion engine and a spark ignite the exhaust flow of an internal combustion engine or may be used Process heat can be used for at least one thermoelectric module 40. The airflow can have different temperatures. [Simplified Schematic] Figure 1 is used to protect the thermoelectric module from over-current, w/amp; Schematic structure of the exhaust system; FIG. 2 is a structure of a thermoelectric generator in an exhaust duct or an exhaust gas recirculation duct; a first embodiment of a phase change material of FIG. 3 of a thermoelectric module; and FIG. Another embodiment of the variable material composition has been incorporated into the package. [Main component symbol description] 10 Exhaust pipe 12 Exhaust pipe for TEG 14 Thermoelectric generator (TEG) 16 Bypass pipe 18 Valve 20 Exhaust flow 22 First exhaust gas flow 24 Second exhaust gas flow 30 Thermoelectric generator (TEG) 158887.doc Cross-section thermoelectric module (TEM) of pipe pipe 32 The inner phase change material (PCM) of the cooling pipe pipe surrounds the outer surface of the exhaust pipe 10 PCM winding package outer surface package outer side first TEM configuration package thickness second TEM configuration • 15-