WO2011006308A1 - 外加电场型温差电池及其制冷装置 - Google Patents
外加电场型温差电池及其制冷装置 Download PDFInfo
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- WO2011006308A1 WO2011006308A1 PCT/CN2009/073041 CN2009073041W WO2011006308A1 WO 2011006308 A1 WO2011006308 A1 WO 2011006308A1 CN 2009073041 W CN2009073041 W CN 2009073041W WO 2011006308 A1 WO2011006308 A1 WO 2011006308A1
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- electric field
- plate
- thermopile
- type semiconductor
- battery
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- 230000005684 electric field Effects 0.000 title claims abstract description 196
- 239000004065 semiconductor Substances 0.000 claims abstract description 91
- 238000002955 isolation Methods 0.000 claims abstract description 23
- 239000003990 capacitor Substances 0.000 claims description 51
- 238000005057 refrigeration Methods 0.000 claims description 32
- 238000010248 power generation Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- 238000004377 microelectronic Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims 1
- 239000000463 material Substances 0.000 description 25
- 239000002184 metal Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000000969 carrier Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 230000002301 combined effect Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
Definitions
- the invention relates to an external electric field type thermoelectric power generation thermopile battery, in particular to provide a regulated electric field for a thermopile battery through an external power source, which can enhance the self-built electric field of the Schottky p-n junction region.
- a refrigeration apparatus comprising such an external electric field type thermoelectric power generation thermopile.
- thermopile battery having a Schottky p-n junction characteristic composed of a p-type semiconductor and an n-type semiconductor, as shown in Fig. 1.
- thermopile battery is composed of: power supply positive plate 2.1, power supply negative plate 2.2, p-type semiconductor 2.3, n-type semiconductor 2.4, stack conductive plate 2.5, upper thermal conductive insulating plate 2.6, lower thermal conductive insulating plate 2.7, pn junction 2.8.
- the figure shows a p-type semiconductor-stack conductive metal plate-n-type semiconductor combination of a thermopile cell, and a self-built electric field of the formed Schottky barrier layer, and the direction of the electric field is directed from the n region to the p region. / 3 ⁇ 4 thermopile output ZX battery.
- the n-type semiconductor is an N-type (electronic type) semiconductor in which an impurity is greatly increased in the intrinsic semiconductor material by doping impurities.
- the P-type semiconductor is doped with impurities to greatly increase the hole concentration, and is called a p-type (hole type) semiconductor.
- the thermal radiation energy of the heat radiator passes through the Schottky junction region (thermoelectric pair) of the thermopile cell, and the thermal radiant energy is greater than the Schottky region energy gap, the thermal radiation can be electron and hole pairs in the Schottky junction region. Absorption, increasing the potential energy of electron and hole pairs. High potential energy electrons and hole pairs will be subjected to Schottky junctions
- the influence of the built electric field flows to the n-zone collector plate and the p-zone collector plate respectively, and generates a thermal current/ ⁇ between the n-zone collector plate and the p-zone collector plate and the load.
- thermopile battery of polycrystalline material is a characteristic parameter of the battery itself. Therefore, the self-built electric field that affects the polycrystalline material thermopile battery has three main effects:
- the grain boundary acts as a crystal defect and acts as an effective composite positive load carrier.
- the Schottky junction region where the metal is directly bonded to the semiconductor exhibits a positive load-to-recombination probability at the semiconductor junction.
- the present invention provides an electric field type thermoelectric power generation thermopile battery structure, in particular, an electric field pole of an electric field type thermopile battery is connected through an external power source to form an enhanced and stabilized self-built electric field in the battery, thereby improving
- the thermoelectric material has a good value coefficient, and forms a battery of an electric field type thermoelectric power generation structure with high conversion efficiency.
- the present invention will also provide a refrigeration apparatus comprising such an external electric field type thermopile. Since the thermopile has a reversible working mode of thermoelectric power generation and thermoelectric cooling, the electric field type thermopile can also form a thermoelectric refrigeration reactor.
- thermoelectric power generation thermoelectric stack battery which is composed of a p-type semiconductor and an n-type semiconductor.
- a stack conductive plate connected with a p-type semiconductor and an n-type semiconductor is provided (also called a conductive metal plate); a p-type semiconductor and an n-type semiconductor and the stack conductive plate are respectively Schottky ⁇ junction regions;
- the power supply positive plate and the power supply negative plate are respectively associated with a p-type semiconductor, An n-type semiconductor connection; at the same time, an upper thermal conductive insulating plate and a lower thermal conductive insulating plate are respectively disposed on the heat source surface and the back surface of the thermopile battery; wherein, in the lower guiding An electric isolation layer is disposed between the thermal insulation board and the positive electrode plate of the power source, and an electric field negative plate of an external voltage (or an external voltage or an external power supply) is disposed under the electric isolation
- the invention accesses an external electric field type thermoelectric power generation thermopile battery through an external power source, and the external power supply voltage range of a single stack battery is 0.5V ⁇ V W ⁇ 2V, wherein the size of the power supply voltage ⁇ and the semiconductor material selected in the n region and the p region are selected.
- the effective thickness L of the stack battery between the electric field plates the greater the thickness, the higher the voltage, the effective thickness L of the general stack battery is between 1.5 mm ⁇ L ⁇ 5 mm, and the effective thickness L of the microelectronic thermopile is Between 0.15 / ⁇ L ⁇ 500 /.
- the electrical isolation layer described above is constructed of a thermally conductive insulating material.
- the non-directional ends of the n-type semiconductor and the p-type semiconductor are bonded by a conductive metal plate, and the bonding surface of the conductive metal plate and the n-type semiconductor and the p-type semiconductor is Each of them forms a Schottky junction region, and the carrier diffusion self-built electric field /2, the n-type semiconductor-conductive metal plate-P-type semiconductor self-built electric field sum is E R , and the E R electric field direction is from the n region to the p region.
- the other ends of the n-type semiconductor and the p-type semiconductor respectively form a negative electrode and a positive electrode of the thermopile battery output through the respective conductive metal plates.
- an electric field plate of an externally isolated external voltage is respectively combined, and the electrical isolation layer is a thermal conductive insulating material.
- the isolated electric field plate of the n-type semiconductor negative electrode composite is connected to the external voltage ⁇ positive electrode
- the isolated electric field plate of the p-type semiconductor positive electrode is connected to the external voltage ⁇ negative electrode
- the n-type semiconductor and the p-type semiconductor are at the same end
- the conductive metal plate is connected to the midpoint voltage V w /2 of the external voltage V w series capacitor, at which time a regulated electric field £ w is formed inside the n-type semiconductor and the p-type semiconductor.
- the electric field type thermopile battery structure is shown in Fig. 5.
- thermoelectric figure of merit of the material Because of different thermoelectric ⁇
- thermoelectric materials have their own suitable operating temperature range. It is customary to use the dimensionless quantity of thermoelectric figure of merit and temperature to describe the thermoelectric properties of the material ( ⁇ is the average temperature of the material). There are generally two ways to increase the enthalpy of thermoelectric materials themselves: one is to increase their power factor ( ⁇ 2 ⁇ ) and the other is to reduce their heat transfer coefficient ( .
- the physical mechanisms affecting the power factor include scattering parameters, energy density, carrier mobility, and Fermi level.
- the essential properties of the material cannot be changed. Therefore, the conventional structure of the thermopile can only be improved by selecting a better and more pure thermoelectric material.
- the physical quantity of the thermoelectric material itself can be controlled by the method of the invention, and a regulated electric field inside the thermopile can be added to increase the energy density, carrier mobility, reduce the scattering parameter, and change the semiconductor doping concentration. To adjust the Fermi level to reach the maximum value.
- Thermal conductivity of solid materials including lattice heat transfer coefficient (K L ) and electron heat transfer coefficient
- thermoelectric material most of the thermal conduction of thermoelectric materials is conducted through the crystal lattice.
- the lattice heat transfer coefficient ( ⁇ ) is proportional to the three basic physical quantities of the thermoelectric material's constant volume specific heat (C), sound velocity, and mean free path.
- C constant volume specific heat
- the first two physical quantities are the essence of the thermoelectric material and cannot be changed, while the mean free path is related to the material.
- the amount of impurities or grain boundaries changes. So today, for thermoelectric materials, when there is no good way to improve the power factor, they focus on the study of nanostructures and the low-dimensional structural features of nanowires. And the hollow quantum effect is expected to fully limit the phonon conduction and reduce the thermal conductivity of the thermoelectric material to improve the thermoelectric figure of merit Z of the material.
- the semiconductor material used should be a compound pair of elements falling on both sides of the metal and non-metal conversion lines of the periodic table.
- the most commonly used elements are: silicon (Si), germanium (Ge), germanium (Bi), antimony (Sb), tellurium (Te), selenium (Se), and half-Heusler, square cobalt. Mines, metal oxides, etc.
- thermopile battery of the present invention can be used in series.
- thermopile refrigeration device which is composed of a p-type semiconductor and an n-type semiconductor, and is provided with a p-type semiconductor, n on the cooling surface of the thermopile refrigeration device.
- a semiconductor-connected stack conductive plate also referred to as a conductive metal plate
- a p-type semiconductor and an n-type semiconductor and the stack conductive plate are respectively Schottky pn junction regions
- the positive electrode plate and the negative electrode plate of the power supply are respectively connected to the p-type semiconductor and the n-type semiconductor; and at the same time, the upper heat conductive insulating plate and the lower heat conductive insulating plate are respectively disposed on the cooling surface and the back surface of the thermopile refrigeration device;
- An electric isolation layer is disposed between the lower thermal conductive insulating plate and the positive electrode plate of the power source, and an electric field negative electrode plate with an external voltage is disposed under the electrical isolation layer; between the lower thermal conductive insulating plate and the negative electrode plate of the power supply, An electric isolation layer is disposed, and an electric field positive electrode plate with an external voltage is disposed under the electric isolation layer; between the electric field positive electrode plate of the external voltage and the electric field negative electrode plate
- the R load is replaced by the cooling power supply, and the refrigeration unit can be constructed.
- the original heat source surface of the battery becomes the cooling surface.
- An external electric field type temperature difference refrigerating thermopile is applied.
- the external power supply voltage range is V w ⁇ l.5V 2
- V 2 is the temperature difference cooling thermopile supply voltage.
- the specific structure of the electric field type thermopile refrigeration device of the present invention is: a battery power positive electrode plate (4.1), a battery power negative electrode plate (4.2), a P-type semiconductor (4.3), an N-type semiconductor (4.4), and a stack conductive Plate (4.5), electric field negative plate (4.7), electric field positive plate (4.6), upper thermal insulating plate (4.8), lower thermal insulating plate (4.9), electric field power supply, capacitor (Cl), capacitor (C2), cooling power supply (V 2 ); in the electric field type thermopile refrigeration device structure, the electric field negative plate (4.7) and the electric field positive plate (4.6) are composited in the lower thermal conductive insulating plate (4.9), and the electric field negative plate (4.7), electric field
- the positive plate (4.6) is electrically isolated from the electrodes of the thermopile refrigeration device; the output of the electric field power supply is connected to a capacitor (Cl) and a capacitor (C2) connected in series, and the capacities of the two capacitors are equal, and the capacitor (Cl) and capacitor (C2)
- the voltage at the midpoint of the connection is V w /2 ; the positive and negative terminals of the electric field power supply V w are connected to the electric field positive plate (4.6) and the electric field negative plate (4.7) respectively, and the series capacitor (Cl) and capacitor (C2) are connected.
- point voltage V w / 2 electrically connected to the conductive plate stack 4.5; this plate (4.5) and the electric field the negative electrode plate (4.7) of P-type semiconductor electric field is formed.
- thermoelectric power generation thermopile battery Like the electric field type thermoelectric power generation thermopile battery, the electric field type thermopile refrigeration apparatus of the present invention can also be used in series.
- Electric field type thermopile cell structure of the present invention is regulated by applying electric field E w, to enhance the stability of the thermopile battery internal self field and improve the Seebeck coefficient ", while the electric field on P + region minority carrier - charge carriers, N zone in the minority - Positive carriers, the negative electrode and the positive electrode of the thermopile battery have blocking and reflection effects, which reduce the combined effect of positive load carriers, and the electric field can adjust the polycrystalline grain boundary barrier between n regions and p regions.
- Electric field thermopile type battery structure regulated by an electric field applied, the battery system optimized thermopile parameters to improve the power factor ( "2 ⁇ ), to achieve the purpose of improving the coefficient ⁇ merit.
- the present invention is an electric field applied by an external power access thermopile type temperature difference between the battery and the external power supply external electric field when formed, an electric field is applied thermopile type temperature difference value battery materials ⁇ 2 with the carrier concentration and field-type battery temperature differential thermopile A comparison of the ⁇ value with the change in the carrier concentration trend is shown in Figure 5.
- thermopile battery 1 is a schematic diagram of a structure of a conventional thermopile battery
- thermopile 2 is a schematic structural view of a structure of an electric field type thermopile according to the present invention
- FIG. 3 is a schematic structural view of the electric field type thermopile refrigeration sheet of the present invention.
- Fig. 4 is a schematic diagram of the working principle of the external electric field power supply in the battery structure of the series electric field type thermopile.
- thermoelectric thermopile battery material ⁇ 2 value with carrier concentration change trend diagram
- an electric field type thermopile battery structure of the present invention is composed of: a battery power positive electrode plate 4.1, a battery power negative electrode plate 4.2, a ⁇ -type semiconductor 4.3, a ⁇ -type semiconductor 4.4, a stack conductive plate 4.5, an electric field positive electrode.
- the plate 4.6, the electric field negative plate 4.7, the upper thermal conductive insulating plate 4.8, the lower thermal conductive insulating plate 4.9, the electric field power supply, the capacitor C1, the capacitor C2, and the load resistor R are composed.
- the electric field negative electrode plate 4.7 and the electric field positive electrode plate 4.6 are composited in the lower thermal conductive insulating plate 4.9, and the electric field negative electrode plate 4.7 and the electric field positive electrode plate 4.6 are electrically isolated from the electrodes of the thermopile battery.
- Electric power output terminal is connected in series with capacitor Cl, capacitor C2, the two capacitors of equal capacity, so that the series capacitor Cl, capacitor C2 is connected to a midpoint voltage V w / 2.
- the electric field power supply V w output terminal is connected to the negative pole and the negative pole respectively 4.6 with the electric field of the positive electrode plate negative electrode plate 4.7, and the series capacitor C1, the capacitor C2 is connected to a midpoint voltage V w / 2 electrically connected to the conductive plate stack 4.5.
- the positive electrode plate and electric conductive plate stack is formed between the n-type semiconductor stack electrically conductive field plate 4.5 4.5 p-type electric field between the anode plate 4.7 forming semiconductor field E w.
- the working principle of the electric field type thermopile battery structure of the present embodiment is: by externally adjusting the electric field, enhancing and stabilizing the self-built electric field inside the thermopile battery, and improving the Seebeck coefficient", while the electric field + pair P Zone minority-loader, N-zone minority-positive carrier, in the thermopile battery output negative electrode, positive electrode has blocking and reflection, which reduces the combined effect of positive load carriers, and the electric field can adjust the N zone
- the P-zone polycrystalline grain boundary barrier direction enhances the migration of carriers and improves the conductivity cr. Therefore, the electric field type thermopile cell structure optimizes the parameters of the thermopile battery system by externally adjusting the electric field, and improves the power.
- the factor (“V) achieves the purpose of increasing the figure of merit Z.
- an electric field type thermopile battery structure of the present embodiment can be connected in series with a plurality of electric field type thermopile batteries.
- the working principle of the external electric field power supply in the series electric field type thermopile battery structure is three electric field type thermoelectrics.
- the electric field type thermopile refrigeration sheet structure of the present invention is composed of: a positive electrode plate 5.1, a negative electrode plate 5.2, a P-type semiconductor 5.3, an N-type semiconductor 5.4, a stack of conductive plates 5.5, an electric field positive electrode. Plate 5.6, electric field negative plate 5.7, upper thermal insulation insulating plate 5.8, lower thermal insulation insulating plate 5.9, electric field power supply, capacitor Cl, capacitor C2, cooling power supply ⁇ .
- the electric field negative plate 5.7 and the electric field positive plate 5.6 are composited in the lower thermal conductive insulating plate 5.9, and the electric field negative plate 5.7 and the electric field positive plate 5.6 are electrically isolated from the electrodes of the thermopile.
- the output of the electric field power supply V w is connected to the capacitor C1 and C2 in series.
- the capacitance of the two capacitors is equal, so the capacitor in series
- the voltage at the midpoint of Cl and capacitor C2 is V w /2.
- VI correct output electric power is connected to the electric field of the positive electrode plate 5.6 5.7 negative electrode and the negative electrode plate, respectively, and the series capacitor Cl
- capacitor C2 is connected to a midpoint voltage V w / 2 electrically connected to the conductive plate stack 5.5.
- an n-type semiconductor forms an electric field between the electric field positive electrode plate 5.6 and the stack conductive plate 5.5, and an electric field is formed between the p-type semiconductor between the stack conductive plate 5.5 and the electric field negative plate 5.7.
- thermopile refrigeration chip structure of the present embodiment is: by externally adjusting the electric field, enhancing and stabilizing the self-built electric field inside the thermopile battery, and improving the Seebeck coefficient", while the electric field + pair
- the P-small sub-loader, the N-zone minority-positive carrier has a blocking and reflection effect on the negative electrode and the positive electrode of the thermopile battery output, which reduces the combined effect of the positive load carriers, and the electric field can adjust n
- the polycrystalline grain boundary barrier between the region and the p region enhances the migration of carriers, improves the conductivity cr, and reduces the internal resistance of the thermopile. Therefore, the structure of the electric field type thermopile is optimized by applying an electric field.
- the thermopile battery system parameters improve the power factor ("V) and achieve the purpose of increasing the figure of merit Z.
- FIG. 4 is a schematic diagram of three electric field type thermopile power generation series circuits (thermome refrigeration operation, replacing R load with refrigeration power supply).
- the P-type output positive electrode of the stack 1 is connected to the N-type output negative electrode of the stack 2
- the P-type output positive electrode of the stack 2 is connected to the N-type output negative electrode of the stack 3
- the P-type output of the stack 3 is positive.
- the electrode and the N-type output negative electrode of the stack 1 constitute the output positive and negative poles of the series electric field type thermopile.
- the electric field power supply V w outputs positive and negative electrodes connected with a series capacitor Cl-C6.
- the electric field power supply V w outputs the positive electrode connected to the stack 1 electric field positive plate, the electric field power output negative electrode is connected to the stack 3 electric field negative plate.
- the intermediate voltage of the series capacitor C1-C2 is connected to the stack conductive plate of the stack 1, and the intermediate voltage V 2 of the series capacitor C2-C3 is connected to the electric
- the intermediate voltage V 2 _ 3 of the series capacitor C3-C4 is connected to the stack conductive plate of the stack 2
- the intermediate voltage V of the series capacitor C4-C5 3 connected to the P-type electric field negative electrode of the stack 2 and the N-type electric field positive electrode of the stack 3
- the intermediate voltage V 3 _ 4 of the series capacitor C5-C6 is connected to the stack conductive plate of the stack 3.
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Description
外加电场型温差电池及其制冷装置 技术领域
本发明涉及一种外加电场型温差发电热电堆电池, 尤其是通过外部电源 为热电堆电池提供一个调控的电场, 该电场可以增强肖特基 p-n结区载流子 扩散自建电场。 提高热电材料 ΖΓ优值系数, 形成转换效率较高的温差热电 堆发电, 以及热电制冷的电堆装置。 本发明还涉及这种外加电场型温差发电 热电堆构成的制冷装置。
背景技术
当前热电堆电池的基本结构, 都是采用 p型半导体、 n型半导体所组成的 具有肖特基 p-n结特征的热电堆电池, 参看附图 1 所示。
热电堆电池是由: 电源正极板 2.1、 电源负极板 2.2、 p型半导体 2.3、 n型 半导体 2.4、 电堆导电板 2.5、上导热绝缘板 2.6、下导热绝缘板 2.7、 pn结 2.8 所 组成。
图中 是热电堆电池 p型半导体-电堆导电金属板 -n型半导体结合, 所形 成的肖特基势垒层的自建电场 , 电场方向从 n区指向 p区。 /¾是热电堆 电池输出电巟。
n型半导体是在本征半导体材料中,掺入杂质使自由电子浓度大大增加, 称为 N型(电子型)半导体。 P型半导体在本征半导体中, 掺入杂质使空穴浓 度大大增加, 称为 p型 (空穴型)半导体。
当热辐射体的热辐射能量通过热电堆电池肖特基结区 (热电对), 并热 辐射能大于肖特基区能隙时, 热辐射能被肖特基结区的电子和空穴对吸收, 提高电子和空穴对的势能。 高势能的电子和空穴对会分别受到肖特基结区自
建电场 的影响, 分别流向 n区集电板与 p区集电板放热, 并在 n区集电板、 p区集电板与负载之间产生热电流 /β。
多晶材料的热电堆电池内自建电场 , 是电池本身的特征参数。 所以, 影响多晶材料热电堆电池的自建电场 , 主要有以下三个方面影响:
1、 晶粒间界处存在势垒, 阻断载流子的通过, 导电率降低。
2、 晶粒间界作为一种晶体缺陷, 起着有效复合正负载流子对中心作用。
3、 金属直接与半导体结合的肖特基结区, 在半导体结合面表现正负载 流子对复合几率增大。
发明内容
为了提高热电堆电池转换效率, 本发明提供一种电场型温差发电热电堆 电池结构, 尤其是通过外部电源接入电场型热电堆电池的电场极, 形成一个 增强与稳定电池内自建电场 , 提高热电材料 ΖΓ优值系数, 形成转换效率 较高的电场型温差发电结构的电池。本发明还将提供由这种外加电场型热电 堆构成的制冷装置。 由于热电堆具有温差发电与热电制冷可逆工作方式, 所 以, 电场型热电堆也可以形成热电制冷的电堆装置。
实现本发明目的技术方案是:
一种外加电场型温差发电热电堆电池, 由 ρ型半导体、 η型半导体组成, 在该热电堆电池的热源面, 设有与 ρ型半导体、 η型半导体连接的电堆导电 板(也称为导电金属板) ; ρ型半导体与 η型半导体与该电堆导电板之间分 别为肖特基 ρη结区; 在该热电堆电池的背面, 电源正极板与电源负极板分 别与 ρ型半导体、 η型半导体连接; 同时, 在该热电堆电池的热源面及其背 面, 分别设置有上导热绝缘板与下导热绝缘板; 其特征在于, 在所述的下导
热绝缘板与电源正极板之间, 设有电隔离层, 该电隔离层下面设有外接电压 (或称为外加电压, 或外接电源)的电场负极板; 在所述的下导热绝缘板与 电源负极板之间, 设有电隔离层, 该电隔离层下面设有外接电压的电场正极 板; 所述的外接电压的电场正极板和所述的外接电压的电场负极板之间, 设 有外加电压; 所述的电堆导电板(也称为导电金属板)与该外加电压的中点 电压连接; 在 N型半导体和 P型半导体内部形成调控电场。
本发明通过外部电源接入外加电场型温差发电热电堆电池, 在单个电堆 电池加外电源电压范围 0.5V≤VW≤2V , 其中电源电压 ^的大小与 n区与 p区 选用的半导体材料, 以及电场极板之间的电堆电池有效厚度 L有关, 厚度越 大, 电压越高, 一般电堆电池有效厚度 L在 1.5mm≤L≤5mm之间, 微电子型 热电堆有效厚度 L在 0.15/ ≤ L≤ 500/ 之间。
以上所述的电隔离层采用导热绝缘材料构成。
换言之, 本发明的电场型温差发电热电堆电池结构中, n型半导体和 p型 半导体的同向一端, 用导电金属板进行结合, 在导电金属板与 n型半导体和 p 型半导体的结合面, 各自形成肖特基结区, 并载流子扩散自建电场 /2 , n 型半导体 -导电金属板 -P型半导体自建电场总和为 ER , ER电场方向从 n区指向 p区。 n型半导体和 p型半导体的另外一端分别通过各自结合的导电金属板, 分别形成热电堆电池输出的负电极与正电极。 在热电堆电池输出的负电极、 正电极与 n型半导体和 p型半导体同向一端的导电金属板外侧, 分别各自复合 一层电隔离的外接电压的电场极板, 电隔离层是导热绝缘材料。 其中, n型 半导体负电极复合的隔离电场极板接外接电压^正极, p型半导体正电极复 合的隔离电场极板接外接电压^负极, n型半导体和 p型半导体同向一端的
导电金属板连接外接电压 Vw串连电容的中点电压 Vw /2 ,此时在 n型半导体和 p型半导体内部形成调控电场 £w。 电场型热电堆电池结构, 参看附图 5所示。
热电堆电池温差发电与热电制冷是基于 Seebeck (赛贝克)效应, Peltier (珀尔帖)效应。 这一理论指出: 优良的热电材料本身, 应具有高的 Seebeck 系数 α (其值为《 = ^ , 其单位 V/°C )、 低的热导率 、 高的电导率 σ, 这三 dT
参数关联起来: τ— ^。 式中 ζ称为材料的热电优值系数。 因为不同的热电 κ
材料都有各自的适宜工作温度范围, ***均温度)。 当今提升热电材料本身 Ζ值的方法一般有两种: 一是提高其功率因子 ( α 2 σ ) , 二是降低其热传导系数 ( 。
影响功率因子的物理机制包括散射参数、 能态密度、 载流子迁移度及费 米能级等四项。 而传统结构的热电堆在前三项是材料的本质性质无法改变。 所以传统结构的热电堆, 只能依靠选择更好更纯的热电材料来改进。 而实际 上能控制热电材料本身功率因子的物理量, 可以通过本发明的方法, 加入热 电堆内部一个调控电场, 提高能态密度、 载流子迁移度, 降低散射参数, 以 及通过改变半导体掺杂浓度来调整费米能级, 以达到最大的 值。
固体材料热传导系数( 包括了晶格热传导系数( KL )及电子热传导系数
( Ke ) , 即 = + ¾。 热电材料之热传导大部份是通过晶格来传导。 晶格热 传导系数 (^)正比于热电材料的定容比热(C )、 声速、 平均自由程三个基本 物理量, 前二个物理量是热电材料的本质, 无法改变, 而平均自由程则随材 料中杂质或晶界的多寡而改变。 所以当今对热电材料而言, 在没有提出好的 办法提高功率因子时, 都集中在研究纳米结构, 以及纳米线的低维结构特征
和空心量子效应, 可望充分限制声子传导, 降低热电材料的热导率 来提 高材料的热电优值系数 Z的目的。
为了提高多晶材料光伏电池与热电堆电池转换效率, 所使用的半导体材 料, 应是落在元素周期表的金属与非金属转换线两侧的元素的化合物对。 最 常用的元素为: 硅(Si )、锗(Ge )、铋(Bi )、锑(Sb )、碲(Te )、 硒(Se ) , 以及半赫斯勒合金(half-Heusler )、 方钴矿、 金属氧化物等。
本发明的外加电场型热电堆电池可以串联使用。
完成本申请第 2个发明任务的方案是:一种外加电场型热电堆制冷装置, 由 p型半导体、 n型半导体组成, 在该热电堆制冷装置的制冷面, 设有与 p 型半导体、 n型半导体连接的电堆导电板(也称为导电金属板) ; p型半导 体与 n型半导体与该电堆导电板之间分别为肖特基 pn结区; 在该热电堆制 冷装置的背面, 电源正极板与电源负极板分别与 p型半导体、 n型半导体连 接; 同时, 在该热电堆制冷装置的制冷面及其背面, 分别设置有上导热绝缘 板与下导热绝缘板;其特征在于,在所述的下导热绝缘板与电源正极板之间, 设有电隔离层, 该电隔离层下面设有外接电压的电场负极板; 在所述的下导 热绝缘板与电源负极板之间, 设有电隔离层, 该电隔离层下面设有外接电压 的电场正极板; 所述的外接电压的电场正极板和所述的外接电压的电场负极 板之间, 设有外加电压; 所述的电堆导电板(也称为导电金属板)与该外加 电压的中点电压连接; 在 N型半导体和 P型半导体内部形成调控电场。 供电 (外加电压同时存在) , 将 R负载换成制冷电源制冷电源, 即可构成制 冷装置, 电池原来的热源面即成为制冷面。
外加电场型温差制冷热电堆, 在单个电堆加外电源电压范围 Vw≥ l.5V2 , V2为温差制冷热电堆供电电压。
换言之, 本发明所述电场型热电堆制冷装置的具体结构是: 电池电源正 极板 (4.1)、 电池电源负极板 (4.2)、 P型半导体 (4.3)、 N型半导体 (4.4)、 电堆导 电板 (4.5)、 电场负极板 (4.7)、 电场正极板 (4.6)、 上导热绝缘板 (4.8)、 下导热 绝缘板 (4.9)、 电场电源 、 电容 (Cl)、 电容 (C2)、 制冷电源 (V2)所组成; 电 场型热电堆制冷装置结构中, 电场负极板 (4.7)、 电场正极板 (4.6)是复合在下 导热绝缘板 (4.9)之中, 并且电场负极板 (4.7)、 电场正极板 (4.6)与热电堆制冷 装置各电极电气隔离; 电场电源 输出端连接串联的电容 (Cl)、 电容 (C2), 两个电容的容量相等, 串联的电容 (Cl)、 电容 (C2)连接中点的电压是 Vw /2 ; 电场电源 Vw输出端正极与负极分别连接电场正极板 (4.6)与电场负极板 (4.7) , 而串联的电容 (Cl)、 电容 (C2)连接中点的电压 Vw /2连接电堆导电板 4.5 ; 此 板 (4.5)与电场负极板 (4.7)之间 P型半导体形成电场 。
与电场型温差发电热电堆电池相同, 本发明的电场型热电堆制冷装置也 可以串联使用。
本发明的电场型热电堆电池结构是通过外加调控电场 Ew , 增强与稳定 热电堆电池内部自建电场 ,提高了 Seebeck系数", 同时电场 + 对 P 区少子 -负载流子, N区少子 -正载流子, 在热电堆电池输出负电极、 正电极 有阻挡和反射作用, 既减少了正负载流子的之复合作用, 而电场 能调整 n 区、 p区多晶体晶粒间界势垒方向, 增强载流子的迁移, 提高了电导率 σ 。
所以电场型热电堆电池结构, 是通过外加调控电场 , 优化热电堆电 池***参数, 提高了功率因子(《2σ ), 达到提高优值系数 Ζ的目的。
本发明通过外部电源接入外加电场型温差热电堆电池, 而外部电源所形 成的外部电场在 时, 外加电场型温差热电堆电池材料 Ζ2值随载流子浓度 与无电场型温差热电堆电池 Ζ值随载流子浓度变化趋势值的对比图, 参看附 图 5所示。
附图说明
图 1为现有热电堆电池结构原理图;
图 2为本发明电场型热电堆电池结构原理图;
图 3为本发明电场型热电堆制冷片结构原理图;
图 4串联电场型热电堆电池结构中外电场电源工作原理图。
图 5外加电场型温差热电堆电池材料 Ζ2值随载流子浓度变化趋势图 具体实施方式
实施例 1
参照附图 2所示, 本发明一种电场型热电堆电池结构是由: 电池电源正 极板 4.1、电池电源负极板 4.2、 Ρ型半导体 4.3、 Ν型半导体 4.4、电堆导电板 4.5、 电场正极板 4.6、 电场负极板 4.7、 上导热绝缘板 4.8、 下导热绝缘板 4.9、 电场 电源 、 电容 Cl、 电容 C2、 负载电阻 R所组成。 电场型热电堆电池结构中, 电场负极板 4.7、 电场正极板 4.6是复合在下导热绝缘板 4.9之中, 并且电场负 极板 4.7、 电场正极板 4.6与热电堆电池各电极电气隔离。 电场电源 输出端 连接串联的电容 Cl、 电容 C2, 两个电容的容量相等, 所以串联的电容 Cl、 电容 C2连接中点的电压是 Vw / 2。 电场电源 Vw输出端正极与负极分别连接电
场正极板 4.6与电场负极板 4.7 , 而串联的电容 C1、 电容 C2连接中点的电压 Vw /2连接电堆导电板 4.5。 此时电场正极板 4.6与电堆导电板 4.5之间 n型半导 体形成电场 电堆导电板 4.5与电场负极板 4.7之间 p型半导体形成电场 Ew。
参照附图 2所示, 本实施例一种电场型热电堆电池结构的工作原理是: 通过外加调控电场 , 增强与稳定热电堆电池内部自建电场 , 提高了 Seebeck系数", 同时电场 + 对 P区少子 -负载流子, N区少子-正载流 子, 在热电堆电池输出负电极、 正电极有阻挡和反射作用, 既减少了正负载 流子的之复合作用, 而电场 能调整 N区、 P区多晶体晶粒间界势垒方向, 增强载流子的迁移, 提高了电导率 cr。 所以电场型热电堆电池结构, 是通 过外加调控电场 , 优化热电堆电池***参数, 提高了功率因子(《V ), 达 到提高优值系数 Z的目的。
参照附图 4所示, 本实施例一种电场型热电堆电池结构, 可以进行多个 电场型热电堆电池串联连接, 串联电场型热电堆电池结构中外电场电源工作 原理图是 3个电场型热电堆电池串联示意图。
实施例 2
参看附图 3所示,, 本发明一种电场型热电堆制冷片结构是由: 电源正 极板 5.1、 电源负极板 5.2、 P型半导体 5.3、 N型半导体 5.4、电堆导电板 5.5、 电场正极板 5.6、 电场负极板 5.7、 上导热绝缘板 5.8、 下导热绝缘板 5.9、 电 场电源 、 电容 Cl、 电容 C2、 制冷电源 ^所组成。 电场型热电堆制冷片结 构中, 电场负极板 5.7、 电场正极板 5.6是复合在下导热绝缘板 5.9之中, 并 且电场负极板 5.7、电场正极板 5.6与热电堆各电极电气隔离。电场电源 Vw输 出端连接串联的电容 Cl、 电容 C2, 两个电容的容量相等, 所以串联的电容
Cl、 电容 C2连接中点的电压是 Vw /2。 电场电源 VI输出端正极与负极分别 连接电场正极板 5.6与电场负极板 5.7, 而串联的电容 Cl、 电容 C2连接中 点的电压 Vw /2连接电堆导电板 5.5。 此时电场正极板 5.6与电堆导电板 5.5 之间 n型半导体形成电场 , 电堆导电板 5.5与电场负极板 5.7之间 p型半 导体形成电场 。
参照附图 3所示,本实施例一种电场型热电堆制冷片结构的工作原理是: 通过外加调控电场 , 增强与稳定热电堆电池内部自建电场 , 提高了 Seebeck系数", 同时电场 + 对 P区少子 -负载流子, N区少子-正载流 子, 在热电堆电池输出负电极、 正电极有阻挡和反射作用, 既减少了正负载 流子的之复合作用, 而电场 能调整 n区、 p区多晶体晶粒间界势垒方向, 增强载流子的迁移, 提高了电导率 cr , 降低了热电堆内阻。 所以电场型热 电堆制冷片结构, 是通过外加调控电场 , 优化热电堆电池***参数, 提 高了功率因子(《V ), 达到提高优值系数 Z的目的。
参照附图 4所示, 本发明的电场型热电堆发电与制冷片结构, 可以进行 多个电场型热电堆发电与制冷片串联连接。 附图 4中是 3个电场型热电堆发 电串联电路示意图 (热电堆制冷工作, 将 R负载换成制冷电源)。 电堆 1的 P型输出正电极与电堆 2的 N型输出负电极连接, 电堆 2的 P型输出正电极 与电堆 3的 N型输出负电极连接, 电堆 3的 P型输出正电极与电堆 1的 N 型输出负电极构成串连电场型热电堆的输出正、 负极。 电场电源 Vw输出正、 负电极连接有串连电容 Cl-C6。 电场电源 Vw输出正极连接电堆 1电场正极 板, 电场电源 输出负极连接电堆 3电场负极板。 串联电容 C1-C2的中间 电压 连接电堆 1的电堆导电板, 串联电容 C2-C3的中间电压 V2连接电
堆 1的 P型电场负电极与电堆 2的 N型电场正电极, 串联电容 C3-C4的中 间电压 V2_3连接电堆 2的电堆导电板, 串联电容 C4-C5的中间电压 V3连接 电堆 2的 P型电场负电极与电堆 3的 N型电场正电极, 串联电容 C5-C6的 中间电压 V3_4连接电堆 3的电堆导电板。
Claims
1、 一种外加电场型温差发电热电堆电池, 由 p型半导体、 n型半导体组 成, 在该热电堆电池的热源面, 设有与 p型半导体、 n型半导体连接的电堆 导电板; p型半导体与 n型半导体与该电堆导电板之间分别为肖特基 pn结区; 在该热电堆电池的背面, 电源正极板与电源负极板分别与 p型半导体、 n型 半导体连接; 同时, 在该热电堆电池的热源面及其背面, 分别设置有上导热 绝缘板与下导热绝缘板; 其特征在于, 在所述的下导热绝缘板与电源正极板 之间, 设有电隔离层, 该电隔离层下面设有外接电压的电场负极板; 在所述 的下导热绝缘板与电源负极板之间, 设有电隔离层, 该电隔离层下面设有外 接电压的电场正极板; 所述的外接电压的电场正极板和所述的外接电压的电 场负极板之间, 设有外加电压; 所述的电堆导电板与该外加电压的中点电压 连接; 在 N型半导体和 P型半导体内部形成调控电场。
2、 根据权利要求 1所述的电场型温差发电热电堆电池, 其特征在于, 所 述的外加电压数值为: 在单个电堆电池加外电源电压范围是: 0.5V~3V。
3、 根据权利要求 1所述的电场型温差发电热电堆电池, 其特征在于, 所 述电堆电池的效厚度为 1.5mm~5mm; 所述微电子型热电堆的有效厚度为 Ο.15μιη~500μιη。
4、 根据权利要求 1所述的电场型温差发电热电堆电池, 其特征在于, 所述的电隔离层采用导热绝缘材料构成。
5、 根据权利要求 1或 2或 3或 4所述的电场型温差发电热电堆电池, 其特 征在于, 所述电场型热电堆电池的具体结构是: 电池电源正极板 (4.1)、 电池 电源负极板 (4.2)、 Ρ型半导体 (4.3)、 Ν型半导体 (4.4)、 电堆导电板 (4.5)、 电场
负极板 (4.7)、 电场正极板 (4.6)、 上导热绝缘板 (4.8)、 下导热绝缘板 (4.9)、 电 场电源 、 电容 (Cl)、 电容 (C2)、 负载电阻 R所组成; 电场型热电堆电池结 构中, 电场负极板 (4.7)、 电场正极板 (4.6)是复合在下导热绝缘板 (4.9)之中, 并且电场负极板 (4.7)、 电场正极板 (4.6)与热电堆电池各电极电气隔离; 电场 电源 输出端连接串联的电容 (Cl)、 电容 (C2), 两个电容的容量相等, 串联 的电容 (Cl)、 电容 (C2)连接中点的电压是 Vw /2 ; 电场电源 Vw输出端正极与 负极分别连接电场正极板 (4.6)与电场负极板 (4.7) , 而串联的电容 (C1)、 电容 (C2)连接中点的电压 Vw / 2连接电堆导电板 4.5; 此时电场正极板 (4.8)与电堆 导电板 (4.5)之间 N型半导体形成电场 , 电堆导电板 (4.5)与电场负极板 (4.7) 之间 P型半导体形成电场 。
6、 根据权利要求 5所述的电场型温差发电热电堆电池, 其特征在于, 所述的若干个电场型热电堆电池串联, 构成串联式电场型热电堆电池。
7、 一种权利要求 1所述的电场型温差发电热电堆电池构成的外加电场 型热电堆制冷装置, 由 p型半导体、 n型半导体组成, 在该热电堆制冷装置 的制冷面, 设有与 p型半导体、 n型半导体连接的电堆导电板; p型半导体 与 n型半导体与该电堆导电板之间分别为肖特基 pn结区; 在该热电堆制冷 装置的背面, 电源正极板与电源负极板分别与 p型半导体、 n型半导体连接; 同时, 在该热电堆制冷装置的制冷面及其背面, 分别设置有上导热绝缘板与 下导热绝缘板; 其特征在于, 在所述的下导热绝缘板与电源正极板之间, 设 有电隔离层, 该电隔离层下面设有外接电压的电场负极板; 在所述的下导热 绝缘板与电源负极板之间, 设有电隔离层, 该电隔离层下面设有外接电压的 电场正极板; 所述的外接电压的电场正极板和所述的外接电压的电场负极板
之间, 设有外加电压; 所述的电堆导电板与该外加电压的中点电压连接; 在
N型半导体和 P型半导体内部形成调控电场。
8、 根据权利要求 7所述的电场型热电堆制冷装置, 其特征在于, 所述电 场型热电堆制冷装置的具体结构是: 电池电源正极板 (4.1)、 电池电源负极板 (4.2)、 P型半导体 (4.3)、 N型半导体 (4.4)、 电堆导电板 (4.5)、 电场负极板 (4.7)、 电场正极板 (4.6)、 上导热绝缘板 (4.8)、 下导热绝缘板 (4.9)、 电场电源 、 电 容 (Cl)、 电容 (C2)、 制冷电源 (V2)所组成; 电场型热电堆制冷装置结构中, 电场负极板 (4.7)、 电场正极板 (4.6)是复合在下导热绝缘板 (4.9)之中, 并且电 场负极板 (4.7)、 电场正极板 (4.6)与热电堆制冷装置各电极电气隔离; 电场电 源 输出端连接串联的电容 (Cl)、 电容 (C2), 两个电容的容量相等, 串联的 电容 (Cl)、 电容 (C2)连接中点的电压是 Vw /2 ; 电场电源 Vw输出端正极与负 极分别连接电场正极板 (4.6)与电场负极板 (4.7),而串联的电容 (Cl)、电容 (C2) 连接中点的电压 Vw / 2连接电堆导电板 4.5; 此时电场正极板 (4.8)与电堆导电 板 (4.5)之间 N型半导体形成电场 Ew , 电堆导电板 (4.5)与电场负极板 (4.7)之间 P型半导体形成电场 。
9、 根据权利要求 7或 8所述的电场型热电堆制冷装置, 其特征在于, 所 述单个电堆的加外电源电压范围大于或等于 1.5倍的温差制冷热电堆供电电 压。
10、 根据权利要求 9所述的电场型热电堆制冷装置, 其特征在于, 所述 的若干个电场型热电堆制冷装置串联, 构成串联式电场型热电堆制冷装置。
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JPH0832127A (ja) * | 1994-07-19 | 1996-02-02 | Seiko Instr Inc | 熱電素子および熱電素子を用いた電子機器 |
CN1330013C (zh) * | 2002-11-29 | 2007-08-01 | 诺亚公司 | 温差式发电装置 |
CN100440560C (zh) * | 2003-10-07 | 2008-12-03 | 株式会社东芝 | 热电池 |
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JPH0832127A (ja) * | 1994-07-19 | 1996-02-02 | Seiko Instr Inc | 熱電素子および熱電素子を用いた電子機器 |
CN1330013C (zh) * | 2002-11-29 | 2007-08-01 | 诺亚公司 | 温差式发电装置 |
CN100440560C (zh) * | 2003-10-07 | 2008-12-03 | 株式会社东芝 | 热电池 |
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