The present disclosure generally relates to material suitable for thermoelectric conversion and particularly to material with nanowire-based and nanoscale heterostructure-based structures and processes of making same.
In the modern world, production of thermal energy is a byproduct of almost every activity. Examples are operating internal combustion engines, lighting incandescent light bulbs, operating power plants, etc. Currently, most of the produced thermal energy is lost, as is thereby considered wasted. It would be beneficial to reclaim some or most of the thermal energy and convert it to a useful form of energy.
Thermoelectric devices provide one way to convert thermal energy into electrical energy. A thermoelectric device positioned between a hot reservoir and a cold reservoir can convert the thermal difference between these reservoirs into an electrical current. The reversal of this process, i.e., application of an electrical current to a thermoelectric device, may be used to transfer heat from a first body to a second body, thereby cooling the first body. Referring to
The mechanism by which thermal energy is converted to electrical current is commonly referred to as the Seebeck effect. The Seebeck effect can be explained as follows. A thermal gradient at a junction of two dissimilar materials, ΔT=TH−TC (see
where S is Seebeck coefficient,
Figure of Merit is one way to measure the efficiency of the thermoelectric material and structure. Figure of Merit is denoted as ZT and is expressed as
where S is the Seebeck coefficient,
Different structures have been investigated by others in the prior art to improve the Figure of Merit for different thermoelectric materials. Examples of the thermoelectric materials are Bismuth telluride (Bi2Te3), and lead telluride (PbTe). However, in addition to material selection, another way to improve efficiency of the thermoelectric conversion is by the structure of the material.
There is a need to provide material selection, structure and method of making same that improves efficiency of thermoelectric conversion.
According to one aspect of the present disclosure an ultrathin tellurium nanowire structure is disclosed. The nanowire structure includes a rod-like crystalline structure of tellurium, wherein the crystalline structure is defined by diameters of between 5-6 nm.
According to another aspect of the present disclosure an ultrathin tellurium-based nanowire structure is disclosed. The nanowire structure includes a rod-like crystalline structure of one of lead telluride and bismuth telluride, wherein an ultrathin tellurium nanowire structure is used as a precursor to generate the rod-like crystalline structure.
According to another aspect of the present disclosure, a nanoscale heterostructure tellurium-based nanowire structure is disclosed. The nanowire structure includes a dumbbell-like crystalline heterostructure having a center rod-like portion and one octahedral structure connected to each end of each of the center rod-like portions, wherein the center rod-like portion is a tellurium-based nanowire structure and the octahedral structures are one of lead telluride, cadmium telluride, and bismuth telluride.
For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made to the embodiments illustrated in the drawings and described in the following written specification. It is understood that no limitation to the scope of the present disclosure is thereby intended. It is further understood that the present disclosure includes any alterations and modifications to the illustrated embodiments and includes further applications as would normally occur to one of ordinary skill in the art to which this disclosure pertains.
The present disclosure provides novel approaches to generate novel ultrathin nanowire-based structures as well as nanoscale heterostructure-based structures for use as material to be used in thermoelectric conversion. First, a novel process is described to generate a novel ultrathin nanowire structure. Second, a novel process is described to generate novel nanoscale heterostructure-based structures.
The present disclosure provides an efficient process for synthesis of ultrathin lead telluride (PbTe) and Bismuth telluride (Bi2Te3) nanowire structures. The process described generates novel nanowire structures with diameters of about or less than 10 nm. The process includes utilizing ultrathin tellurium (Te) nanowire structures as in-situ templates. Phase transfer from Te to PbTe or to BixTe1−x is accomplished through injection of lead (Pb) or bismuth (Bi) precursor solutions to a solution containing Te nanowire.
The synthesized PbTe and Bi2Te3 ultrathin nanowire structures are fabricated through a two-step process. First, the Te nanowire structures are synthesized to be used as in-situ templates.
Synthesis of Ultrathin Te nanowire Structures
In a typical synthesis, a volume of ethylene glycol (CH2OHCH2OH), e.g., 10 ml, an amount of polyvinylpyrrolidone (PVP), e.g., 0.1-1 g, an amount of an alkali (sodium hydroxide (NaOH) or potassium hydroxide (KOH)), e.g., 0.2-0.8 g, and an amount of tellurium dioxide (TeO2) or tellurite salts (sodium tellurite (Na2TeO3), or potassium tellurite (K2TeO3)), e.g., 0.2-2 mmol, are dissolved in ethylene glycol by heating to form a transparent/translucent solution. Next, an amount of hydrazine hydrate (H2NNH2.H2O) solution, e.g., 0.2-1 ml, is added into the as-prepared solution at 100-180 ° C. The concentration of hydrazine can be between 24-100%, After about 20 minutes, ultrathin Te nanowire structures with average diameters of 5.5±0.5 nm and lengths up to several micrometers can be obtained. Referring to
Using the synthesized ultrathin Te nanowire structures as in-situ templates, metal telluride nanowire structures can be produced by injecting associated metal precursors into the solution containing Te nanowire structures. The PbTe nanowire crystalline structures with diameters of 9.5±0.5 nm and Bix Te1−x nanowire crystalline structures with diameters of 7.5±0.5 nm can be obtained by injecting lead acetate tri-hydrate (Pb(CH3COO)2.3H2O) and bismuth nitrate penta-hydrate (Bi(NO3)3.5H2O) in ethylene glycol precursor solution, respectively and allowing the solution to react for about 30 minutes. The quantity of the injected metal precursor is calculated according to the molar ratio of elements in corresponding compounds. Referring to
To verify the phase transfer from Te to PbTe or Bi2Te3 nanowire structures, X-ray diffraction patterns of these three materials were obtained. Referring to
PbTe and Bi2Te3 are well suited candidates for thermoelectric conversion at a temperature of about room temperature and 500° K, respectively. By fabricating novel nanowire structure with diameters less than 10 nm, the thermal conductivity can be significantly reduced to enhance the thermoelectric figure of merits by increasing the Seebeck coefficient. It should be understood that the solution phase method, described above, is easily scalable and reproducible for large-scale deployment of thermoelectric conversion devices.
The synthesized nanowire structures are uniform and crystalline with diameters less than 10 nm (e.g., PbTe having diameters of about 9.5±0.5 nm; and Bi2Te3 having diameters of about 7.5±0.5 nm) and lengths up to several micrometers. In addition, both PbTe and Bi2Te3 nanowire structures possess rough surfaces. These properties contribute to reduce the thermal conductivity of these materials as compared to corresponding bulk material. Also, the exact formation of the PbTe and Bi2Te3 nanowire structures can be controlled by adjusting the molar ratio between the Pb or Bi precursor and TeO2. This feature may help to determine the most efficient material systems for the application of thermoelectric devices. It should be understood that the disclosed process can also be used to synthesize other metal telluride nanowire structures by simply changing the precursor solutions.
The present disclosure describes process steps resulting in synthesis of novel nanoscale heterostructure-based structures suitable for thermoelectric conversion. The process describes use of an ethylene glycol based solution for synthesizing three novel dumbbell-like nanowire heterostructures. These structures are based on tellurium-lead telluride (Te—PbTe), cadmium telluride-lead telluride (CdTe—PbTe) and bismuth telluride-lead telluride (Bi2Te3—PbTe) compositions. First, well-defined Te nanowire structures with diameters of about 20 nm are developed. Thereafter, a Pb precursor solution is injected into the solution containing Te nanowire structures. As a result, PbTe octahedral structures are selectively grown at both ends of the Te nanowire structures to form Te—PbTe dumbbell-like structures. In order to obtain CdTe—PbTe and Bi2Te3—PbTe dumbbell-like structure, a cadmium (Cd) precursor or a bismuth (Bi) precursor solution is injected to the Te—PbTe heterostructure nanowire solution, respectively. The center Te portion reacts with the reduced Cd or Bi atoms to form CdTe or Bi2Te3 nanowire structures, and then the CdTe—PbTe and Bi2Te3—PbTe part can be obtained.
The process for synthesizing Te nanowire structures is similar to the process of synthesizing ultrathin nanowire structures, described above. However, one difference is at the end of the nanowire synthesis process, after adding the hydrazine hydrate solution at 100-180° C., the resulting solution is allowed to sit for about 20 minutes to one hour. The Te nanowire structures obtained have average diameters of about 20±2 nm and lengths ranging from 1.2 to 1.5 micrometers. Referring to
To generate Te—PbTe heterostructure nanowire structures, a Pb precursor solution is prepared by dissolving Pb(CH3COO)23H2O or Pb(NO3)23H2O into 1-3 ml ethylene glycol. The molar ratio between Pb(CH3COO)23H2O or Pb(NO3)3H2O and TeO2, for the synthesis of Te nanowire structures is preferably less than 1. To synthesize Te—PbTe dumbbell-like heterostructure nanowire structures, the Pb precursor solution is injected to the Te nanowire solution at 100-180° C., followed by the addition of another 0.2-1 ml hydrazine solution with the concentration of 24-80%. After about 20 minutes, the Te—PbTe dumbbell-like heterostructure nanowire structures can be obtained.
Referring to
The synthesized Te—PbTe dumbbell-like structures can be further converted to cadmium telluride-lead telluride (CdTe—PbTe) and bismuth telluride-lead telluride (BixTe1−x—PbTe) dumbbell-like heterostructure nanowire structures by selectively reacting the center Te nanowire portion with cadmium (Cd) or Bi precursor. For the synthesis of CdTe—PbTe dumbbell-like heterostructure nanowire structures, a Cd precursor solution can be used. The Cd precursor solution can be prepared by dissolving cadmium chloride (CdCl2) or cadmium nitrate (Cd(NO3)) or cadmium acetate (Cd(Ac)2) into 1-3 ml ethylene glycol. The Cd precursor can then be injected into the solution containing the Te—PbTe dumbbell-like heterostructure nanowire structures. The molar ratio between the Cd and Te is about as 1:1 and the quantity can be calculated by subtracting those reacted with Pb precursors with the total Te precursor. For the synthesis of BixTe1−x—PbTe dumbbell-like heterostructure nanowire structures, the Bi precursor solution prepared by dissolving BiCl3 or Bi(NO3)3 or Bi(CH3COO)3 into 1-3 ml ethylene glycol.
The Bi precursor can then be injected into the solution containing Te—PbTe dumbbell-like heterostructure nanowire structures. The x content in the BixTe1−x can be controlled by adjusting the quantity of the Bi precursor when preparing the Bi precursor solution. Referring to
The morphology of the resulting products is quite similar to that of Te—PbTe dumbbell-like structures except that the diameter of the center CdTe part is about 30 nm, which is slightly larger than that of center Te part in the Te—PbTe dumbbell-like structure. In addition, the XRD pattern of the CdTe—PbTe resulting products is quite different from that of Te—PbTe dumbbell structure. Referring to
The PbTe and Bi2Te3 are well-suited for thermoelectric conversion at temperature close to near room temperature and 500 K, respectively. By fabricating these novel nanoscale heterostructure-based nanowire structures with the above-identified materials, both the thermal conductivity and the Seebeck coefficient, particularly the former, can be significantly optimized to enhance the thermoelectric Figure of Merit. The above-referenced solution phase synthesis is easily scalable and reproducible for large-scale deployment of thermoelectric conversion devices.
The thermal conductivity of the materials could be further reduced due to combination of the interface scattering effect and size confinement effect compared with the conventional nanowire structures. The teachings of the present disclosure can be extended to other nanowire heterostructure synthesis by changing the precursor solution to provide other tellurium-based thermoelectric materials.
To demonstrate the improved efficiency of the synthesized thermoelectric structures as compared to bulk material, thermoelectric properties of PbTe was measured. Referring to
The Seebeck coefficient is largely enhanced compared with that of bulk sample, about 2 to 4 times higher than that of bulk sample. Referring to
Those skilled in the art will recognize that numerous modifications can be made to the specific implementations described above. Therefore, the following claims are not to be limited to the specific embodiments illustrated and described above. The claims, as originally presented and as they may be amended, encompass variations, alternatives, modifications, improvements, equivalents, and substantial equivalents of the embodiments and teachings disclosed herein, including those that are presently unforeseen or unappreciated, and that, for example, may arise from applicants/patentees and others.
This application claims the benefit of two U.S. Provisional Applications Ser. Nos. 61/327,192 and 61/327,199 the entire contents of which are incorporated herein by reference.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US11/33798 | 4/25/2011 | WO | 00 | 10/23/2012 |
Number | Date | Country | |
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61327199 | Apr 2010 | US | |
61327192 | Apr 2010 | US |