WO2020108383A1 - Silver-sulfide-based inorganic thermoelectric material, preparation method therefor and use thereof - Google Patents

Silver-sulfide-based inorganic thermoelectric material, preparation method therefor and use thereof Download PDF

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WO2020108383A1
WO2020108383A1 PCT/CN2019/120005 CN2019120005W WO2020108383A1 WO 2020108383 A1 WO2020108383 A1 WO 2020108383A1 CN 2019120005 W CN2019120005 W CN 2019120005W WO 2020108383 A1 WO2020108383 A1 WO 2020108383A1
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thermoelectric
silver sulfide
based inorganic
flexible
thermoelectric material
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PCT/CN2019/120005
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French (fr)
Chinese (zh)
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史迅
仇鹏飞
杨世琪
梁佳晟
王拓
陈立东
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中国科学院上海硅酸盐研究所
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Publication of WO2020108383A1 publication Critical patent/WO2020108383A1/en

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    • 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
    • H10N10/01—Manufacture or treatment
    • 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
    • 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
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Definitions

  • the invention relates to a silver sulfide-based inorganic thermoelectric material and a preparation method and application thereof, which belong to the field of flexible wearable electronics.
  • Flexible electronics is an emerging electronic technology that produces electronic devices of organic/inorganic materials on flexible/ductile substrates.
  • Flexible electronics covers organic electronics, plastic electronics, bioelectronics, nanoelectronics, printed electronics, etc., including RFID, flexible display, organic electroluminescence (OLED) display and lighting, chemical and biosensors, flexible photovoltaic, flexible logic and storage, flexible Various applications such as batteries and wearable devices.
  • OLED organic electroluminescence
  • flexible electronics have greater flexibility, can adapt to different working environments, and meet the requirements of different shapes of equipment. With the rapid development of flexible electronics, the fields involved have been further expanded. At present, flexible electronics has become a research hotspot in interdisciplinary fields.
  • thermoelectric technology based on the Seebeck effect and the Peltier effect has gained widespread attention in the field of flexible wearable electronics.
  • Flexible thermoelectric technology can convert the heat of the human body or the environment into stable power to power electronic devices, avoiding the series of problems caused by the traditional lithium batteries that need to be frequently charged or replaced, so in the fields of wearable sensors, micro generators, etc.
  • the N-type and P-type flexible thermoelectric arms are connected in series through electrode materials to form thermoelectric pairs, which are adhered to the flexible substrate material, which can be adapted to different curved surfaces such as human skin, and have great application prospects.
  • the wide application of flexible thermoelectric technology requires not only high-performance thermoelectric materials with good flexibility and plasticity and environmental friendliness, but also corresponding thermoelectric device preparation methods.
  • conductive polymer organic thermoelectric materials such as poly(3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS) or polyaniline (PANI), are currently the main candidates for flexible thermoelectric technology.
  • These conductive polymer organic thermoelectric materials have good flexibility and can be bent greatly, but due to their low carrier mobility, the output power density of organic flexible thermoelectric devices composed of these conductive polymer organic thermoelectric materials is generally Lower.
  • additional contact resistance is added, which will also deteriorate the output power density of the organic flexible thermoelectric device. For example, Olga Bubnova et al.
  • thermoelectric device used toluenesulfonic acid-poly(3,4-ethylenedioxythiophene) and tetrathiofulvalene-7,7,8,8-tetracyanodimethanequinoline as P-type and N-type thermoelectricity, respectively Arm, the prepared all-organic thermoelectric device can only get a power density of 0.25 mW m -2 at a temperature difference of 10 K (Bubnova O, et al. Nature materials, 2011, 10(6) , 429).
  • the flexible thermoelectric device based on fullerene/titanium disulfide organic/inorganic composite materials prepared by Wang et al. has a maximum power density of only 1.68 Wm -2 at a temperature difference of 20 K (L Wang, et al. Energy Environ. Sci. 2018 , 11 , 1307-1317). Therefore, at present, organic flexible thermoelectric devices based on conductive polymer organic thermoelectric materials cannot meet the actual application requirements.
  • thermoelectric materials Compared with organic thermoelectric materials, inorganic thermoelectric materials have better carrier mobility, so their thermoelectric properties are generally superior to organic thermoelectric materials. However, most inorganic thermoelectric materials do not have plasticity and cannot be directly fabricated into flexible thermoelectric devices. Recently, Shi et al. found that silver sulfide inorganic semiconductor materials have good flexibility (Shi X, et al. Nature materials. 2018, 17, 421–426). In the three-point bending test, the silver sulfide block can withstand 12% mechanical strain; in the compression test, the silver sulfide block can withstand up to 50% mechanical strain without cracking. At the same time, silver sulfide has high carrier mobility, and its value is as high as 70 cm 2 /Vs at room temperature. However, the carrier concentration of silver sulfide is very low, which is not suitable for thermoelectric materials. At present, the research on inorganic thermoelectric material-based flexible thermoelectric devices and their preparation methods is still blank, and no public reports have been reported.
  • the present invention provides a silver sulfide-based inorganic thermoelectric material with good flexibility and high output power density and a preparation method thereof, and for the first time the silver sulfide-based inorganic thermoelectric material is prepared into a flexible thermoelectric device, which is expected to be able to simultaneously To achieve good plasticity and high output power density, to achieve a wide range of applications in wearable sensors and other electronic devices, and then is expected to promote the development of flexible thermoelectric technology.
  • the present invention provides a silver sulfide-based inorganic thermoelectric material whose chemical formula is Ag 2 (S 1-x M x ), where M is at least one of the elements Se and Te Species, 0.001 ⁇ x ⁇ 0.9.
  • the silver sulfide-based inorganic thermoelectric material itself has good plasticity similar to metals, and the silver sulfide-based thermoelectric device exhibits flexible characteristics comparable to conventional organic thermoelectric devices. At the same time, due to its high mobility and high Seebeck coefficient, its thermoelectric performance is significantly better than traditional organic thermoelectric materials, which in turn leads to silver sulfide-based thermoelectric devices having much higher performance than traditional organic thermoelectric devices at the same temperature difference. Power density.
  • Se solid solution or Te solid solution silver sulfide-based inorganic thermoelectric materials have excellent thermoelectric properties. For example, at room temperature, the Se-dissolved silver sulfide-based inorganic thermoelectric material has a thermoelectric figure of merit of 0.26, much higher than traditional organic thermoelectric materials.
  • the thermal value of the silver sulfide-based inorganic thermoelectric material is 0.05-0.8; the power factor of the silver sulfide-based inorganic thermoelectric material at 300 K is 2.0-10.0 ⁇ W ⁇ Cm -1 ⁇ K -2 .
  • the silver sulfide-based inorganic thermoelectric material undergoes no more than 20% mechanical strain without breaking in the three-point bending test, and no more than 70% mechanical strain without breaking in the compression test.
  • the present invention also provides a method for preparing a silver sulfide-based inorganic thermoelectric material as described above, including:
  • the chemical formula of the silver sulfide-based inorganic thermoelectric material Ag, S, Se, and Te are weighed and mixed, first melted at 800 to 1300 °C for 2 to 120 hours, and then annealed at 300 to 700 °C for 5 to 80 Hour, get single-phase ingot of silver sulfide-based inorganic thermoelectric material;
  • the obtained single-phase ingot of silver sulfide-based inorganic thermoelectric material is pulverized into powder, and then subjected to hot-press sintering or spark plasma sintering to obtain the silver sulfide-based inorganic thermoelectric material.
  • the temperature of the hot press sintering is 190-600°C, the time is 10-1000 minutes, and the pressure is 30-70 MPa; the temperature of the spark plasma sintering is 190-600°C, the time is 10-1000 minutes .
  • the temperature increase rate of the melt treatment is 0.5-2.0°C/min.
  • the present invention provides a flexible thermoelectric device with high power density based on silver sulfide-based inorganic thermoelectric material, wherein at least one of the N-type thermoelectric arm and the P-type thermoelectric arm in the flexible thermoelectric device is formed by the above Prepared by silver-based inorganic thermoelectric materials.
  • the height range of the thermoelectric arm is 0.0001 mm ⁇ 0.1 mm, the length and width range is 0.1 mm ⁇ 50 mm.
  • the high-temperature end electrode and the low-temperature end electrode of the flexible thermoelectric device are copper foil, nickel foil, aluminum foil, tin foil or gold foil; the thickness range of the high-temperature end electrode and the low-temperature end electrode is 0.0001 mm ⁇ 0.1 mm.
  • the high-temperature end electrode and the low-temperature end electrode are respectively connected to the thermoelectric arm to form a thermoelectric pair in series, and the obtained multiple sets of thermoelectric pairs are adhered to a flexible substrate to obtain a flexible thermoelectric device; preferably, the flexible substrate It is one of polyvinyl chloride, polypropylene, polyimide, parylene, polydimethylsiloxane, and polyethylene terephthalate.
  • the flexible thermoelectric device based on silver sulfide-based inorganic thermoelectric materials provided by the present invention not only has good flexibility comparable to organic thermoelectric devices, but also has the characteristics of high energy conversion rate, low impedance and high temperature resistance comparable to inorganic thermoelectric devices.
  • the curved surface with complex shapes, such as the surface of human skin, can meet the requirements of flexible wearable electronic devices.
  • the preparation method of the flexible thermoelectric device based on the silver sulfide-based inorganic thermoelectric material provided by the present invention does not cause pollution to the environment, the process is simple, and it is easy to prepare in large quantities, and has huge application prospects in the field of wearable electronics.
  • Figure 1 shows a schematic diagram of the structure of a common flexible thermoelectric device, a: in-plane type (heat flow parallel to the substrate); b: out-of-plane type (heat flow perpendicular to the substrate), c: mixed type (heat flow through two directions);
  • 1 is an N-type thermoelectric arm
  • 2 is a P-type thermoelectric arm
  • 3 is an electrode
  • 4 is a heat flow direction
  • 5 is a substrate
  • 6 is an adhesive
  • 7 is an insulating layer
  • Figure 2 shows a: conductivity of three kinds of selenium and tellurium solid solution silver sulfide (chemical formulas Ag 2 S 0.5 Se 0.5 , Ag 2 S 0.6 Te 0.4 , Ag 2 S 0.5 Se 0.4 Te 0.1 ); b: Seebeck coefficient ; C: power factor and d: power factor compared with organic thermoelectric materials, where SWNT: single-walled carbon nanotubes, PANI: polyaniline, P3HT: poly 3-hexylthiophene, TCB: trichlorobenzene, PBTTT: poly (2 ,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-B]thiophene), PDPP3T: polythiophene-pyrrolopyrrole dione, PSBTBT: poly[2,1,3- Benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-silacyclopenta[3,2-
  • Figure 3 shows a schematic diagram of the structure of six pairs of in-plane silver sulfide-based flexible inorganic thermoelectric devices, where 1 is an N-type thermoelectric arm, the component is selenium element solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.5 ), and 2 is a P-type thermoelectric Arm, the composition is Pt-Ru, 3 is the electrode, 4 is the substrate;
  • Figure 4 shows a: voltage-current curve and b: power-current curve of six pairs of in-plane silver sulfide-based flexible inorganic thermoelectric devices
  • Figure 5 shows the power density comparison of silver sulfide-based flexible inorganic thermoelectric devices (the material composition is selenium element solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.5 )) and organic thermoelectric devices, where SWNT: single-walled carbon nanotubes, PANI: polyaniline, CNT: carbon nanotubes, Poly[Ax(M-ett)]: poly 1,1,2,2-ethylene tetrathiol (5-ethylthiotetrazolium), Polystyrene: polystyrene , PEDOT: Tos: toluenesulfonic acid-poly(3,4-ethylenedioxythiophene), PEDOT: poly(3,4-ethylenedioxythiophene), Graphene: graphene, carbon: carbon;
  • Figure 6 shows the change of the internal resistance of the silver sulfide-based flexible inorganic thermoelectric device with the number of bendings.
  • the bending radius is 10 mm, and the material composition is selenium element solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.5 );
  • Figure 7 shows a schematic diagram of the structure of six pairs of out-of-plane silver sulfide-based flexible inorganic thermoelectric devices, where 1 is an N-type thermoelectric arm, the component is tellurium solid solution silver sulfide (chemical formula Ag 2 S 0.6 Te 0.4 ), and 2 is a P type Thermoelectric arm, the composition is Pt-Ru, 3 is the electrode, 4 is the substrate;
  • FIG. 8 shows a: voltage-current curve and b: power-current curve of six pairs of out-of-plane silver sulfide-based flexible inorganic thermoelectric devices.
  • Figure 9 shows a schematic diagram of the structure of six pairs of hybrid silver sulfide-based flexible inorganic thermoelectric devices, where 1 is an N-type thermoelectric arm, and the components are selenium and tellurium solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.4 Te 0.1 ), 2 is a P-type thermoelectric arm, the composition is Pt-Ru, 3 is an electrode, 4 is a substrate, and 5 is a thermal insulation layer;
  • FIG. 10 shows a: voltage-current curve and b: power-current curve of six pairs of hybrid silver sulfide-based flexible inorganic thermoelectric devices.
  • thermoelectric properties of silver sulfide-based materials in which Se and Te solid solutions are studied for the first time that while retaining the flexibility of silver sulfide, Se and Te solid solution sulfides Silver materials exhibit excellent thermoelectric properties.
  • Se solid solution silver sulfide-based thermoelectric materials have a thermoelectric figure of merit of 0.26, which is much higher than traditional organic thermoelectric materials. If the silver sulfide-based inorganic thermoelectric material is made into a thermoelectric device, it is expected to achieve good plasticity and high output power density at the same time, and achieve wide application in wearable sensors and other electronic devices, and is expected to promote the development of flexible thermoelectric technology.
  • thermoelectric materials used in flexible thermoelectric devices are silver sulfide-based inorganic thermoelectric materials, whose chemical formula is Ag 2 (S 1-x M x ), where M can be one or two of Se element and Te element, which is used as The solid solution element is solid-dissolved in the S lattice position, and its solid solution amount range is 0.001 ⁇ x ⁇ 0.9.
  • thermoelectricity value of the silver sulfide-based inorganic thermoelectric material is 0.05 to 0.8; the power factor of the silver sulfide-based inorganic thermoelectric material at 300 K is 2.0 to 10.0 ⁇ W ⁇ cm -1 ⁇ K -2 .
  • the silver sulfide-based inorganic thermoelectric material withstands up to 20% mechanical strain without cracking in the three-point bending test. Withstands up to 70% of mechanical strain in the compression test without breaking.
  • a dense bulk silver sulfide-based inorganic thermoelectric material can be obtained by high-temperature melting, and spark plasma sintering or hot-press sintering.
  • spark plasma sintering or hot-press sintering The following exemplarily illustrates the preparation method of the silver sulfide-based inorganic thermoelectric material.
  • the ingot of silver sulfide-based inorganic thermoelectric material or the powder prepared from the ingot is prepared into a dense block with a specific shape by hot pressing sintering or spark plasma sintering technology.
  • the temperature of hot pressing sintering can be 190-600 °C, the time can be 10-1000 minutes, and the pressure can be 30-70 MPa.
  • the temperature of spark plasma sintering may be 190-600°C, and the time may be 10-1000 minutes.
  • thermoelectric device based on silver sulfide-based inorganic thermoelectric materials
  • the thermoelectric device is environmentally friendly, can work stably in the air for a long time, and can well meet the requirements of flexible wearable electronic devices.
  • a method for preparing a flexible thermoelectric device based on a silver sulfide-based inorganic thermoelectric material includes: cutting a thermoelectric arm of a specific size from a dense bulk silver sulfide-based inorganic thermoelectric material.
  • the electrode is connected with a silver sulfide-based thermoelectric arm to form a thermoelectric pair in series.
  • Multiple sets of thermoelectric pairs composed of silver sulfide-based inorganic thermoelectric materials are adhered to a flexible substrate to obtain a flexible thermoelectric device.
  • the silver sulfide-based inorganic thermoelectric material is prepared as a thermoelectric arm in a silver sulfide-based inorganic flexible thermoelectric device, which includes: using a diamond cutting machine from a silver sulfide-based inorganic thermoelectric material ingot or a sintered silver sulfide-based thermoelectric material dense block , Inner circle cutting machine, outer circle cutting machine, electric spark cutting machine cut out a thin sheet of silver sulfide-based thermoelectric material of a specific size.
  • thermoelectric arm suitable for inorganic flexible thermoelectric devices.
  • At least one of the N-type thermoelectric arm and the P-type thermoelectric arm in the thermoelectric device is composed of a silver sulfide-based inorganic thermoelectric material.
  • the surface of the thermoelectric arm should be clean and free of impurities such as oil to ensure good ohmic contact between the thermoelectric arm and the electrode.
  • the flake-shaped silver sulfide-based inorganic thermoelectric material can have a height of 0.0001 mm to 0.1 mm, the length and width may range from 0.1 mm to 50 mm; preferably, the height of the flake-shaped silver sulfide-based inorganic thermoelectric material ranges from 0.01 mm to 0.05 mm.
  • At least one of copper foil, nickel foil, aluminum foil, tin foil and gold foil is selected as the high-temperature terminal electrode material and the low-temperature terminal electrode material of the flexible thermoelectric device based on the silver sulfide-based inorganic thermoelectric material to realize the N-type thermoelectric arm and the thermoelectric device P series thermoelectric arms are electrically connected in series.
  • the copper foil, nickel foil, aluminum foil, tin foil and gold foil selected as the electrode material should have good flexibility, can realize large-scale repeated bending, and the thickness range can be 0.0001 mm ⁇ 0.1 mm.
  • the electrode material and the thermoelectric arm can also be connected by silver paste, carbon paste, indium welding, tin welding, laser welding, diffusion welding, or voltage sintering.
  • the electrode material and the thermoelectric arm after connection should have as small contact resistance and thermal resistance as possible, and have high reliability during repeated bending, and no cracking or falling off at the interface.
  • the overall electrical series connection of multiple pairs of thermoelectric arms depends on the actual use environment and the shape requirements of the flexible thermoelectric devices.
  • the overall electrical series connection of multiple pairs of thermoelectric arms can be assembled according to the in-plane type (heat flow parallel to the substrate) structure shown in a of FIG. 1, or according to the out-of-plane type shown in b of FIG. 1 (heat flow is perpendicular to Substrate) and the hybrid type (heat flow through two directions) structure shown in c in Figure 1 is assembled.
  • the assembled flexible thermoelectric device should ensure that the device can make full use of the heat generated by the heat source and reduce unnecessary heat loss.
  • an adhesive can also be used to attach to a substrate of a certain size to obtain a flexible thermoelectric device based on a silver sulfide-based inorganic thermoelectric material.
  • an adhesive can also be used to attach to a substrate of a certain size to obtain a flexible thermoelectric device based on a silver sulfide-based inorganic thermoelectric material.
  • generally used adhesives and substrates should ensure good thermal conductivity to reduce heat loss from the heat source to the hot end of the device.
  • the substrate of the flexible thermoelectric device may be an organic polymer such as polyvinyl chloride, polypropylene, polyimide, parylene, polydimethylsiloxane, and polyethylene terephthalate.
  • the flexible substrate should ensure good flexibility and stability in a large temperature range around room temperature, and it is not easy to soften, decompose, volatilize, and produce substances harmful to the human body.
  • the organic polymer constituting the substrate should be resistant to corrosion, waterproof, insulating, non-toxic, and not easy to age, crack, peel or peel.
  • the silver sulfide-based inorganic thermoelectric material and the electrode can be attached to the substrate using polydimethylsiloxane or parylene as the adhesive material.
  • the adhesive may be polydimethylsiloxane, parylene or the like.
  • the adhesive should ensure good flexibility and stability in a large temperature range around room temperature, and it is not easy to soften, decompose, volatilize, and produce harmful substances to the human body.
  • the materials that make up the adhesive should be resistant to corrosion, waterproof, insulating, non-toxic, and not easy to age, crack, peel or peel.
  • the adhesive and the substrate need to have good affinity and bonding strength, and it is not easy to detach from the substrate. In addition, the adhesive needs to maintain good mechanical strength to ensure a durable and stable bond between the device and the substrate.
  • This embodiment 1 is an in-plane type device.
  • Preparation of N-type Ag 2 S 0.5 Se 0.5 material Weigh high-purity Ag, S and Se elements according to the 4:1:1 stoichiometric ratio. It is added to a ⁇ 10 thick quartz tube for vacuum packaging; the encapsulated quartz tube is heated to 1000°C at a heating rate of 40 hours and held for 12 hours, then cooled to 100°C within 25 hours, and then the quartz tube is annealed at 450°C 5 day. The annealed Ag 2 S 0.5 Se 0.5 ingot was crushed into a powder with a stainless steel pestle under a liquid nitrogen environment.
  • the powder was then sintered at 190°C for 0.5 hours using spark plasma sintering, and finally a dense N-type Ag 2 S 0.5 Se 0.5 bulk was obtained.
  • the dense N-type Ag 2 S 0.5 Se 0.5 block can withstand 12% of the mechanical strain without cracking; in the compression test, the dense N-type Ag 2 S 0.5 Se 0.5 block can withstand Up to 55% mechanical strain without cracking.
  • Its thermoelectric performance is shown in Figure 2. At 300 K, its power factor is 4.8 ⁇ W ⁇ cm -1 ⁇ K -2 , which is much higher than traditional organic thermoelectric materials.
  • the N-type thermoelectric arm, platinum-rhodium wire and copper foil were welded into 6 sets of Ag 2 S 0.5 Se 0.5 /Pt-Rh thermoelectric pairs as shown in FIG. 3.
  • Apply 0.3 g of polydimethylsiloxane Apply it to the center of the substrate, and then lay 6 sets of thermoelectric pairs on the polydimethylsiloxane, and then add 0.5 g of polydimethylsiloxane to cover the surface of the thermoelectric pair.
  • the polydimethylsiloxane component is: body to curing agent ratio 10:1. After all the thermoelectric pairs were uniformly wrapped in polydimethylsiloxane, they were placed in an oven and cured at 70°C for 60 minutes. Finally, an in-plane flexible inorganic thermoelectric device based on Ag 2 S 0.5 Se 0.5 was obtained. As shown in Figure 4, the test results show that the in-plane flexible inorganic thermoelectric device has a 20 KV temperature difference, an output voltage of 20 mV, a maximum output power of 10 ⁇ W, and an energy density of 5.5 Wcm -2 . As shown in Figure 5, its power density is much higher than traditional flexible thermoelectric devices based on organic thermoelectric materials. In particular, after repeated bending for 100 times, the internal resistance of the silver sulfide-based inorganic flexible thermoelectric device remained basically unchanged, indicating that it had good stability (see Figure 6).
  • This embodiment 2 is an out-of-plane device.
  • Preparation of N-type Ag 2 S 0.6 Te 0.4 material according to the stoichiometric ratio of 10:3:2, weigh high-purity Ag, S, Te elements. It is added to a ⁇ 10 thick quartz tube for vacuum packaging; the encapsulated quartz tube is heated to 1000 °C at a heating rate of 40 hours and held for 12 hours, then cooled to 100 °C within 25 hours, and then the quartz tube is annealed at 450 °C 5 day. The annealed Ag 2 S 0.6 Te 0.4 ingot was crushed into a powder with a stainless steel pestle under a liquid nitrogen environment.
  • the powder was then sintered at 320°C for 0.5 hours using spark plasma sintering, and finally a dense N-type Ag 2 S 0.6 Te 0.4 block was obtained.
  • Its thermoelectric performance is shown in Figure 2.
  • its power factor is 3.1 ⁇ W ⁇ cm -1 ⁇ K -2 , which is much higher than traditional organic thermoelectric materials.
  • the dense N-type Ag 2 S 0.6 Te 0.4 block can withstand 8% mechanical strain without cracking; in the compression test, the dense N-type Ag 2 S 0.6 Te 0.4 block can withstand Up to 45% mechanical strain without cracking.
  • the obtained Ag 2 S 0.6 Te 0.4 dense block was directly cut into 0.1 mm slices with a diamond cutter, and then the Ag 2 S 0.6 Te 0.4 slices were further polished with fine sandpaper until the sample surface was free of impurities.
  • a copper wire with a diameter of 0.1 mm and a length of about 10 mm was used as the P-type thermoelectric arm; a nickel foil of 20 ⁇ m thick, 6 mm long and 4 mm wide was used as the electrode material.
  • thermoelectric arm and nickel foil are connected by diffusion welding; the P-type thermoelectric arm (copper wire) and nickel foil are connected by low-temperature silver paste.
  • the connection effect is shown in Figure 7 6 groups of Ag 2 S 0.6 Te 0.4 /Pt -Rh thermoelectric pair. Take 0.3 mm thick, 50 mm long and 30 mm wide polyvinyl chloride as the substrate. The surface of the polyvinyl chloride is scrubbed and dried with alcohol to remove oil stains and impurities on the surface, and 0.3 g of parylene is coated on the center of the substrate Then, lay 6 sets of thermoelectric pairs on parylene, and then add 0.5 g of parylene to cover the surface of the thermoelectric pairs.
  • thermoelectric pairs were uniformly wrapped in parylene, they were placed in an oven and cured at 70°C for 60 minutes. Finally, an out-of-plane flexible inorganic thermoelectric device based on Ag 2 S 0.6 Te 0.4 was obtained. As shown in Figure 8, the test results show that the out-of-plane flexible inorganic thermoelectric device has a temperature difference of 20 K, an output voltage of 8 mV, and a maximum output power of 1.3 ⁇ W.
  • This embodiment is a hybrid device.
  • Preparation of N-type Ag 2 S 0.5 Se 0.4 Te 0.1 material According to the stoichiometric ratio of 20:5:4:1, high-purity Ag, S, Se, Te elements are weighed. It is added to a ⁇ 10 thick quartz tube for vacuum packaging; the encapsulated quartz tube is heated to 1000 °C at a heating rate of 40 hours and held for 12 hours, then cooled to 100 °C within 25 hours, and then the quartz tube is annealed at 450 °C 5 day. The annealed Ag 2 S 0.5 Se 0.4 Te 0.1 ingot was crushed into a powder with a stainless steel pestle under a liquid nitrogen environment.
  • the powder was sintered using spark plasma sintering at 400 °C for 0.5 hours, and finally a dense N-type Ag 2 S 0.5 Se 0.4 Te 0.1 block was obtained.
  • Its thermoelectric performance is shown in FIG. 2, at 300 K, its power factor is 2.7 ⁇ W ⁇ cm -1 ⁇ K -2 , much higher than traditional organic thermoelectric materials.
  • the dense N-type Ag 2 S 0.5 Se 0.4 Te 0.1 block can withstand 11% of the mechanical strain without cracking; in the compression test, the dense N-type Ag 2 S 0.5 Se 0.4 Te 0.1 The block can withstand up to 50% mechanical strain without breaking.
  • the obtained Ag 2 S 0.5 Se 0.4 Te 0.1 dense block was directly cut into 0.1 mm thin slices using a diamond cutter, and then the fine Ag 2 S 0.5 Se 0.4 Te 0.1 thin slices were further polished to the surface of the sample without impurities.
  • thermoelectric arm Use a platinum rhodium (90%Pt-10%Rh) wire with a diameter of 0.1 mm and a length of about 20 mm as the P-type thermoelectric arm; the hot end uses 30 ⁇ m thick, 5 mm long and 4 mm wide copper foil as the electrode material; cold A copper foil 20 ⁇ m thick, 10 mm long, and 8 mm wide was used as the electrode material.
  • the N-type thermoelectric arm and copper foil are connected by indium welding; the P-type thermoelectric arm and copper foil are connected by low-temperature silver paste, and the connection effect is shown in Figure 9 6 groups of Ag 2 S 0.5 Se 0.4 Te 0.1 /Pt-Rh Thermoelectric pair.
  • thermoelectric pair Take 0.3 mm thick, 50 mm long and 30 mm wide PVC as the substrate, according to the schematic diagram of c and 9 in Fig. 1, hollow the substrate under the copper foil at the hot end to form a groove, the surface of the PVC Use alcohol to scrub and dry to remove oil stains and impurities on the surface, apply 0.3 g of parylene to the center of the substrate, then lay 6 sets of thermoelectric pairs on parylene, and then add 0.5 g of parylene Cover the surface of the thermoelectric pair. Note that the hot-end copper foil should be hidden into the corresponding groove and pass through the substrate to the back of the substrate.
  • This design is to introduce heat flow from the heat source on the back of the substrate; the cold-end copper foil should have a larger surface area than the hot-end copper foil, and its The lower surface is attached to the surface of the substrate by coating polyxylene to keep the bottom surface insulated from the heat source on the back of the substrate.
  • the upper surface of the cold end is not coated with polyxylene to keep the cold end in contact with the environment and facilitate heat dissipation; Polyxylene is added as a heat insulation layer, and the upper surface of the hot-end copper foil is wrapped with N and P materials.
  • thermoelectric pair After the thermoelectric pair is evenly wrapped in parylene, it is placed in an oven and cured at 70 °C for 60 minutes, and finally a hybrid flexible inorganic thermoelectric device based on Ag 2 S 0.5 Se 0.4 Te 0.1 is obtained.
  • the heat flow is first conducted perpendicular to the substrate to the hot end electrode, and then parallel to the substrate through the thermoelectric material to the cold end electrode, and is dissipated by the cold end copper foil to the environment.
  • the test results show that the hybrid flexible inorganic thermoelectric device has a temperature output of 15 K, the device's output voltage is 6 mV, and the maximum output power is 0.5 ⁇ W.

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Abstract

Disclosed are a silver-sulfide-based inorganic thermoelectric material, a preparation method therefor and the use thereof, wherein the chemical formula of the silver-sulfide-based inorganic thermoelectric material is Ag2(S1-xMx), M is at least one of Se and Te, and 0.001 ≤ x ≤ 0.9.

Description

一种硫化银基无机热电材料及其制备方法和应用Silver sulfide-based inorganic thermoelectric material and preparation method and application thereof 技术领域Technical field
本发明涉及一种硫化银基无机热电材料及其制备方法和应用，属于柔性可穿戴电子领域。 The invention relates to a silver sulfide-based inorganic thermoelectric material and a preparation method and application thereof, which belong to the field of flexible wearable electronics.
背景技术Background technique
柔性电子是一种将有机/无机材料电子器件制作在柔性/可延性基板上的新兴电子技术。柔性电子涵盖有机电子、塑料电子、生物电子、纳米电子、印刷电子等，包括RFID、柔性显示、有机电致发光(OLED)显示与照明、化学与生物传感器、柔性光伏、柔性逻辑与存储、柔性电池、可穿戴设备等多种应用。相对于传统电子，柔性电子具有更大的灵活性，能够适应不同的工作环境，满足不同形状的设备的要求。随着柔性电子的快速发展，其涉及到的领域也进一步扩展，目前柔性电子已经成为交叉学科中的研究热点。Flexible electronics is an emerging electronic technology that produces electronic devices of organic/inorganic materials on flexible/ductile substrates. Flexible electronics covers organic electronics, plastic electronics, bioelectronics, nanoelectronics, printed electronics, etc., including RFID, flexible display, organic electroluminescence (OLED) display and lighting, chemical and biosensors, flexible photovoltaic, flexible logic and storage, flexible Various applications such as batteries and wearable devices. Compared with traditional electronics, flexible electronics have greater flexibility, can adapt to different working environments, and meet the requirements of different shapes of equipment. With the rapid development of flexible electronics, the fields involved have been further expanded. At present, flexible electronics has become a research hotspot in interdisciplinary fields.
近年来，基于塞贝克效应和帕尔贴效应的柔性热电技术在柔性可穿戴电子领域获得了广泛关注。柔性热电技术可以将人体或环境的热量转换为稳定的电力进而为电子设备供电，避免了传统锂电池需要经常充电或更换所带来的一系列问题，因此在可穿戴传感器、微型发电机等领域拥有巨大的应用前景。将N型和P型柔性热电臂通过电极材料串联成热电对，粘附于柔性衬底材料上，可以适应于人体皮肤等不同曲面，具有极大的应用前景。柔性热电技术的广泛应用，不仅需要具有良好柔性和塑性以及对环境友好的高性能热电材料，而且需要相应的热电器件制备方法。In recent years, flexible thermoelectric technology based on the Seebeck effect and the Peltier effect has gained widespread attention in the field of flexible wearable electronics. Flexible thermoelectric technology can convert the heat of the human body or the environment into stable power to power electronic devices, avoiding the series of problems caused by the traditional lithium batteries that need to be frequently charged or replaced, so in the fields of wearable sensors, micro generators, etc. Has huge application prospects. The N-type and P-type flexible thermoelectric arms are connected in series through electrode materials to form thermoelectric pairs, which are adhered to the flexible substrate material, which can be adapted to different curved surfaces such as human skin, and have great application prospects. The wide application of flexible thermoelectric technology requires not only high-performance thermoelectric materials with good flexibility and plasticity and environmental friendliness, but also corresponding thermoelectric device preparation methods.
传统的导电高分子有机热电材料，如聚(3,4-乙烯二氧噻吩)：聚苯乙烯磺酸（PEDOT:PSS），或者聚苯胺（PANI），是目前柔性热电技术的主要候选材料。这些导电高分子有机热电材料具有良好的柔性，可以大幅度弯曲，但是受限于其较低的载流子迁移率，由这些导电高分子有机热电材料所构成的有机柔性热电器件输出功率密度普遍较低。特别是，由于导电高分子和金属电极之间往往出现非欧姆接触，增加了额外的接触电阻，也将恶化有机柔性热电器件的输出功率密度。例如，Olga Bubnova等利用甲苯磺酸-聚(3,4-乙烯二氧噻吩)和四硫富瓦烯-7,7,8,8-四氰二甲烷喹啉分别作为P型和N型热电臂，制备出的全有机热电器件在10 K的温差下仅能得到0.25 mW m -2的功率密度（Bubnova O, et al. Nature materials, 2011, 10(6), 429）。Masakazu Mukaida等制备的聚(3,4-乙烯二氧噻吩)：聚苯乙烯磺酸基有机柔性热电器件，在50 K的温差下最高功率密度仅为0.24 Wm -2 (Mukaida M, et al. Synthetic Metals. 2017, 225, 64-69)。 Wang等制备的基于富勒烯/二硫化钛有机/无机复合材料的柔性热电器件，在20 K的温差下最高功率密度仅为1.68 Wm -2（L Wang, et al. Energy Environ. Sci. 2018, 11, 1307-1317）。因此，目前基于导电高分子有机热电材料构成的有机柔性热电器件尚无法满足实际应用需求。 Traditional conductive polymer organic thermoelectric materials, such as poly(3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS) or polyaniline (PANI), are currently the main candidates for flexible thermoelectric technology. These conductive polymer organic thermoelectric materials have good flexibility and can be bent greatly, but due to their low carrier mobility, the output power density of organic flexible thermoelectric devices composed of these conductive polymer organic thermoelectric materials is generally Lower. In particular, since non-ohmic contact often occurs between the conductive polymer and the metal electrode, additional contact resistance is added, which will also deteriorate the output power density of the organic flexible thermoelectric device. For example, Olga Bubnova et al. used toluenesulfonic acid-poly(3,4-ethylenedioxythiophene) and tetrathiofulvalene-7,7,8,8-tetracyanodimethanequinoline as P-type and N-type thermoelectricity, respectively Arm, the prepared all-organic thermoelectric device can only get a power density of 0.25 mW m -2 at a temperature difference of 10 K (Bubnova O, et al. Nature materials, 2011, 10(6) , 429). Poly(3,4-ethylenedioxythiophene) prepared by Masakazu Mukaida et al.: polystyrene sulfonate-based organic flexible thermoelectric device with a maximum power density of only 0.24 Wm -2 at a temperature difference of 50 K (Mukaida M, et al. Synthetic Metals. 2017, 225, 64-69). The flexible thermoelectric device based on fullerene/titanium disulfide organic/inorganic composite materials prepared by Wang et al. has a maximum power density of only 1.68 Wm -2 at a temperature difference of 20 K (L Wang, et al. Energy Environ. Sci. 2018 , 11 , 1307-1317). Therefore, at present, organic flexible thermoelectric devices based on conductive polymer organic thermoelectric materials cannot meet the actual application requirements.
技术问题technical problem
相对于有机热电材料，无机热电材料具有更优的载流子迁移率，因此其热电性能普遍优于有机热电材料。但是，绝大部分无机热电材料都不具有塑性，无法直接制备成柔性热电器件。最近，史等人发现硫化银无机半导体材料具有良好的柔性（Shi X, et al. Nature materials. 2018, 17, 421–426）。在三点弯曲测试中，使用硫化银块体可以承受12%的机械应变；在压缩测试中，硫化银块体可以承受高达50%的机械应变而不破裂。同时，硫化银具有高载流子迁移率，在室温时其数值高达70 cm 2/Vs。但硫化银的载流子浓度很低，不适合作为热电材料，且目前无机热电材料基柔性热电器件及其制备方法的研究尚为空白，未见任何公开报道。 Compared with organic thermoelectric materials, inorganic thermoelectric materials have better carrier mobility, so their thermoelectric properties are generally superior to organic thermoelectric materials. However, most inorganic thermoelectric materials do not have plasticity and cannot be directly fabricated into flexible thermoelectric devices. Recently, Shi et al. found that silver sulfide inorganic semiconductor materials have good flexibility (Shi X, et al. Nature materials. 2018, 17, 421–426). In the three-point bending test, the silver sulfide block can withstand 12% mechanical strain; in the compression test, the silver sulfide block can withstand up to 50% mechanical strain without cracking. At the same time, silver sulfide has high carrier mobility, and its value is as high as 70 cm 2 /Vs at room temperature. However, the carrier concentration of silver sulfide is very low, which is not suitable for thermoelectric materials. At present, the research on inorganic thermoelectric material-based flexible thermoelectric devices and their preparation methods is still blank, and no public reports have been reported.
技术解决方案Technical solution
针对上述问题，本发明提供了一种兼具良好柔性和高输出功率密度的硫化银基无机热电材料及其制备方法，并首次将硫化银基无机热电材料制备成柔性热电器件，将有望可以同时实现良好的塑性和高的输出功率密度，实现在可穿戴传感器和其他电子设备的广泛应用，进而有望推动柔性热电技术的发展。In view of the above problems, the present invention provides a silver sulfide-based inorganic thermoelectric material with good flexibility and high output power density and a preparation method thereof, and for the first time the silver sulfide-based inorganic thermoelectric material is prepared into a flexible thermoelectric device, which is expected to be able to simultaneously To achieve good plasticity and high output power density, to achieve a wide range of applications in wearable sensors and other electronic devices, and then is expected to promote the development of flexible thermoelectric technology.
一方面，本发明提供了一种硫化银基无机热电材料，所述硫化银基无机热电材料的化学式为Ag 2(S 1-xM x)，其中M为Se元素和Te元素中的至少一种，0.001≤x≤0.9。 In one aspect, the present invention provides a silver sulfide-based inorganic thermoelectric material whose chemical formula is Ag 2 (S 1-x M x ), where M is at least one of the elements Se and Te Species, 0.001≤x≤0.9.
在本公开中，硫化银基无机热电材料自身具有类似于金属的良好塑性，硫化银基热电器件表现出与传统有机热电器件相当的柔性特征。同时，由于硫化银基化合物自身的高迁移率和高塞贝克系数等属性，其热电性能明显优于传统有机热电材料，进而导致硫化银基热电器件在同等温差下具有远高于传统有机热电器件的功率密度。本发明中，Se固溶或Te固溶的硫化银基无机热电材料具有优良的热电性能。例如，在室温下，Se固溶的硫化银基无机热电材料的热电优值为0.26，远高于传统的有机热电材料。In the present disclosure, the silver sulfide-based inorganic thermoelectric material itself has good plasticity similar to metals, and the silver sulfide-based thermoelectric device exhibits flexible characteristics comparable to conventional organic thermoelectric devices. At the same time, due to its high mobility and high Seebeck coefficient, its thermoelectric performance is significantly better than traditional organic thermoelectric materials, which in turn leads to silver sulfide-based thermoelectric devices having much higher performance than traditional organic thermoelectric devices at the same temperature difference. Power density. In the present invention, Se solid solution or Te solid solution silver sulfide-based inorganic thermoelectric materials have excellent thermoelectric properties. For example, at room temperature, the Se-dissolved silver sulfide-based inorganic thermoelectric material has a thermoelectric figure of merit of 0.26, much higher than traditional organic thermoelectric materials.
较佳地，室温（15～35 ℃）下，所述硫化银基无机热电材料的热电优值为0.05～0.8；所述硫化银基无机热电材料在300 K时的功率因子为2.0～10.0 μW·cm -1·K -2。 Preferably, at room temperature (15-35 ℃), the thermal value of the silver sulfide-based inorganic thermoelectric material is 0.05-0.8; the power factor of the silver sulfide-based inorganic thermoelectric material at 300 K is 2.0-10.0 μW ·Cm -1 ·K -2 .
较佳地，所述硫化银基无机热电材料在三点弯曲测试中承受不超过20%的机械应变而不破裂，在压缩测试中承受不超过70%的机械应变而不破裂。Preferably, the silver sulfide-based inorganic thermoelectric material undergoes no more than 20% mechanical strain without breaking in the three-point bending test, and no more than 70% mechanical strain without breaking in the compression test.
另一方面，本发明还提供了一种如上述的硫化银基无机热电材料的制备方法，包括：On the other hand, the present invention also provides a method for preparing a silver sulfide-based inorganic thermoelectric material as described above, including:
按照所述硫化银基无机热电材料的化学式称取Ag、S、Se和Te单质并混合，先在800～1300 ℃下熔融处理2～120小时，再于300～700 ℃下退火处理5～80小时，得到单相的硫化银基无机热电材料铸锭；According to the chemical formula of the silver sulfide-based inorganic thermoelectric material, Ag, S, Se, and Te are weighed and mixed, first melted at 800 to 1300 ℃ for 2 to 120 hours, and then annealed at 300 to 700 ℃ for 5 to 80 Hour, get single-phase ingot of silver sulfide-based inorganic thermoelectric material;
将所得单相的硫化银基无机热电材料铸锭粉碎成粉末，再经过热压烧结或放电等离子烧结，得到所述硫化银基无机热电材料。The obtained single-phase ingot of silver sulfide-based inorganic thermoelectric material is pulverized into powder, and then subjected to hot-press sintering or spark plasma sintering to obtain the silver sulfide-based inorganic thermoelectric material.
较佳地，所述热压烧结的温度为190～600℃，时间为10～1000分钟，压力为30～70 MPa；所述放电等离子烧结的温度为190～600℃，时间为10～1000分钟。Preferably, the temperature of the hot press sintering is 190-600°C, the time is 10-1000 minutes, and the pressure is 30-70 MPa; the temperature of the spark plasma sintering is 190-600°C, the time is 10-1000 minutes .
较佳地，所述熔融处理的升温速率为0.5～2.0 ℃/分钟。Preferably, the temperature increase rate of the melt treatment is 0.5-2.0°C/min.
再一方面，本发明提供了一种具有高功率密度的基于硫化银基无机热电材料的柔性热电器件，所述柔性热电器件中N型热电臂和P型热电臂中至少有一种由上述的硫化银基无机热电材料制备得到。 In still another aspect, the present invention provides a flexible thermoelectric device with high power density based on silver sulfide-based inorganic thermoelectric material, wherein at least one of the N-type thermoelectric arm and the P-type thermoelectric arm in the flexible thermoelectric device is formed by the above Prepared by silver-based inorganic thermoelectric materials.
较佳地，所述硫化银基无机热电材料构成的热电臂，所述热电臂的高度范围为0.0001 mm～0.1 mm，长和宽的范围为0.1 mm～50 mm。Preferably, for the thermoelectric arm composed of the silver sulfide-based inorganic thermoelectric material, the height range of the thermoelectric arm is 0.0001 mm～0.1 mm, the length and width range is 0.1 mm～50 mm.
较佳地，所述柔性热电器件的高温端电极和低温端电极为铜箔、镍箔、铝箔、锡箔或金箔；所述高温端电极和低温端电极的厚度范围为0.0001 mm～0.1 mm。Preferably, the high-temperature end electrode and the low-temperature end electrode of the flexible thermoelectric device are copper foil, nickel foil, aluminum foil, tin foil or gold foil; the thickness range of the high-temperature end electrode and the low-temperature end electrode is 0.0001 mm～0.1 mm.
较佳地，将高温端电极和低温端电极分别与热电臂连接，构成串联的热电对，将所得多组热电对黏附于柔性衬底上，获得柔性热电器件；优选地，所述柔性衬底为聚氯乙烯、聚丙烯、聚酰亚胺、聚对二甲苯、聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯中的中一种。Preferably, the high-temperature end electrode and the low-temperature end electrode are respectively connected to the thermoelectric arm to form a thermoelectric pair in series, and the obtained multiple sets of thermoelectric pairs are adhered to a flexible substrate to obtain a flexible thermoelectric device; preferably, the flexible substrate It is one of polyvinyl chloride, polypropylene, polyimide, parylene, polydimethylsiloxane, and polyethylene terephthalate.
有益效果Beneficial effect
本发明所提供的基于硫化银基无机热电材料的柔性热电器件不仅具有与有机热电器件相当的良好柔性，还具有与无机热电器件相当的高能量转换率、低阻抗以及耐高温的特点，可以用于人体皮肤表面等具有复杂形状的曲面，很好的满足柔性可穿戴电子器件的要求。本发明所提供的基于硫化银基无机热电材料的柔性热电器件的制备方法不会对环境产生污染，工艺简单，易于大批量制备，在可穿戴电子领域具有巨大的应用前景。The flexible thermoelectric device based on silver sulfide-based inorganic thermoelectric materials provided by the present invention not only has good flexibility comparable to organic thermoelectric devices, but also has the characteristics of high energy conversion rate, low impedance and high temperature resistance comparable to inorganic thermoelectric devices. The curved surface with complex shapes, such as the surface of human skin, can meet the requirements of flexible wearable electronic devices. The preparation method of the flexible thermoelectric device based on the silver sulfide-based inorganic thermoelectric material provided by the present invention does not cause pollution to the environment, the process is simple, and it is easy to prepare in large quantities, and has huge application prospects in the field of wearable electronics.
附图说明BRIEF DESCRIPTION
图1示出常见柔性热电器件的结构示意图，a：面内型（热流平行于衬底）；b：面外型（热流垂直于衬底），c：混合型（热流经过两个方向）；其中1为N型热电臂，2为P型热电臂，3为电极，4为热流方向，5为衬底，6为胶粘剂，7为绝热层；Figure 1 shows a schematic diagram of the structure of a common flexible thermoelectric device, a: in-plane type (heat flow parallel to the substrate); b: out-of-plane type (heat flow perpendicular to the substrate), c: mixed type (heat flow through two directions); Among them, 1 is an N-type thermoelectric arm, 2 is a P-type thermoelectric arm, 3 is an electrode, 4 is a heat flow direction, 5 is a substrate, 6 is an adhesive, and 7 is an insulating layer;
图2示出三种硒、碲元素固溶硫化银（化学式Ag 2S 0.5Se 0.5、Ag 2S 0.6Te 0.4、Ag 2S 0.5Se 0.4Te 0.1）的a：电导率；b：塞贝克系数；c：功率因子以及d：功率因子与有机热电材料的比较，其中SWNT：单壁碳纳米管，PANI：聚苯胺，P3HT：聚3-己基噻吩，TCB：三氯苯，PBTTT：聚(2,5-双(3-十四烷基噻吩-2-基)噻吩并[3,2-B]噻吩)，PDPP3T：聚噻吩-吡咯并吡咯二酮，PSBTBT：聚[2,1,3-苯并噻二唑-4,7-二基[4,4-双(2-乙基己基)-4H-硅杂环戊二烯并[3,2-B:4,5-B']二噻吩-2,6-二基]]；e：热导率；f：热电优值； Figure 2 shows a: conductivity of three kinds of selenium and tellurium solid solution silver sulfide (chemical formulas Ag 2 S 0.5 Se 0.5 , Ag 2 S 0.6 Te 0.4 , Ag 2 S 0.5 Se 0.4 Te 0.1 ); b: Seebeck coefficient ; C: power factor and d: power factor compared with organic thermoelectric materials, where SWNT: single-walled carbon nanotubes, PANI: polyaniline, P3HT: poly 3-hexylthiophene, TCB: trichlorobenzene, PBTTT: poly (2 ,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-B]thiophene), PDPP3T: polythiophene-pyrrolopyrrole dione, PSBTBT: poly[2,1,3- Benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-silacyclopenta[3,2-B:4,5-B']di Thiophene-2,6-diyl]]; e: thermal conductivity; f: thermoelectric figure of merit;
图3示出六对面内型硫化银基柔性无机热电器件结构示意图，其中1为N型热电臂，组分为硒元素固溶硫化银（化学式Ag 2S 0.5Se 0.5），2为P型热电臂，组分为Pt-Ru，3为电极，4为衬底； Figure 3 shows a schematic diagram of the structure of six pairs of in-plane silver sulfide-based flexible inorganic thermoelectric devices, where 1 is an N-type thermoelectric arm, the component is selenium element solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.5 ), and 2 is a P-type thermoelectric Arm, the composition is Pt-Ru, 3 is the electrode, 4 is the substrate;
图4示出六对面内型硫化银基柔性无机热电器件的a：电压-电流曲线和b：功率-电流曲线；Figure 4 shows a: voltage-current curve and b: power-current curve of six pairs of in-plane silver sulfide-based flexible inorganic thermoelectric devices;
图5示出硫化银基柔性无机热电器件（材料组分为硒元素固溶硫化银（化学式Ag 2S 0.5Se 0.5））与有机热电器件功率密度的比较，其中SWNT：单壁碳纳米管，PANI：聚苯胺，CNT：碳纳米管，Poly[Ax(M-ett)]：聚1,1,2,2-乙烯四硫醇（5-乙硫基四氮唑），Polystyrene：聚苯乙烯，PEDOT:Tos：甲苯磺酸-聚(3,4-乙烯二氧噻吩)，PEDOT：聚(3,4-乙烯二氧噻吩)，Graphene：石墨烯，carbon：碳； Figure 5 shows the power density comparison of silver sulfide-based flexible inorganic thermoelectric devices (the material composition is selenium element solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.5 )) and organic thermoelectric devices, where SWNT: single-walled carbon nanotubes, PANI: polyaniline, CNT: carbon nanotubes, Poly[Ax(M-ett)]: poly 1,1,2,2-ethylene tetrathiol (5-ethylthiotetrazolium), Polystyrene: polystyrene , PEDOT: Tos: toluenesulfonic acid-poly(3,4-ethylenedioxythiophene), PEDOT: poly(3,4-ethylenedioxythiophene), Graphene: graphene, carbon: carbon;
图6示出硫化银基柔性无机热电器件内阻随弯折次数的变化，弯折半径为10 mm，材料组分为硒元素固溶硫化银（化学式Ag 2S 0.5Se 0.5）； Figure 6 shows the change of the internal resistance of the silver sulfide-based flexible inorganic thermoelectric device with the number of bendings. The bending radius is 10 mm, and the material composition is selenium element solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.5 );
图7示出六对面外型硫化银基柔性无机热电器件的结构示意图，其中1为N型热电臂，组分为碲元素固溶硫化银（化学式Ag 2S 0.6Te 0.4），2为P型热电臂，组分为Pt-Ru，3为电极，4为衬底； Figure 7 shows a schematic diagram of the structure of six pairs of out-of-plane silver sulfide-based flexible inorganic thermoelectric devices, where 1 is an N-type thermoelectric arm, the component is tellurium solid solution silver sulfide (chemical formula Ag 2 S 0.6 Te 0.4 ), and 2 is a P type Thermoelectric arm, the composition is Pt-Ru, 3 is the electrode, 4 is the substrate;
图8示出六对面外型硫化银基柔性无机热电器件的a：电压-电流曲线和b：功率-电流曲线。FIG. 8 shows a: voltage-current curve and b: power-current curve of six pairs of out-of-plane silver sulfide-based flexible inorganic thermoelectric devices.
图9示出六对混合型硫化银基柔性无机热电器件的结构示意图，其中1为N型热电臂，组分为硒、碲元素固溶硫化银（化学式Ag 2S 0.5Se 0.4Te 0.1），2为P型热电臂，组分为Pt-Ru，3为电极，4为衬底，5为绝热层； Figure 9 shows a schematic diagram of the structure of six pairs of hybrid silver sulfide-based flexible inorganic thermoelectric devices, where 1 is an N-type thermoelectric arm, and the components are selenium and tellurium solid solution silver sulfide (chemical formula Ag 2 S 0.5 Se 0.4 Te 0.1 ), 2 is a P-type thermoelectric arm, the composition is Pt-Ru, 3 is an electrode, 4 is a substrate, and 5 is a thermal insulation layer;
图10示出六对混合型硫化银基柔性无机热电器件的a：电压-电流曲线和b：功率-电流曲线。FIG. 10 shows a: voltage-current curve and b: power-current curve of six pairs of hybrid silver sulfide-based flexible inorganic thermoelectric devices.
本发明的实施方式Embodiments of the invention
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。The present invention will be further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, but not to limit the present invention.
在本公开中，本发明人对Se固溶与Te固溶的硫化银基材料进行了大量热电性能方面的研究，首次发现在保留硫化银的柔性的同时，Se固溶与Te固溶的硫化银材料表现出优良的热电性能。例如，在室温下，Se固溶的硫化银基热电材料的热电优值为0.26，远高于传统的有机热电材料。如果将硫化银基无机热电材料制备成热电器件，将有望可以同时实现良好的塑性和高的输出功率密度，实现在可穿戴传感器和其他电子设备的广泛应用，进而有望推动柔性热电技术的发展。柔性热电器件所使用的主要热电材料为硫化银基无机热电材料，其化学式为Ag 2(S 1-xM x)，其中M可以为Se元素和Te元素中的一种或两种，其作为固溶元素固溶于S晶格位置，其固溶量范围为0.001≤x≤0.9。 In the present disclosure, the inventors conducted a large number of studies on the thermoelectric properties of silver sulfide-based materials in which Se and Te solid solutions, and found for the first time that while retaining the flexibility of silver sulfide, Se and Te solid solution sulfides Silver materials exhibit excellent thermoelectric properties. For example, at room temperature, Se solid solution silver sulfide-based thermoelectric materials have a thermoelectric figure of merit of 0.26, which is much higher than traditional organic thermoelectric materials. If the silver sulfide-based inorganic thermoelectric material is made into a thermoelectric device, it is expected to achieve good plasticity and high output power density at the same time, and achieve wide application in wearable sensors and other electronic devices, and is expected to promote the development of flexible thermoelectric technology. The main thermoelectric materials used in flexible thermoelectric devices are silver sulfide-based inorganic thermoelectric materials, whose chemical formula is Ag 2 (S 1-x M x ), where M can be one or two of Se element and Te element, which is used as The solid solution element is solid-dissolved in the S lattice position, and its solid solution amount range is 0.001≤x≤0.9.
在可选的实施方式中，室温下，所述硫化银基无机热电材料的热电优值为0.05～0.8；所述硫化银基无机热电材料在300 K时的功率因子为2.0～10.0 μW·cm -1·K -2。 In an alternative embodiment, at room temperature, the thermoelectricity value of the silver sulfide-based inorganic thermoelectric material is 0.05 to 0.8; the power factor of the silver sulfide-based inorganic thermoelectric material at 300 K is 2.0 to 10.0 μW·cm -1 ·K -2 .
在可选的实施方式中，硫化银基无机热电材料在三点弯曲测试中承受高达20%的机械应变而不破裂。在压缩测试中承受高达70%的机械应变而不破裂。In an alternative embodiment, the silver sulfide-based inorganic thermoelectric material withstands up to 20% mechanical strain without cracking in the three-point bending test. Withstands up to 70% of mechanical strain in the compression test without breaking.
在本发明一实施方式中，可以通过高温熔融、以及放电等离子烧结或热压烧结得到致密的块状硫化银基无机热电材料。以下示例性地说明硫化银基无机热电材料的制备方法。In one embodiment of the present invention, a dense bulk silver sulfide-based inorganic thermoelectric material can be obtained by high-temperature melting, and spark plasma sintering or hot-press sintering. The following exemplarily illustrates the preparation method of the silver sulfide-based inorganic thermoelectric material.
按化学计量比称取高纯的Ag、S、M元素单质，将其放置于石英管中进行真空封装，然后在800～1300摄氏度进行熔融，熔融时间为2～120小时。熔融结束后，在300～700摄氏度对熔融产物进行退火处理，获得单相的硫化银基无机热电材料铸锭。其中，熔融处理的升温速率为0.5～2.0 ℃/分钟。Weigh high-purity Ag, S, and M elemental elements in stoichiometric ratio, place them in a quartz tube for vacuum packaging, and then melt at 800 to 1300 degrees Celsius for a melting time of 2 to 120 hours. After the melting is completed, the molten product is annealed at 300 to 700 degrees Celsius to obtain a single-phase ingot of silver sulfide-based inorganic thermoelectric material. Among them, the temperature increase rate of the melt treatment is 0.5 to 2.0°C/min.
根据应用需求，将硫化银基无机热电材料铸锭或者由上述铸锭制备的粉末，利用热压烧结或放电等离子烧结技术制备成具有特定形状的致密块体。热压烧结的温度可为190～600 ℃，时间可为10～1000分钟，压力可为30～70 MPa。放电等离子烧结的温度可为190～600 ℃，时间可为10～1000分钟。According to application requirements, the ingot of silver sulfide-based inorganic thermoelectric material or the powder prepared from the ingot is prepared into a dense block with a specific shape by hot pressing sintering or spark plasma sintering technology. The temperature of hot pressing sintering can be 190-600 ℃, the time can be 10-1000 minutes, and the pressure can be 30-70 MPa. The temperature of spark plasma sintering may be 190-600°C, and the time may be 10-1000 minutes.
在本发明一实施方式中，基于硫化银基无机热电材料的柔性热电器件的制备方法简单，易于实现大批量制备。特别是，该热电器件对环境友好，在空气中可以长时间稳定工作，可以很好的满足柔性可穿戴电子器件的要求。.In an embodiment of the present invention, a method for preparing a flexible thermoelectric device based on silver sulfide-based inorganic thermoelectric materials is simple, and it is easy to realize mass production. In particular, the thermoelectric device is environmentally friendly, can work stably in the air for a long time, and can well meet the requirements of flexible wearable electronic devices. .
在本发明一实施方式中，基于硫化银基无机热电材料的柔性热电器件制备方法包括：从致密的块体硫化银基无机热电材料上切割出特定尺寸的热电臂。将电极与由硫化银基热电臂连接，构成串联的热电对。将由硫化银基无机热电材料构成的多组热电对黏附于具有柔性的衬底之上，获得柔性热电器件。In an embodiment of the present invention, a method for preparing a flexible thermoelectric device based on a silver sulfide-based inorganic thermoelectric material includes: cutting a thermoelectric arm of a specific size from a dense bulk silver sulfide-based inorganic thermoelectric material. The electrode is connected with a silver sulfide-based thermoelectric arm to form a thermoelectric pair in series. Multiple sets of thermoelectric pairs composed of silver sulfide-based inorganic thermoelectric materials are adhered to a flexible substrate to obtain a flexible thermoelectric device.
将硫化银基无机热电材料制备成硫化银基无机柔性热电器件中的热电臂，包括：从硫化银基无机热电材料铸锭或经过烧结的硫化银基热电材料致密块体上，利用金刚石切割机、内圆切割机、外圆切割机、电火花切割机切割出特定尺寸的薄片状的硫化银基热电材料。The silver sulfide-based inorganic thermoelectric material is prepared as a thermoelectric arm in a silver sulfide-based inorganic flexible thermoelectric device, which includes: using a diamond cutting machine from a silver sulfide-based inorganic thermoelectric material ingot or a sintered silver sulfide-based thermoelectric material dense block , Inner circle cutting machine, outer circle cutting machine, electric spark cutting machine cut out a thin sheet of silver sulfide-based thermoelectric material of a specific size.
将切割的薄片状的硫化银基无机热电材料表面用砂纸打磨干净或在酒精或去离子水中超声清洗干净，最终获得适用于无机柔性热电器件的热电臂。热电器件中N型热电臂和P型热电臂中至少有一种由硫化银基无机热电材料构成。其热电臂表面应清洁、无油污等杂质，以确保热电臂与电极之间良好的欧姆接触。薄片状的硫化银基无机热电材料的高度范围可为0.0001 mm～0.1 mm，长和宽的范围可为0.1 mm～50 mm；优选地，薄片状的硫化银基无机热电材料的高度范围为0.01 mm～0.05 mm。The surface of the cut sheet-shaped silver sulfide-based inorganic thermoelectric material is polished with sandpaper or ultrasonically cleaned in alcohol or deionized water to finally obtain a thermoelectric arm suitable for inorganic flexible thermoelectric devices. At least one of the N-type thermoelectric arm and the P-type thermoelectric arm in the thermoelectric device is composed of a silver sulfide-based inorganic thermoelectric material. The surface of the thermoelectric arm should be clean and free of impurities such as oil to ensure good ohmic contact between the thermoelectric arm and the electrode. The flake-shaped silver sulfide-based inorganic thermoelectric material can have a height of 0.0001 mm to 0.1 mm, the length and width may range from 0.1 mm to 50 mm; preferably, the height of the flake-shaped silver sulfide-based inorganic thermoelectric material ranges from 0.01 mm to 0.05 mm.
选取铜箔、镍箔、铝箔、锡箔、金箔中的至少一种作为基于硫化银基无机热电材料的柔性热电器件的高温端电极材料和低温端电极材料，实现热电器件中的N型热电臂和P型热电臂的电串联。所选取作为电极材料的铜箔、镍箔、铝箔、锡箔、金箔应具有良好的柔性，可实现大幅度的重复弯折，其厚度范围可为0.0001 mm～0.1 mm。At least one of copper foil, nickel foil, aluminum foil, tin foil and gold foil is selected as the high-temperature terminal electrode material and the low-temperature terminal electrode material of the flexible thermoelectric device based on the silver sulfide-based inorganic thermoelectric material to realize the N-type thermoelectric arm and the thermoelectric device P series thermoelectric arms are electrically connected in series. The copper foil, nickel foil, aluminum foil, tin foil and gold foil selected as the electrode material should have good flexibility, can realize large-scale repeated bending, and the thickness range can be 0.0001 mm～0.1 mm.
电极材料与热电臂之间还可通过银浆、碳浆、铟焊、锡焊、激光焊、扩散焊、或电压烧结方式连接。连接后的电极材料与热电臂应该具有尽可能小的接触电阻和热阻，并且在多次反复弯折过程中具有高可靠性，界面处不发生开裂或脱落。The electrode material and the thermoelectric arm can also be connected by silver paste, carbon paste, indium welding, tin welding, laser welding, diffusion welding, or voltage sintering. The electrode material and the thermoelectric arm after connection should have as small contact resistance and thermal resistance as possible, and have high reliability during repeated bending, and no cracking or falling off at the interface.
多对热电臂的整体电串联方式根据实际使用环境对柔性热电器件的形状要求而定。一般的，多对热电臂的整体电串联方式可以按照图1中a所示的面内型（热流平行于衬底）结构组装，或者按照图1中b所示的面外型（热流垂直于衬底）以及图1中c所示的混合型（热流经过两个方向）结构组装。组装后的柔性热电器件应确保器件可以充分利用热源产生的热量，减少不必要的热损失。The overall electrical series connection of multiple pairs of thermoelectric arms depends on the actual use environment and the shape requirements of the flexible thermoelectric devices. In general, the overall electrical series connection of multiple pairs of thermoelectric arms can be assembled according to the in-plane type (heat flow parallel to the substrate) structure shown in a of FIG. 1, or according to the out-of-plane type shown in b of FIG. 1 (heat flow is perpendicular to Substrate) and the hybrid type (heat flow through two directions) structure shown in c in Figure 1 is assembled. The assembled flexible thermoelectric device should ensure that the device can make full use of the heat generated by the heat source and reduce unnecessary heat loss.
将热电臂与电极连接好之后，还可使用胶粘剂附着在一定尺寸的衬底上得到基于硫化银基无机热电材料的柔性热电器件。非特殊设计要求，一般使用的胶粘剂和衬底应保证良好的导热性，以减少从热源到器件热端之间的热损失。After the thermoelectric arm and the electrode are connected, an adhesive can also be used to attach to a substrate of a certain size to obtain a flexible thermoelectric device based on a silver sulfide-based inorganic thermoelectric material. Without special design requirements, generally used adhesives and substrates should ensure good thermal conductivity to reduce heat loss from the heat source to the hot end of the device.
柔性热电器件的衬底可以为聚氯乙烯、聚丙烯、聚酰亚胺、聚对二甲苯、聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯等有机聚合物。柔性衬底要在室温附近较大温度范围内保证良好的柔韧性和稳定性，不容易发生软化、分解、挥发、产生对人体有害的物质。组成衬底的有机聚合物应耐腐蚀、防水、绝缘、无毒，且不易老化、开裂、起皮、剥落。The substrate of the flexible thermoelectric device may be an organic polymer such as polyvinyl chloride, polypropylene, polyimide, parylene, polydimethylsiloxane, and polyethylene terephthalate. The flexible substrate should ensure good flexibility and stability in a large temperature range around room temperature, and it is not easy to soften, decompose, volatilize, and produce substances harmful to the human body. The organic polymer constituting the substrate should be resistant to corrosion, waterproof, insulating, non-toxic, and not easy to age, crack, peel or peel.
硫化银基无机热电材料和电极可使用聚二甲基硅氧烷或聚对二甲苯作为胶粘剂材料黏附于衬底之上。胶粘剂可以为聚二甲基硅氧烷、聚对二甲苯等。胶粘剂要在室温附近较大温度范围内保证良好的柔韧性和稳定性，不容易发生软化、分解、挥发、产生对人体有害的物质。组成胶粘剂的材料应耐腐蚀、防水、绝缘、无毒，且不易老化、开裂、起皮、剥落。胶粘剂与衬底之间需有良好的亲和性和粘结强度，不易从衬底上脱离。此外胶粘剂需要保持良好的机械强度，确保器件和衬底之间持久稳定的结合。The silver sulfide-based inorganic thermoelectric material and the electrode can be attached to the substrate using polydimethylsiloxane or parylene as the adhesive material. The adhesive may be polydimethylsiloxane, parylene or the like. The adhesive should ensure good flexibility and stability in a large temperature range around room temperature, and it is not easy to soften, decompose, volatilize, and produce harmful substances to the human body. The materials that make up the adhesive should be resistant to corrosion, waterproof, insulating, non-toxic, and not easy to age, crack, peel or peel. The adhesive and the substrate need to have good affinity and bonding strength, and it is not easy to detach from the substrate. In addition, the adhesive needs to maintain good mechanical strength to ensure a durable and stable bond between the device and the substrate.
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。The following further exemplifies the examples to illustrate the present invention in detail. It should also be understood that the following embodiments are only used to further illustrate the present invention, and cannot be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention belong to the present invention. Scope of protection. The specific process parameters and the like in the following examples are only examples in the appropriate range, that is, those skilled in the art can make selections within the appropriate range through the description herein, and are not limited to the specific numerical values in the examples below.
实施例Examples 11
此实施例1为面内型器件。制备N型Ag 2S 0.5Se 0.5材料：按照4:1:1化学计量比，称取高纯Ag、S、Se元素。其加入Φ10厚石英管中进行真空封装；将封装后的石英管以40小时的升温速度升温至1000℃并保温12小时，然后在25小时内冷却至100℃，之后石英管在450℃退火5天。将退火后的Ag 2S 0.5Se 0.5铸锭在液氮环境下用不锈钢杵砸碎成粉。然后将粉末使用放电等离子体烧结在190℃下烧结0.5小时，最终得到致密的N型Ag 2S 0.5Se 0.5块体。在三点弯曲测试中，使用致密的N型Ag 2S 0.5Se 0.5块体可以承受12%的机械应变而不破裂；在压缩测试中，致密的N型Ag 2S 0.5Se 0.5块体可以承受高达55%的机械应变而不破裂。其热电性能如图2所示，在300 K，其功率因子为4.8 μW·cm -1·K -2，远高于传统的有机热电材料。使用金刚刀切割机将所得Ag 2S 0.5Se 0.5致密块体直接切割成0.15 mm的薄片，然后进一步使用细砂纸将Ag 2S 0.5Se 0.5薄片打磨至厚度0.1 mm左右；使用剪刀将Ag 2S 0.5Se 0.5薄片裁剪成长15 mm宽3 mm的长条作为器件的N型热电臂。使用直径0.1 mm，长约20 mm的铂铑(90%Pt-10%Rh) 线作为P型热电臂；使用10 μm厚、长6 mm、宽4 mm的铜箔作为电极材料。使用激光点焊将N型热电臂、铂铑线与铜箔焊接成如图3所示6组Ag 2S 0.5Se 0.5/Pt-Rh热电对。取0.3 mm厚、长50 mm宽40 mm大小的聚酰亚胺作为衬底，聚酰亚胺表面使用酒精擦洗、烘干，除去表面油污和杂质，将0.3 g聚二甲基硅氧烷涂敷在衬底中央，然后将6组热电对平铺在聚二甲基硅氧烷上，再加0.5 g聚二甲基硅氧烷覆盖在热电对表面。聚二甲基硅氧烷成分为：本体与固化剂比例10：1。待热电对全部均匀包裹在聚二甲基硅氧烷中后，将其置于烘箱中在70℃下固化60分钟，最终得到基于Ag 2S 0.5Se 0.5的面内型柔性无机热电器件。如图4所示，测试结果表明，该面内型柔性无机热电器件在20 K的温差下，器件的输出电压为20 mV，输出最大功率10 μW，能量密度达到5.5 Wcm -2。如图5所示，其功率密度远高于传统的基于有机热电材料的柔性热电器件。特别是，经过反复弯折100次，硫化银基无机柔性热电器件内阻基本不变，表明其具有良好的稳定性（参见图6）。 This embodiment 1 is an in-plane type device. Preparation of N-type Ag 2 S 0.5 Se 0.5 material: Weigh high-purity Ag, S and Se elements according to the 4:1:1 stoichiometric ratio. It is added to a Φ10 thick quartz tube for vacuum packaging; the encapsulated quartz tube is heated to 1000°C at a heating rate of 40 hours and held for 12 hours, then cooled to 100°C within 25 hours, and then the quartz tube is annealed at 450°C 5 day. The annealed Ag 2 S 0.5 Se 0.5 ingot was crushed into a powder with a stainless steel pestle under a liquid nitrogen environment. The powder was then sintered at 190°C for 0.5 hours using spark plasma sintering, and finally a dense N-type Ag 2 S 0.5 Se 0.5 bulk was obtained. In the three-point bending test, the dense N-type Ag 2 S 0.5 Se 0.5 block can withstand 12% of the mechanical strain without cracking; in the compression test, the dense N-type Ag 2 S 0.5 Se 0.5 block can withstand Up to 55% mechanical strain without cracking. Its thermoelectric performance is shown in Figure 2. At 300 K, its power factor is 4.8 μW·cm -1 ·K -2 , which is much higher than traditional organic thermoelectric materials. Use the diamond cutter to cut the obtained Ag 2 S 0.5 Se 0.5 dense block directly into 0.15 mm thin pieces, and then use fine sandpaper to polish the Ag 2 S 0.5 Se 0.5 thin pieces to a thickness of about 0.1 mm; use scissors to cut the Ag 2 S 0.5 Se 0.5 slices are cut into 15 mm wide and 3 mm long strips as N-type thermoelectric arms of the device. A platinum rhodium (90%Pt-10%Rh) wire with a diameter of 0.1 mm and a length of about 20 mm was used as the P-type thermoelectric arm; a copper foil of 10 μm thick, 6 mm long and 4 mm wide was used as the electrode material. Using laser spot welding, the N-type thermoelectric arm, platinum-rhodium wire and copper foil were welded into 6 sets of Ag 2 S 0.5 Se 0.5 /Pt-Rh thermoelectric pairs as shown in FIG. 3. Take 0.3 mm thick polyimide with a length of 50 mm and a width of 40 mm as the substrate. The surface of the polyimide is scrubbed with alcohol and dried to remove oil stains and impurities on the surface. Apply 0.3 g of polydimethylsiloxane Apply it to the center of the substrate, and then lay 6 sets of thermoelectric pairs on the polydimethylsiloxane, and then add 0.5 g of polydimethylsiloxane to cover the surface of the thermoelectric pair. The polydimethylsiloxane component is: body to curing agent ratio 10:1. After all the thermoelectric pairs were uniformly wrapped in polydimethylsiloxane, they were placed in an oven and cured at 70°C for 60 minutes. Finally, an in-plane flexible inorganic thermoelectric device based on Ag 2 S 0.5 Se 0.5 was obtained. As shown in Figure 4, the test results show that the in-plane flexible inorganic thermoelectric device has a 20 KV temperature difference, an output voltage of 20 mV, a maximum output power of 10 μW, and an energy density of 5.5 Wcm -2 . As shown in Figure 5, its power density is much higher than traditional flexible thermoelectric devices based on organic thermoelectric materials. In particular, after repeated bending for 100 times, the internal resistance of the silver sulfide-based inorganic flexible thermoelectric device remained basically unchanged, indicating that it had good stability (see Figure 6).
实施例Examples 22
此实施例2为面外型器件。制备N型Ag 2S 0.6Te 0.4材料：按照10:3:2化学计量比，称取高纯Ag、S、Te元素。其加入Φ10厚石英管中进行真空封装；将封装后的石英管以40小时的升温速度升温至1000 ℃并保温12小时，然后在25小时内冷却至100 ℃，之后石英管在450 ℃退火5天。将退火后的Ag 2S 0.6Te 0.4铸锭在液氮环境下用不锈钢杵砸碎成粉。然后将粉末使用放电等离子体烧结在320 ℃下烧结0.5小时，最终得到致密的N型Ag 2S 0.6Te 0.4块体。其热电性能如图2所示，在300 K，其功率因子为3.1 μW·cm -1·K -2，远高于传统的有机热电材料。在三点弯曲测试中，使用致密的N型Ag 2S 0.6Te 0.4块体可以承受8%的机械应变而不破裂；在压缩测试中，致密的N型Ag 2S 0.6Te 0.4块体可以承受高达45%的机械应变而不破裂。使用金刚刀切割机将将所得Ag 2S 0.6Te 0.4致密块体直接切割成0.1 mm的薄片，然后进一步使用细砂纸将Ag 2S 0.6Te 0.4薄片打磨至样品表面无杂质。使用剪刀将Ag 2S 0.6Te 0.4薄片裁剪成长5 mm宽3 mm的长条作为器件的N型热电臂。使用直径0.1 mm，长约10 mm的铜线作为P型热电臂；使用20 μm厚、长6 mm、宽4 mm的镍箔作为电极材料。N型热电臂与镍箔之间使用扩散焊连接；P型热电臂（铜线）与镍箔之间使用低温银浆连接，连接效果如图7所示6组Ag 2S 0.6Te 0.4/Pt-Rh热电对。取0.3 mm厚、长50 mm宽30 mm大小的聚氯乙烯作为衬底，聚氯乙烯表面使用酒精擦洗、烘干，除去表面油污和杂质，将0.3 g聚对二甲苯涂敷在衬底中央，然后将6组热电对平铺在聚对二甲苯上，再加0.5 g聚对二甲苯覆盖在热电对表面。待热电对全部均匀包裹在聚对二甲苯中后，将其置于烘箱中在70℃下固化60分钟，最终得到基于Ag 2S 0.6Te 0.4的面外型柔性无机热电器件。如图8所示，测试结果表明，该面外型柔性无机热电器件在20 K的温差下，器件的输出电压为8 mV，输出最大功率1.3 μW。 This embodiment 2 is an out-of-plane device. Preparation of N-type Ag 2 S 0.6 Te 0.4 material: according to the stoichiometric ratio of 10:3:2, weigh high-purity Ag, S, Te elements. It is added to a Φ10 thick quartz tube for vacuum packaging; the encapsulated quartz tube is heated to 1000 ℃ at a heating rate of 40 hours and held for 12 hours, then cooled to 100 ℃ within 25 hours, and then the quartz tube is annealed at 450 ℃ 5 day. The annealed Ag 2 S 0.6 Te 0.4 ingot was crushed into a powder with a stainless steel pestle under a liquid nitrogen environment. The powder was then sintered at 320°C for 0.5 hours using spark plasma sintering, and finally a dense N-type Ag 2 S 0.6 Te 0.4 block was obtained. Its thermoelectric performance is shown in Figure 2. At 300 K, its power factor is 3.1 μW·cm -1 ·K -2 , which is much higher than traditional organic thermoelectric materials. In the three-point bending test, the dense N-type Ag 2 S 0.6 Te 0.4 block can withstand 8% mechanical strain without cracking; in the compression test, the dense N-type Ag 2 S 0.6 Te 0.4 block can withstand Up to 45% mechanical strain without cracking. The obtained Ag 2 S 0.6 Te 0.4 dense block was directly cut into 0.1 mm slices with a diamond cutter, and then the Ag 2 S 0.6 Te 0.4 slices were further polished with fine sandpaper until the sample surface was free of impurities. Use scissors to cut the Ag 2 S 0.6 Te 0.4 sheet into a 5 mm wide and 3 mm long strip as the N-type thermoelectric arm of the device. A copper wire with a diameter of 0.1 mm and a length of about 10 mm was used as the P-type thermoelectric arm; a nickel foil of 20 μm thick, 6 mm long and 4 mm wide was used as the electrode material. The N-type thermoelectric arm and nickel foil are connected by diffusion welding; the P-type thermoelectric arm (copper wire) and nickel foil are connected by low-temperature silver paste. The connection effect is shown in Figure 7 6 groups of Ag 2 S 0.6 Te 0.4 /Pt -Rh thermoelectric pair. Take 0.3 mm thick, 50 mm long and 30 mm wide polyvinyl chloride as the substrate. The surface of the polyvinyl chloride is scrubbed and dried with alcohol to remove oil stains and impurities on the surface, and 0.3 g of parylene is coated on the center of the substrate Then, lay 6 sets of thermoelectric pairs on parylene, and then add 0.5 g of parylene to cover the surface of the thermoelectric pairs. After all the thermoelectric pairs were uniformly wrapped in parylene, they were placed in an oven and cured at 70°C for 60 minutes. Finally, an out-of-plane flexible inorganic thermoelectric device based on Ag 2 S 0.6 Te 0.4 was obtained. As shown in Figure 8, the test results show that the out-of-plane flexible inorganic thermoelectric device has a temperature difference of 20 K, an output voltage of 8 mV, and a maximum output power of 1.3 μW.
实施例Examples 33
此实施例为混合型器件。制备N型Ag 2S 0.5Se 0.4Te 0.1材料：按照20:5:4:1化学计量比，称取高纯Ag、S、Se、Te元素。其加入Φ10厚石英管中进行真空封装；将封装后的石英管以40小时的升温速度升温至1000 ℃并保温12小时，然后在25小时内冷却至100 ℃，之后石英管在450 ℃退火5天。将退火后的Ag 2S 0.5Se 0.4Te 0.1铸锭在液氮环境下用不锈钢杵砸碎成粉。然后将粉末使用放电等离子体烧结在400 ℃下烧结0.5小时，最终得到致密的N型Ag 2S 0.5Se 0.4Te 0.1块体，其热电性能如图2所示，在300 K，其功率因子为2.7 μW·cm -1·K -2，远高于传统的有机热电材料。在三点弯曲测试中，使用致密的N型Ag 2S 0.5Se 0.4Te 0.1块体可以承受11 %的机械应变而不破裂；在压缩测试中，致密的N型Ag 2S 0.5Se 0.4Te 0.1块体可以承受高达50%的机械应变而不破裂。使用金刚刀切割机将将所得Ag 2S 0.5Se 0.4Te 0.1致密块体直接切割成0.1 mm的薄片，然后进一步使用细砂纸将Ag 2S 0.5Se 0.4Te 0.1薄片打磨至样品表面无杂质。使用剪刀将Ag 2S 0.5Se 0.4Te 0.1薄片裁剪成长15 mm宽3 mm的长条作为器件的N型热电臂。使用直径0.1 mm，长约20 mm的铂铑(90%Pt-10%Rh) 线作为P型热电臂；热端使用30 μm厚、长5 mm、宽4 mm的铜箔作为电极材料；冷端使用20 μm厚、长10 mm、宽8 mm的铜箔作为电极材料。N型热电臂与铜箔之间使用铟焊连接；P型热电臂与铜箔之间使用低温银浆连接，连接效果如图9所示6组Ag 2S 0.5Se 0.4Te 0.1/Pt-Rh热电对。取0.3 mm厚、长50 mm宽30 mm大小的聚氯乙烯作为衬底，按照图1中c及图9的结构示意，将热端铜箔下面的基底掏空形成凹槽，聚氯乙烯表面使用酒精擦洗、烘干，除去表面油污和杂质，将0.3 g聚对二甲苯涂敷在衬底中央，然后将6组热电对平铺在聚对二甲苯上，再加0.5 g聚对二甲苯覆盖在热电对表面。注意热端铜箔应藏入对应凹槽，且穿过衬底到达衬底背面，这样的设计是为了从衬底背部热源导入热流；冷端铜箔应比热端铜箔表面积大，且其下表面以涂敷聚二甲苯的方式附着在衬底表面，保持下表面与衬底背部热源的绝热，冷端上表面不涂敷聚二甲苯，以保持冷端和环境的接触，利于散热；添加聚二甲苯作为绝热层，将热端铜箔上表面和N、P材料一起包裹。待热电对均匀包裹在聚对二甲苯中后，将其置于烘箱中在70 ℃下固化60分钟，最终得到基于Ag 2S 0.5Se 0.4Te 0.1的混合型柔性无机热电器件。由热源开始，热流首先垂直于衬底传导至热端电极，再平行于衬底穿过热电材料到达冷端电极，并由冷端的铜箔散热至环境中。如图10所示，测试结果表明，该混合型柔性无机热电器件在15 K的温差下，器件的输出电压为6 mV，输出最大功率0.5 μW。 This embodiment is a hybrid device. Preparation of N-type Ag 2 S 0.5 Se 0.4 Te 0.1 material: According to the stoichiometric ratio of 20:5:4:1, high-purity Ag, S, Se, Te elements are weighed. It is added to a Φ10 thick quartz tube for vacuum packaging; the encapsulated quartz tube is heated to 1000 ℃ at a heating rate of 40 hours and held for 12 hours, then cooled to 100 ℃ within 25 hours, and then the quartz tube is annealed at 450 ℃ 5 day. The annealed Ag 2 S 0.5 Se 0.4 Te 0.1 ingot was crushed into a powder with a stainless steel pestle under a liquid nitrogen environment. Then the powder was sintered using spark plasma sintering at 400 ℃ for 0.5 hours, and finally a dense N-type Ag 2 S 0.5 Se 0.4 Te 0.1 block was obtained. Its thermoelectric performance is shown in FIG. 2, at 300 K, its power factor is 2.7 μW·cm -1 ·K -2 , much higher than traditional organic thermoelectric materials. In the three-point bending test, the dense N-type Ag 2 S 0.5 Se 0.4 Te 0.1 block can withstand 11% of the mechanical strain without cracking; in the compression test, the dense N-type Ag 2 S 0.5 Se 0.4 Te 0.1 The block can withstand up to 50% mechanical strain without breaking. The obtained Ag 2 S 0.5 Se 0.4 Te 0.1 dense block was directly cut into 0.1 mm thin slices using a diamond cutter, and then the fine Ag 2 S 0.5 Se 0.4 Te 0.1 thin slices were further polished to the surface of the sample without impurities. Use scissors to cut the Ag 2 S 0.5 Se 0.4 Te 0.1 sheet into a 15 mm wide and 3 mm long strip as the N-type thermoelectric arm of the device. Use a platinum rhodium (90%Pt-10%Rh) wire with a diameter of 0.1 mm and a length of about 20 mm as the P-type thermoelectric arm; the hot end uses 30 μm thick, 5 mm long and 4 mm wide copper foil as the electrode material; cold A copper foil 20 μm thick, 10 mm long, and 8 mm wide was used as the electrode material. The N-type thermoelectric arm and copper foil are connected by indium welding; the P-type thermoelectric arm and copper foil are connected by low-temperature silver paste, and the connection effect is shown in Figure 9 6 groups of Ag 2 S 0.5 Se 0.4 Te 0.1 /Pt-Rh Thermoelectric pair. Take 0.3 mm thick, 50 mm long and 30 mm wide PVC as the substrate, according to the schematic diagram of c and 9 in Fig. 1, hollow the substrate under the copper foil at the hot end to form a groove, the surface of the PVC Use alcohol to scrub and dry to remove oil stains and impurities on the surface, apply 0.3 g of parylene to the center of the substrate, then lay 6 sets of thermoelectric pairs on parylene, and then add 0.5 g of parylene Cover the surface of the thermoelectric pair. Note that the hot-end copper foil should be hidden into the corresponding groove and pass through the substrate to the back of the substrate. This design is to introduce heat flow from the heat source on the back of the substrate; the cold-end copper foil should have a larger surface area than the hot-end copper foil, and its The lower surface is attached to the surface of the substrate by coating polyxylene to keep the bottom surface insulated from the heat source on the back of the substrate. The upper surface of the cold end is not coated with polyxylene to keep the cold end in contact with the environment and facilitate heat dissipation; Polyxylene is added as a heat insulation layer, and the upper surface of the hot-end copper foil is wrapped with N and P materials. After the thermoelectric pair is evenly wrapped in parylene, it is placed in an oven and cured at 70 ℃ for 60 minutes, and finally a hybrid flexible inorganic thermoelectric device based on Ag 2 S 0.5 Se 0.4 Te 0.1 is obtained. Starting from the heat source, the heat flow is first conducted perpendicular to the substrate to the hot end electrode, and then parallel to the substrate through the thermoelectric material to the cold end electrode, and is dissipated by the cold end copper foil to the environment. As shown in Figure 10, the test results show that the hybrid flexible inorganic thermoelectric device has a temperature output of 15 K, the device's output voltage is 6 mV, and the maximum output power is 0.5 μW.

Claims (10)

  1. 一种硫化银基无机热电材料，其特征在于，所述硫化银基无机热电材料的化学式Ag 2(S 1-xM x)，其中M为Se元素和Te元素中的至少一种，0.001≤x≤0.9。 A silver sulfide-based inorganic thermoelectric material, characterized in that the chemical formula Ag 2 (S 1-x M x ) of the silver sulfide-based inorganic thermoelectric material, wherein M is at least one of Se element and Te element, 0.001≤ x≤0.9.
  2. 根据权利要求1所述的硫化银基无机热电材料，其特征在于，室温下，所述硫化银基无机热电材料的热电优值为0.05～0.8；所述硫化银基无机热电材料在300 K时的功率因子为2.0～10.0 μW·cm -1·K -2。 The silver sulfide-based inorganic thermoelectric material according to claim 1, characterized in that, at room temperature, the thermoelectric merit value of the silver sulfide-based inorganic thermoelectric material is 0.05 to 0.8; the silver sulfide-based inorganic thermoelectric material is at 300 K The power factor is from 2.0 to 10.0 μW·cm -1 ·K -2 .
  3. 根据权利要求1或2所述的硫化银基无机热电材料，其特征在于，所述硫化银基无机热电材料在三点弯曲测试中承受不超过20%的机械应变而不破裂，在压缩测试中承受不超过70%的机械应变而不破裂。The silver sulfide-based inorganic thermoelectric material according to claim 1 or 2, wherein the silver sulfide-based inorganic thermoelectric material is subjected to a mechanical strain of not more than 20% without breaking during a three-point bending test, and is subjected to compression test Withstand no more than 70% mechanical strain without breaking.
  4. 一种如权利要求1-3中任一项所述的硫化银基无机热电材料的制备方法，其特征在于，包括：A method for preparing a silver sulfide-based inorganic thermoelectric material according to any one of claims 1 to 3, characterized in that it includes:
    按照所述硫化银基无机热电材料的化学式称取Ag、S、Se和Te单质并混合，先在800～1300 ℃下熔融处理2～120小时，再于300～700 ℃下退火处理5～80小时，得到单相的硫化银基无机热电材料铸锭；According to the chemical formula of the silver sulfide-based inorganic thermoelectric material, Ag, S, Se, and Te are weighed and mixed, first melted at 800 to 1300 ℃ for 2 to 120 hours, and then annealed at 300 to 700 ℃ for 5 to 80 Hour, get single-phase ingot of silver sulfide-based inorganic thermoelectric material;
    将所得单相的硫化银基无机热电材料铸锭或单相的硫化银基无机热电材料铸锭粉碎成粉末，再经过热压烧结或放电等离子烧结，得到所述硫化银基无机热电材料。The obtained single-phase silver sulfide-based inorganic thermoelectric material ingot or single-phase silver sulfide-based inorganic thermoelectric material ingot is pulverized into powder, and then subjected to hot-press sintering or discharge plasma sintering to obtain the silver sulfide-based inorganic thermoelectric material.
  5. 根据权利要求4所述的制备方法，其特征在于，所述热压烧结的温度为190～600 ℃，时间为10～1000分钟，压力为30～70 MPa；所述放电等离子烧结的温度为190～600 ℃，时间为10～1000分钟。The preparation method according to claim 4, characterized in that the temperature of the hot-press sintering is 190-600°C, the time is 10-1000 minutes, and the pressure is 30-70 MPa; the temperature of the spark plasma sintering is 190 ~600 ℃, time is 10~1000 minutes.
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述熔融处理的升温速率为0.5～2.0 ℃/分钟。The preparation method according to claim 4 or 5, wherein the temperature increase rate of the melt treatment is 0.5 to 2.0°C/min.
  7. 一种基于硫化银基无机热电材料的柔性热电器件，其特征在于，所述柔性热电器件中N型热电臂和P型热电臂中至少有一种由权利要求1-3中任一项所述的硫化银基无机热电材料制备得到。A flexible thermoelectric device based on silver sulfide-based inorganic thermoelectric material, characterized in that at least one of the N-type thermoelectric arm and the P-type thermoelectric arm in the flexible thermoelectric device is described in any one of claims 1-3 Prepared by silver sulfide-based inorganic thermoelectric materials.
  8. 根据权利要求7所述的柔性热电器件，其特征在于，所述硫化银基无机热电材料构成的热电臂，所述热电臂的高度范围为0.0001 mm～0.1 mm，长和宽的范围为0.1 mm～50 mm。The flexible thermoelectric device according to claim 7, wherein the thermoelectric arm made of the silver sulfide-based inorganic thermoelectric material has a height range of 0.0001 mm to 0.1 mm and a length and width range of 0.1 mm ~50 mm.
  9. 根据权利要求7或8所述的柔性热电器件，其特征在于，所述柔性热电器件的高温端电极和低温端电极为铜箔、镍箔、铝箔、锡箔或金箔；所述高温端电极和低温端电极的厚度范围为0.0001 mm～0.1 mm。The flexible thermoelectric device according to claim 7 or 8, wherein the high-temperature terminal electrode and the low-temperature terminal electrode of the flexible thermoelectric device are copper foil, nickel foil, aluminum foil, tin foil or gold foil; the high-temperature terminal electrode and low temperature The thickness of the terminal electrode ranges from 0.0001 mm to 0.1 mm.
  10. 根据权利要求7-9中任一项所述的柔性热电器件，其特征在于，将高温端电极和低温端电极分别与热电臂连接，构成串联的热电对，将所得多组热电对黏附于柔性衬底上，获得柔性热电器件；优选地，所述柔性衬底为聚氯乙烯、聚丙烯、聚酰亚胺、聚对二甲苯、聚二甲基硅氧烷、聚对苯二甲酸乙二醇酯中的中一种。The flexible thermoelectric device according to any one of claims 7-9, characterized in that the high-temperature end electrode and the low-temperature end electrode are respectively connected to the thermoelectric arm to form a thermoelectric pair in series, and the obtained multiple sets of thermoelectric pairs are adhered to the flexible On the substrate, a flexible thermoelectric device is obtained; preferably, the flexible substrate is polyvinyl chloride, polypropylene, polyimide, parylene, polydimethylsiloxane, polyethylene terephthalate One of alcohol esters.
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