CN106711318B - A kind of oxide thermoelectricity electricity generation module, system and preparation method - Google Patents
A kind of oxide thermoelectricity electricity generation module, system and preparation method Download PDFInfo
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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
- H10N10/10—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
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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
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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
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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- H—ELECTRICITY
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
- H10N19/101—Multiple thermocouples connected in a cascade arrangement
Abstract
The invention discloses a kind of oxide thermoelectricity electricity generation modules, system and preparation method, based on the oxide thermoelectricity electricity generation module, its structure includes the oxide heat-conducting plate of about two layings, N-type and p-type thermoelectric power generation component are provided between two oxide heat-conducting plates, the thermoelectric power generation component is fixedly connected with oxide heat-conducting plate, the N-type and p-type thermoelectric power generation component are doped with rare earth element, and wire mesh is provided with the contact surface of oxide heat-conducting plate, the present invention can obtain preferable thermoelectric power generation property, realize the environmentally protective and inexpensive of device itself and use process.
Description
Technical field
The present invention relates to a kind of oxide thermoelectricity electricity generation module, system and preparation methods.
Background technique
Existing thermal power generation unit can only achieve 40% or so to the utilization efficiency of chemical energy in fossil fuel, with fossil
The energy is petered out, and waste heat utilization how is improved, and realizes maximally utilizing just increasingly by people to fossil energy
Concern.And thermoelectric power generation, as a kind of novel energy utilization type, the Waste Heat Reuse for occasions such as heat power stations is provided
One good solution.
Thermoelectric power generation is an important application of thermoelectric material.Thermoelectric generation module is the basic unit of thermoelectric power generation, by
Electrification component, electrode and heat-conducting plate are constituted.It is applied to the electrothermal module to generate electricity at present mainly based on alloy material, alloy thermoelectricity
Module is applied in special dimensions such as space probations since transfer efficiency is higher, technical maturity.But there are costs for it
The problems such as height, fusing point are low, oxidizable, containing heavy metal, should not especially be applied to the big temperature difference and high temperature thermoelectric power field.And oxygen
Compound material comparatively have many advantages, such as it is at low cost, without heavy metal, Applicable temperature is high, can establish the big temperature difference, therefore develop
Oxide pyroelectric material makes it to be applied to high temperature thermoelectric power field, becomes the development trend of current thermoelectric generation module.
Meanwhile existing electrothermal module, to there is module bonding strength itself under conditions of temperature gap is big unstable more,
Resistance is big, will cause the problem of irrecoverability damage in use, in specifically used, because playing the weldering of connection function
Expect that melt temperature is low, under repeatedly heated working condition, pad portion softening or thawing cause bad connection, and component loosens,
It causes resistance to become larger, or even produces fracture equal irrecoverabilities damage.
Existing electrothermal module is coated with solder based on alloy material between heat-conducting plate and alloy thermoelectric material, leads to
Crossing heating and cooling process makes solder solidification, achievees the purpose that connect alloy thermoelectric material and heat-conducting plate.Alloy material itself
Preparation temperature is lower (< 800 DEG C), and the solder melt temperature used is also low (< 600 DEG C), is not applied for high temperature and the big temperature difference
Thermoelectric power generation field.Even if in the thermoelectric power generation field of lower temperature, alloy thermoelectric material there is also it is easy to oxidize, at high cost,
The problems such as containing heavy metal.
Summary of the invention
The present invention to solve the above-mentioned problems, proposes a kind of oxide thermoelectricity electricity generation module, system and preparation method, this
Invention can obtain preferable thermoelectric power generation property, realize the environmentally protective and inexpensive of device itself and use process.
The first object of the present invention is to provide a kind of oxide thermoelectricity electricity generation module, which is π type component, uses oxide
Component replaces conventional alloys component, has many advantages, such as high temperature resistant, can be applied to the big temperature difference, is not oxidizable, having stable high-temperature performance.
The second object of the present invention is to provide a kind of electricity generation system based on above-mentioned electricity generation module, this system can obtain compared with
Good thermoelectric power generation property and efficiency, can provide good solution for the Waste Heat Reuse of the occasions such as heat power station.
The third object of the present invention is to provide a kind of method for preparing above-mentioned oxide thermoelectricity electricity generation module, this method operation
Simply, cost input is small and what is needed prepares that environment is simple, can guarantee the environmentally protective and inexpensive of preparation process.
The fourth object of the present invention is to provide a kind of method for preparing above-mentioned electricity generation system, and this method is by by multiple oxidations
Object thermoelectric generation module is connected, the preparation manipulation based on monomeric oxide thermoelectric generation module is simple, cost input is small and
Environment is simple for preparing of needing, can guarantee whole preparation process it is environmentally protective, reduce environmental pollution, improve thermoelectrical efficiency.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of oxide thermoelectricity electricity generation module, the oxide heat-conducting plate laid including about two, two oxides are thermally conductive
N-type and p-type thermoelectric power generation component are provided between plate, the thermoelectric power generation component is fixedly connected with oxide heat-conducting plate, the N
Type and p-type thermoelectric power generation component are provided with wire with the contact surface of oxide heat-conducting plate doped with rare earth element
Net.
In the opposite one side of described two oxide heat-conducting plates, it is coated with silver paste, and two oxide heat-conducting plates are smeared
Silver paste position it is corresponding.
The N-type and p-type thermoelectric power generation component are oxide thermoelectricity power generation material, preferably calcium manganate, cobalt acid calcium, cobalt acid
The oxide materials such as lanthanum, strontium carbonate or zinc oxide.
The p-type thermoelectric power generation component is cuboid, and the N-type thermoelectric power generation component is cylindrical body.
The rare earth element is doped into thermoelectric power generation component by solid phase reaction method.
A kind of oxide thermoelectricity electricity generation system, including multiple oxide thermoelectricity electricity generation module soldering connections in the form of concatenated
On heat-conducting plate.
The preparation method of the oxide thermoelectricity electricity generation module, comprising the following steps:
(1) N-type containing rare earth element and p-type thermoelectric power generation component are prepared respectively using solid phase reaction method；
(2) silver paste is diluted, is applied in two oxide heat-conducting plate one sides, so that on two oxide heat-conducting plates
Silver paste application area matches；
(3) wire mesh is individually positioned in the silver paste application area of two oxide heat-conducting plates, and on a wire mesh
Silver paste is smeared, N-type and p-type thermoelectric power generation component are respectively placed on wire mesh, keep a fixed spacing；
(4) two oxide heat-conducting plate cooperations are correspondingly arranged, make N-type and p-type thermoelectric power generation component being located at two oxygen
Between compound heat-conducting plate, high temperature sintering is carried out after compacting, completes welding.
In the step (4), oxide thermoelectricity module is set in thermostat, and temperature is 800-900 DEG C.
In the step (4), the sintering time includes heating and soaking time, sintering time 200-300min.
The preparation method of the oxide thermoelectricity electricity generation system, comprising the following steps:
(1) N-type containing rare earth element and p-type thermoelectric power generation component are prepared respectively using solid phase reaction method；
(2) silver paste is smeared in the wherein one side of two oxide heat-conducting plates, it is in array that entire application area, which has multiple,
The region corresponding with each oxide thermoelectricity electricity generation module of formula distribution, so that in a line and same row in array, phase
Two adjacent thermoelectric power generation components are not identical, guarantee that N-type and p-type thermoelectric power generation component are successively spaced setting；
(3) the adjacent N-type for belonging to different oxide thermoelectricity electricity generation modules in an array and p-type thermoelectric power generation component pair
It answers region to carry out smearing silver paste, different oxide thermoelectricity electricity generation modules is enable to connect, and silver paste on two oxide heat-conducting plates
Application area matches；
(4) wire mesh is individually positioned in the silver paste application area of two oxide heat-conducting plates, and on a wire mesh
Silver paste is smeared, N-type and p-type thermoelectric power generation component are set on the wire mesh of oxide heat-conducting plate, two oxides are thermally conductive
Plate cooperation is correspondingly arranged, and makes for N-type and p-type thermoelectric power generation component to be located between two oxide heat-conducting plates, is carried out after compacting high
Temperature sintering, completes welding.
As preferred alternative, several concatenated oxide thermoelectricity hairs are set between two oxide heat-conducting plates
Electric module, production form an oxide thermoelectricity generating set, and multiple oxide thermoelectricity generating sets are connected by conductor wire, gone here and there
Connection forms oxide thermoelectricity electricity generation system.
This setup can conveniently be found out and connect bad position and replacement, avoid well connecting because of certain
It connects, and influences the normal work of entire series circuit.
Compared with prior art, the invention has the benefit that
(1) cost of raw material selected is cheap, and preparation process is simple, large-scale production and application easy to accomplish, and can
To obtain biggish power output by less module number；
(2) replace conventional alloys component with oxide component, there is high temperature resistant, can be applied to the big temperature difference, is not oxidizable, high
Warm steady performance；
(3) using the technique of soldering, in the electrification component (N-type leg, p-type leg) and upper and lower aluminium oxide of oxide thermoelectricity module
Construction junction insertion wire mesh (such as copper mesh) of heat-conducting plate gets up junction integral solder using silver paste as solder, realizes
The building of pyroelectric oxide π pattern block, while by conducting wire --- the thermoelectric ceramics or silver paste --- connection type of thermoelectric ceramics
It is improved to the mode of silver paste --- wire mesh --- thermoelectric ceramics, greatly strengthens connective stability, the resistance to compression energy of π pattern block
Power and resistance to stress ability, improve practical value.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the temperature difference at both ends after 43 π modular assemblies of the invention are connected with the changing rule of temperature end temperature；
It is defeated on the electric furnace of two different capacities that Fig. 2 (a) and Fig. 2 (b) are respectively that 43 π modular assemblies of the invention are assigned to
Out voltage with the temperature difference changing rule；
Fig. 3 (a) and Fig. 3 (b) are that 3 π modular assemblies of the invention are assigned on the electric furnace of two different capacities and export respectively
Power with the temperature difference changing rule；
Fig. 4 is the schematic diagram of oxide thermoelectricity electricity generation module of the present invention；
Fig. 5 is the aluminium oxide heat-conducting plate silver paste application area schematic diagram of single π module of the invention；
Fig. 6 is the aluminium oxide heat-conducting plate silver paste application area schematic diagram of 3 π modules of the invention；
Fig. 7 is 3 π module connection diagrams of the invention.
Specific embodiment:
The invention will be further described with embodiment with reference to the accompanying drawing.
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
In a kind of typical embodiment of the application, as shown in figure 4, a kind of oxide thermoelectricity electricity generation module, including two
A oxide heat-conducting plate laid up and down, is provided with N-type and p-type thermoelectric power generation component between two oxide heat-conducting plates, described
Thermoelectric power generation component is fixedly connected with oxide heat-conducting plate, and the N-type and p-type thermoelectric power generation component are doped with rare earths member
Element, and it is provided with wire mesh with the contact surface of oxide heat-conducting plate, to form conductive electrode.
In the opposite one side of two oxide heat-conducting plates, it is coated with silver paste, and the silver that two oxide heat-conducting plates are smeared
It is corresponding to starch position.
N-type and p-type thermoelectric power generation component be oxide thermoelectricity power generation material, preferably calcium manganate, cobalt acid calcium, cobalt acid lanthanum,
The oxide materials such as strontium carbonate or zinc oxide.
P-type thermoelectric power generation component is cuboid, and the N-type thermoelectric power generation component is cylindrical body.
Rare earth element is doped into thermoelectric power generation component by solid phase reaction method.
The rare earth oxide refers to that period of element atom ordinal number is 57 to 71 15 kinds of lanthanide series oxygen
Compound, and the oxide of scandium similar with lanthanide series chemical property (Sc) and yttrium (Y) totally 17 kinds of elements.
Light rare earth includes: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium.
Heavy rare earth includes: terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium.
As a kind of exemplary embodiments of the invention, the preparation method of specific oxide thermoelectricity electricity generation module includes:
1: the preparation of oxide component
1-1:P type oxide component Ca3Co4O9Preparation
(the Ca of Lu doping is prepared using solid phase reaction method1-xLux)3Co4O9(x=0.00,0.03,0.05,0.10) oxygen
Compound sample.Starting material uses analytical chemistry reagent Lu2O3(purity 99.8%), Co2O3(purity 99%), CaCO3(purity
99%) etc., ingredient is stoichiometrically weighed, is made pottery by pyroelectric oxides such as mixing, pre-burning, crushing, molding, dumping, sintering
(the Ca of Lu doping is prepared in the preparation flow of porcelain1-xLux)3Co4O9Oxide samples.
1-2:N type oxide component CaMnO3Preparation
Ca is prepared using solid phase reaction method0.9-xYbxDy0.1MnO3(x=0.00,0.03,0.05,0.10) ceramics sample.
Starting material uses analytical chemistry reagent C aCO3(purity 99%), MnO2(purity 97.5%), Yb2O3(purity 99.9%),
Dy2O5(purity 99.5%) etc., stoichiometrically weighs ingredient, passes by mixing, pre-burning, crushing, molding, dumping, sintering etc.
The preparation flow of system pyroelectric oxide ceramics, is prepared Ca0.9-xYbxDy0.1MnO3Oxide samples.
Under the inspiration of the present invention, p-type oxide component or N-type oxide component are aoxidized by certain those skilled in the art
The parameter of object sample, ingredient are modified, to obtain similar thermoelectric power generation as a result, belonging to not need to make the creative labor
Simple replacement, ought to belong to the scope of protection of the present invention.
2: the cutting of oxide component
The present invention is for convenience of oxide samples machine-shaping, by p-type Ca3Co4O9Thin discs are made in oxide, then cut
For 15.00mm × 12.00mm × 3.00mm cuboid.N-type CaMnO3Oxide is prepared into diameter 10.00mm, height
15.00mm cylindrical body.
Certainly, those skilled in the art are entirely possible under the enlightenment of the working principle of the invention, by aforementioned p-type oxide
The shape of component or N-type oxide component, dimensional parameters are modified, to obtain the electricity generation module of more suitable applications scene,
Belong to the conventional replacement that this field is readily apparent that.
3: the soldering connection of single π module
3-1: drawing the part for needing to smear silver paste as shown in Figure 5 on upper and lower two pieces of aluminium oxide heat-conducting plates, and left side is round
(matching with the N-type oxide element shapes after cutting), rectangular (matching with the p-type oxide element shapes after cutting) yin
Shadow area portions respectively correspond Chong Die with right side circle, rectangular shaded area part；
3-2: wire mesh (copper mesh is used in the present invention) is cut into shape identical with silver paste area is smeared in step 3-1
It is spare；
3-3: silver paste is uniformly applied in the region that step 3-1 is drawn；
3-4: the wire mesh for being cut into correspondingly-shaped is placed on the region smeared in step 3-3, in wire mesh
On smear one layer of silver paste again；
3-5: cylindrical N-type oxide and rectangle p-type oxide component one end are placed in the wire after smearing silver paste
On web area, the other end covers second aluminium oxide thermally conductive sheet for arranging silver paste and wire mesh.It will be according in step 3-1
Corresponding position is put well, compacting.
3-6: will it is above-mentioned made of single π component sintering curing at high temperature.The mode of sintering curing is as follows:
π component is put into heater box, is begun to warm up from room temperature, temperature is slowly raised to 850 DEG C by 180min, then
60min is kept the temperature at 850 DEG C, terminates heating, is cooled to room temperature automatically, and module sintering curing is completed.
Based on above-mentioned module, can be configured to provide the thermoelectric heat generation system of larger generated energy.
By several thermoelectricity π module in the form of concatenated in soldering connection to one piece of heat-conducting plate.In electrothermal module series electrical
Lu Zhong is unable to good connection if having at one, certainly will influence the normal work of entire series circuit.It is convenient to avoid this problem
Bad position will be connected to find out and replace, in the present embodiment using first make 3 π block coupled in series component, if then again by
Dry 3 π modular assemblies series connection.If having conductive undesirable position in so entire series circuit, the 3 π modular assembly is only replaced i.e.
It can, it is not necessary to destroy entire soldering connection circuit.
3 π modular assemblies the preparation method is as follows:
4-1: drawing the part for needing to smear silver paste as shown in Figure 6 on upper and lower two pieces of aluminium oxide heat-conducting plates, upper rounded,
Rectangular shaded area part respectively corresponds Chong Die with lower circular, rectangular shaded area part；
4-2: several wire meshes (copper mesh is used in the present invention) are cut into identical with silver paste area is smeared in step 4-1
Shape is spare；
4-3: silver paste is uniformly applied in the region that step 4-1 is drawn；
4-4: the wire mesh for being cut into correspondingly-shaped is placed on the region smeared in step 4-3, in wire mesh
On smear one layer of silver paste again；
4-5: three cylindrical N-type oxides and three rectangle p-type oxide component one end are placed in after smearing silver paste
Wire net area on, the other end covers second aluminium oxide thermally conductive sheet for arranging silver paste and wire mesh.It will be according to step
Corresponding position in rapid 4-1 is put well, is compacted.
4-6: will it is above-mentioned made of three π components sintering curing at high temperature.The mode of sintering curing is as follows:
3 π components are put into heater box, are begun to warm up from room temperature, temperature are slowly raised to 850 DEG C by 180min, so
60min is kept the temperature at 850 DEG C afterwards, terminates heating, is cooled to room temperature automatically, module sintering curing is completed.
The series connection of multiple 3 π modular assemblies
To obtain preferable thermoelectric power generation effect, several 3 π modular assemblies are connected in practical application.In the present invention
Copper conductor is clamped between each 3 π modular assembly by copper sheet, realizes and 43 π modular assemblies is connected.
Test experiments are carried out to the thermoelectric heat generation system built, in an experiment in the heating one end of module, the other end is natural
Heat dissipation.The temperature at thermoelectric generation module both ends is tested in this test using multi-functional data scanning card cooperation KEITHLEY 2010
And output voltage, the output voltage of lower module is recorded with KEITHLEY 2010 using 10s as interval.
43 π modular assembly every two are divided into one group in experiment, totally two groups, are individually positioned in the electric furnace of 2kW and 1kW
On.Using electric furnace as heat source, the one end for being close to electric furnace is temperature end, and other end natural heat dissipation is low-temperature end.
Fig. 1 show the temperature difference at both ends after 43 π modular assemblies are connected with the changing rule of temperature end temperature.By can in figure
To see, as the thermoelectric generation module temperature end temperature constantly increases, the temperature difference of module temperature end and low-temperature end is also gradually
Increase.As two electric furnace constant powers of heat source in test process, respective 23 π modular assembly heat supplies are persistently given.Module
The temperature difference at both ends is also influenced by electric furnace heating power, from the figure, it can be seen that for 2kW electric furnace, when temperature end temperature reaches
When to 960 DEG C, the temperature difference at 15mm module both ends can achieve 630 DEG C.For 1kW electric furnace, when temperature end temperature reaches 800 DEG C
When, the temperature difference at 15mm module both ends also can achieve 340 DEG C.Illustrated by data in figure, heat source because rate of heat delivery difference,
It will affect the temperature difference at modular assembly both ends in certain time.Powerful heat source can within a certain period of time module both ends establish compared with
The big temperature difference, low power heat source can only establish the lesser temperature difference in the same time.But in test, even 1kW electric furnace
It is also very big for currently used alloy electrothermal module in 340 DEG C of temperature difference that module both ends generate.As for 2kW electricity
630 DEG C of temperature difference that furnace provides, it is in existing other oxide modules report at present and biggish.
Fig. 2 (a), Fig. 2 (b) show the output voltage after 43 π modular assemblies series connection with the changing rule of the temperature difference.43
π modular assembly every two is divided into one group, is assigned on the electric furnace of two different capacities.From the foregoing, it can be understood that two groups of module both ends
The temperature difference is different, therefore the output voltage of two groups of modules is also different.By in figure it can be seen that, for distribute on two electric furnaces 4
A 3 π modular assembly, as thermoelectric generation module temperature difference between the two ends constantly increase, the output voltage at module both ends is also gradually increased.Often
Two 3 π modular assemblies can obtain the voltage output of 0.8V or so under the respective temperature difference.Therefore when 43 π modular assemblies series connection
Afterwards, available maximum output voltage is in 1.5V or so.
After Fig. 3 (a), Fig. 3 (b) show 43 π modular assemblies series connection, the output power of 3 π module of two of them is with the temperature difference
Changing rule.43 π modular assembly every two are divided into one group, are assigned on the electric furnace of two different capacities.From the foregoing, it can be understood that
The temperature difference at two groups of module both ends is different, causes the output voltage of two groups of modules also different, corresponding output power is also had any different.It is real
Test the power for measuring 23 π modules in 43 π modular assemblies.The two 3 π modules are on different electric furnaces, and both ends have
The different temperature difference.Having in figure can see, and module temperature difference between the two ends are bigger, and output power is bigger.As one on 2kW stove
For 3 π module temperature difference between the two ends at 550 DEG C, output power can be in 40mW or so.A 3 π module both ends on 1kW stove
For the temperature difference at 450 DEG C, output power is also in 25mW or so.It is possible thereby to estimate, 43 π module groups on two heating furnaces
The power output of part in total is in 130mW or so.
Table 1: different oxide pyroelectric materials prepare the data comparison of electricity generation module
Table 1 show the data comparison of the electricity generation module of different oxide pyroelectric material preparations.It can be seen by data in table
Out, the CaMnO that the present invention passes through doping vario-property3And Ca3Co4O9Base oxide constructs thermoelectric generation module, can be in higher temperature
Degree is lower to be used, and can realize the biggish temperature difference at module both ends.And compared with other prior arts, in similar operating temperature
Under, the present invention can realize biggish power output by using less π pattern block.
Wherein, the prior art for the comparative test being previously mentioned is respectively as follows:
Ref1:W.Shin, N.Murayama, K.Ikeda, and S.Sago, J.PowerSource103,80 (2001)
Ref2:R.Funahashi and S.Urata, Int.J.Appl.Ceram.Technol.4,297 (2007)
Ref3:S.M.Choi, K.H.Lee, C.H.Lim, and W.S.Seo, J.EnergyConvers.Manag.52,
335(2011).
From test result, the present invention replaces conventional alloys component with oxide component, has high temperature resistant, can be applied to
The big temperature difference, not oxidizable, the advantages that having stable high-temperature performance.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (9)
1. a kind of oxide thermoelectricity electricity generation module, the oxide heat-conducting plate laid including about two, two oxide heat-conducting plates
Between be provided with N-type and p-type thermoelectric power generation component, the thermoelectric power generation component is fixedly connected with oxide heat-conducting plate, feature
Be: the N-type and p-type thermoelectric power generation component are respectively provided with doped with rare earth element with the contact surface of oxide heat-conducting plate
There is wire mesh；
In the opposite one side of described two oxide heat-conducting plates, it is coated with silver paste, and the silver that two oxide heat-conducting plates are smeared
It is corresponding to starch position；Entire application area has multiple in the right respectively with each oxide thermoelectricity electricity generation module of array distribution
The region answered guarantees N-type and p-type so that two adjacent thermoelectric power generation components are not identical in a line and same row in array
Thermoelectric power generation component is successively spaced setting；The adjacent N-type and p-type for belonging to different oxide thermoelectricity electricity generation modules in an array
Thermoelectric power generation component corresponding region carries out smearing silver paste, and different oxide thermoelectricity electricity generation modules is enable to connect.
2. a kind of oxide thermoelectricity electricity generation module as described in claim 1, it is characterized in that: the N-type and p-type thermoelectric power generation group
Part is oxide thermoelectricity power generation material, the preferably oxide materials such as calcium manganate, cobalt acid calcium, cobalt acid lanthanum, strontium carbonate or zinc oxide.
3. a kind of oxide thermoelectricity electricity generation module as described in claim 1, it is characterized in that: the p-type thermoelectric power generation component is
Cuboid, the N-type thermoelectric power generation component are cylindrical body.
4. a kind of oxide thermoelectricity electricity generation module as described in claim 1, it is characterized in that: the rare earth element passes through solid phase
Reaction method is doped into thermoelectric power generation component.
5. a kind of oxide thermoelectricity electricity generation system, it is characterized in that: including multiple such as oxidation of any of claims 1-4
Object thermoelectric generation module in the form of concatenated soldering connection on heat-conducting plate.
6. as oxide thermoelectricity electricity generation module of any of claims 1-4 preparation method, it is characterized in that: include with
Lower step:
(1) N-type containing rare earth element and p-type thermoelectric power generation component are prepared respectively using solid phase reaction method；
(2) silver paste is diluted, is applied in two oxide heat-conducting plate one sides, so that silver paste on two oxide heat-conducting plates
Application area matches；
(3) wire mesh is individually positioned in the silver paste application area of two oxide heat-conducting plates, and is smeared on a wire mesh
Silver paste, N-type and p-type thermoelectric power generation component are respectively placed on wire mesh, keep a fixed spacing；
(4) two oxide heat-conducting plate cooperations are correspondingly arranged, make N-type and p-type thermoelectric power generation component being located at two oxides
Between heat-conducting plate, high temperature sintering is carried out after compacting, completes welding.
7. preparation method as claimed in claim 6, it is characterized in that: being set to oxide thermoelectricity module in the step (4)
In thermostat, and temperature is 800-900 DEG C；
Or in the step (4), the sintering time includes heating and soaking time, sintering time 200-300min.
8. the preparation method of oxide thermoelectricity electricity generation system as claimed in claim 4, it is characterized in that: the following steps are included:
(1) N-type containing rare earth element and p-type thermoelectric power generation component are prepared respectively using solid phase reaction method；
(2) silver paste is smeared in the wherein one side of two oxide heat-conducting plates, entire application area has multiple in array point
The region corresponding with each oxide thermoelectricity electricity generation module of cloth, so that in a line and same row in array, it is adjacent
Two thermoelectric power generation components are not identical, guarantee that N-type and p-type thermoelectric power generation component are successively spaced setting；
(3) in an array the adjacent N-type for belonging to different oxide thermoelectricity electricity generation modules and p-type thermoelectric power generation component corresponds to area
Domain carries out smearing silver paste, and different oxide thermoelectricity electricity generation modules is enable to connect, and silver paste is smeared on two oxide heat-conducting plates
Region matches；
(4) wire mesh is individually positioned in the silver paste application area of two oxide heat-conducting plates, and is smeared on a wire mesh
N-type and p-type thermoelectric power generation component are arranged on the wire mesh of oxide heat-conducting plate, two oxide heat-conducting plates are matched for silver paste
Conjunction is correspondingly arranged, and makes for N-type and p-type thermoelectric power generation component to be located between two oxide heat-conducting plates, high temperature burning is carried out after compacting
Knot completes welding.
9. preparation method as claimed in claim 8, it is characterized in that: several series connection are arranged between two oxide heat-conducting plates
Oxide thermoelectricity electricity generation module, production forms an oxide thermoelectricity generating set, and multiple oxide thermoelectricity generating sets are by leading
Electric wire connection, connects, and forms oxide thermoelectricity electricity generation system.
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| JP3565503B2 (en) * | 2000-09-07 | 2004-09-15 | 大研化学工業株式会社 | Oxide thermoelectric conversion material |
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