CN107032763A - One kind prepares n-type CaMnO3The method of base thermoelectric ceramics - Google Patents
One kind prepares n-type CaMnO3The method of base thermoelectric ceramics Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 229910002969 CaMnO3 Inorganic materials 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 230000005619 thermoelectricity Effects 0.000 claims abstract description 12
- 239000003595 mist Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 37
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910019850 NaxCoO2 Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/016—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on manganites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
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- Organic Chemistry (AREA)
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- Structural Engineering (AREA)
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Abstract
N-type CaMnO is prepared the invention discloses one kind3The method of base thermoelectric ceramics, the raw material of the thermoelectric ceramics include graphite and CaMnO3；Its preparation method comprises the following steps：（1）By part graphite and CaMnO3Mixing, then carries out pre-sintering, obtains sintering feed；（2）By step（1）The graphite of surplus is added after the sintering feed of gained is broken, is well mixed, grinding, sieving obtains micro mist；（3）By step（2）The micro mist shaping of gained, sintering can obtain finished product n-type CaMnO3Base thermoelectric ceramics.The thermoelectric ceramics of the present invention has preferable thermoelectricity capability, and technological operation is simple, require low, environment-friendly to appointed condition and cost is relatively low, the characteristics of resulting materials have big thermoelectromotive force, small high-temperature resistivity and larger power factor.
Description
Technical field
N-type CaMnO is prepared the present invention relates to a kind of method for preparing thermoelectric ceramics, particularly one kind3Base thermoelectric ceramics
Method.
Background technology
Thermoelectric material is to realize the functional material that heat energy is directly mutually changed with electric energy, and the refrigeration machine being made using it can
For floride-free and local refrigeration, the thermal generator being made generates electricity available for Waste Heat Recovery.Compared with conventional heat engines, by thermoelectricity material
The element that material makes has the protrusion such as small volume, light weight, noiseless, movement-less part, service life length, environment friendly and pollution-free excellent
Point, has pole in fields such as superconductor, Large-power High-Speed computer, Aero-Space, microelectric technique, the processing of civilian Waste Heat Recovery
Big application prospect.
The energy conversion efficiency of thermoelectric material generally utilizes dimensionless figure of merit ZT (=S2T/ρ κ) weigh, wherein S
For Seebeck coefficients, ρ is resistivity, and T is absolute temperature, and κ is thermal conductivity, and power factor PF is by PF=S2/ ρ is derived and obtained.
High performance thermoelectric material requires big Seebeck absolute coefficients, high electrical conductivity and low thermal conductivity.
The thermoelectric material being widely used is main based on alloy system, mainly there is Bi2Te3Base thermoelectricity material, PbTe
Base thermoelectricity material, SiGe base thermoelectricity materials etc..There are many shortcomings in alloy pyroelectric material, and 1, contain the poisonous member of heavy metal mostly
Element and noble metal；2nd, as a result of fusing point is low or volatile metallic element, therefore the height of alloy system thermoelectric material
Temperature application is restricted；3rd, preparation process needs protection of reducing atmosphere, to avoid raw material and sample by the dioxygen oxidation in air,
And also need face coat protection to change its electric heating transmission performance to avoid sample from being oxidized during use.Therefore, alloy
The popularization and application of pyroelectric material have certain limitation.
Compared with conventional alloys system thermoelectric material, metal oxide body pyroelectric material has the advantage that.First, they
There is good chemical stability and high-temperature stability, therefore go for air atmosphere and very big thermograde.Second, he
Have it is environment-friendly and economical and practical.3rd, they are presented under conditions of larger thermograde with novel non-thread
Property pyroelectric effect, and then be conducive to improve thermoelectric figure of merit.4th, their thermoelectricity capability can be caused by changing its structure and composition
Change within a large range.
Cobalt/cobalt oxide NaCo2O4With sizable power factor 5*10-3W/mK2, research discovery in recent years is such as
NaxCoO2, the improvement such as Ca-Co-O and BiSrCoO cobalt/cobalt oxide be good p-type thermoelectric material.On the other hand, as p-type
The matching thing of material, n-type oxide pyroelectric material is indispensable for constructing electrothermal module.
Numerous studies prove perovskite manganites it be a kind of great potential n-type high-temperature thermoelectric material.Document
Report such as La, Dy, Yb, Bi doping can strengthen CaMnO3The pyroelectric effect of material, therefore metallic element doping is a kind of
CaMnO can be effectively improved3The method of ceramic thermoelectric performance.At room temperature, undoped with CaMnO3Power factor be about 0.99 μ W/
cmK2, and Ankam Bhaskar et al. are promoted to 2.99 μ W/cmK by the way of Bi doping2, corresponding Seebeck systems
Number is -159 μ V/K；Wish the CaMnO of Dy/Bi dual elements doping prepared by first tiger et al.3Power factor is about 4.2 μ under 850K
W/cmK2, correspondence Seebeck absolute coefficients are only 80 μ V/K, metal-doped to cause high temperature section thermoelectromotive force drastically to drop
It is low.Up to the present, it can match without a kind of n-type oxide material with the performance of p-type oxide thermoelectric material, seek heat
The good n-type oxide pyroelectric material of electrical property, which is still one, the work urgently completed.
The content of the invention
It is an object of the present invention to provide one kind prepares n-type CaMnO3The method of base thermoelectric ceramics.The thermoelectricity pottery of the present invention
Porcelain has preferable thermoelectricity capability, and technological operation is simple, require low, environment-friendly to appointed condition and cost is relatively low, gained
The characteristics of material has big thermoelectromotive force, small high-temperature resistivity and larger power factor.
Technical scheme：One kind prepares n-type CaMnO3The method of base thermoelectric ceramics, the former material of the thermoelectric ceramics
Material includes graphite and CaMnO3；Its preparation method comprises the following steps：
（1）By part graphite and CaMnO3Mixing, then carries out pre-sintering, obtains sintering feed；
（2）By step（1）The graphite of surplus is added after the sintering feed of gained is broken, is well mixed, grinding, sieving obtains micro mist；
（3）By step（2）The micro mist shaping of gained, sintering can obtain finished product n-type CaMnO3Base thermoelectric ceramics.
Foregoing preparation n-type CaMnO3The method of base thermoelectric ceramics, methods described is comprised the following steps that：
（1）By 1/3-1/2 graphite and CaMnO3Mixing, then carries out pre-sintering at 1000-1200 DEG C, obtains sintering feed；
（2）By step（1）The graphite of surplus is added after the sintering feed of gained is broken, is well mixed, grinding, 200 mesh sieves is crossed, obtains micro-
Powder；
（3）By step（2）The micro mist shaping of gained, finished product n-type CaMnO can be obtained in 1100-1280 DEG C of sintering3Base thermoelectricity is made pottery
Porcelain.
Foregoing preparation n-type CaMnO3The method of base thermoelectric ceramics, the raw material of the thermoelectric ceramics by 0.1-2% stone
The CaMnO of ink and 98%-99.9%3Composition.
Foregoing preparation n-type CaMnO3The method of base thermoelectric ceramics, the purity of the graphite is more than 99.9%.
Foregoing preparation n-type CaMnO3The method of base thermoelectric ceramics, the particle size range of the graphite is 0.1-2 μm.
Foregoing preparation n-type CaMnO3The method of base thermoelectric ceramics, the graphite surface carries negative electrical charge.
Foregoing preparation n-type CaMnO3The method of base thermoelectric ceramics, the CaMnO3Preparation method be：By by CaCO3
And MnO2Powder is mixed, then ball milling, then is obtained through 800-900 DEG C of calcining 12h.
Beneficial effects of the present invention：
1st, gained ceramic material Seebeck coefficient is negative value, belongs to n-type semiconductor thermoelectric material, and pyroelectric effect is obvious, under 450K
Seebeck coefficients reach that Seebeck coefficients reach -400 μ V/K under -540 μ V/K, 800K；
2nd, there is high power factor in high temperature section, be conducive to thermoelectric material power under the application of hot environment, 800K
The factor reaches 4.03 μ W/cmK2；
3rd, the CaMnO of graphite is added3Ceramics have semiconductor transportation characterization, and resistivity is small under high temperature, are conducive to improving material
Thermoelectricity capability；
4th, graphite additive is lower compared with metallic element or graphene cost, with reference to more excellent thermoelectricity capability, is the wide of thermo-electric device
General application provides feasible scheme.
The present invention realizes the principle of the effect above：
One of the reason for performance boost of the present invention, which is to adulterate, causes have higher carrier concentration in system, and essence is oxygen
Room and Mn3+Ion ratio rises.Therefore the key of preparation method lifting material property is to enable graphite fully and base material
Reaction, influences Lacking oxygen therein, Mn3+And carrier concentration.It is a step dispensing that solid phase method in document, which prepares ceramic step,
Multistep crushes forming and sintering.More ceramics occur in the process for repeating crushing grinding using substep addition graphite in we
Grain section, now adding graphite can make graphite be contacted with each other with new section, and benefit has three：First, it is anti-to overcome solid phase
Answer the slow problem of diffusion mass transfer itself；Second, the substance reaction of graphite and particle surface forms more Lacking oxygens, always
Precursor reactant is more abundant, without hindering densified sintering product process due to amount big not enough disperse；Third, micron particles are reduced
Requirement to preparation condition, while substep addition graphite ensure that the abundant degree and final performance boost effect of reaction.
Embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as to the foundation of the invention limited.
Embodiments of the invention
Embodiment 1：
Stoichiometrically weigh CaCO3、MnO2Material powder, CaMnO is obtained through ball milling and 950 DEG C of calcining 12h3Precursor
End, powdered graphite and CaMnO are weighed in graphite ratio 0.1%wt3Precursor powder, then first adds 1/2 powdered graphite
CaMnO3In precursor powder, in 1100 DEG C of pre-sinterings, sintering feed is obtained, sintering feed is added to the powdered graphite of surplus after broken,
Then grinding, and cross 200 mesh sieves, outsifting is molded and uses solid phase method to be placed in 1190 DEG C of heat preservation sintering 24h, is obtained containing stone
The CaMnO of ink3Thermoelectric ceramics.Overall process is prepared to carry out in air atmosphere.
Sample is n-type semiconductor thermoelectric material in the embodiment, and material under high temperature electric conductivity is good.Under 450K
Seebeck coefficients are -327.46 μ V/K, the Ω cm of resistivity 1.06；The power factor of sample is about 2.87 μ W/ under 800K
cmK2, the μ V/K of the Ω cm of resistivity 0.015 correspondence Seebeck coefficients -213.66.
Embodiment 2：
Preparation process is similar to Example 1, and difference is to weigh powdered graphite and CaMnO in graphite ratio 0.5%wt3Before
Drive body powder.Semiconductor transportation characterization is presented in sample in the embodiment, and material under high temperature electric conductivity is good.Under 450K
Seebeck coefficients are the Ω cm of -429.97 μ V/K resistivity 3.64；The power factor of sample reaches 4.038 μ W/ under 800K
cmK2, the μ V/K of the Ω cm of resistivity 0.02 correspondence Seebeck coefficients -290.25.
Embodiment 3：
Preparation process is similar to Example 1, and difference is：1st, the amount of the powdered graphite added during first sintering is 1/3,
And the temperature of first sintering is 1100 DEG C；2nd, powdered graphite and CaMnO are weighed in graphite ratio 1%wt3Precursor powder.Should
Semiconductor transportation characterization is presented in sample in embodiment, and material under high temperature electric conductivity is good.Under 450K Seebeck coefficients for-
The Ω cm of 344.01 μ V/K resistivity 0.225；The power factor of sample reaches 3.48 μ W/cmK under 800K2, resistivity 0.016
The μ V/K of Ω cm correspondence Seebeck coefficients -239.38.
Claims (6)
1. one kind prepares n-type CaMnO3The method of base thermoelectric ceramics, it is characterised in that：The raw material of the thermoelectric ceramics include
Graphite and CaMnO3；Its preparation method comprises the following steps：
（1）By part graphite and CaMnO3Mixing, then carries out pre-sintering, obtains sintering feed；
（2）By step（1）The graphite of surplus is added after the sintering feed of gained is broken, is well mixed, grinding, sieving obtains micro mist；
（3）By step（2）The micro mist shaping of gained, sintering can obtain finished product n-type CaMnO3Base thermoelectric ceramics.
2. preparation n-type CaMnO according to claim 13The method of base thermoelectric ceramics, it is characterised in that the tool of methods described
Body step is as follows：
（1）By 1/3-1/2 graphite and CaMnO3Mixing, then carries out pre-sintering at 1000-1200 DEG C, obtains sintering feed；
（2）By step（1）The graphite of surplus is added after the sintering feed of gained is broken, is well mixed, grinding, 200 mesh sieves is crossed, obtains micro-
Powder；
（3）By step（2）The micro mist shaping of gained, finished product n-type CaMnO can be obtained in 1100-1280 DEG C of sintering3Base thermoelectric ceramics.
3. preparation n-type CaMnO according to claim 1 or 23The method of base thermoelectric ceramics, it is characterised in that：The thermoelectricity
The raw material of ceramics are by 0.1-2% graphite and 98%-99.9% CaMnO3Composition.
4. preparation n-type CaMnO according to claim 1 or 23The method of base thermoelectric ceramics, it is characterised in that：The graphite
Purity be more than 99.9%.
5. preparation n-type CaMnO according to claim 1 or 23The method of base thermoelectric ceramics, it is characterised in that：The graphite
Particle size range be 0.1-2 μm.
6. preparation n-type CaMnO according to claim 1 or 23The method of base thermoelectric ceramics, it is characterised in that：It is described
CaMnO3Preparation method be：By by CaCO3And MnO2Powder is mixed, then ball milling, then through 800-900 DEG C of calcining 12h
.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107507910A (en) * | 2017-08-30 | 2017-12-22 | 贵州大学 | A kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material |
| CN112582527A (en) * | 2020-12-13 | 2021-03-30 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
| CN114656243A (en) * | 2022-02-25 | 2022-06-24 | 纯钧新材料(深圳)有限公司 | Calcium-manganese-oxygen thermoelectric material and preparation method thereof |
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| CN112582527A (en) * | 2020-12-13 | 2021-03-30 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
| CN112582527B (en) * | 2020-12-13 | 2022-12-02 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
| CN114656243A (en) * | 2022-02-25 | 2022-06-24 | 纯钧新材料(深圳)有限公司 | Calcium-manganese-oxygen thermoelectric material and preparation method thereof |
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