CN107507910A - A kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material - Google Patents

A kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material Download PDF

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CN107507910A
CN107507910A CN201710763353.0A CN201710763353A CN107507910A CN 107507910 A CN107507910 A CN 107507910A CN 201710763353 A CN201710763353 A CN 201710763353A CN 107507910 A CN107507910 A CN 107507910A
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resistivity
thermoelectric material
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camno
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CN107507910B (en
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李翠芹
陈前林
赵颖
周栋珍
孙丽娟
文娅
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Guizhou University
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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
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
    • 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
    • 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
    • H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material

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Abstract

The invention discloses a kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material, comprises the following steps：1) calcium nitrate solution and manganese nitrate solution are mixed, obtains mixed liquor, cetyl trimethylammonium bromide is first added into mixed liquor, then adds NH4HCO3To precipitation is produced, A product are obtained；2) A product are filtered, takes precipitation to dry, obtain B product；3) bismuth metal is added in B product and be well mixed, obtain C product；4) it is C product loading mould is compressing, obtain D product；5) D product are sintered, obtains low-resistivity CaMnO3Composite thermoelectric material.The present invention has the characteristics of preparation time is short, and simple to operate, production cost is low, can be widely applied for industrial production, and resistivity is low.

Description

A kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material
Technical field
The present invention relates to a kind of CaMnO3The preparation method of composite thermoelectric material, particularly a kind of CaMnO of low-resistivity3 The preparation method of composite thermoelectric material.
Background technology
Thermoelectric material (thermoelectricmaterials) can realize the mutual conversion of heat energy and electric energy, and this makes it As used heat to change into the green energy converslon materials of electricity, the efficiency of thermoelectric material can with dimensionless thermoelectric figure of merit come Represent, ZT=S2T/ ρ κ, S are Seebeck coefficients（Or hot merit, unit VK-1), ρ and κ are resistivity and thermal conductivity respectively, and T is Absolute temperature.Semiconductor has relatively low carrier density, causes it to have larger S values, and κ values mainly have phonon thermal conductivity Leading, thermal conductivity can be realized by adulterating the atom of high molecular weight, and the atom of high molecular weight can reduce sound Propagation rate, but now also without CaMnO of the ZT values more than 13Thermoelectric material.PF=S2σ, therefore high power factor and lower thermal conductivity It is the necessary condition of thermoelectric material and related device application.
Traditional thermoelectric material includes Bi-Te series, Pb-Te series and Si-Ge series, wherein Bi2Te3Base thermoelectricity material It is proved to be block thermoelectric material best at room temperature.It is but the of a relatively high cost of inorganic semiconductor thermoelectric material, poor Processing characteristics and heavy metal pollution problem, hinder their application.Relative to conventional conductor material, oxide material has money Source is enriched, and is not afraid of oxidation, without toxic element and it is pollution-free the advantages that, the research before some shows CaMnO3It is latent to be that one kind has The N-type thermoelectric material of power, having document report, it has high Seebeck coefficient, but because its resistivity is big, thermal conductivity is big, causes ZT values are not high at high temperature for it, CaMnO3With orthorhombic crystal structure, belong to Pnma space groups, there are many researchs by mixing Miscellaneous to improve its thermoelectricity capability, general Study concentrates on the resistivity for reducing material but not the obvious Sai Beike systems for reducing material Number and thermal conductivity, in some cases, in calcium position, rare earth doped element can reduce electrical conductivity and thermal conductivity simultaneously, when some trivalents CaMnO is introduced into quadrivalent metallic ion3When in lattice, the electricity with low electrical conductivity and moderate Seebeck coefficient can be obtained Sub- doping type thermoelectric material, there is the thermoelectricity capability that some researchs improve material by adulterating the method that bismuth regulates and controls.
Ohtaki etc. prepares doping by solid reaction process and adulterates CaMnO for the calcium position of 10% bismuth3Can notable conductance Rate, and SeeBeCK index impacts are little, so as to improve the value of power factor, Ca0.9Bi0.1MnO3Power factor can reach 2.8×10-4Wm-1K-2, ZT values reach 0.095 at 900 degree, the mobility of carrier are added when article is thought.But simultaneously Think to add carrier concentration.Another report equally prepares Ca with solid reaction process1-xBixMnO3, dopping effect concentration is 0.02,0.03,0.04,0.06,0.1, this paper is reported in 473K when dopping effect amount is 0.03, and power factor reaches 4.67×10-4Wm-1K-2, it is 0.03 temperature in 973K that doping, which occurs, in minimum thermal conductivity, now the minimum 1.4Wm of thermal conductivity-1K-2, now, ZT values can reach 0.25.It thinks that bismuth doping makes a part of Mn4+It is converted into Mn3+, in the preparation process of material Micropore increases the electrical conductivity of material, reduces the thermal conductivity of material.
But existing method is to use solid phase method, and Bi is actually added into system using solid phase reaction2O3, because of original Material needs sufficient solid phase reaction, so preparation time is grown, complex operation, production cost is high, limits their industrially wide General application, and the thermoelectric material resistivity prepared is also higher.
The content of the invention
It is an object of the present invention to provide a kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material.The present invention The characteristics of short with preparation time, simple to operate, production cost is low, can be widely applied for industrial production, and resistivity is low.
Technical scheme：A kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material, including following step Suddenly：
1) calcium nitrate solution and manganese nitrate solution are mixed, obtains mixed liquor, NH is added into mixed liquor4HCO3Precipitated to producing, Obtain A product；
2) A product are filtered, takes precipitation to dry, obtain B product；
3) bismuth metal is added in B product and be well mixed, obtain C product；
4) it is C product loading mould is compressing, obtain D product；
5) D product are sintered, obtains low-resistivity CaMnO3Composite thermoelectric material.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, the step 1）In, calcium nitrate solution Concentration is 1molL-1, manganese nitrate solution concentration is 1molL-1；The mol ratio of calcium nitrate and manganese nitrate in the mixed liquor For Ca:Mn=1:0.5-1.5.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, calcium nitrate and nitric acid in the mixed liquor The mol ratio of manganese is Ca:Mn=1:1.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, the step 2）In, A product are first aged 0.5- 2 hours, then refilter.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, the A product are first aged 1 hour, Ran Houzai Filtering.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, the step 3）In, bismuth metal and B product Mol ratio is 1:50-10.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, the mol ratio of the bismuth metal and B product are 1:25。
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, methods described comprise the following steps that：
1）Calcium nitrate solution and manganese nitrate solution are mixed, mixed liquor is obtained, NH is added into mixed liquor4HCO3, in reaction temperature 40-60 DEG C, reaction is complete to precipitating under conditions of mixing speed 400-600r/min, obtain A product；
2）A product are filtered, precipitation is taken, washing precipitate, then in 80-120 DEG C of drying, obtains B product；
3）Bismuth metal is added in B product and is well mixed, 6-12 hours is ground, obtains C product；
4）C product are fitted into mould, it is compressing under 8-10MPa pressure, obtain D product；
5）D product are put into sintering furnace, 1120-1180 DEG C is heated in air atmosphere, are incubated 15-25 hours, natural cooling Take out, then grind again, tabletting after to room temperature, then 20-28 hours and furnace cooling are incubated to room under the conditions of 1120-1180 DEG C Temperature, grey black blocks of solid is obtained, produce low-resistivity CaMnO3Composite thermoelectric material.
Foregoing low-resistivity CaMnO3The preparation method of composite thermoelectric material, C product tabletting in grinding tool is put into Before, the first pre-burning 7-11 hours under conditions of 850-950 DEG C.
Beneficial effects of the present invention：The present invention using coprecipitation by being first prepared presoma powder, then by gold Category bismuth is added in presoma powder as second, and CaMnO is prepared3Composite thermoelectric material, it is not required in whole preparation process The too long of reaction time is wanted, the production time greatly shortens, meanwhile, can be significantly simple directly by required metal addition system Change operation, reduced production cost, be adapted to extensive use in the industrial production；Meanwhile thermoelectric material prepared by the present invention Reduce the resistivity of thermoelectric composite material.
Bismuth and the resistivity using thermoelectric material made from doping metals bismuth of the present invention are adulterated using conventional solid reaction method Vary with temperature result as shown in Figure 1, wherein a is represented:CaMnO made from conventional solid reaction method3Resistivity with temperature Change curve, b are represented:CaMnO made from doping metals bismuth of the present invention3Resistivity vary with temperature curve（Bismuth metal: CaMnO3Precursor powder is 1:25).From accompanying drawing 1 as can be seen that the resistivity of thermoelectric material produced by the present invention substantially reduces.
Brief description of the drawings
Fig. 1 is that resistivity varies with temperature curve.
Embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
Embodiments of the invention
Embodiment 1, a kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material, methods described comprise the following steps that：
（1）First by calcium nitrate and manganese nitrate Ca in molar ratio:Mn=1:1 is dissolved in water, and the content that calcium nitrate and manganese nitrate is made is 1mol·L-1Mixed liquor, then by NH4HCO3Solution is added in calcium manganese mixed nitrate solution, is 50 DEG C in reaction temperature, Reaction is complete to precipitating under the reaction condition that mixing speed is 500r/min, obtains A product；
（2）Filtration washing after A product precipitation is aged 1 hour, in 100 DEG C of drying, obtain B product；
（3）By bismuth metal and B product bismuth metal in molar ratio：B product=1:25 mixing, grind 9 hours, obtain C product；
（4）C product are placed in sintering furnace pre-burning 9 hours under conditions of 900 DEG C, are then charged into mould, are 9MPa's in pressure It is compressing under pressure, obtain D product；
（5）D product are put into sintering furnace, 1150 DEG C are heated in air atmosphere, 20 hours are incubated, after naturally cooling to room temperature Take out, then grinding, tabletting, then under the conditions of 1150 DEG C be incubated 24 hours and furnace cooling is to room temperature, it is block to obtain grey black Solid, get product.
Embodiment 2, a kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material, methods described specific steps are such as Under：
（1）First by calcium nitrate and manganese nitrate Ca in molar ratio:Mn=1:0.5 is dissolved in water, and the content that calcium nitrate and manganese nitrate is made is equal For 1molL-1Mixed liquor, then by NH4HCO3Solution is added in calcium manganese mixed nitrate solution, is 40 in reaction temperature DEG C, reaction is complete to precipitating under the reaction condition that mixing speed is 600r/min, obtains A product；
（2）Filtration washing after A product precipitation is aged 0.5 hour, in 80 DEG C of drying, obtain B product；
（3）By bismuth metal and B product bismuth metal in molar ratio：Presoma powder=1:10 mixing, grind 6 hours, obtain C product；
（4）C product are placed in sintering furnace pre-burning 11 hours under conditions of 850 DEG C, are then charged into mould, are 8MPa's in pressure It is compressing under pressure, obtain D product；
（5）D product are put into sintering furnace, 1120 DEG C are heated in air atmosphere, 25 hours are incubated, after naturally cooling to room temperature Take out, then grinding, tabletting, then under the conditions of 1120 DEG C be incubated 28 hours and furnace cooling is to room temperature, it is block to obtain grey black Solid, get product.
Embodiment 3, a kind of low-resistivity CaMnO3The preparation method of composite thermoelectric material, methods described specific steps are such as Under：
（1）First by calcium nitrate and manganese nitrate Ca in molar ratio:Mn=1:1.5 are dissolved in water, and the content of calcium nitrate and manganese nitrate is made It is 1molL-1Mixed liquor, then by NH4HCO3Solution is added in calcium manganese mixed nitrate solution, is 60 in reaction temperature DEG C, reaction is complete to precipitating under the reaction condition that mixing speed is 400r/min, obtains A product；
（2）Filtration washing after A product precipitation is aged 2 hours, in 120 DEG C of drying, obtain B product；
（3）By bismuth metal and B product bismuth metal in molar ratio：Presoma powder=1:50 mixing, grind 6 hours, obtain C product；
（4）C product are placed in sintering furnace pre-burning 7 hours under conditions of 950 DEG C, are then charged into mould, are 10MPa's in pressure It is compressing under pressure, obtain D product；
（5）D product are put into sintering furnace, 1180 DEG C are heated in air atmosphere, 15 hours are incubated, after naturally cooling to room temperature Take out, then grinding, tabletting, then under the conditions of 1180 DEG C be incubated 20 hours and furnace cooling is to room temperature, it is block to obtain grey black Solid, get product.

Claims (9)

  1. A kind of 1. low-resistivity CaMnO3The preparation method of composite thermoelectric material, it is characterised in that：Comprise the following steps：
    1) calcium nitrate solution and manganese nitrate solution are mixed, obtains mixed liquor, NH is added into mixed liquor4HCO3To precipitation is produced, obtain A product；
    2) A product are filtered, takes precipitation to dry, obtain B product；
    3) bismuth metal is added in B product and be well mixed, obtain C product；
    4) it is C product loading mould is compressing, obtain D product；
    5) D product are sintered, obtains low-resistivity CaMnO3Composite thermoelectric material.
  2. 2. low-resistivity CaMnO according to claim 13The preparation method of composite thermoelectric material, it is characterised in that：It is described Step 1）In, the concentration of calcium nitrate solution is 1molL-1, manganese nitrate solution concentration is 1molL-1；Nitre in the mixed liquor The mol ratio of sour calcium and manganese nitrate is Ca:Mn=1:0.5-1.5.
  3. 3. low-resistivity CaMnO according to claim 23The preparation method of composite thermoelectric material, it is characterised in that：It is described The mol ratio of calcium nitrate and manganese nitrate in mixed liquor is Ca:Mn=1:1.
  4. 4. low-resistivity CaMnO according to claim 13The preparation method of composite thermoelectric material, it is characterised in that：It is described Step 2）In, A product are first aged 0.5-2 hours, then refilter.
  5. 5. low-resistivity CaMnO according to claim 43The preparation method of composite thermoelectric material, it is characterised in that：The A Product are first aged 1 hour, are then refiltered.
  6. 6. low-resistivity CaMnO according to claim 13The preparation method of composite thermoelectric material, it is characterised in that：It is described Step 3）In, the mol ratio of bismuth metal and B product is 1:50-10.
  7. 7. low-resistivity CaMnO according to claim 63The preparation method of composite thermoelectric material, it is characterised in that：It is described The mol ratio of bismuth metal and B product is 1:25.
  8. 8. according to the low-resistivity CaMnO described in claim any one of 1-73The preparation method of composite thermoelectric material, its feature exist In methods described comprises the following steps that：
    1）Calcium nitrate solution and manganese nitrate solution are mixed, mixed liquor is obtained, NH is added into mixed liquor4HCO3, in reaction temperature 40-60 DEG C, reaction is complete to precipitating under conditions of mixing speed 400-600r/min, obtain A product；
    2）A product are filtered, precipitation is taken, washing precipitate, then in 80-120 DEG C of drying, obtains B product；
    3）Bismuth metal is added in B product and is well mixed, 6-12 hours is ground, obtains C product；
    4）C product are fitted into mould, it is compressing under 8-10MPa pressure, obtain D product；
    5）D product are put into sintering furnace, 1120-1180 DEG C is heated in air atmosphere, are incubated 15-25 hours, natural cooling Take out, then grind again, tabletting after to room temperature, then 20-28 hours and furnace cooling are incubated to room under the conditions of 1120-1180 DEG C Temperature, grey black blocks of solid is obtained, produce low-resistivity CaMnO3Composite thermoelectric material.
  9. 9. low-resistivity CaMnO according to claim 83The preparation method of composite thermoelectric material, it is characterised in that：The C Product are being fitted into grinding tool before tabletting, first the pre-burning 7-11 hours under conditions of 850-950 DEG C.
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Cited By (1)

* Cited by examiner, † Cited by third party
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CN110407561A (en) * 2019-08-13 2019-11-05 合肥工业大学 A kind of preparation method of liquid-phase sintering calcium manganate base oxide pyroelectric material

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