CN1389430A - Calcium cobaltate-based oxide thermoelectric material and its prepn. - Google Patents

Calcium cobaltate-based oxide thermoelectric material and its prepn. Download PDF

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CN1389430A
CN1389430A CN 02121433 CN02121433A CN1389430A CN 1389430 A CN1389430 A CN 1389430A CN 02121433 CN02121433 CN 02121433 CN 02121433 A CN02121433 A CN 02121433A CN 1389430 A CN1389430 A CN 1389430A
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thermoelectric material
based oxide
oxide thermoelectric
citric acid
calcium
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CN1182070C (en
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南策文
南军
邬俊波
邓元
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Tsinghua University
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Abstract

The present invention relates to a calcium cobaltate base oxide thermoelectric material and its preparation method. Said invention utilizes sel-gel process, uses inorganic nitrate as raw material, uses citric acid as complexing agent to form sol at 60 deg.C-100 deg.C and form gel at 100 deg.C-130 deg.c, then utilizes presintering process to obtain precursor nano powder, finally utilzies sintering process to obtain block body material. The non-dimensional thermoelectric optimum value ZT of said prepared Ca3Co4O9 base oxide thermoelectric material is about 0.2 (in 1000 K). Said invented product can be used in the field of waste-head utilization and high-temp. power generation.

Description

A kind of calcium cobaltate-based oxide thermoelectric material and preparation method thereof
Technical field
The present invention relates to the novel method of a kind of synthetic calcium cobaltate-based oxide (Ca-Co-O) thermoelectric material.Belong to oxide pyroelectric material and preparing technical field thereof in the functional materials.
Background technology
Rowe is described in detail thermoelectric material in its " CRC Handbook of Thermoelectrics " that writes (being published by CRC Press1995) book.In present all thermoelectric materials (promptly having thermoelectric power generation and thermoelectric refrigeration materials with function), lead telluride (PbTe) based semiconductor material is to generally acknowledge best middle warm area thermoelectric material at present.It has warm electric quality factor the ZT (=T σ S of senior middle school 2/ λ, T=temperature, σ=specific conductivity, λ=thermal conductivity, S=Seebeck coefficient).
The Ca-Co-O base oxide pyroelectric material is compared characteristics such as have the oxidation of not being afraid of, cost of material is cheap, toxicity is little with traditional lead telluride alloy thermoelectric material.Oxide pyroelectric material mainly adopts solid state reaction synthetic.Analytically pure initial reactant powder or particle are mixed by stoichiometric ratio, and grind the calcining back, adopts modes such as no pressure, hot pressing and electrical spark plasma sintering to sinter block materials into again.As people such as Ichiro Matsubara with Gd 2O 3, CaCO 3, Co 3O 4For raw material has synthesized Ca 2.75Gd 0.25Co 4O 9Material (J.Appl.Phys.2001,90 (1), 462).This method reaction time consumption, reactant mixes even inadequately.Some propose innovative approach on this basis, adopt mixture after the long-time calcining of ball milling repeatedly of high energy mechanical ball mill as people such as K.Takahata, and the compressing tablet sintering has prepared (Na, Ca) Co then 2O 4Thermoelectric material (Phys.Rev.B.2000,61 (19), 12551).Also there is problem consuming time in method after the improvement, and mechanical milling process is easily introduced impurity, the difficult quality control of product.
Summary is got up, and solid phase method is synthetic to exist that temperature of reaction is higher, the reaction times is long relatively and chemical uniformity is bad, energy consumption is big, and is difficult to obtain the nano level thermoelectric compound.
Summary of the invention
The objective of the invention is problems, a kind of novel method of utilizing the synthetic calcium cobaltate-based oxide thermoelectric material of sol-gel method is provided at the existence of available technology adopting solid phase method synthesis oxide thermoelectric material; Can be in lower temperature of reaction with under than the short reaction times, synthetic a kind of chemical uniformity is good, the Ca-Co-O base oxide pyroelectric material of uniform crystal particles and adulterated polynary Ca-Co-O base oxide pyroelectric material.
The present invention is achieved through the following technical solutions:
A kind of calcium cobaltate-based oxide thermoelectric material is characterized in that having following physicochemical characteristic:
(1) molecular formula: Ca 3Co 4O 9
(2) precursor compound median size: 30 nanometers;
(3) under 700 ℃, this thermoelectric material is characterized by: conductivity=10S/cm; Seebeck coefficient S=120 μ V/K; Power factor PF=0.14 * 10-4W/mK 2ZT=0.13;
A kind of method of synthetic above-mentioned calcium cobaltate-based oxide thermoelectric material, it is characterized in that: this method adopts sol-gel method, with the inorganic nitrate is raw material, citric acid is a complexing agent, after forming colloidal sol, gel, obtain the presoma nanometer powder by pre-burning again, sintering forms then, and its technology is carried out as follows:
(1) by stoichiometric ratio nitrocalcite, Xiao Suangu are added in the reaction vessel, add 1.3～2 times to the citric acid of the total mole number of calcium, cobalt, add the deionized water dissolving mixture, be stirred to clear solution, be warming up to 60 ℃～100 ℃, become the colloidal sol shape until solution, 100 ℃～130 ℃ following dryings make xerogel;
(2) with gained xerogel in the step (1) after grinding 400 ℃～600 ℃ pre-burnings, remove wherein citric acid and nitrate, gained powder sintering under 800 ℃～950 ℃ temperature condition promptly gets calcium cobaltate-based oxide thermoelectric material.
The present invention also provides the calcium cobaltate-based oxide thermoelectric material of a kind of doping metals silver, nickel, lanthanum or sodium, it is characterized in that having following physicochemical characteristic:
(1) molecular formula: (Ca xM y) 3Co 4O 9
Wherein: x=0.95～0.90; Y=1-x; M is silver, lanthanum, sodium or nickel;
(2) precursor compound median size: 30 nanometers;
(3) under 700 ℃, ZT=0.13～0.22.
The method of the calcium cobaltate-based oxide thermoelectric material of a kind of synthetic described doping metals silver, nickel, lanthanum or sodium, this method is carried out as follows:
(1) mol ratio is 0.15～0.3: 2.85～2.70: 4 argent or nickel or lanthanum or sodium and nitrocalcite, Xiao Suangu add in the reaction vessel, add 1.3～2 times of citric acids again to the above-mentioned raw materials total mole number, add the deionized water dissolving mixture, be stirred to clear solution, be warming up to 60 ℃～100 ℃, become the colloidal sol shape until solution, make xerogel 100 ℃～130 ℃ following dryings;
(2) with xerogel after grinding 400 ℃～600 ℃ pre-burnings, remove wherein citric acid and nitrate, the gained powder promptly gets the calcium cobaltate-based oxide thermoelectric material of silver-doped, nickel, lanthanum or sodium at 800 ℃～950 ℃ of sintering.
The present invention compared with prior art, have the following advantages and beneficial effect: the present invention adopts synthetic calcium cobaltate-based oxide (Ca-Co-O) of solution chemical processes (sol-gel method) and adulterated thermoelectric material thereof, its precursor is synthetic have simple to operate, temperature of reaction is low, the reaction times is short, energy consumption is low, chemical uniformity is good, crystal grain is little and even characteristics such as (about average 30 nanometers), the ZT value of the block thermoelectric material behind sintering is 0.13～0.22.
Description of drawings
Fig. 1 synthetic Ca 3Co 4O 9XRD spectrum.
Fig. 2 synthetic Ca 3Co 4O 9The SEM photo.
The mix XRD spectrum of Ca-Co-O based compound of Ag of Fig. 3.
Fig. 4 (Ca 0.95Ag 0.05) 3Co 4O 9Block materials SEM photo.
Fig. 5 (Ca 0.9Ag 0.1) 3Co 4O 9Block materials SEM photo.
Fig. 6 synthetic (Ca 0.92Ag 0.08) 3Co 4O 9The SEM photo.
Fig. 7 synthetic (Ca 0.9La 0.1) 3Co 4O 9XRD spectrum.
Fig. 8 synthetic (Ca 0.9La 0.1) 3Co 4O 9The SEM photo.
Fig. 9 synthetic (Ca 0.9Na 0.1) 3Co 4O 9XRD spectrum.
Figure 10 synthetic (Ca 0.9Na 0.1) 3Co 4O 9The SEM photo.
Figure 11 synthetic (Ca 0.9Ni 0.1) 3Co 4O 9XRD spectrum.
Figure 12 synthetic (Ca 0.9Ni 0.1) 3Co 4O 9The SEM photo.
Embodiment
All chemical are commercially available analytical pure, without being further purified.
Embodiment 1.Ca 3Co 4O 9
Ca (NO 3) 24H 2O (30mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (105mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution; Elevated temperature to 60 ℃ becomes the colloidal sol shape until solution.100 ℃ of dryings are 12 hours then.Xerogel 400 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 800 ℃ of sintering.Compound characterizes sees Fig. 1 and 2.Under 700 ℃, conductivity=10S/cm, Seebeck coefficient S=120 μ V/K, power factor PF=0.14 * 10 -4W/mK 2, ZT=0.13.
Embodiment 2.Ca 3Co 4O 9
Ca (NO 3) 24H 2O (30mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (91mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 100 ℃ becomes the colloidal sol shape until solution.130 ℃ of dryings are 10 hours then.Xerogel 600 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 950 ℃ of sintering.Under 700 ℃, conductivity=10S/cm, Seebeck coefficient S=120 μ V/K, power factor PF=0.14 * 10 -4W/mK 2, ZT=0.13.
Embodiment 3.Ca 3Co 4O 9
Ca (NO 3) 24H 2O (30mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (140mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 80 ℃ becomes the colloidal sol shape until solution.110 ℃ of dryings are 12 hours then.Xerogel 500 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 850 ℃ of sintering.Under 700 ℃, conductivity=10S/cm, Seebeck coefficient S=120 μ V/K, power factor PF=0.14 * 10 -4W/mK 2, ZT=0.13.
Embodiment 4. (Ca 0.95Ag 0.05) 3Co 4O 9(being called for short the W sample)
Ca (NO 3) 24H 2O (27.5mmol), AgNO 3(1.5mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (89mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 70 ℃ becomes the colloidal sol shape until solution.130 ℃ of dryings are 12 hours then.Xerogel 600 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 900 ℃ of sintering.Compound characterizes sees Fig. 3 and 4.Under 700 ℃, conductivity=42S/cm, Seebeck coefficient S=132 μ V/K, power factor PF=0.6 * 10 -4W/mK 2, ZT=0.18.
Embodiment 5. (Ca 0.9Ag 0.1) 3Co 4O 9(being called for short the C sample)
Ca (NO 3) 24H 2O (27mmol), AgNO 3(3mmol), Co (NO 3) 26H 2O (40 mmol), C 6H 8O 7H 2O (140mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 100 ℃ becomes the colloidal sol shape until solution.120 ℃ of dryings are 10 hours then.Xerogel 500 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 950 ℃ of sintering.Compound characterizes sees Fig. 3 and 5.Under 700 ℃, conductivity=43S/cm, Seebeck coefficient S=135 μ V/K, power factor PF=0.7 * 10 -4W/mK 2, ZT=0.21.
Embodiment 6. (Ca 0.92Ag 0.08) 3Co 4O 9
Ca (NO 3) 24H 2O (27.6mmol), AgNO 3(2.4mmol), Co (NO 3) 26H 2O (40 mmol), C 6H 8O 7H 2O (112mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 80 ℃ becomes the colloidal sol shape until solution.100 ℃ of dryings are 10 hours then.Xerogel 500 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 800 ℃ of sintering.Compound characterizes sees Fig. 6.Under 700 ℃, conductivity=42S/cm, Seebeck coefficient S=133 μ V/K, power factor PF=0.6 * 10 -4W/mK 2, ZT=0.20.
Embodiment 7. (Ca 0.9La 0.1) 3Co 4O 9
Ca (NO 3) 24H 2O (27mmol), La (NO 3) 36H 2O (3mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (112mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 80 ℃ becomes the colloidal sol shape until solution.100 ℃ of dryings are 10 hours then.Xerogel 500 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 900 ℃ of sintering.Compound characterizes sees Fig. 7 and 8.Under 700 ℃, conductivity=65S/cm, Seebeck coefficient S=130 μ V/K, power factor PF=1 * 10 -4W/mK 2, ZT=0.22.
Embodiment 8. (CA 0.9Na 0.1) 3Co 4O 9
Ca (NO 3) 24H 2O (27mmol), NaNO 3(3mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (112mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 80 ℃ becomes the colloidal sol shape until solution.100 ℃ of dryings are 10 hours then.Xerogel 500 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 900 ℃ of sintering.Compound characterizes sees Fig. 9 and 10.Under 700 ℃, conductivity=8S/cm, Seebeck coefficient S=110 μ V/K, power factor PF=1 * 10 -4W/mK 2, ZT=0.19.
Embodiment 9. (Ca 0.9Ni 0.1) 3Co 4O 9
Ca (NO 3) 24H 2O (27mmol), Ni (NO 3) 2(3mmol), Co (NO 3) 26H 2O (40mmol), C 6H 8O 7H 2O (112mmol) adds in the beaker, uses the deionized water dissolving mixt then, is stirred to clear solution.Elevated temperature to 80 ℃ becomes the colloidal sol shape until solution.100 ℃ of dryings are 10 hours then.Xerogel 500 ℃ of pre-burnings, is removed wherein citric acid and nitrate after grinding.The gained powder promptly gets block thermoelectric material at 900 ℃ of sintering.Compound characterizes sees Figure 11 and 12.Under 700 ℃, conductivity=5.6S/cm, Seebeck coefficient S=132 μ V/K, power factor PF=0.8 * 10 -4W/mK 2, ZT=0.2.

Claims (4)

1. calcium cobaltate-based oxide thermoelectric material is characterized in that having following physicochemical characteristic:
(1) molecular formula: Ca 3Co 4O 9
(2) precursor compound median size: 30 nanometers;
(3) under 700 ℃, this thermoelectric material is characterized by: conductivity=10S/cm; Seebeck coefficient S=120 μ V/K; Power factor PF=0.14 * 10-4W/mK 2ZT=0.13;
2. one kind is synthesized the method for calcium cobaltate-based oxide thermoelectric material according to claim 1, it is characterized in that: this method adopts sol-gel method, with the inorganic nitrate is raw material, citric acid is a complexing agent, after forming colloidal sol, gel, obtain the presoma nanometer powder by pre-burning again, sintering forms then, and its technology is carried out as follows:
(1) by stoichiometric ratio nitrocalcite, Xiao Suangu are added in the reaction vessel, add 1.3～2 times to the citric acid of the total mole number of calcium, cobalt, add the deionized water dissolving mixture, be stirred to clear solution, be warming up to 60 ℃～100 ℃, become the colloidal sol shape until solution, 100 ℃～130 ℃ following dryings make xerogel;
(2) with gained xerogel in the step (1) after grinding 400 ℃～600 ℃ pre-burnings, remove wherein citric acid and nitrate, gained powder sintering under 800 ℃～950 ℃ temperature condition promptly gets calcium cobaltate-based oxide thermoelectric material.
3. the calcium cobaltate-based oxide thermoelectric material of a doping metals silver, nickel, lanthanum or sodium is characterized in that having following physicochemical characteristic:
(1) molecular formula: (Ca xM y) 3Co 4O 9
Wherein: x=0.95～0.90; Y=1-x; M is silver, lanthanum, sodium or nickel;
(2) precursor compound median size: 30 nanometers;
(3) under 700 ℃, this series thermoelectric material ZT=0.13～0.22.
4. the method for a synthetic calcium cobaltate-based oxide thermoelectric material as claimed in claim 3, this method is carried out as follows:
(1) be 0.15～0.3: 2.85～2.70 with mol ratio: 4 argent or nickel or lanthanum or sodium and nitrocalcite, Xiao Suangu add in the reaction vessel, add 1.3～2 times of citric acids again to the above-mentioned raw materials total mole number, add the deionized water dissolving mixture, be stirred to clear solution, be warming up to 60 ℃～100 ℃, become the colloidal sol shape until solution, make xerogel 100 ℃～130 ℃ following dryings;
(2) with xerogel after grinding 400 ℃～600 ℃ pre-burnings, remove wherein citric acid and nitrate, the gained powder promptly gets the calcium cobaltate-based oxide thermoelectric material of silver-doped, nickel, lanthanum or sodium at 800 ℃～950 ℃ of sintering.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006111522A (en) * 2004-09-16 2006-04-27 Tokyo Univ Of Science Method for manufacturing thermoelectric conversion material
CN100424904C (en) * 2006-06-01 2008-10-08 吉林大学 Thermoelectric material of isotope battery and its preparation method
CN102627443A (en) * 2012-04-17 2012-08-08 中国科学院青海盐湖研究所 Preparation method of Ca3Co4O9/Ag composite ceramic thermoelectric material with special morphology
CN106082355A (en) * 2016-05-23 2016-11-09 贵州民族大学 A kind of Ca3co2o6the preparation method of powder
CN106187265A (en) * 2016-06-30 2016-12-07 贵州民族大学 A kind of Ca3co4o9the preparation method of thermoelectric material
CN108531182A (en) * 2018-05-31 2018-09-14 陕西科技大学 Thermoelectric material area load Ca2MgSi2O7：Eu2+, Dy3+The preparation method of long after glow luminous material
CN109735310A (en) * 2019-01-16 2019-05-10 南京航空航天大学 A kind of full spectrum light hot-cast socket heat accumulating and preparation method thereof
CN112624924A (en) * 2020-12-23 2021-04-09 河南大学 Application of Ca-based solid base heterogeneous catalyst in preparation of dimethyl carbonate
CN115710137A (en) * 2022-10-31 2023-02-24 西安建筑科技大学 Calcium cobaltate thermoelectric ceramic with oriented micro-nano through holes and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006111522A (en) * 2004-09-16 2006-04-27 Tokyo Univ Of Science Method for manufacturing thermoelectric conversion material
CN100424904C (en) * 2006-06-01 2008-10-08 吉林大学 Thermoelectric material of isotope battery and its preparation method
CN102627443A (en) * 2012-04-17 2012-08-08 中国科学院青海盐湖研究所 Preparation method of Ca3Co4O9/Ag composite ceramic thermoelectric material with special morphology
CN106082355A (en) * 2016-05-23 2016-11-09 贵州民族大学 A kind of Ca3co2o6the preparation method of powder
CN106187265A (en) * 2016-06-30 2016-12-07 贵州民族大学 A kind of Ca3co4o9the preparation method of thermoelectric material
CN108531182A (en) * 2018-05-31 2018-09-14 陕西科技大学 Thermoelectric material area load Ca2MgSi2O7：Eu2+, Dy3+The preparation method of long after glow luminous material
CN109735310A (en) * 2019-01-16 2019-05-10 南京航空航天大学 A kind of full spectrum light hot-cast socket heat accumulating and preparation method thereof
CN112624924A (en) * 2020-12-23 2021-04-09 河南大学 Application of Ca-based solid base heterogeneous catalyst in preparation of dimethyl carbonate
CN115710137A (en) * 2022-10-31 2023-02-24 西安建筑科技大学 Calcium cobaltate thermoelectric ceramic with oriented micro-nano through holes and preparation method thereof
CN115710137B (en) * 2022-10-31 2023-05-12 西安建筑科技大学 Calcium cobaltate thermoelectric ceramic with directional micro-nano through holes and preparation method thereof

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