CN101254952B - Preparation method of acetate doping natrium cobaltite thermoelectric materials - Google Patents

Preparation method of acetate doping natrium cobaltite thermoelectric materials Download PDF

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CN101254952B
CN101254952B CN2008101032593A CN200810103259A CN101254952B CN 101254952 B CN101254952 B CN 101254952B CN 2008101032593 A CN2008101032593 A CN 2008101032593A CN 200810103259 A CN200810103259 A CN 200810103259A CN 101254952 B CN101254952 B CN 101254952B
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王蕾
王鸣
杜兆富
赵栋梁
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Central Iron and Steel Research Institute
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Abstract

The invention belongs to the technology field of oxide thermoelectric materials of the functional materials and the preparation thereof, and relates in particular to thermoelectric materials of acetate doping with co-o-Na. The invention utilizes sol-gal method, takes the acetate as the raw material and the citric acid as the complexing agent. The sol is formed at the temperature of 353 K to 363K and the xerogel is formed at the temperature of 323 K to 393K. The precursor nano meter powder can be obtained by gel pyrolysis and roasting; and the bulk material can be got by sintering finally. Theinvention utilizes the common water metal acetate as the raw material and the whole preparation process does not produce poisonous and harmful gas. The synthesis technology is simple and safe; furthermore, the drying process adopts decompression drying and realizes the drying process with low temperature and short time; also, the precursor powder has good uniformity and obvious layered structure,which is helpful to producing the bulk thermoelectric materials with high crystal orientation and high performance.

Description

The preparation method of acetate doping natrium cobaltite thermoelectric materials
Technical field
The invention belongs to oxide pyroelectric material and preparing technical field thereof in the functional materials, particularly a kind of preparation method of acetate doping natrium cobaltite thermoelectric materials.
Background technology
Thermoelectric material is a kind of functional materials that heat energy and electric energy can be transformed mutually.The thermo-electric device of being made by this material does not have mechanical driving part, compact construction, have the work noiselessness, pollution-free, the life-span is long, advantages such as environmental protection, can be widely used in fields such as military generator, vehicle exhaust generator, the generating of industrial gaseous waste heat, be a kind of environmental friendliness energy and material that has application potential.The quality of pyroelectric material performance zero dimension constant ZT commonly used represents: ZT=TS 2/ ρ κ.Wherein, S is the Seebeck coefficient, is also referred to as Seebeck coefficient; ρ is a resistivity, and κ is a thermal conductivity.The ZT value of material is big more, and conversion efficiency of thermoelectric is high more.Traditional thermoelectric material is as Bi 2Te 3, SiGe alloy etc., at high temperature decompose easily or oxidation, influenced the performance and the life-span of using.
NaCo 2O 4Thermoelectric material has good thermoelectricity capability, and resistivity is 0.2m Ω cm during room temperature, and S is 100 μ VK -1And this material is not afraid of oxidation, nontoxic, non-environmental-pollution, is a kind of novel thermoelectric candidate material.To NaCo 2O 4Carry out an amount of doping of suitable element, also can further improve its thermoelectricity capability.Current, solid reaction process is adopted in the preparation of doping cobalt acid na oxide thermoelectric material mostly, is doped raw material (K.Park, Materials Science ﹠amp with the metal oxide; Engineering B, 2006,129,200-206), be about to analytically pure initial reactant powder or particle and mix by stoichiometric ratio, grind the calcining back, adopts modes such as no pressure, hot pressing and electrical spark plasma sintering to sinter block materials into again.But be difficult to obtain the homogeneous single phase product, oxide compound is residual more serious, and whole process need repeats to grind and roasting, and process cycle is long, and grain fineness number is restive.Go through Ying Dengren at this problem, with the metal nitrate is raw material, adopt the citric acid sol-gel method to cobalt acid sodium (the non-ferrous metal journal that mixes, 2006,16 (1), 142-146), be about to nitrate raw material and be dissolved in aqueous citric acid solution, through heating, evaporation, drying, the conversion of---colloidal sol---gel of finishing solution is just finally made block through roasting, sintering again.This method reaction is even, abundant, but still has some problems, as discharging a large amount of NO in the solution heat-processed 2Yellow toxic gas; In addition, drying process is if adopt high temperature, then the time spent shorter, but gel easily breaks; And cryodrying is consuming time oversize, is difficult to accurately hold drying process.
Summary of the invention
The purpose of this invention is to provide a kind of acetate doping natrium cobaltite thermoelectric materials and preparation method thereof, do not produce toxic and harmful in the whole process of preparation; In drying process, adopt drying under reduced pressure, realize that temperature is low, the drying process of weak point consuming time, and the forerunner's powder good uniformity that makes, laminate structure is remarkable, helps preparing high crystalline orientation, high performance block thermoelectric material.
In order to achieve the above object, the present invention is achieved in that
A kind of acetate doping natrium cobaltite thermoelectric materials, molecular formula are Na 1.5(Co 0.9Ni 0.1) 2O 4The median size of the middle powder before the presintering is 3-6 μ m;
Under 673K, the performance of described thermoelectric material is: crystalline orientation degree f=0.91; Electricalresistivity=62.4 μ Ω m; Seebeck coefficient S=145 μ V/K; Thermal conductivity к=1.29W/mK; Thermoelectric quality factor ZT=0.176.
A kind of acetate doping natrium cobaltite thermoelectric materials, molecular formula are Na 1.5(Co 1-xCu x) 2O 4, x=0.1～0.15 wherein; The powder median size is 6-10 μ m after the roasting; Block crystalline orientation degree f＞0.75 behind the sintering.
A kind of acetate doping natrium cobaltite thermoelectric materials, molecular formula are (Na 1-yLi y) Co 2O 4, y=0.40～0.50 wherein; The powder median size is 0.5～3 μ m after the roasting; Block crystalline orientation degree f＞0.70 behind the sintering.
Described thermoelectric material adopts the sol-gel method preparation, is raw material with the acetate, and citric acid is a complexing agent, behind formation colloidal sol, the gel, obtains the presoma nanometer powder by pyrolysis, roasting again, and sintering is finished then.
A kind of preparation method of acetate doping natrium cobaltite thermoelectric materials adopts the sol-gel method preparation, comprises step:
A. by stoichiometric ratio the acetate raw material fully is dissolved in the aqueous citric acid solution, citrate is 3: 1 with the ratio of metal ion, forms homogeneous solution;
Wherein said acetate comprises matrix acetate and doping acetate, and the matrix acetate is (CH 3COO) 2Co and CH 3COONa, doping acetate are (CH 3COO) 2Ni, (CH 3COO) 2Cu, CH 3At least a among the COOLi;
B. heated and stirred forms homogeneous solution under 313K～333K temperature condition;
C. described thickness colloidal sol is placed loft drier, drying under reduced pressure obtains xerogel under 323K～393K temperature condition;
D. with the pyrolysis under 693K～773K temperature condition of described xerogel, remove remaining organism wherein; Roasting under the condition of 993K～1053K obtains black forerunner powder;
E. described black forerunner powder is ground evenly, sintering forms acetate doping natrium cobaltite thermoelectric materials under the temperature condition of 1133K～1173K;
Wherein the drying under reduced pressure among the step C carries out under the following conditions: pressure is smaller or equal to 0.1MPa, and the time is 100-150 minute.
Before carrying out step C, also comprise the step of described thickness colloidal sol being carried out constant pressure and dry.
When preparation nickel doping cobalt acid sodium, described acetate is (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O and (CH 3COO) 2Ni4H 2O.
When preparation copper or lithium doping cobalt acid sodium, described acetate is (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O and (CH 3COO) 2CuH 2O or CH 3COOLi2H 2O.
Technical scheme of the present invention can obtain following several acetate doping natrium cobaltite thermoelectric materials:
Nickel doping cobalt acid na oxide thermoelectric material
Have following physicochemical characteristic:
(1) its molecular formula is: Na 1.5(Co 0.9Ni 0.1) 2O 4
(2) the powder median size is 3-6 μ m after the roasting of described nickel doping cobalt acid na oxide;
(3) under 673K, the performance of described nickel doping cobalt acid na oxide thermoelectric material is: crystalline orientation degree f=0.91; Electricalresistivity=62.4 μ Ω m; Seebeck coefficient S=145 μ V/K; Thermal conductivity к=1.29W/mK; Thermoelectric quality factor ZT=0.176.
A kind of method for preparing above-mentioned nickel doping cobalt acid na oxide thermoelectric material, it is characterized by: this method adopts sol-gel method, with the acetate is raw material, citric acid is a complexing agent, after forming colloidal sol, gel, obtain the presoma nanometer powder by pyrolysis, roasting again, sintering is finished then, and its technology is carried out according to following steps:
(1) presses stoichiometric ratio with (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O, (CH 3COO) 2Ni4H 2O fully is dissolved in aqueous citric acid solution, and citrate is 3: 1 with the ratio of metal ion; Heated and stirred forms homogeneous solution under 313K～333K temperature condition; Under 353K～363K temperature condition, carry out reduction vaporization, become thickness colloidal sol until described homogeneous solution;
(2) described thickness colloidal sol is placed loft drier, drying under reduced pressure obtains xerogel under 323K～393K temperature condition;
(3), remove remaining organism wherein with the pyrolysis under 693K～773K temperature condition of described xerogel; Roasting under the condition of 993K～1053K obtains black forerunner powder;
(4) described black forerunner powder is ground evenly, sintering forms described nickel doping cobalt acid na oxide thermoelectric material under the temperature condition of 1133K～1173K.
Drying under reduced pressure step described in the step (2) preferably is controlled at pressure smaller or equal to 0.1MPa, and the time is 100-150 minute.
For avoiding thickness colloidal sol to splash, the preceding step of described thickness colloidal sol being carried out constant pressure and dry that also can comprise of step (2).
Copper doping cobalt acid na oxide thermoelectric material
Adopt (CH 3COO) 2CuH 2O, (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O is raw material and above preparation technology's method, has prepared the copper doping cobalt acid na oxide thermoelectric material with following physicochemical characteristic:
(1) molecular formula: Na 1.5(Co 1-xCu x) 2O 4, x=0.1～0.15 wherein
(2) the powder median size is 6-10 μ m after the roasting of described copper doping cobalt acid na oxide; Block crystalline orientation degree f＞0.75 behind the sintering.
Lithium doping cobalt acid na oxide thermoelectric material
Adopt CH 3COOLi2H 2O, (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O is raw material and above preparation technology's method, has prepared the lithium doping cobalt acid na oxide thermoelectric material with following physicochemical characteristic:
(1) molecular formula: (Na 1-yLi y) Co 2O 4, y=0.40～0.50 wherein
(2) the powder median size is 0.5-3 μ m after the roasting of described lithium doping cobalt acid na oxide; Block crystalline orientation degree f＞0.70 behind the sintering.
Compared with prior art, beneficial effect of the present invention is:
It is the cobalt acid sodium thermoelectric material of raw material synthesizing blender that the present invention adopts acetate, can not produce toxic gas in whole process of preparation; This method adopts the drying under reduced pressure process, can finish drying process at lower drying temperature with under than short time of drying.And gel expands in the drying under reduced pressure process, is subjected to the tensile influence, and crystal grain obtains on the surface stretching, and is easy to form sheet structure.But this method synthetic chemistry homogeneity height, the significant acetate doping natrium cobaltite thermoelectric materials of laminate structure.
Description of drawings
Fig. 1 Na 1.5(Co 0.9Ni 0.1) 2O 4The XRD spectrum of sintering block.
Fig. 2 Na 1.5(Co 0.9Ni 0.1) 2O 4The SEM photo of powder.
Fig. 3 Na 1.5(Co 0.9Ni 0.1) 2O 4The SEM photo on block materials surface.
Fig. 4 Na 1.5(Co 0.9Ni 0.1) 2O 4The SEM photo of block materials section.
Fig. 5 Na 1.5(Co 0.9Cu 0.1) 2O 4The XRD spectrum of sintering block.
Fig. 6 Na 1.5(Co 0.9Cu 0.1) 2O 4The SEM photo of powder.
Fig. 7 Na 1.5(Co 0.9Cu 0.1) 2O 4The SEM photo on block materials surface.
Fig. 8 Na 1.5(Co 0.9Cu 0.1) 2O 4The SEM photo of block materials section.
Fig. 9 (NaLi 0.5) Co 2O 4The XRD spectrum of sintering block.
Figure 10 (NaLi 0.5) Co 2O 4The SEM photo of powder.
Figure 11 (NaLi 0.5) Co 2O 4The SEM photo on block materials surface.
Figure 12 (NaLi 0.5) Co 2O 4The SEM photo of block materials section.
Embodiment
All chemical are commercially available analytical pure, without being further purified.
Embodiment 1.Na 1.5(Co 0.9Ni 0.1) 2O 4
CH 3COONa3H 2O (75mmol), (CH 3COO) 2Co4H 2O (90mmol), (CH 3COO) 2Ni4H 2O (10mmol), C 6H 8O 7H 2O (525mmol) adds in the beaker, uses 1600ml deionized water dissolving mixture then.Heated and stirred under the 323K forms homogeneous solution.Be poured in the Rotary Evaporators, temperature be 353K, pressure less than the 0.1MP environment under, reduction vaporization 1 hour, solution presents thick gradually.Thickness colloidal sol places baking oven, 373K constant temperature, pressure less than the 0.1MP environment under, drying under reduced pressure 120 minutes forms fluffy xerogel.Remaining organism is fully driven away in further pyrolysis 6 hours under 693K of xerogel, forms the black presoma.Pass through the 1033K roasting again 6 hours, and formed sintering forerunner powder.Sintering forerunner powder is ground to uniform powder, extrusion forming under the pressure of 560MP, pressureless sintering promptly got block thermoelectric material in 16 hours under 1153K.Compound characterizes sees Fig. 1～Fig. 4.Crystalline orientation degree f=0.91; When 673K, electricalresistivity=62.4 μ Ω m; Seebeck coefficient S=145 μ V/K; Thermal conductivity к=1.29W/mK; Thermoelectric quality factor ZT=0.176.
Embodiment 2.Na 1.5(Co 0.9Cu 0.1) 2O 4
CH 3COONa3H 2O (75mmol), (CH 3COO) 2Co4H 2O (90mmol), (CH 3COO) 2CuH 2O (10mmol), C 6H 8O 7H 2O (525mmol) adds in the beaker, uses 1600ml deionized water dissolving mixture then.In temperature is heated and stirred under 313K～333K, forms homogeneous solution.Be poured in the Rotary Evaporators, temperature be 353K～363K, pressure less than the 0.1MP environment under, reduction vaporization 1 hour, solution presents thick gradually.Thickness colloidal sol places baking oven, temperature 323K～393K, pressure less than the 0.1MP environment under, drying under reduced pressure 110 minutes forms fluffy xerogel.Remaining organism is fully driven away in further pyrolysis 7 hours under 693K～773K of xerogel, forms the black presoma.Pass through 993K～1053K roasting again 6 hours, and formed sintering forerunner powder.Sintering forerunner powder is ground to uniform powder, and extrusion forming under the pressure of 560MP is that pressureless sintering promptly got block thermoelectric material in 15 hours under 1133K～1173K in temperature.Compound characterizes sees Fig. 5～Fig. 8.Crystalline orientation degree f=0.76.
Embodiment 3.Na 1.5(Co 0.85Cu 0.15) 2O 4
CH 3COONa3H 2O (75mmol), (CH 3COO) 2Co4H 2O (85mmol), (CH 3COO) 2CuH 2O (15mmol), C 6H 8O 7H 2O (525mmol) adds in the beaker, uses 1600ml deionized water dissolving mixture then.In temperature is heated and stirred under the 313K, forms homogeneous solution.Be poured in the Rotary Evaporators, temperature be 353K, pressure less than the 0.1MP environment under, reduction vaporization 1 hour, solution presents thick gradually.Thickness colloidal sol places baking oven 323K constant temperature, and pressure is less than under the 0.1MP environment, and drying under reduced pressure formed fluffy xerogel in 100 minutes.Remaining organism is fully driven away in further pyrolysis 6 hours under 773K of xerogel, forms the black presoma.Pass through the 1053K roasting again 6 hours, and formed sintering forerunner powder.Sintering forerunner powder is ground to uniform powder, extrusion forming under the pressure of 560MP, pressureless sintering promptly got block thermoelectric material in 16 hours under 1173K.Crystalline orientation degree f=0.81.
Embodiment 4. (NaLi 0.5) Co 2O 4
CH 3COONa3H 2O (50mmol), (CH 3COO) 2Co4H 2O (100mmol), CH 3COOLi2H 2O (25mmol), C 6H 8O 7H 2O (525mmol) adds in the beaker, uses 1600ml deionized water dissolving mixture then.Heated and stirred under the 328K forms homogeneous solution.Be poured in the Rotary Evaporators, temperature be 358K, pressure less than the 0.1MP environment under, reduction vaporization 1 hour, solution presents thick gradually.Thickness colloidal sol places baking oven 323K constant temperature, and pressure is less than under the 0.1MP environment, and drying under reduced pressure formed fluffy xerogel in 130 minutes.Remaining organism is fully driven away in further pyrolysis 4 hours under 773K of xerogel, forms the black presoma.Pass through the 1033K roasting again 6 hours, and formed sintering forerunner powder.Sintering forerunner powder is ground to uniform powder, extrusion forming under the pressure of 560MP, pressureless sintering promptly got block thermoelectric material in 16 hours under 1173K.Compound characterizes sees Fig. 9～Figure 12.Crystalline orientation degree f=0.71.
Embodiment 5. (Na 1.1Li 0.4) Co 2O 4
CH 3COONa3H 2O (55mmol), (CH 3COO) 2Co4H 2O (100mmol), CH 3COOLi2H 2O (20mmol), C 6H 8O 7H 2O (525mmol) adds in the beaker, uses 1600ml deionized water dissolving mixture then.In temperature is heated and stirred under the 338K, forms homogeneous solution.Being poured in the Rotary Evaporators, is 353K in temperature, and pressure is less than under the 0.1MP environment, reduction vaporization 1 hour, and solution presents thick gradually.Thickness colloidal sol places baking oven 393K constant temperature, and pressure is less than under the 0.1MP environment, and drying under reduced pressure formed fluffy xerogel in 150 minutes.Remaining organism is fully driven away in further pyrolysis 4 hours under 773K of xerogel, forms the black presoma.Pass through the 1033K roasting again 6 hours, and formed sintering forerunner powder.Sintering forerunner powder is ground to uniform powder, extrusion forming under the pressure of 560MP, pressureless sintering promptly got block thermoelectric material in 16 hours under 1173K.Crystalline orientation degree f=0.76.

Claims (6)

1. the preparation method of nickel doping cobalt acid sodium thermoelectric material, the preparation of employing sol-gel method, it is characterized in that, with the acetate is raw material, citric acid is a complexing agent, behind formation colloidal sol, the gel, obtains the presoma nanometer powder by pyrolysis, roasting again, sintering is finished then, and its technology is carried out according to following steps:
A. press stoichiometric ratio with (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O and (CH 3COO) 2Ni4H 2O fully is dissolved in the aqueous citric acid solution, and citrate is 3: 1 with the ratio of metal ion;
B. heated and stirred forms homogeneous solution under 313K～333K temperature condition; Under 353K～363K temperature condition, carry out reduction vaporization, become thickness colloidal sol until described homogeneous solution;
C. described thickness colloidal sol is placed loft drier, drying under reduced pressure obtains xerogel under 323K～393K temperature condition, and described drying under reduced pressure carries out under the following conditions: pressure is smaller or equal to 0.1MPa, and the time is 100-150 minute;
D. with the pyrolysis under 693K～773K temperature condition of described xerogel, remove remaining organism wherein; Roasting under the condition of 993K～1053K obtains black forerunner powder;
E. described black forerunner powder is ground evenly, sintering forms nickel doping cobalt acid sodium thermoelectric material under the temperature condition of 1133K～1173K;
Wherein, described nickel doping cobalt acid sodium thermoelectric material has following physicochemical characteristic:
(1) molecular formula is: Na 1.5(Co 0.9Ni 0.1) 2O 4
(2) the powder median size is 3-6 μ m after the roasting of nickel doping cobalt acid na oxide;
(3) under 673K, the performance of described nickel doping cobalt acid na oxide thermoelectric material is: crystalline orientation degree f=0.91; Electricalresistivity=62.4 μ Ω m; Seebeck coefficient S=145 μ V/K; Thermal conductivity κ=1.29W/mK; Thermoelectric quality factor ZT=0.176.
2. the method for claim 1 is characterized in that: also comprise the step of described thickness colloidal sol being carried out constant pressure and dry before carrying out step C.
3. the preparation method of copper doping cobalt acid sodium thermoelectric material, the preparation of employing sol-gel method, it is characterized in that, with the acetate is raw material, citric acid is a complexing agent, behind formation colloidal sol, the gel, obtains the presoma nanometer powder by pyrolysis, roasting again, sintering is finished then, and its technology is carried out according to following steps:
A. press stoichiometric ratio with (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O and (CH 3COO) 2CuH 2O fully is dissolved in the aqueous citric acid solution, and citrate is 3: 1 with the ratio of metal ion;
B. heated and stirred forms homogeneous solution under 313K～333K temperature condition; Under 353K～363K temperature condition, carry out reduction vaporization, become thickness colloidal sol until described homogeneous solution;
C. described thickness colloidal sol is placed loft drier, drying under reduced pressure obtains xerogel under 323K～393K temperature condition, and described drying under reduced pressure carries out under the following conditions: pressure is smaller or equal to 0.1MPa, and the time is 100-150 minute;
D. with the pyrolysis under 693K～773K temperature condition of described xerogel, remove remaining organism wherein; Roasting under the condition of 993K～1053K obtains black forerunner powder;
E. described black forerunner powder is ground evenly, sintering forms copper doping cobalt acid sodium thermoelectric material under the temperature condition of 1133K～1173K;
Wherein, described copper doping cobalt acid sodium thermoelectric material has following physicochemical characteristic:
(1) molecular formula: Na 1.5(Co 1-xCu x) 2O 4, x=0.1～0.15 wherein;
(2) the powder median size is 6-10 μ m after the roasting of copper doping cobalt acid na oxide; Block crystalline orientation degree f＞0.75 behind the sintering.
4. method as claimed in claim 3 is characterized in that: also comprise the step of described thickness colloidal sol being carried out constant pressure and dry before carrying out step C.
5. the preparation method of lithium doping cobalt acid sodium thermoelectric material, the preparation of employing sol-gel method, it is characterized in that, with the acetate is raw material, citric acid is a complexing agent, behind formation colloidal sol, the gel, obtains the presoma nanometer powder by pyrolysis, roasting again, sintering is finished then, and its technology is carried out according to following steps:
A. press stoichiometric ratio with (CH 3COO) 2Co4H 2O, CH 3COONa3H 2O and CH 3COOLi2H 2O fully is dissolved in the aqueous citric acid solution, and citrate is 3: 1 with the ratio of metal ion;
B. heated and stirred forms homogeneous solution under 313K～333K temperature condition; Under 353K～363K temperature condition, carry out reduction vaporization, become thickness colloidal sol until described homogeneous solution;
C. described thickness colloidal sol is placed loft drier, drying under reduced pressure obtains xerogel under 323K～393K temperature condition, and described drying under reduced pressure carries out under the following conditions: pressure is smaller or equal to 0.1MPa, and the time is 100-150 minute;
D. with the pyrolysis under 693K～773K temperature condition of described xerogel, remove remaining organism wherein; Roasting under the condition of 993K～1053K obtains black forerunner powder;
E. described black forerunner powder is ground evenly, sintering forms lithium doping cobalt acid sodium thermoelectric material under the temperature condition of 1133K～1173K;
Wherein, described lithium doping cobalt acid sodium thermoelectric material has following physicochemical characteristic:
(1) molecular formula: (Na 1-yLi y) Co 2O 4, y=0.40～0.50 wherein
(2) the powder median size is 0.5-3 μ m after the roasting of lithium doping cobalt acid na oxide; Block crystalline orientation degree f＞0.70 behind the sintering.
6. method as claimed in claim 5 is characterized in that: also comprise the step of described thickness colloidal sol being carried out constant pressure and dry before carrying out step C.
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