CN110407561A - A kind of preparation method of liquid-phase sintering calcium manganate base oxide pyroelectric material - Google Patents
A kind of preparation method of liquid-phase sintering calcium manganate base oxide pyroelectric material Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of liquid-phase sintering calcium manganate base oxide pyroelectric material, first uniformly mix the nitrate of the Mn of high-purity and Ca using sol-gel method, have prepared the CaMnO of uniform and smooth3The powder of oxide pyroelectric material utilizes the method for wet-milling by Cu powder and CaMnO afterwards3Pure phase powder uniformly mixes, and normal pressure-sintered method is recycled successfully to prepare target product, realizes Cu in CaMnO3Liquid-phase sintering in matrix.Resulting materials of the present invention are the same as pure phase CaMnO3It compares, has high conductivity (3~4 times of pure phase), high-compactness, to improve thermoelectricity capability；Meanwhile preparation method of the invention has many advantages, such as that simple process, synthesis and molding time are short.
Description
Technical field
The present invention relates to a kind of preparation methods of liquid-phase sintering calcium manganate base oxide pyroelectric material, belong to thermoelectric ceramics neck
Domain.
Background technique
Energy resources shortage and environmental problem are increasingly serious in global range, and the exploitation and use of environmentally friendly material become
It obtains particularly important.And utilize Seebeck effect and Peltier effect realization temperature-difference refrigerating and the thermoelectric material of waste-heat power generation to section
About the energy plays important function.Thermoelectric material is a kind of to be directly realized by thermal energy and electric energy phase using solid interior carrier moving
The new energy material mutually converted, when mutually converting without chemical reaction and fluid media (medium), and it is in space flight, the fields such as military affairs
Important application, cause the extensive research of people.
At this stage, thermoelectric material is mainly divided to two classes, i.e. alloy material and oxide pyroelectric material.But due to block alloy material
Material haves the defects that certain, and such as: the oxidizable decomposition of high temperature, earth's crust content is few, expensive etc., so that research hotspot turns to
Cheap, the high oxide pyroelectric material of environmental stability.Wherein CaMnO3It is a kind of structure is perovskite orthohormbic structure
Thermoelectric material, CaMnO3Seebeck coefficient with higher, but CaMnO3The shortcomings that base oxide is resistivity height, this causes
CaMnO3The thermoelectricity capability of pure phase oxide thermoelectric material is not high, but determine can for its unique crystal structure and transmission characteristic
With by doping, nano combined method regulates and controls its Electrical transport, to improve its thermoelectricity capability.
And selecting suitable complex element, compound quantity and preparation method is to improve CaMnO3The key of thermoelectricity capability is asked
Topic.Cu is located at transition element area in the periodic table of elements, and relative atomic mass 63.54 is usually easy power loss in compound state
Son is shown as+Divalent.And the physicochemical property of Cu is relatively stable, electric conductivity and thermal conductivity are all higher in all metals.Due to
The fusing point of Cu is low, and ductility is good, and the method for utilizing liquid-phase sintering at this time, during sintering, Ni metal is in CaMnO3Matrix
In reach fusing point, be changed into liquid phase, be enriched in the grain boundaries of matrix, filled up the hole of matrix, so that the consistency of material increases
Add, and makes Cu-CaMnO3It is connected with each other perforation, forms new conductive path, increases carrier mobility, to increase heat
The conductivity of electric material, and then influence the thermoelectricity capability of material.
Summary of the invention
The present invention is intended to provide a kind of preparation method of liquid-phase sintering calcium manganate base oxide pyroelectric material, this method can be with
The mobility of carrier is greatly improved, so that conductivity can also keep higher Seebeck coefficient while increase, to make
Power factor improves.
The preparation method of liquid-phase sintering calcium manganate base oxide pyroelectric material of the present invention uses citric acid sol-gel method first
Method uniformly mixes the nitrate of the Mn of high-purity and Ca, has prepared the CaMnO of uniform and smooth3The powder of oxide pyroelectric material
End utilizes the method for wet-milling by Cu powder and CaMnO afterwards3Pure phase powder uniformly mixes, and normal pressure-sintered method is recycled successfully to make
Standby target product out realizes Cu in CaMnO3Liquid-phase sintering in matrix.
Specifically comprise the following steps:
Step 1: by Ca (NO3)2·4H2O、Mn(NO3)2Deionization is dissolved according to the molar ratio mixing of 1:1:6 with citric acid
In water, and suitable ethylene glycol (the 1/20 of deionized water) is added, is uniformly mixed, obtains mixed solution；It is again that the mixing is molten
Liquid is placed in 80~90 DEG C of waters bath with thermostatic control and reacts 12~14h, obtains brown wet gel；The brown wet gel is dry to completely de-
Water obtains xerogel predecessor；After the xerogel predecessor crushing grinding, 950 DEG C of calcining 5h in Muffle furnace are placed in, are obtained
CaMnO3Oxide pure phase powder；
Step 2: the CaMnO that step 1 is obtained3Oxide pure phase powder and Cu powder are mixed and added into polytetrafluoroethylene (PTFE) ball milling
In tank, 3~5h of wet-milling obtains uniformly mixed composite powder；After the composite powder is ground repeatedly, it is dense that appropriate quality is added
The polyvinyl alcohol of degree 7% is uniform, the pre-molding under 5MPa pressure, obtains just base；It is cold by being placed in after the just base sealing
In isostatic pressing machine, 1~6min is suppressed with the pressure of 200MPa, obtains molded samples；
Step 3: the molded samples that step 2 is obtained are placed in 550 DEG C of heat preservation 2~5h of dumping in Muffle furnace, after obtaining dumping
Sample；Liquid-phase sintering will be carried out in sample merging high temperature process furnances after the dumping, i.e. acquisition CaMnO3Base oxide heat
Electric block.
It is the method implementation by including the following steps by brown wet gel drying to complete dehydration in step 1:
The brown wet gel is placed in drying box, first in 90 DEG C of freeze-day with constant temperature 36h, then is warming up to 120 DEG C and perseverance
Dry 3~the 5h of temperature, then raises temperature to 140 DEG C and 4~6h of freeze-day with constant temperature, is finally warming up to 160 DEG C and 1~3h of freeze-day with constant temperature.
In step 1, Ca in gained mixed solution2+Concentration is 0.2mol/L.
In step 2, the size of the Cu powder is 200nm.
In step 2, CaMnO3Oxide pure phase powder and Cu powder 1:(0.04~0.08 in molar ratio) ratio mix.
In step 2, the mass ratio of the polyvinyl alcohol of mass concentration 7% and composite powder is 1:(10~20) ratio it is mixed
It closes.
In step 2, the wet-milling is using alcohol as ball-milling medium 3~5h of wet-milling, and ratio of grinding media to material is (6~12): 1.
In step 3, the parameter setting of the liquid-phase sintering is as follows: 1100 are warming up to the heating rate of 3 DEG C/min~
1500 DEG C, after keeping the temperature 12~16h, 300 DEG C is cooled to the rate of temperature fall of 1~3 DEG C/min, then cools to room temperature with the furnace.
The beneficial effects of the present invention are embodied in:
1, with pure phase CaMnO3It compares, CaMnO prepared by the present invention3Base oxide pyroelectric material, in sintering process, Cu powder
It is liquid by Solid State Transformation, is enriched in the grain boundaries of matrix, has filled up the hole of matrix, so that material has high-compactness, and
And make Cu-CaMnO3It is connected with each other perforation, new conductive path, and the high conductivity of Cu is formed, is more advantageous to materials conductive
The raising of performance.
2, thermoelectric material provided by the invention, raw material is simple, low in cost, and preparation process is easy, and resulting materials are anti-oxidant
Property is strong, can work, and excellent in high-temperature behavior in air, be good high temperature material.
Detailed description of the invention
Fig. 1 is CaMnO3The XRD diagram of base oxide pyroelectric material；
Fig. 2 is CaMnO3The fracture apperance figure of base oxide pyroelectric material.
Specific embodiment
Embodiment 1:
The present embodiment prepares CaMnO as follows3Base oxide pyroelectric material:
1, by Ca (NO3)2·4H2O、Mn(NO3)2With citric acid according to the molar ratio weighing of 1:1:6 after, mixing be dissolved in from
In sub- water, and suitable ethylene glycol (the 1/20 of amount of deionized water) is added, is uniformly mixed, obtaining mixed solution, (gained mixing is molten
Ca in liquid2+Concentration is 0.2mol/L)；Mixed solution is placed in 85 DEG C of water bath with thermostatic control reaction 12h again, obtains brown wet gel；It will
The brown wet gel is placed in drying box, dry to complete dehydration, obtains xerogel predecessor；By the xerogel forerunner
After object crushing grinding, 950 DEG C of calcining 5h in Muffle furnace are placed in, CaMnO is obtained3Oxide pure phase powder；
2, again by the molar ratio of pure phase powder and the Cu powder of 200nm be by the molar ratio weighing of 1:0.04 after, by 8:1 ball material
Than being put into polytetrafluoroethylene (PTFE) ball grinder, and suitable alcohols are added, after wet-milling 4h, obtain being uniformly mixed CaMnO3With nanometer Cu's
Composite powder；After the composite powder is ground repeatedly, the polyvinyl alcohol of mass concentration 7% is added, by the poly- of mass concentration 7%
Vinyl alcohol is uniformly mixed with composite powder with the mass ratio of 1:15, the pre-molding under 5MPa pressure, obtains just base；It will be described first
It is placed in cold isostatic press after base sealing, 5min is suppressed with the pressure of 200MPa, obtains molded samples；
3, sample taking-up after molding is placed in 550 DEG C of heat preservation dumping 5h in Muffle furnace, the sample after obtaining dumping；It will be described
Liquid-phase sintering is carried out in sample merging high temperature process furnances after dumping, is warming up to 1200 DEG C with the heating rate of 3 DEG C/min, heat preservation
After 12h, after being cooled to 300 DEG C with 2 DEG C of rate of temperature fall, then furnace cooling, i.e. acquisition CaMnO3Base oxide thermoelectric block body.
Embodiment 2:
The present embodiment prepares multiphase complex Ca MnO by the identical method of embodiment 13Base oxide pyroelectric material, difference is only
It is: pure phase CaMnO in step 23It is 1:0.08 with 200nmCu powder molar ratio, ratio of grinding media to material is 10:1 when wet-milling.
Fig. 1 is CaMnO prepared by above-described embodiment3The XRD diagram of base oxide pyroelectric material, wherein (A) curve is pure
Phase CaMnO3Standard diffraction map, (B), (C) curve respectively correspond the sample of embodiment 1, embodiment 2.It can be seen that sample
In there are CaMnO3With Cu two-phase.
Fig. 2 is CaMnO prepared by above-described embodiment3The fracture apperance figure of base oxide pyroelectric material, wherein (A), (B)
Respectively correspond the sample of embodiment 1, embodiment 2.As can be seen that the thermoelectric material powder consolidates preferable, consistency height and Cu
In the grain boundaries in matrix grain, new conductive channel is formed.
Table 1 be measure 550 DEG C at CaMnO3The electric property of base oxide pyroelectric material.Test data shows: with
Pure phase CaMnO3It compares, CaMnO prepared by embodiment 13The conductivity of base oxide pyroelectric material improves 3.6 times, Seebeck system
Number reduces 25%, power factor and improves about 2 times, and electric property is greatly improved.
CaMnO at 1 550 DEG C of table3The electric property of base thermoelectricity material
Claims (9)
1. a kind of preparation method of liquid-phase sintering calcium manganate base oxide pyroelectric material, it is characterised in that:
The nitrate of the Mn of high-purity and Ca is uniformly mixed using sol-gel method first, has prepared uniform and smooth
CaMnO3The powder of oxide pyroelectric material utilizes the method for wet-milling by Cu powder and CaMnO afterwards3Pure phase powder uniformly mixes, then
Target product is successfully prepared using normal pressure-sintered method, realizes Cu in CaMnO3Liquid-phase sintering in matrix.
2. preparation method according to claim 1, it is characterised in that include the following steps:
Step 1: by Ca (NO3)2·4H2O、Mn(NO3)2It is dissolved in deionized water with citric acid according to the molar ratio mixing of 1:1:6,
And ethylene glycol is added, it is uniformly mixed, obtains mixed solution；The mixed solution is placed in 80~90 DEG C of water bath with thermostatic control reactions 12 again
~14h obtains brown wet gel；The brown wet gel is dry to complete dehydration, obtain xerogel predecessor；It will be described dry
After gel predecessor crushing grinding, 950 DEG C of calcining 5h in Muffle furnace are placed in, CaMnO is obtained3Oxide pure phase powder；
Step 2: the CaMnO that step 1 is obtained3Oxide pure phase powder and Cu powder are mixed and added into polytetrafluoroethylene (PTFE) ball grinder,
3~5h of wet-milling obtains uniformly mixed composite powder；After the composite powder is ground repeatedly, the poly- of mass concentration 7% is added
Vinyl alcohol is uniformly mixed, the pre-molding under 5MPa pressure, obtains just base；Cold isostatic press will be placed in after the just base sealing
In, 1~6min is suppressed with the pressure of 200MPa, obtains molded samples；
Step 3: the molded samples that step 2 is obtained are placed in 550 DEG C of heat preservation 2~5h of dumping, the sample after obtaining dumping in Muffle furnace
Product；Liquid-phase sintering will be carried out in sample merging high temperature process furnances after the dumping, i.e. acquisition CaMnO3Base oxide thermoelectricity block
Body.
3. preparation method according to claim 2, it is characterised in that:
It is the method implementation by including the following steps by brown wet gel drying to complete dehydration in step 1:
The brown wet gel is placed in drying box, first in 90 DEG C of freeze-day with constant temperature 36h, then to be warming up to 120 DEG C and constant temperature dry
Dry 3~5h then raises temperature to 140 DEG C and 4~6h of freeze-day with constant temperature, is finally warming up to 160 DEG C and 1~3h of freeze-day with constant temperature.
4. preparation method according to claim 2, it is characterised in that:
In step 1, Ca in gained mixed solution2+Concentration is 0.2mol/L.
5. preparation method according to claim 2, it is characterised in that:
In step 2, the size of the Cu powder is 200nm.
6. preparation method according to claim 2, it is characterised in that:
In step 2, CaMnO3Oxide pure phase powder and Cu powder 1:(0.04~0.08 in molar ratio) ratio mix.
7. preparation method according to claim 2 or 5, it is characterised in that:
In step 2, the mass ratio of the polyvinyl alcohol of mass concentration 7% and composite powder is 1:(10~20) ratio mix.
8. preparation method according to claim 2, it is characterised in that:
In step 2, the wet-milling is using alcohol as ball-milling medium 3~5h of wet-milling, and ratio of grinding media to material is (6~12): 1.
9. preparation method according to claim 2, it is characterised in that:
In step 3, the parameter setting of the liquid-phase sintering is as follows: 1100~1500 DEG C are warming up to the heating rate of 3 DEG C/min,
After keeping the temperature 12~16h, 300 DEG C are cooled to the rate of temperature fall of 1~3 DEG C/min, then cools to room temperature with the furnace.
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| CN111994959A (en) * | 2020-07-17 | 2020-11-27 | 中山大学 | CaMnO3Perovskite material and preparation method and application thereof |
| CN114133215A (en) * | 2021-12-03 | 2022-03-04 | 西安建筑科技大学 | A-site high-entropy perovskite ReMnO3Thermoelectric ceramic and preparation method thereof |
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| CN114133215A (en) * | 2021-12-03 | 2022-03-04 | 西安建筑科技大学 | A-site high-entropy perovskite ReMnO3Thermoelectric ceramic and preparation method thereof |
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