CN110190311A - A kind of preparation method of high-densit apatite-type solid electrolyte material - Google Patents
A kind of preparation method of high-densit apatite-type solid electrolyte material Download PDFInfo
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- CN110190311A CN110190311A CN201910632533.4A CN201910632533A CN110190311A CN 110190311 A CN110190311 A CN 110190311A CN 201910632533 A CN201910632533 A CN 201910632533A CN 110190311 A CN110190311 A CN 110190311A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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Abstract
The present invention relates to a kind of preparation methods of high-densit apatite-type solid electrolyte material, belong to electrolyte preparation technical field.Technical solution of the present invention uses gadolinium oxide to prepare composite material for raw material and is added to solid electrolyte material, since the solid electrolyte of Gd2 O3 being made by sol-gel method, and the doping of gadolinium does not destroy apatite structure and improves conductivity by gadolinium-doped not by apatite structure is changed to realize, mainly pass through the increase of doping, grain size gradually becomes smaller, the reason for this is that the doping of gadolinium ion inhibits the migration of crystal boundary, that is increasing with Gd2 O3 amount, resistance suffered by the growth process of crystal grain increases, therefore, the size of crystal grain gradually becomes smaller, material structure performance becomes fine and close, further improve the structural strength of material, simultaneously because the increase of Gd2 O3 amount, it can reduce the transition potential barrier of oxonium ion, to improve oxygen ion transport rate, further increase the chemical property of solid electrolyte material.
Description
Technical field
The present invention relates to a kind of preparation methods of high-densit apatite-type solid electrolyte material, belong to electrolyte system
Standby technical field.
Background technique
As factor most important during human development --- the energy, the science and technology that restrict the mankind always is changed, to people
The clothing, food, lodging and transportion -- basic necessities of life etc. of class solid oxide fuel cell suffer from tremendous influence, are the life breath manner of breathing with us
It closes.And even to this day, as solid oxide fuel cell resource, natural environment and climate problem highlight, the whole world is step by step
The energy revolution for marching toward a new round, the exploitation of past energy solid oxide fuel cell, conversion and all existed using form
Gradually it is eliminated, and new energy cause is also quietly being risen.Solid oxide fuel cell fuel cell is after water conservancy, thermoelectricity
And the forth generation power generator after nuclear energy.It first will combustion solid oxide fuel cell material and oxidant compared to traditional combustion engine
In chemical energy be first converted into thermal energy, and then be converted into mechanical energy and electric energy is compared, fuel cell can be fired with soild oxide
Expect that battery in power generation process, directly converts electric energy for the chemical energy of fuel, to not limited by Carnot cycle effect.This
Big solid oxide fuel cell improves greatly energy transformation ratio --- and the cogeneration of heat and power of high temperature solid oxide fuel cell is imitated
Rate is up to 80%.Fuel electricity solid oxide fuel cell pond includes alkaline fuel cell, phosphoric acid cells, fused carbonate electricity
Pond, solid oxide cell and proton exchange membrane electricity solid oxide fuel cell pond).
Solid oxide fuel cell is a kind of directly to convert the chemical energy of fuel and oxidant by electrochemical reaction
For the novel energy reforming unit of electric energy.For this device because of its structure of whole solid state, fuel utilization efficiency is high and is concerned.Solid
Oxide fuel cell not still a kind of quite efficient energy conversion device and a kind of very clean energy source device: can
Using multiple gases as fuel, when power generation, seldom gives off pernicious gas；With structure of whole solid state, without transmission parts, therefore
Also the problem of corroding without noise pollution and conventional battery electrolyte.Therefore, based on its structure of whole solid state, fuel tolerance by force with
And the advantages of high power density, on the other hand, fuel cell at this stage is mainly high-temperature fuel cell, i.e., is existed using temperature
800 DEG C or more of fuel cell.This makes fuel cell start-up slower, and the connector of complete high-temperature fuel cell and encapsulation
Material all must be ceramic material, this not only brings and is difficult to the shortcomings that transporting processing, but also such fuel cell cost compared with
High and service life is shorter.Therefore, the middle low temperature (400-800 DEG C) of solid oxide fuel cell is research heat in recent years
Point.The filming of solid-oxide fuel battery electrolyte and electrolyte in searching under low temperature with higher conductivity is existing
Two important directions of research.Solid oxide fuel cell includes porous anode, oxide electrolyte and porous cathode three
Layer structure.Solid oxide fuel cell separates the redox reaction of fuel combustion by fine and close electrolyte, so that
Electronics can be shifted orderly along external circuit, to directly convert electric energy for the chemical energy of fuel.If with H2As fuel, electricity
Chemical principle can sum up are as follows: be passed through H in porous anode2, fuel is in electrolyte/electronic conductor three phase boundary
(boundary between TPB, i.e. gas phase, ion conductor and electronic conductor), H2In this interface and the oxygen migrated from electrolyte
Anion reaction, loses outermost electronics, electronics flows to cathode along external circuit.Anode is needed as fuel electrode very wide
It is compatible with electrolyte heat-mechanical property (from room temperature to operating temperature) in temperature range.Meanwhile anode material should also be a kind of
Good electronic conductor has certain catalytic activity and compatibility, so that ohmic loss is preferably minimized.
The middle low temperature of fuel cell is the trend of SOFCs development, and MDLS because its ionic conductivity with higher, compared with
Low activation energy and there is the thermal expansion coefficient to match with common electrode, and obtains the extensive concern of researcher.But LSO conduct
Electrolyte is applied in fuel cell, also encounters some problems:
LSO electrolyte sintering temperature height brings the lower problem of consistency after sintering, the electrolyte mechanical performance of preparation
Lower, conductivity is lower than theoretical value.Apatite-type electrolyte is prepared, plasma spraying process, rf magnetron sputtering are generallyd use
Method, silk screen print method.Since LSO sintering temperature is very high, more than 1600 DEG C ability densified sintering products are generally required, and directly by solid
The LSO purity of phase reaction method preparation is lower.Therefore the practical property under middle low temperature of the LSO type fuel cell of preparation electrolyte-supported
It can be difficult to reach theoretical value.Realize the volume production of SOFCs and cost effective, the middle low temperature of fuel cell is the trend developed,
SOFCs need to be studied at two aspects of electrolyte and electrolyte thin membranization.Therefore, in terms of electrolyte, we
Selecting LSO, this has the electrolyte of high conductivity under middle low temperature.In terms of electrolyte thin membranization, research master at this stage
Concentrate on battery of the electrolyte thickness at 10 μm or more.Existing apatite-type lanthanum silicate full battery there are still electrolyte compared with
Thickness, thin electrolyte unsound problem mostly, this makes battery cause resistance higher due to polarization problem.So preparing one kind
High-densit apatite-type solid electrolyte material is extremely urgent.
Summary of the invention
The technical problems to be solved by the invention: burning is brought for existing apatite-type solid electrolyte sintering temperature height
The problem of electrolyte mechanical performance of the lower problem of consistency after knot, preparation is lower, and conductivity is lower than theoretical value, provides one
The preparation method of kind polymolecularity plant fiber absorbing material.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) according to parts by weight, 45~50 parts of dehydrated alcohols, 3~5 parts of deionized waters and 6~8 parts of positive silicic acid are weighed respectively
Ethyl ester is placed in conical flask, is stirred and ultrasonic disperse, collection dispersion liquid simultaneously adjust pH to 3.0, be stirred and keep the temperature
Reaction, obtains matrix sol solutions；Score meter by weight again weighs 45~50 parts of deionized waters, 45~50 parts of dehydrated alcohols, 25 respectively
~30 parts of zirconium oxychlorides and 10~15 parts of hydrogen peroxide are placed in three-necked flask, are stirred and ammonium hydroxide is added dropwise to three-necked flask
In, it is stirred to obtain complex sol liquid, in mass ratio 1:1, complex sol liquid and matrix sol solutions are stirred and are placed in room
Temperature is lower to be aged 6~8h, must be aged modification sol liquid；
(2) 1:15 in mass ratio, gadolinium oxide is added in nitric acid solution, is stirred and is collected to obtain lysate, by body
Lysate is mixed with absolute ethyl alcohol and stirring than 1:15, obtains solution A, then 1:10 in mass ratio, lanthanum nitrate is added to anhydrous by product
In ethyl alcohol, it is stirred to obtain solution B, in mass ratio 1:1, solution A and solution B are stirred and mixed liquor, adjusts mixed liquor
PH to 2.0, is stirred and is placed in three-necked flask, after insulation reaction, obtains reaction solution；
(3) 1:8 in mass ratio, ethyl orthosilicate is added dropwise in reaction solution, after being added dropwise to complete, is stirred and is kept the temperature
Dry that desiccant gel liquid is placed in tube-type atmosphere furnace, heating heating and thermal insulation processing, standing is cooled to room temperature, is ground up, sieved,
Obtain blapharoplast；
(4) score meter by weight weighs 45~50 parts of ageing modification sol liquid, 45~50 parts of blapharoplasts and 3~5 respectively
Part poly-vinyl alcohol solution is placed in mortar, and milled processed simultaneously collects dispersion slurries, dispersion slurries is placed in mold, compression moulding
Afterwards, heat preservation sintering, standing are cooled to room temperature, and can be prepared into the high-densit apatite-type solid electrolyte material.
The ammonia concn is 0.8mol/L.
The adjusting pH of mixed adjusts pH of mixed to 2.0 with glacial acetic acid and 10% ammonium hydroxide of mass fraction to 2.0.
The ethyl orthosilicate drop rate is 0.1mL/min.
The heating heating and thermal insulation processing is is heated to 550~650 DEG C by 6 DEG C/min heating, 1~2h of insulation reaction
Afterwards, then by 8 DEG C/min 1000~1200 DEG C are warming up to, 3~5h of heat preservation calcining.
The blapharoplast partial size is 500 mesh.
The compression moulding pressure is 10~20MPa.
The heat preservation sintering is 3~5h of heat preservation sintering at 1500~1600 DEG C.
The poly-vinyl alcohol solution mass fraction is 5%.
The present invention is compared with other methods, and advantageous effects are:
(1) technical solution of the present invention uses gadolinium oxide to prepare composite material for raw material and adds to solid electrolyte material
Add, since the solid electrolyte of Gd2 O3 being made by sol-gel method, and the doping of gadolinium does not destroy apatite structure and passes through
Gadolinium-doped is realized to improve conductivity not by apatite structure is changed, and mainly passes through the increase of doping, brilliant
Granularity gradually becomes smaller, the reason for this is that the doping of gadolinium ion inhibits the migration of crystal boundary, i.e. increasing with Gd2 O3 amount, crystal grain
Resistance suffered by growth process increases, and therefore, the size of crystal grain gradually becomes smaller, and material structure performance becomes fine and close, further changes
The structural strength of kind material, simultaneously because the increase of Gd2 O3 amount, can reduce the transition potential barrier of oxonium ion, thus improve oxygen from
Sub- transmission rate further increases the chemical property of the solid electrolyte material of material；
(2) technical solution of the present invention carries out part doping vario-property to material by gel oxidizing zirconia material, due to zirconium ion
It is smaller, preparing in composite material causes lattice to be distorted due to the difference of ionic radius, generates a large amount of lattices and lacks
It falls into, activates lattice, while increase cation vacancy concns, improve sintering driving force, shorten needed for sintering neck contraction
Time, and the incorporation of zirconium oxide makes the reduction of diffusion activation energy needed for sintering process, improves diffusion coefficient, accelerates diffusion speed
Rate promotes sample sintering densification, sample densification degree is greatly improved, simultaneously because particle growth causes crystallite dimension
Increase, and little particle is adsorbed on large particle surface, will leave tiny hole, the long conference of crystal grain after little particle disappearance
Causing the hole between neighboring particles to be connected and increases hole quantity, this all declines the consistency of material, so this
The doping of the zirconium of inventive technique scheme can make the average crystal grain of material become thinner, to generate product to sintering densification process
The influence of pole.
Specific embodiment
According to parts by weight, 45~50 parts of dehydrated alcohols, 3~5 parts of deionized waters and 6~8 parts of positive silicic acid second are weighed respectively
Ester is placed in conical flask, is stirred and is placed in 10~15min of ultrasonic disperse under 200~300W, is collected dispersion liquid and is used in combination
0.5mol/L salt acid for adjusting pH is stirred to 3.0 and is placed in 3~5h of insulation reaction at 75~85 DEG C, obtain matrix sol solutions；Again
Score meter by weight, weigh respectively 45~50 parts of deionized waters, 45~50 parts of dehydrated alcohols, 25~30 parts of zirconium oxychlorides and 10~
15 parts of hydrogen peroxide are placed in three-necked flask, are stirred and the 0.8mol/L ammonium hydroxide of dehydrated alcohol quality 50% is added dropwise to three mouthfuls
In flask, it is stirred to obtain complex sol liquid；Complex sol liquid and matrix sol solutions are stirred juxtaposition by 1:1 in mass ratio
It is aged 6~8h at room temperature, modification sol liquid must be aged；Gadolinium oxide is added to 45% nitre of mass fraction by 1:15 in mass ratio
It in acid solution, is stirred and collects to obtain lysate, by volume 1:15, lysate is mixed with absolute ethyl alcohol and stirring, is obtained molten
Liquid A, then 1:10 in mass ratio, lanthanum nitrate is added in dehydrated alcohol, is stirred to obtain solution B, in mass ratio 1:1, will be molten
Liquid A and solution B are stirred and mixed liquor, adjusts pH of mixed to 2.0 with glacial acetic acid and 10% ammonium hydroxide of mass fraction, stirring is mixed
Merging is placed in three-necked flask, then at 75~85 DEG C after 3~5h of insulation reaction, obtains reaction solution, then 1:8 in mass ratio, will just
Silester is added dropwise in reaction solution, and control drop rate is that 0.1mL/min is stirred after being added dropwise to complete and is placed in 130
2~3h of heat preservation and dryness at~150 DEG C obtains desiccant gel liquid and is placed in tube-type atmosphere furnace, is heated to 550 by 6 DEG C/min heating
~650 DEG C, after 1~2h of insulation reaction, then by 8 DEG C/min 1000~1200 DEG C are warming up to, heat preservation 3~5h of calcining stands cooling
To room temperature, ground 500 mesh obtains blapharoplast；Score meter by weight, respectively weigh 45~50 parts of ageing modification sol liquid,
45~50 parts of blapharoplasts and 3~5 parts of 5% poly-vinyl alcohol solutions of mass fraction are placed in mortar, and milled processed simultaneously collects dispersion
Dispersion slurries are placed in mold by slurries, then after compression moulding under 10~20MPa, then are kept the temperature and burnt at 1500~1600 DEG C
3~5h of knot, standing are cooled to room temperature, and can be prepared into the high-densit apatite-type solid electrolyte material.
Embodiment 1
According to parts by weight, 45 parts of dehydrated alcohols, 3 parts of deionized waters and 6 parts of ethyl orthosilicates are weighed respectively be placed in triangle
In flask, be stirred and be placed in ultrasonic disperse 10min under 200W, collect dispersion liquid and with 0.5mol/L salt acid for adjusting pH extremely
3.0, it is stirred and is placed in insulation reaction 3h at 75 DEG C, obtain matrix sol solutions；Score meter by weight again weighs 45 parts respectively and goes
Ionized water, 45 parts of dehydrated alcohols, 25 parts of zirconium oxychlorides and 10 parts of hydrogen peroxide are placed in three-necked flask, are stirred and nothing is added dropwise
The 0.8mol/L ammonium hydroxide of water-ethanol quality 50% is stirred to obtain complex sol liquid into three-necked flask；1:1 in mass ratio, will
Complex sol liquid and matrix sol solutions are stirred juxtaposition and are aged 6h at room temperature, must be aged modification sol liquid；In mass ratio 1:
15, gadolinium oxide is added in 45% nitric acid solution of mass fraction, is stirred and collects to obtain lysate, by volume 1:15,
Lysate is mixed with absolute ethyl alcohol and stirring, solution A, then 1:10 in mass ratio is obtained, lanthanum nitrate is added in dehydrated alcohol, is stirred
It mixes and mixes to obtain solution B, in mass ratio 1:1, solution A and solution B are stirred and mixed liquor, with glacial acetic acid and mass fraction
10% ammonium hydroxide adjusts pH of mixed to 2.0, is stirred and is placed in three-necked flask, then obtains after insulation reaction 3h at 75 DEG C
Reaction solution, then 1:8 in mass ratio, ethyl orthosilicate is added dropwise in reaction solution, and control drop rate is 0.1mL/min, wait drip
It after the completion of adding, is stirred and is placed in heat preservation and dryness 2h at 130 DEG C, obtain desiccant gel liquid and be placed in tube-type atmosphere furnace, by 6
DEG C/min heating is heated to 550 DEG C, after insulation reaction 1h, then by 8 DEG C/min 1000 DEG C, heat preservation calcining 3h are warming up to, standing is cold
But to room temperature, ground 500 mesh obtains blapharoplast；Score meter by weight weighs 45 parts of ageing modification sol liquid, 45 respectively
Part blapharoplast and 3 parts of 5% poly-vinyl alcohol solutions of mass fraction are placed in mortar, and milled processed simultaneously collects dispersion slurries, will be divided
Scattered slurries are placed in mold, then after compression moulding under 10MPa, then the heat preservation sintering 3h at 1500 DEG C, standing are cooled to room temperature,
The high-densit apatite-type solid electrolyte material can be prepared into.
Embodiment 2
According to parts by weight, 47 parts of dehydrated alcohols, 4 parts of deionized waters and 7 parts of ethyl orthosilicates are weighed respectively be placed in triangle
In flask, be stirred and be placed in ultrasonic disperse 12min under 250W, collect dispersion liquid and with 0.5mol/L salt acid for adjusting pH extremely
3.0, it is stirred and is placed in insulation reaction 4h at 77 DEG C, obtain matrix sol solutions；Score meter by weight again weighs 47 parts respectively and goes
Ionized water, 47 parts of dehydrated alcohols, 27 parts of zirconium oxychlorides and 12 parts of hydrogen peroxide are placed in three-necked flask, are stirred and nothing is added dropwise
The 0.8mol/L ammonium hydroxide of water-ethanol quality 50% is stirred to obtain complex sol liquid into three-necked flask；1:1 in mass ratio, will
Complex sol liquid and matrix sol solutions are stirred juxtaposition and are aged 7h at room temperature, must be aged modification sol liquid；In mass ratio 1:
15, gadolinium oxide is added in 45% nitric acid solution of mass fraction, is stirred and collects to obtain lysate, by volume 1:15,
Lysate is mixed with absolute ethyl alcohol and stirring, solution A, then 1:10 in mass ratio is obtained, lanthanum nitrate is added in dehydrated alcohol, is stirred
It mixes and mixes to obtain solution B, in mass ratio 1:1, solution A and solution B are stirred and mixed liquor, with glacial acetic acid and mass fraction
10% ammonium hydroxide adjusts pH of mixed to 2.0, is stirred and is placed in three-necked flask, then obtains after insulation reaction 4h at 77 DEG C
Reaction solution, then 1:8 in mass ratio, ethyl orthosilicate is added dropwise in reaction solution, and control drop rate is 0.1mL/min, wait drip
It after the completion of adding, is stirred and is placed in heat preservation and dryness 2h at 140 DEG C, obtain desiccant gel liquid and be placed in tube-type atmosphere furnace, by 6
DEG C/min heating is heated to 600 DEG C, after insulation reaction 2h, then by 8 DEG C/min 1100 DEG C, heat preservation calcining 4h are warming up to, standing is cold
But to room temperature, ground 500 mesh obtains blapharoplast；Score meter by weight weighs 47 parts of ageing modification sol liquid, 47 respectively
Part blapharoplast and 4 parts of 5% poly-vinyl alcohol solutions of mass fraction are placed in mortar, and milled processed simultaneously collects dispersion slurries, will be divided
Scattered slurries are placed in mold, then after compression moulding under 15MPa, then the heat preservation sintering 4h at 1550 DEG C, standing are cooled to room temperature,
The high-densit apatite-type solid electrolyte material can be prepared into.
Embodiment 3
According to parts by weight, 50 parts of dehydrated alcohols, 5 parts of deionized waters and 8 parts of ethyl orthosilicates are weighed respectively be placed in triangle
In flask, be stirred and be placed in ultrasonic disperse 15min under 300W, collect dispersion liquid and with 0.5mol/L salt acid for adjusting pH extremely
3.0, it is stirred and is placed in insulation reaction 5h at 85 DEG C, obtain matrix sol solutions；Score meter by weight again weighs 50 parts respectively and goes
Ionized water, 50 parts of dehydrated alcohols, 30 parts of zirconium oxychlorides and 15 parts of hydrogen peroxide are placed in three-necked flask, are stirred and nothing is added dropwise
The 0.8mol/L ammonium hydroxide of water-ethanol quality 50% is stirred to obtain complex sol liquid into three-necked flask；1:1 in mass ratio, will
Complex sol liquid and matrix sol solutions are stirred juxtaposition and are aged 8h at room temperature, must be aged modification sol liquid；In mass ratio 1:
15, gadolinium oxide is added in 45% nitric acid solution of mass fraction, is stirred and collects to obtain lysate, by volume 1:15,
Lysate is mixed with absolute ethyl alcohol and stirring, solution A, then 1:10 in mass ratio is obtained, lanthanum nitrate is added in dehydrated alcohol, is stirred
It mixes and mixes to obtain solution B, in mass ratio 1:1, solution A and solution B are stirred and mixed liquor, with glacial acetic acid and mass fraction
10% ammonium hydroxide adjusts pH of mixed to 2.0, is stirred and is placed in three-necked flask, then obtains after insulation reaction 5h at 85 DEG C
Reaction solution, then 1:8 in mass ratio, ethyl orthosilicate is added dropwise in reaction solution, and control drop rate is 0.1mL/min, wait drip
It after the completion of adding, is stirred and is placed in heat preservation and dryness 2h at 150 DEG C, obtain desiccant gel liquid and be placed in tube-type atmosphere furnace, by 6
DEG C/min heating is heated to 650 DEG C, after insulation reaction 2h, then by 8 DEG C/min 1200 DEG C, heat preservation calcining 5h are warming up to, standing is cold
But to room temperature, ground 500 mesh obtains blapharoplast；Score meter by weight weighs 50 parts of ageing modification sol liquid, 50 respectively
Part blapharoplast and 5 parts of 5% poly-vinyl alcohol solutions of mass fraction are placed in mortar, and milled processed simultaneously collects dispersion slurries, will be divided
Scattered slurries are placed in mold, then after compression moulding under 20MPa, then the heat preservation sintering 5h at 1600 DEG C, standing are cooled to room temperature,
The high-densit apatite-type solid electrolyte material can be prepared into.
By embodiment 1, embodiment 2 and the embodiment 3 of technical solution of the present invention preparation and it is not added with ageing modification sol liquid
The electrolyte of preparation sintering preparation carries out performance detection and control, and specific testing result is as shown in following table table 1:
The 1 performance table of comparisons of table
As seen from the above table, solid electrolyte prepared by the present invention has excellent performance and compact texture.
Claims (9)
1. a kind of preparation method of high-densit apatite-type solid electrolyte material, it is characterised in that specific preparation step are as follows:
(1) according to parts by weight, 45~50 parts of dehydrated alcohols, 3~5 parts of deionized waters and 6~8 parts of ethyl orthosilicates are weighed respectively
It is placed in conical flask, is stirred and ultrasonic disperse, collection dispersion liquid simultaneously adjust pH to 3.0, be stirred simultaneously insulation reaction,
Obtain matrix sol solutions；Score meter by weight again weighs 45~50 parts of deionized waters, 45~50 parts of dehydrated alcohols, 25~30 respectively
Part zirconium oxychloride and 10~15 parts of hydrogen peroxide are placed in three-necked flask, are stirred and ammonium hydroxide is added dropwise into three-necked flask, stir
It mixes and mixes to obtain complex sol liquid, in mass ratio 1:1, it is old at room temperature that complex sol liquid with matrix sol solutions is stirred juxtaposition
Change 6~8h, modification sol liquid must be aged；
(2) 1:15 in mass ratio, gadolinium oxide is added in nitric acid solution, is stirred and is collected to obtain lysate, by volume
1:15 mixes lysate with absolute ethyl alcohol and stirring, obtains solution A, then 1:10 in mass ratio, lanthanum nitrate is added to dehydrated alcohol
In, be stirred to obtain solution B, in mass ratio 1:1, solution A and solution B be stirred and mixed liquor, adjust pH of mixed to
2.0, it is stirred and is placed in three-necked flask, after insulation reaction, obtain reaction solution；
(3) 1:8 in mass ratio, ethyl orthosilicate is added dropwise in reaction solution, after being added dropwise to complete, is stirred simultaneously heat preservation and dryness
It obtains desiccant gel liquid to be placed in tube-type atmosphere furnace, heating heating and thermal insulation processing, standing is cooled to room temperature, is ground up, sieved, and obtains base
Body particle；
(4) score meter by weight weighs 45~50 parts of ageing modification sol liquid respectively, 45~50 parts of blapharoplasts and 3~5 parts gather
Glycohol solution is placed in mortar, and milled processed simultaneously collects dispersion slurries, and dispersion slurries are placed in mold, after compression moulding,
Heat preservation sintering, standing are cooled to room temperature, and can be prepared into the high-densit apatite-type solid electrolyte material.
2. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the ammonia concn is 0.8mol/L.
3. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the adjusting pH of mixed to 2.0 is to adjust pH of mixed to 2.0 with glacial acetic acid and 10% ammonium hydroxide of mass fraction.
4. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the ethyl orthosilicate drop rate is 0.1mL/min.
5. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the described heating heating and thermal insulation processing to be heated to 550~650 DEG C by 6 DEG C/min heating, after 1~2h of insulation reaction, then press
8 DEG C/min is warming up to 1000~1200 DEG C, 3~5h of heat preservation calcining.
6. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the blapharoplast partial size is 500 mesh.
7. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the compression moulding pressure is 10~20MPa.
8. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the heat preservation sintering is 3~5h of heat preservation sintering at 1500~1600 DEG C.
9. a kind of preparation method of high-densit apatite-type solid electrolyte material according to claim 1, feature exist
In: the poly-vinyl alcohol solution mass fraction is 5%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410087A (en) * | 2020-11-18 | 2021-02-26 | 江苏沃特优新能源科技有限公司 | Catalyst gasification device and energy-saving integrated combustion-supporting equipment with same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410087A (en) * | 2020-11-18 | 2021-02-26 | 江苏沃特优新能源科技有限公司 | Catalyst gasification device and energy-saving integrated combustion-supporting equipment with same |
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Application publication date: 20190830 |