CN110176616A - A kind of SDC-LSO composite electrolyte and preparation method thereof - Google Patents

A kind of SDC-LSO composite electrolyte and preparation method thereof Download PDF

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CN110176616A
CN110176616A CN201910449294.9A CN201910449294A CN110176616A CN 110176616 A CN110176616 A CN 110176616A CN 201910449294 A CN201910449294 A CN 201910449294A CN 110176616 A CN110176616 A CN 110176616A
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sdc
lso
composite electrolyte
nitrate
preparation
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杨晓伟
蔡铜祥
黄兵
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Yancheng City New Forms Of Energy Chemical Energy Storage And Electrical Source Of Power Research Center
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Yancheng City New Forms Of Energy Chemical Energy Storage And Electrical Source Of Power Research Center
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1069Polymeric electrolyte materials characterised by the manufacturing processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Life Sciences & Earth Sciences (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention belongs to solid electrolyte fields, more particularly to a kind of SDC-LSO composite electrolyte and preparation method thereof, with lanthanum salt, tetraethyl orthosilicate, acetic acid and 1,4- butanediol is that Materials Solvents thermal method prepares apatite-type LSO nano-powder, LSO nano-powder is mixed into dispersion with SDC nano-powder, degreasing is heated, and heats up and calcines certain time, obtains SDC-LSO composite electrolyte.Nano combined electrolyte powder of the invention has very high sintering activity, and sintering temperature is lower, and conductivity is higher, and preparation method is simple, easy industrialized production.

Description

A kind of SDC-LSO composite electrolyte and preparation method thereof
Technical field
The invention belongs to solid electrolyte fields, and in particular to a kind of SDC-LSO composite electrolyte and preparation method thereof.
Background technique
Solid oxide fuel cell (Solid Oxide Fuel Cells, SOFCs) is a kind of novel energy conversion Device, it has many advantages, such as that energy conversion efficiency is high, environmental pollution is small, fuel tolerance is strong, and traditional SOFCs is because in high temperature It works under (~1000 DEG C) and bad interfacial reaction between electrolyte/electrode, electrode/bipolar plates, electrode activity sintering is easily caused to be moved back Change, interfacial electrochemistry reduced performance and the series of technical such as encapsulation difficulty is big and so that its commercialization is had difficulty in taking a step.SOFCs's Middle low temperature has become the inexorable trend of its business development.Wherein, the development of NEW TYPE OF COMPOSITE electrolyte is realized in SOFCs One of key technology of low temperature.
CeO is concentrated mainly on about SOFCs combined electrolysis Quality Research in document at present2Based composite electrolyte, however, CeO2There is also obvious disadvantages for base electrolyte: CeO2Operating temperature range is narrow, unstable under low oxygen partial pressure and reducing atmosphere, Ce4+Easily it is reduced into Ce3+, there is electronic conductance, make internal short-circuit of battery, reduce SOFCs efficiency, Ce4+It is reduced into Ce3+When CeO2Lattice dilatation, it is easy to crack, it is difficult to be sintered.Ions dosage usually contributes maximum conductivity when being 20mol.%, 10-3~ 10-2S/cm, the requirement with high performance fuel cell electrolytic conductivity: 10-1S/cm is also differed farther out.
Summary of the invention
Technical problem solved by the invention is to prepare a kind of NEW TYPE OF COMPOSITE electrolyte and preparation method thereof.
SDC is Ce in the present invention0.8Sm0.2O1.9, LSO La9.33Si6O26
The present invention is realized by the following scheme: a kind of preparation method of SDC-LSO composite electrolyte, which is characterized in that with Lanthanum salt, tetraethyl orthosilicate, acetic acid and 1,4-butanediol are that Materials Solvents thermal method prepares apatite-type LSO nano-powder, will LSO nano-powder mixes dispersion with SDC nano-powder, heats degreasing, and heat up and calcine certain time, and it is compound to obtain SDC-LSO Electrolyte.
Further, the SDC nano-powder is original with cerous nitrate, samaric nitrate, citric acid, ethylene glycol and ammonium nitrate Material, prepares SDC by sol-gel auto-combustion.
Preferably, the lanthanum salt is lanthanum nitrate, lanthanum nitrate is dissolved in the mixed solution of ethyl alcohol and water, and positive silicic acid is added Tetra-ethyl ester, acetic acid and 1,4-butanediol, stirring, 80 DEG C of 2~6h of water-bath form gel a;1,4- butanediol is dispersed by gel a In water mixed solution, stirring, and KOH is added, solvent thermal reaction, post-processing obtains LSO nano-powder.
Further, the temperature of the solvent thermal reaction is 160 DEG C~280 DEG C, and the solvent thermal reaction time is 12~36h.
Preferably, the volume ratio of the ethyl alcohol and water is 3:1~1:3, the volume ratio of the 1,4-butanediol and water is The mole ratio of 1:1~5:1, KOH and lanthanum nitrate is (0.2~1.6): 1.
Preferably, the molar ratio of the cerous nitrate and samaric nitrate is 1:4, and the nitric acid and samaric nitrate is soluble in water, The mixed nitrate solution of 2mol/L-5mol/L is formed, and sequentially adds citric acid and ethylene glycol, the ethylene glycol and citric acid Molar ratio be 1:1~3:1, and ammonium nitrate is added, stirs, and ammonium hydroxide is added and adjusts pH value to 6~9.5, stirring is anti-at room temperature It answers, 80 DEG C of stirred in water bath 2~6h evaporation waters obtain gel b, and it is dry, and cause certainly in 300~450 DEG C of Muffle furnace Combustion, obtains SDC.
It is further preferable that the nitrate mixed solution and citric acid are according to metal in citric acid and nitrate mixed solution Molar ratio=1:1~3:1 of ion.
Preferably, the SDC nano-powder is mixed with LSO nano-powder according to volume ratio 9:1~2:8, and is added 0.1% ~3% PVA dispersion, is granulated, and carry out degreasing in 600 DEG C of heat preservations under 100~300MPa pressure, then heats up, and respectively 1~8h is calcined under the conditions of 1200~1600 DEG C of temperature.
The invention also includes another technical solution, a kind of SDC-LSO composite electrolyte, prepared by above-mentioned preparation method and ?.
Preferably, the SDC content accounts for 80%, conductivity 0.0327S/ in the SDC-LSO composite electrolyte cm。
The utility model has the advantages that
Nano combined electrolyte powder of the invention has very high sintering activity, than the powder of conventional solid reaction method preparation The sintering temperature of body reduces 300 DEG C, and when the volume content of SDC is up to 80%, conductivity 0.0327S/cm is alreadyd exceed pure The conductivity of SDC, and preparation method is simple, easy industrialized production.
Detailed description of the invention
Fig. 1 is the TEM figure of the LSO nano-powder of the embodiment of the present invention 1;
Fig. 2 is the FESEM figure of the SDC-LSO composite electrolyte of the embodiment of the present invention 1;
Fig. 3 is the FESEM figure of the SDC-LSO composite electrolyte of the embodiment of the present invention 2;
Fig. 4 is impedance spectra of the SDC-LSO composite electrolyte of the embodiment of the present invention 2 at 500 DEG C;
Fig. 5 is impedance spectra of the SDC-LSO composite electrolyte of the embodiment of the present invention 2 at 600 DEG C;
Fig. 6 is impedance spectra of the SDC-LSO composite electrolyte of the embodiment of the present invention 2 at 700 DEG C;
Fig. 7 is that the conductivity of the embodiment of the present invention 7 varies with temperature curve graph.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but does not limit the present invention.
Embodiment 1
A kind of preparation method of SDC-LSO composite electrolyte of the present embodiment, specifically includes that
A, the lanthanum nitrate of 0.5mol is dissolved in the mixed solution of 40ml second alcohol and water, wherein the volume ratio of ethyl alcohol and water is 1:1 forms clear transparent solutions through magnetic agitation at room temperature, then measures ratio for tetraethyl orthosilicate and second according to LSO Acid is added into above-mentioned clear solution, and the molar ratio of the specific tetraethyl orthosilicate and the lanthanum nitrate is 9.33:6, this reality The tetraethyl orthosilicate that 0.7775mol is added in example is applied, forms clear viscous colloidal sol through room temperature magnetic agitation, colloidal sol is through 80 DEG C of water It is transformed into gel after bath processing 3h.By wet gel ultrasonic disperse in 50ml1,4- butanediol and water mixed solution (wherein 1,4- The volume ratio of butanediol and water is 1:1), the KOH of 0.5mol is added under stirring conditions, is then transferred to polytetrafluoroethylene (PTFE) height Press reaction kettle.Then it is sealed against and is put into the oil bath that set temperature is 200 DEG C, heat preservation is for 24 hours.After reaction, to product It after natural cooling, is respectively washed three times with deionized water and dehydrated alcohol, obtains LSO nano-powder in 70 DEG C of drying 3h thereafter. The TEM for the LSO nano-powder that Fig. 1 gives schemes, it can be seen that LSO nano-powder has subsphaeroidal pattern, and average-size is 40nm。
B, according to molecular formula Ce0.8Sm0.2O1.9, stoichiometrically (nSm/nCe=1:4) by the cerous nitrate of 0.1mol and Samaric nitrate is dissolved in the mixed solution that nitrate is configured in 30ml deionized water.Citric acid is heated into mixed nitrate solution, Wherein the molar ratio of citric acid and metal cation in nitrate solution is 1:1, and is added auxiliary with citric acid equal molar amount Then oxygenate content in 0.5mol ammonium nitrate adjustment system is added in complexing-aid agent ethylene glycol.Magnetic agitation is molten under room temperature Xie Hou, the ammonia spirit that mass concentration 28% is added dropwise adjust the pH value of solution to 7.This solution system is persistently stirred in room temperature, with The abundant complexing for guaranteeing metal ion and citrate, then obtains mixed solution in 80 DEG C of stirred in water bath 2h evaporation waters Gel, the drying in 80 DEG C of convection ovens of gained gel for 24 hours, exclude the moisture in gel.Gel after drying is placed in 350 DEG C In Muffle furnace, 3 minutes inner gels are ignited and spontaneous combustion, finally obtain the target product SDC nano-powder of puffy.
C, SDC is mixed with LSO nano-powder with volume ratio 5:1,50ml ethyl alcohol, sufficiently ultrasound is added in mixed powder Dispersion, is uniformly mixed SDC nano particle with LSO nano particle, and avoiding respectively reuniting influences later period sintering, is added after dispersion 0.5% PVA is granulated, after being fully ground in the agate mortar, in 100MPa forming under the pressure slabbing biscuit, by biscuit It is put into box high temperature resistance furnace and is slowly heated to 600 DEG C of heat preservations and carry out degreasing 2h, then heat under the conditions of 1200 DEG C of temperature and forge It burns 4h and obtains SDC-LSO composite electrolyte.
Fig. 2 is the FESEM figure of the SDC-LSO composite electrolyte of the present embodiment, it can be seen from the figure that burning at 1200 DEG C In the sample of knot, particle is largely sintered together, and sintered density is higher, but there are a small amount of stomata, average crystalline substances for intercrystalline Grain size about 300nm.
Embodiment 2
A kind of preparation method of SDC-LSO composite electrolyte of the present embodiment, specifically includes that
A, the lanthanum nitrate of 0.5mol is dissolved in the mixed solution of 40ml second alcohol and water, wherein the volume ratio of ethyl alcohol and water is 1:3 forms clear transparent solutions through magnetic agitation at room temperature, then measures ratio for tetraethyl orthosilicate and second according to LSO Acid is added into above-mentioned clear solution, forms clear viscous colloidal sol through room temperature magnetic agitation, colloidal sol is after 80 DEG C of water bath processing 4h It is transformed into gel.By wet gel ultrasonic disperse in 50ml1,4- butanediol and water mixed solution (wherein 1,4- butanediol and water Volume ratio be 3:1), under stirring conditions be added 0.3mol KOH, be then transferred to polytetrafluoroethylene (PTFE) autoclave. Then it is sealed against and is put into the oil bath that set temperature is 240 DEG C, keep the temperature 20h.After reaction, to product natural cooling Afterwards, it is respectively washed three times with deionized water and dehydrated alcohol, obtains LSO nano-powder in 70 DEG C of drying 4h thereafter.
B, according to molecular formula Ce0.8Sm0.2O1.9, stoichiometrically (nSm/nCe=1:4) by the cerous nitrate of 0.1mol and Samaric nitrate is dissolved in the mixed solution that nitrate is configured in 30ml deionized water.Citric acid is added into mixed nitrate solution, Wherein, the molar ratio of citric acid and the metal cation in nitrate solution is 3:1, and is added and 2 times of moles of citric acid Then oxygenate content in 1mol ammonium nitrate adjustment system is added in auxiliary complex-former ethylene glycol.Magnetic agitation is molten under room temperature Xie Hou, the ammonia spirit that mass concentration 28% is added dropwise adjust the pH value of solution to 9.This solution system is persistently stirred in room temperature, with The abundant complexing for guaranteeing metal ion and citrate, then obtains mixed solution in 80 DEG C of stirred in water bath 4h evaporation waters Gel, the drying in 80 DEG C of convection ovens of gained gel for 24 hours, exclude the moisture in gel.Gel after drying is placed in 400 DEG C In Muffle furnace, 3 minutes inner gels are ignited and spontaneous combustion, finally obtain the target product SDC nano-powder of puffy.
C, SDC is mixed respectively with volume ratio 4:1 with LSO nano-powder, 50ml ethyl alcohol is added in mixed powder, sufficiently Ultrasonic disperse is uniformly mixed SDC nano particle with LSO nano particle, and avoiding respectively reuniting influences later period sintering, adds after dispersion Enter 1% PVA to be granulated, after being fully ground in the agate mortar, in 300MPa forming under the pressure slabbing biscuit, by biscuit It is put into box high temperature resistance furnace and is slowly heated to 600 DEG C of heat preservations and carry out degreasing 2h, then heat under the conditions of 1400 DEG C of temperature and forge It burns 6h and obtains SDC-LSO composite electrolyte.Product labelling is SL8020.
Fig. 3 is that the FESEM of SDC-LSO composite electrolyte schemes, it can be seen from the figure that the sample being sintered at 1400 DEG C In, stomata significantly reduces, and consistency is up to 90% or more, only individual small holes, and crystal grain is also slightly grown up, and average crystal grain is big Small about 400nm, grain size are also more close.The powder that this result is prepared with conventional solid-state method is obtained in 1700 DEG C of sintering Sample apparent density it is close.Therefore, the sintering temperature of the superfine powder of this method is than powder prepared by conventional solid reaction method Sintering temperature reduce 300 DEG C, show the composite nano-powder prepared have very high sintering activity.
Fig. 4-Fig. 6 be in this implementation the SDC-LSO composite electrolyte prepared of example in the differences such as 500 DEG C, 600 DEG C, 700 DEG C At a temperature of impedance spectra.Spectrogram is formed by respectively corresponding several circular arcs that different electrochemistry forms, and wherein square dot is several Strong point, curve be through Equivalent Circuit Fitting as a result, it can be seen from the figure that with test temperature raising, impedance spectrum gradually to Low-resistance region is mobile, illustrates to increase with temperature, the resistance of electrolyte is gradually reduced, and conductance gradually increases.500 DEG C of tests obtain Ac impedance spectroscopy include two sections of circular arcs, the substance for respectively corresponding transition process on ion crystal boundary and occurring on the electrode is handed over / charge transfer process is changed, as test temperature increases, the transfer ability of ion becomes strong, and polarization becomes faster, and corresponds to grain boundaries ion The circular arc of transition process starts to degenerate, and becomes imperfect, and the enhancing of composite electrolyte effective conductivity is from composite electrolyte The appearance of two-phase interface area Proton conducting.
Embodiment 3
A kind of preparation method of SDC-LSO composite electrolyte of the present embodiment, specifically includes that
A, the lanthanum nitrate of 0.5mol is dissolved in the mixed solution of 40ml second alcohol and water, wherein the volume ratio of ethyl alcohol and water is 3:1 forms clear transparent solutions through magnetic agitation at room temperature, then measures ratio for tetraethyl orthosilicate and second according to LSO Acid is added into above-mentioned clear solution, forms clear viscous colloidal sol through room temperature magnetic agitation, colloidal sol is after 80 DEG C of water bath processing 2h It is transformed into gel.By wet gel ultrasonic disperse in 50ml1,4- butanediol and water mixed solution (wherein 1,4- butanediol and water Volume ratio be 4:1), under stirring conditions be added 0.2mol KOH, be then transferred to polytetrafluoroethylene (PTFE) autoclave. Then it is sealed against and is put into the oil bath that set temperature is 280 DEG C, keep the temperature 12h.After reaction, to product natural cooling Afterwards, it is respectively washed three times with deionized water and dehydrated alcohol, obtains LSO nano-powder in 70 DEG C of drying 5h thereafter.
B, according to molecular formula Ce0.8Sm0.2O1.9, stoichiometrically (nSm/nCe=1:4) by the cerous nitrate of 0.1mol and Samaric nitrate is dissolved in the mixed solution that nitrate is configured in 50ml deionized water.Citric acid is added into mixed nitrate solution, The molar ratio of metal cation is 2:1 in citric acid and nitrate solution, and the auxiliary network with citric acid three times mole is added Then oxygenate content in 1.5mol ammonium nitrate adjustment system is added in mixture ethylene glycol.Under room temperature after magnetic agitation dissolution, The ammonia spirit that mass concentration 28% is added dropwise adjusts the pH value of solution to 6.This solution system is persistently stirred in room temperature, with guarantee fund Belong to the abundant complexing of ion and citrate, mixed solution then obtained into gel in 80 DEG C of stirred in water bath 4h evaporation waters, The drying in 80 DEG C of convection ovens of gained gel for 24 hours, excludes the moisture in gel.Gel after drying is placed in 300 DEG C of Muffle In furnace, 5 minutes inner gels are ignited and spontaneous combustion, finally obtain the target product SDC nano-powder of puffy.
C, SDC is mixed respectively with volume ratio 3:7 with LSO nano-powder, 60ml ethyl alcohol is added in mixed powder, sufficiently Ultrasonic disperse is uniformly mixed SDC nano particle with LSO nano particle, and avoiding respectively reuniting influences later period sintering, adds after dispersion Enter 2% PVA to be granulated, after being fully ground in the agate mortar, in 200MPa forming under the pressure slabbing biscuit, by biscuit It is put into box high temperature resistance furnace and is slowly heated to 600 DEG C of heat preservations and carry out degreasing 2h, then heat under the conditions of 1500 DEG C of temperature and forge It burns 6h and obtains SDC-LSO composite electrolyte.
Embodiment 4
A kind of preparation method of SDC-LSO composite electrolyte of the present embodiment, specifically includes that
A, the lanthanum nitrate of 0.5mol is dissolved in the mixed solution of 40ml second alcohol and water, wherein the volume ratio of ethyl alcohol and water is 2:1 forms clear transparent solutions through magnetic agitation at room temperature, then by 0.3003mol tetraethyl orthosilicate, acetic acid be added to In above-mentioned clear solution, clear viscous colloidal sol is formed through room temperature magnetic agitation, colloidal sol is transformed into solidifying after 80 DEG C of water bath processing 5h Glue.By wet gel ultrasonic disperse in 50ml 1,4- butanediol and water mixed solution (the wherein volume ratio of 1,4- butanediol and water For 5:1), the KOH of 0.8mol is added under stirring conditions, is then transferred to polytetrafluoroethylene (PTFE) autoclave.Then by it It seals and is put into the oil bath that set temperature is 250 DEG C, keep the temperature 18h.After reaction, after product natural cooling, spend from Sub- water and dehydrated alcohol are respectively washed three times, obtain LSO nano-powder in 70 DEG C of drying 6h thereafter.
B, according to molecular formula Ce0.8Sm0.2O1.9, stoichiometrically (nSm/nCe=1:4) by the cerous nitrate of 0.1mol and Samaric nitrate is dissolved in the mixed solution that nitrate is configured in 80ml deionized water.Citric acid is added into mixed nitrate solution, The molar ratio of metal cation is 1.5:1 in citric acid and nitrate solution, and the auxiliary with citric acid three times mole is added Then oxygenate content in 1mol ammonium nitrate adjustment system is added in complexing agent ethylene glycol.Under room temperature after magnetic agitation dissolution, The ammonia spirit that mass concentration 28% is added dropwise adjusts the pH value of solution to 8.5.This solution system is persistently stirred in room temperature, to guarantee Then the abundant complexing of metal ion and citrate is coagulated mixed solution in 80 DEG C of stirred in water bath 6h evaporation waters Glue, the drying in 80 DEG C of convection ovens of gained gel for 24 hours, exclude the moisture in gel.Gel after drying is placed in 450 DEG C of horse Not in furnace, 3 minutes inner gels are ignited and spontaneous combustion, finally obtain the target product SDC nano-powder of puffy.
C, SDC is mixed respectively with volume ratio 2:8 with LSO nano-powder, 70ml ethyl alcohol is added in mixed powder, sufficiently Ultrasonic disperse is uniformly mixed SDC nano particle with LSO nano particle, and avoiding respectively reuniting influences later period sintering, adds after dispersion Enter 3% PVA to be granulated, after being fully ground in the agate mortar, in 150MPa forming under the pressure slabbing biscuit, by biscuit It is put into box high temperature resistance furnace and is slowly heated to 600 DEG C of heat preservations and carry out degreasing 2h, then heat under the conditions of 1600 DEG C of temperature and forge It burns 2h and obtains SDC-LSO composite electrolyte.
Embodiment 5
The difference is that, SDC is mixed respectively with volume ratio 1:1 with LSO nano-powder in step C with embodiment 2, Final SDC-LSO composite electrolyte product obtained, is labeled as SL5050;Remaining is same as Example 2.
Embodiment 6
The difference is that, SDC is mixed respectively with volume ratio 3:7 with LSO nano-powder in step C with embodiment 2, SDC-LSO composite electrolyte product obtained is labeled as SL3070;Remaining is same as Example 2.
Embodiment 7
The SDC that 2 step B of embodiment is prepared, the LSO that 2 step A of embodiment is prepared, embodiment 2 are prepared labeled It is real for the SDC-LSO composite electrolyte for being marked as SL5050 prepared by the SDC-LSO composite electrolyte of SL8020, embodiment 5 The SDC-LSO composite electrolyte for being marked as SL3070 for applying the preparation of example 6 carries out conductivity test, test knot at different temperatures Fruit is illustrated in figure 7 the SDC-LSO composite electrolyte that the SDC-LSO electrolyte sample through different volumes ratio is sintered through 1400 DEG C Conductivity varies with temperature curve graph, and the conductivity of pure LSO is minimum, the conductivity of SDC-LSO composite electrolyte with SDC content Increase and increase, when the volume content of SDC is up to 80%, conductivity 0.0327S/cm alreadys exceed the conductivity of pure SDC.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention Any modification and improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of SDC-LSO composite electrolyte, which is characterized in that with lanthanum salt, tetraethyl orthosilicate, acetic acid and 1, 4- butanediol is that Materials Solvents thermal method prepares apatite-type LSO nano-powder, and LSO nano-powder and SDC nano-powder are mixed Dispersion is closed, heats degreasing, and heat up and calcine certain time, obtains SDC-LSO composite electrolyte.
2. a kind of preparation method of SDC-LSO composite electrolyte according to claim 1, which is characterized in that the SDC receives Rice flour body is prepared using cerous nitrate, samaric nitrate, citric acid, ethylene glycol and ammonium nitrate as raw material by sol-gel auto-combustion SDC。
3. a kind of preparation method of SDC-LSO composite electrolyte according to claim 1, which is characterized in that the lanthanum salt For lanthanum nitrate, lanthanum nitrate is dissolved in the mixed solution of ethyl alcohol and water, and tetraethyl orthosilicate, acetic acid and 1,4-butanediol is added, Stirring, 80 DEG C of 2~6h of water-bath form gel a;It disperses gel a in 1,4-butanediol and water mixed solution, stirs, and add Enter KOH, solvent thermal reaction, post-processing obtains LSO nano-powder.
4. a kind of preparation method of SDC-LSO composite electrolyte according to claim 3, which is characterized in that the solvent The temperature of thermal response is 160 DEG C~280 DEG C, and the solvent thermal reaction time is 12~36h.
5. a kind of preparation method of SDC-LSO composite electrolyte according to claim 3, which is characterized in that the nitric acid The molar ratio of lanthanum and the tetraethyl orthosilicate is 9.33:6, and the volume ratio of the ethyl alcohol and water is 3:1~1:3, the Isosorbide-5-Nitrae- The volume ratio of butanediol and water is 1:1~5:1, and the mole ratio of KOH and lanthanum nitrate is (0.2~1.6): 1.
6. a kind of preparation method of SDC-LSO composite electrolyte according to claim 2, which is characterized in that the nitric acid The molar ratio of sub- cerium and samaric nitrate is 1:4, and the nitric acid and samaric nitrate is soluble in water, forms the mixing of 2mol/L-5mol/L Nitrate solution, and citric acid and ethylene glycol are sequentially added, the molar ratio of the ethylene glycol and citric acid is 1:1~3:1, and is added Enter ammonium nitrate, stir, and ammonium hydroxide is added and adjusts pH value to 6~9.5, is stirred to react at room temperature, 80 DEG C of 2~6h of stirred in water bath steam Shampoo separately wins to obtain gel b, dry, and causes spontaneous combustion in 300~450 DEG C of Muffle furnace, obtains SDC.
7. a kind of preparation method of SDC-LSO composite electrolyte according to claim 6, which is characterized in that the lemon The molar ratio of acid and the metal ion in nitrate mixed solution is 1:1~3:1.
8. a kind of preparation method of SDC-LSO composite electrolyte according to claim 1, which is characterized in that the SDC receives Rice flour body is mixed with LSO nano-powder according to volume ratio 9:1~2:8, and 0.1%~3% PVA dispersion is added, 100~ It is granulated under 300MPa pressure, and carries out degreasing in 600 DEG C of heat preservations, then heated up, and respectively in 1200~1600 DEG C of temperature conditions 1~8h of lower calcining.
9. a kind of SDC-LSO composite electrolyte, which is characterized in that it is prepared by claim 1-8 any one preparation method, SDC and LSO are compounded to form dense body in this composite electrolyte.
10. a kind of SDC-LSO composite electrolyte, which is characterized in that in the SDC-LSO composite electrolyte, the SDC content is accounted for 80%, the conductivity of the SDC-LSO composite electrolyte is 0.0327S/cm.
CN201910449294.9A 2019-05-28 2019-05-28 A kind of SDC-LSO composite electrolyte and preparation method thereof Pending CN110176616A (en)

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Application publication date: 20190827