CN108794001A - A kind of modified ZrO2The preparation method of base composite solid electrolyte ceramic material - Google Patents

A kind of modified ZrO2The preparation method of base composite solid electrolyte ceramic material Download PDF

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CN108794001A
CN108794001A CN201810997230.8A CN201810997230A CN108794001A CN 108794001 A CN108794001 A CN 108794001A CN 201810997230 A CN201810997230 A CN 201810997230A CN 108794001 A CN108794001 A CN 108794001A
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zro
solid electrolyte
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ceo
powder
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阳杰
董强
魏安乐
尹奇异
徐洁
孟俊杰
贺浪欣
余向阳
夏鹏鹏
陈志强
廖文浩
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Hefei University
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Abstract

A kind of modified ZrO2The preparation method of base composite solid electrolyte ceramic material, is related to solid electrolyte ceramic technical field of material.Zirconium nitrate, cerous nitrate, copper nitrate are weighed, is added in distilled water, citric acid is then added, is sufficiently stirred and makes it dissolve；Ethylene glycol is added into mixed liquor, ultrasound makes ethylene glycol be uniformly dispersed；Water bath with thermostatic control heating stirring stands until forming colloidal sol and forms gel after adjusting solution ph；It is calcined after gel is dried, superfine powder is ground to after calcining, obtain electrolyte powder material；PVA is added to be granulated, tabletted under pressure, temperature programming stove is sintered up to ZrO2Base composite solid electrolyte ceramic material.The present invention prepares solid electrolyte using ultrasonic wave assisting sol gel method, doping production cerium oxide and copper oxide in aoxidizing zirconium base, it is expected to improve the conductivity of oxidation zirconium base.

Description

A kind of modified ZrO2The preparation method of base composite solid electrolyte ceramic material
Technical field
The present invention relates to solid electrolyte ceramic technical field of material, are specifically related to a kind of modified ZrO2Base solid The preparation method of combined electrolysis ceramics.
Background technology
The essence of solid fuel cell (Solid Oxide Fuel Cell, SOFCs) is a kind of will to be difficult in fuel Chemical energy or the low-down chemical energy of service efficiency be converted into the electric energy that people can be easy to use.Solid fuel cell it is interior Portion is by many baby batteries by being formed by connecting.The primary structure of each baby battery is cathode, anode, click separator and Electrolyte and connector jointly constructs form.In solid oxide fuel cell, most important is exactly electrolyte, most of It is made of oxide ceramics, the general electrical property of these ceramics is more outstanding.In SOFCs, why electrolyte is extremely important, It is because it is to make that between electrode electronics can be conducted, so for the electrolyte of SOFCs as a kind of channel, connection electrode The requirement of ceramic making material is very strict.
The rough course of work of solid fuel cell is that fuel enters from anode first, reacts, discharge in anode Go out energy, be converted to electric current, electric energy is provided for extraneous electronic component, and bear E-communication in inside is exactly to be electrolysed Matter.Oxygen is entered by cathode, provides oxonium ion.In inside by electrolysis mass transter electronics, so for the electric conductivity of electrolyte It can require very high.
Monocline ZrO2Do not have an electric conductivity, and four directions ZrO2Conductivity is very low, so generally using cube ZrO of doping2 As electrolyte.Numerous studies show：By to ZrO2The alkaline earth oxide of the certain divalent of middle doping or trivalent is (such as CaO、MgO、Y2O3、Sc2O3、Yb2O3、CeO2) etc., cubic phase solid solution is formed, trivalent or bivalent rare earth ionic compartmentation Zr are made4+, It is all cubic phase from room temperature to high temperature to make it, increases Lacking oxygen, improves its oxygen-ion conduction performance.
For synthesis, zirconium oxide base electrolyte is expected to become most commercially valuable high-temperature oxide fuel cell.Generally ZrO2Based solid electrolyte material at a higher temperature (usual 1000 DEG C or so) operation, at 1000 DEG C, conductivity compared with Height, but also with some problems, such as the slow decomposition of material, the diffusion of phase border and the corrosion etc. of metal connecting material.In addition 800 DEG C or so, O2-The solid electrolyte material comparison of conductivity and other type is still relatively low.In order to improve the conductivity of the material, grind Study carefully personnel never to rest, they are in ZrO2Doping vario-property in terms of carried out numerous studies, and achieve many achievements.Research The result shows that the addition of some dopants can be larger raising oxidation zirconium base conductivity.
ZrO is prepared using traditional high temperature solid-state method2-CeO2- CuO composite materials, it usually needs carried out at 1500 DEG C or more Sintering, be easy to cause the volatilization of CuO components in raw material, leads to ZrO2Or the precipitation of other dephasigns, it is very difficult to obtain pure phase, organize branch Become not easy to control.The present invention is using ultrasonic wave assisting sol gel method for preparing Zr O2Base composite solid electrolyte ceramics material Material, sol-gel method is because easy to operate, uniform particle sizes of obtained powder and smaller, and performance is good, and experimentation is easy to operate and again Renaturation is good and is widely used.
Invention content
For the technical problems in the prior art, the present invention provides a kind of modified ZrO2Base composite solid electrolyte The preparation method of ceramic material.The modification ZrO of acquisition2Base composite solid electrolyte ceramic material has excellent electric conductivity.
To achieve the goals above, the technical solution adopted in the present invention is：A kind of modified ZrO2Base solid combined electrolysis The preparation method of ceramics, steps are as follows：
1., according to target sample (ZrO2)0.89(CeO2)x(CuO)0.11-xStoichiometric ratio, weigh zirconium nitrate, nitric acid Cerium, copper nitrate are added in 30ml distilled water, citric acid are then added, is sufficiently stirred and makes it dissolve；
2., ethylene glycol is added into mixed liquor, then solution is placed in supersonic wave cleaning machine ultrasonic, ethylene glycol is made to disperse Uniformly；
3., using weak aqua ammonia as pH adjusting agent volumetric soiutions, it is 7 to adjust solution ph；
4., in 80 DEG C of water bath with thermostatic control heating stirrings, until forming colloidal sol, gel is formed after standing a period of time；
5., gel is put into baking oven and is dried 24 hours, be put into after taking-up in Muffle furnace and calcined 10 hours at 700 DEG C, forged It is down to room temperature after burning, takes out crucible, powder is fully ground to superfine powder, (ZrO is obtained2)0.89(CeO2)x(CuO)0.11-x Electrolyte powder material；
6., PVA be added in the superfine powder of acquisition be granulated, must assure that during granulation be fully ground so that powder and PVA is uniformly mixed；Powder is tabletted under 14Mpa pressure；The temperature programming stove that the piece of compression moulding is put into is burnt Knot, 200 minutes are kept the temperature to get ZrO at 1350 DEG C2Base composite solid electrolyte ceramic material (ZrO2)0.89(CeO2)x (CuO)0.11-xPotsherd.
The optimal technical scheme of preparation method as the present invention, target sample (ZrO2)0.89(CeO2)x(CuO)0.11-xIn X=0~0.10.The molal weight of citric acid is 1.5 times of the amount of the metal ion contained in component, and the weight of ethylene glycol is lemon 1.2 times of lemon acid weight.
Compared with prior art, beneficial effects of the present invention are shown：
The present invention passes through to solid oxide fuel cell (ZrO2)0.89(CeO2)x(CuO)0.11-xTernary system (x=0, 0.02,0.04,0.06,0.08,0.10) six components are explored, and solid electricity is prepared using ultrasonic wave assisting sol gel method Xie Zhi, doping production cerium oxide and copper oxide in aoxidizing zirconium base, it is expected to improve the conductivity of oxidation zirconium base.Preparation method packet Superfine powder, then repressed molding is made after including the preparation of colloidal sol, drying, roasting, grinding, electricity is made in sample sintering after molding Solve matter potsherd.Pass through xerogel infrared, that thermogravimetric differential scanning calorimetry, XRD, scanning electron microscope, ac impedance measurement are to obtained by Powder and corresponding ZrO2-CeO2The performance of composite material is characterized.Experimental result shows the (ZrO prepared2)0.89 (CeO2)x(CuO)0.11-xThe conductivity of system is relatively low, but comparatively, it can be seen that with CeO2The increase of content, conductivity It increases：At 800 DEG C, 0.00375Scm when by x=0-1It is increased to 0.00665Scm when x=0.10-1。
Description of the drawings
Fig. 1 is the (ZrO obtained in embodiment 12)0.89(CeO2)x(CuO)0.11-xThe XRD diagram of electrolyte powder material.
Fig. 2 is the infrared light collection of illustrative plates of different doping ratio xerogel powders.
Fig. 3 is (ZrO2)0.89(CeO2)0.10(CuO)0.01The TG-DSC thermal analysis curves of xerogel.
Fig. 4 is (ZrO2)0.89(CeO2)0.1(CuO)0.01The impedance spectra that electrolyte sample obtains at different temperatures.
Fig. 5 is the conductivity map of different component electrolyte sample.
Fig. 6 is different component sample temperature and conductivity Arrhenius curve graph.
Fig. 7 is 1350 DEG C and is sintered obtained (ZrO2)0.89(CeO2)0.1(CuO)0.01The SEM of sample difference enlargement ratio schemes.
Specific implementation mode
With reference to embodiments with attached drawing to the modification ZrO of the present invention2The preparation of base composite solid electrolyte ceramic material Method, which is made, to be discussed further.
Embodiment 1
A kind of modified ZrO2The preparation method of base composite solid electrolyte ceramic material, steps are as follows：
1., according to target sample (ZrO2)0.89(CeO2)x(CuO)0.11-xStoichiometric ratio, weigh zirconium nitrate, nitric acid Cerium, copper nitrate are added in 30ml distilled water, citric acid are then added, is sufficiently stirred and makes it dissolve.Experiment is 6 groups total, x difference It is derived from 0,0.02,0.04,0.06,0.08,0.10.For each group of experiment, the molal weight of citric acid is to contain in component 1.5 times of the amount of metal ion.
2., ethylene glycol 1.2 times of citric acid weight (weight be) is added into mixed liquor, solution is then placed on ultrasonic wave It is ultrasonic in cleaning machine, so that ethylene glycol is uniformly dispersed.
3., using weak aqua ammonia as pH adjusting agent volumetric soiutions, it is 7 to adjust solution ph.
4., in 80 DEG C of water bath with thermostatic control heating stirrings, until forming colloidal sol, gel is formed after standing a period of time.
5., gel is put into baking oven and is dried 24 hours, be put into after taking-up in Muffle furnace and calcined 10 hours at 700 DEG C, forged It is down to room temperature after burning, takes out crucible, powder is fully ground to superfine powder, (ZrO is obtained2)0.89(CeO2)x(CuO)0.11-x Electrolyte powder material.
6., PVA be added in the superfine powder of acquisition be granulated, must assure that during granulation be fully ground so that powder and PVA is uniformly mixed；Powder is tabletted under 14Mpa pressure；The temperature programming stove that the piece of compression moulding is put into is burnt Knot, 200 minutes are kept the temperature to get ZrO at 1350 DEG C2Base composite solid electrolyte ceramic material (ZrO2)0.89(CeO2)x (CuO)0.11-xPotsherd.
Embodiment 2
(ZrO2)0.89(CeO2)x(CuO)0.11-xThe performance characterization of potsherd
1, X-ray diffraction analysis
Diffraction pattern is generally different caused by the different crystal of atomic arrangement, and diffraction geometry and intensity are to measure crystal knot Two aspects of the range of information such as structure, can be extrapolated the related lattice structure of crystal, size and shape of structure cell etc. by them Information.
According to diffraction conditions, bragg's formula is utilized：2dsin θ=n λ, then the specific wavelength X by measuring, can calculate Go out the lattice constant of sample.
Fig. 1 is the (ZrO obtained in embodiment 12)0.89(CeO2)x(CuO)0.11-xThe XRD diagram of electrolyte powder material.By Fig. 1 can clearly be seen that the indices of crystallographic plane corresponding to its three strongest peak are (011), (020) and (121).Remaining weaker diffraction maximum The corresponding indices of crystallographic plane (110), (111), (200), (002) etc..And work as CeO2Doping be 0mol%, 2mol%, When 4mol%, the component diffracting spectrum and ZrO2Monocline PDF#37-1484 is corresponded to preferably, and the crystalline phase of substance is largely single Monoclinic phase zirconium oxide, fraction are tetragonal zircite, this just illustrates CeO2Doping is 0 or seldom, raw when CuO dopings are larger At a small amount of stabilizing zirconia.The ZrO2Composite material is mainly monoclinic phase ZrO2.Work as CeO2Doping is 6mol% and 8mol% When, crystal structure is mainly tetragonal phase and cubic phase, along with CeO2The increase of incorporation, monoclinic phase fade away, when mixing Enter amount be 10mol% when, at this time diffracting spectrum it is corresponding with tetragonal PDF#50-1089 cards well, ZrO2-CeO2- CuO is multiple The phase structure of condensation material is mainly tetragonal phase, is secondly cubic phase, this illustrates Ce4+And Cu2+It is most of to enter ZrO2Crystal knot In structure, solid solution is formed, tetragonal crystal system can be stably kept at room temperature, this illustrates Cu2+Cooperate with Ce4+Play stable ZrO2 Effect.
Pure cubic phase is ionic conduction, and conductivity is very high, but has very poor mechanical strength, is carrying out high temperature burning Cracking is easy in knot；And pure tetragonal phase mechanical strength is very high, but conductivity is but very low.Thus, if electrolyte crystal structure Cubic phase and tetragonal phase can be possessed simultaneously, good electric conductivity and mechanical performance can just have both.
It is sintered obtained (ZrO for 700 DEG C using Jade softwares pair2)0.89(CeO2)0.1(CuO)0.01Powder is handled, and Utilize Debye Scherrer formula：
In formula, D：Grain size (nm)；K：Scherrer constant (0.89)；λ：The wavelength (λ=0.154056nm) of X-ray；θ： The angle of diffraction；β：The halfwidth of corresponding diffraction maximum.It is as shown in table 1 that its grain size data can be obtained：
The data of 1 main diffraction peak of table
2, consistency measures
The porosity is measured using Archimedes's drainage.Its calculation formula is as follows：
In formula：m0:Dry weight, m1:Suspending weight (is suspended on the quality claimed in water) after sample water suction saturation, m2:Weight in wet base (sample Quality after water suction saturation), p:The porosity.Result of calculation is as shown in table 2.
2 each doping ratio sample porosity summary sheet of table
By the data of porosity it is found that the relative density of sample is only partially larger than 95% after 1350 DEG C of sintering, this is caused The reason of kind phenomenon, may there is the following：Cause molten with the presence of error in pH adjustment processes are observed using pH test paper first Granular size prepared by sol-gel is inconsistent, and then influences sintered density, and secondly some components are ground in granulation process Mill is not enough, and is finally that position difference causes non-uniform temperature is caused to cause in high temperature furnace burner hearth residing for sample in sintering process Density is different.And for electrolyte, the consistency the high more is conducive to the raising of electrical property, this is because asymmetrical stomata The transporting mechanism of oxonium ion may be changed and reduce conductivity.
3, infrared test
Infrared intensity is existing qualitative and the time the Quantitative measurement of chemical substance or functional group, can also be from absorption Peak width and transition point know its stress, strain, crystallinity and inhomogeneities.
Fig. 2 is the infrared light collection of illustrative plates of different doping ratio xerogel powders.Work as x=0.00 in figure, 0.02,0.08,0.10 When, 3436cm-1、1618cm-1、1396cm-1、1093cm-1、920cm-1、860cm-1、685cm-1There is apparent feature to inhale at position Receive peak.Work as x=0.04, when 0.06, infrared test curve is smooth-out.In addition it is in 1400~2400cm in wavelength-1Between when There is wider phenomenon in curve, this may be due to the use of the improper problem of test machine.
On figure in absorption peak, in 3436cm-1The absorption peak at place is wider, it is known that herein to be shaken with the contraction of hydrogen bond association O-H It is dynamic.This absorption peak Producing reason, may there is the following aspects：First, sample itself also has a certain amount of crystallization water；Two It is that the water prepared when sample is tested in ambient enviroment enters in sample.Third, in should be the ethylene glycol of addition, there are hydroxyls. 1618cm-1With COO-Antisymmetric stretching vibration peak correspond to.NO- 3Antisymmetric stretching vibration peak then correspond to 1396cm-1Place, The presence of this characteristic peak has demonstrated NO3 -It is present in colloid, 1093cm-1It may be the stretching vibration peak due to C-O.920cm-1For the characteristic absorption peak of C-O-C, the presence at this feature peak illustrates to be formed during gel that there are esterifications.860cm-1、 685cm-1、534cm-1Absorption peak existing at position can be attributed to O-M, and (wherein M may be Ce4+、Cu2+、Zr4+) stretch and shake Dynamic characteristic peak, free COOH also do not show in figure, and it is complete to illustrate that the ion of doping and complexing agent combine.
4, heat analysis
Thermogravimetry (TG) is that determinand quality is at any time or a kind of detection technique of the variation of temperature under programed temperature.Difference Show that scanning calorimetry then studies the determinand relationship synthermal with heat flow difference in reference substance, it can be by any time neither endothermic nor exothermic Rate embody.
Fig. 3 is (ZrO2)0.89(CeO2)0.10(CuO)0.01The TG-DSC thermal analysis curves of xerogel, test condition are nitrogen Atmosphere, setting heating rate are 10 DEG C/min.Reaction process is divided into three phases as shown in Figure 3：DEG C it is first from 25 DEG C to 180 A zero-g period, weightlessness about 12%.The mainly moisture of xerogel presoma and partial organic substances are thought according to the experiment Caused by evaporation.180 DEG C to 500 DEG C are second zero-g periods, it can be seen that from fast to slow, sample loses the downward trend of TG curves Weigh about is 38%.The DSC curve of second stage T=250 DEG C, T=375 DEG C respectively occur an exothermic peak, this may be because Redox reaction heat release, which has occurred, in organic matter, nitrate or metal ion of the presoma in system under heating environment causes 's.Last phase III namely 480 DEG C of later samples are intended to constant weight, about 50%, it is known that last object mutually forms and becomes In stabilization.
5, electric performance test
What AC impedance spectroscopy measured is impedance and the relationship of perturbation frequency of battery.
Impedance analyzer used in laboratory mainly measures the relationship of impedance and frequency, utilizes Zsimpwin impedance analysis softwares The all-in resistance for analyzing sample, is calculated by formula, conductivity can be obtained.Calculation formula is：
In formula, σ：Conductivity；L：Thickness of sample；S：Sample in cross section area.
Conductivity and temperature meet Arrhenius theory, meet following formula：
In formula, A:Characteristic constant；T:Absolute temperature；Ea:Activation energy；R:Gas constant.
5.1, AC impedance spectroscopy
Fig. 4 is (ZrO2)0.89(CeO2)0.1(CuO)0.01The impedance spectra that electrolyte sample obtains at different temperatures is surveyed Examination is in air atmosphere.Shown in figure 4 do not have at a temperature of impedance spectra, as seen from the figure, 500 DEG C and 600 DEG C of low temperature Impedance spectra contain the circular arcs of 3 different frequencies, correspond to grain resistance and grain boundary resistance and electrode-interface resistance respectively. The core of EIS is to distinguish the process of friction speed in electrochemical reaction process by the variation of frequency, high-frequency region Related with the crystal boundary of electrolyte, resistance may be since the dissociation impedance of oxonium ion and the electric charge transfer of interface are drawn under intermediate frequency It rises.It is and i.e. electrochemical reaction rates are most slow at low frequency, mainly due to diffusion process.In addition, with the raising of temperature To 700 DEG C~800 DEG C, circular arc reduces and polarization resistance disappears, and is only left grain boundary resistance within this range.
5.2, the conductivity under different temperatures
The all-in resistance (all-in resistance=grain resistance+grain boundary resistance) of electrolyte can be measured by electrochemical analysis instrument, The temperature range of measurement is 400~800 DEG C and can be obtained by Zsimpwin software analysis datas as shown in table 3：
3 (ZrO of table2)0.89(CeO2)0.1(CuO)0.01Electrical performance data analysis
The conductivity that can calculate other components according to upper table is summarized and is mapped by Origin with the raised data of temperature It can be obtained shown in Fig. 5, it is in increasing trend that the conductivity of whole system is increased with temperature, by impedance spectra it is found that with temperature liter Height, crystal grain and grain boundary resistance constantly reduce, and oxonium ion rate travel is accelerated, thus conductivity is ever-increasing.Work as x=0.10 When, the conductivity highest of 800 DEG C of zirconium oxide cerium oxide composite sample, about 0.0067Scm-1, as a complete unit, with Ce4+Doping increase, the conductivity of the material has raising slightly.
The relationship of conductivity and temperature meets Arrhenius curve, and expression formula is as follows：
In formula, σ0：Pre-exponential factor, K：Boltzmann constant, Ea：Activation energy.
Fig. 6 is different component sample temperature and conductivity Arrhenius curve graph.As shown in fig. 6, slope shows in figure With the raising of temperature, curve is almost linear to increase and not to have apparent turning point, and the raising of conductivity is due to Cu2+Or Ce4+Replace Zr4+It generates charge compensation and forms Lacking oxygen in the unit cell, increase the channel of oxonium ion diffusion.In addition, all Doping ratio in curve be all closer to, illustrate that influence of the doping ratio for conductive mechanism be not notable, wherein adulterating The corresponding highest conductivity 0.0067Scm of 800 DEG C of sample of ratio x=0.10-1, minimum activation energy is 1.24eV, tool Volume data is as shown in table 4：
4 (ZrO of table2)0.89(CeO2)x(CuO)0.11-xIn each doping ratio basic parameter
6, scanning electron microscope
Equipment transmitting electronics can interact with substance, after interaction generation secondary electron, auger electrons and Various rays etc. all carry the information of the substance, and the various physics and chemistry of measured matter are can be obtained by obtaining this category information Matter.
Fig. 7 is 1350 DEG C and is sintered obtained (ZrO2)0.89(CeO2)0.1(CuO)0.01The SEM of sample difference enlargement ratio schemes. Fig. 7 a, b are under different amplification, and 1350 degree are sintered obtained (ZrO2)0.89(CeO2)0.1(CuO)0.01The microcosmic surface of sample Pattern, this figure are consistency and the preferable one group of sample of conductivity.As we can see from the figure clearly between particle and crystal grain Gap, be between particle it is complete be coupled cause with the presence of a large amount of gap, crystal boundary is wider, and the crystal grain of sample is smaller, and sintered body is big Part is that polygon equiax crystal forms, and particle size is more uniform.There is agglomeration in part.Fig. 7 c, d are different times magnifications Several lower sintering idiosome fracture SEM pictures, as can be seen from the figure powder particle merging is grown into crystal grain and is stayed in high-temperature sintering process Under trace.Because crystal grain and crystal boundary have important role in terms of the conduction behavior in controlling the electrolyte materials system； In addition, stomata delivers important influence for oxonium ion, the transmission energy of oxonium ion known to electrolyte operation principle Power affects the electric conductivity of the material.But make sample more as can be seen that sintering temperature should be further increased from the above analysis Densification is to improve the conductivity of this composite material.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art It makes various modifications or additions to the described embodiments or substitutes by a similar method, without departing from invention Design or beyond the scope defined by this claim, be within the scope of protection of the invention.

Claims (3)

1. a kind of modified ZrO2The preparation method of base composite solid electrolyte ceramic material, which is characterized in that steps are as follows：
1., according to target sample (ZrO2)0.89(CeO2)x(CuO)0.11-xStoichiometric ratio, weigh zirconium nitrate, cerous nitrate, nitric acid Copper is added in 30ml distilled water, citric acid is then added, is sufficiently stirred and makes it dissolve；
2., ethylene glycol is added into mixed liquor, then solution is placed in supersonic wave cleaning machine ultrasonic, keeps ethylene glycol dispersion equal It is even；
3., using weak aqua ammonia as pH adjusting agent volumetric soiutions, it is 7 to adjust solution ph；
4., in 80 DEG C of water bath with thermostatic control heating stirrings, until forming colloidal sol, gel is formed after standing a period of time；
5., gel is put into baking oven and is dried 24 hours, be put into after taking-up in Muffle furnace and calcined 10 hours at 700 DEG C, calcining knot It is down to room temperature after beam, takes out crucible, powder is fully ground to superfine powder, (ZrO is obtained2)0.89(CeO2)x(CuO)0.11-xElectrolysis Matter powder body material；
6., PVA be added in the superfine powder of acquisition be granulated, must assure that and be fully ground so that powder is mixed with PVA during granulation It closes uniform；Powder is tabletted under 14Mpa pressure；The temperature programming stove that the piece of compression moulding is put into is sintered, 200 minutes are kept the temperature to get ZrO at 1350 DEG C2Base composite solid electrolyte ceramic material (ZrO2)0.89(CeO2)x(CuO)0.11-xPottery Tile.
2. preparation method as described in claim 1, which is characterized in that target sample (ZrO2)0.89(CeO2)x(CuO)0.11-xMiddle x =0~0.10.
3. preparation method as claimed in claim 1 or 2, which is characterized in that the molal weight of citric acid is to contain in component 1.5 times of the amount of metal ion, the weight of ethylene glycol are 1.2 times of citric acid weight.
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Cited By (5)

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CN109650873A (en) * 2018-12-10 2019-04-19 合肥学院 A kind of Ca-W mixing and doping Bi2O3Method for preparing solid electrolyte
CN109942293A (en) * 2019-03-21 2019-06-28 合肥学院 A kind of method that the combustion-supporting method of microwave prepares LMO-YSZ composite solid electrolyte
CN116023133A (en) * 2021-10-26 2023-04-28 国家能源投资集团有限责任公司 Composite zirconia powder and preparation method thereof
CN116496076A (en) * 2023-04-27 2023-07-28 江苏大学 Al (aluminum) alloy 2 O 3 TiC composite material and preparation method and electrochemical repair method thereof
CN116496076B (en) * 2023-04-27 2024-06-07 江苏大学 Al (aluminum) alloy2O3TiC composite material and preparation method and electrochemical repair method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109650873A (en) * 2018-12-10 2019-04-19 合肥学院 A kind of Ca-W mixing and doping Bi2O3Method for preparing solid electrolyte
CN109650873B (en) * 2018-12-10 2021-07-06 合肥学院 Ca-W mixed doped Bi2O3Method for preparing solid electrolyte
CN109942293A (en) * 2019-03-21 2019-06-28 合肥学院 A kind of method that the combustion-supporting method of microwave prepares LMO-YSZ composite solid electrolyte
CN116023133A (en) * 2021-10-26 2023-04-28 国家能源投资集团有限责任公司 Composite zirconia powder and preparation method thereof
CN116023133B (en) * 2021-10-26 2024-04-05 国家能源投资集团有限责任公司 Composite zirconia powder and preparation method thereof
CN116496076A (en) * 2023-04-27 2023-07-28 江苏大学 Al (aluminum) alloy 2 O 3 TiC composite material and preparation method and electrochemical repair method thereof
CN116496076B (en) * 2023-04-27 2024-06-07 江苏大学 Al (aluminum) alloy2O3TiC composite material and preparation method and electrochemical repair method thereof

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