CN104282868A - Electrolyte ceramic membrane supported by modified porous membrane and preparation method of electrolyte ceramic membrane - Google Patents

Electrolyte ceramic membrane supported by modified porous membrane and preparation method of electrolyte ceramic membrane Download PDF

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CN104282868A
CN104282868A CN201310294796.1A CN201310294796A CN104282868A CN 104282868 A CN104282868 A CN 104282868A CN 201310294796 A CN201310294796 A CN 201310294796A CN 104282868 A CN104282868 A CN 104282868A
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barrier film
electrolyte ceramics
perforated membrane
electrolyte
ceramics barrier
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CN104282868B (en
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温兆银
张敬超
吴相伟
胡英瑛
吴梅芬
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • H01M10/3918—Sodium-sulfur cells characterised by the electrolyte
    • H01M10/3927—Several layers of electrolyte or coatings containing electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention relates to an electrolyte ceramic membrane supported by a modified porous membrane and a preparation method of the electrolyte ceramic membrane. The electrolyte ceramic membrane comprises a Na-beta'-Al2O3 dense layer and a modified porous membrane supporting the Na-beta'-Al2O3 dense layer, wherein the basic component of the modified porous membrane is Na-beta'-Al2O3 and/or alpha-Al2O3; and the modification component refers to Ni, Co and/or oxides thereof. According to the electrolyte ceramic membrane for a sodium battery provided by the invention, the modified porous membrane is well combined with the Na-beta'-Al2O3 electrolyte, the problems that the battery is invalid due to possible drop in the operating process and the like can be effectively solved, the modified metal medium in the porous membrane is high in electronic conductivity, and the internal resistance of the battery is not increased.

Description

Electrolyte ceramics barrier film that modified perforated membrane supports and preparation method thereof
Technical field
The present invention relates to field of energy source materials, particularly relate to a kind of method improving sode cell especially ZEBRA battery performance, specifically relate to a kind of electrolyte ceramics barrier film for sode cell newly and preparation method thereof to improve sode cell, especially Na-β "-Al in ZEBRA battery 2o 3electrolyte performance.
Background technology
Compared with Li, the rich content of Na in the earth's crust, cheap, in recent years, the research of sode cell more and more receives the concern of people, especially with sodium-sulphur battery and sodium-chloride battery for representative.The application advantage of this kind of battery in Large Copacity stored energy and electric powered motor power supply etc. is obvious.β "-Al 2o 3pottery Na at normal temperatures +ionic conductivity can reach 10 -2the order of magnitude of S/cm is Na known at present +the solid electrolyte material system that ionic conductivity is the highest.β "-Al 2o 3pottery plays Na in sode cell +the double action of ion conductor and both positive and negative polarity barrier film is the core component of the multiple electrochemical devices such as sode cell.
ZEBRA battery is the active material using sodium and nickel chloride as battery cathode and positive pole, with Na-β "-Al 2o 3as a kind of high energy sodium rechargeable battery of electrolyte and both positive and negative polarity barrier film.Because positive electrode is solid porous nickel chloride, so also need to add NaAlCl 4fused salt serves as second liquid electrolyte at Na-β "-Al 2o 3conducts sodium ions effect is played between tube-surface and solid porous nickel chloride.ZEBRA battery has series of advantages, its open circuit voltage high (being 2.58V when 300 DEG C), specific energy is high, and (theory is 790Wh/kg, actually reach 125Wh/kg), energy conversion efficiency high (without self discharge, 100% coulombic efficiency), quickly-chargeable (charging in 30 minutes reaches 50% discharge capacity), operating temperature range wide (broader region of 250 ~ 350 DEG C), capacity and discharge rate irrelevant (internal resistance of cell is ohmic internal resistance substantially), overcharging resisting, overdischarge (the second electrolyte NaAlCl 4reaction can be participated in), without Liquid Sodium troublesome poeration (battery assembles in the discharged condition), easy maintenance (all-sealed structure, cell damage are low resistance mode), safe and reliable (without low boiling, high-vapor-pressure material, be at present unique battery system by United States advanced battery associating association (USABC) 22 safety tests).Therefore, ZEBRA battery is a kind of desirable battery for electric automobile, also can be used as the internal motivation of ship for civil use and military submarines.
The core component of ZEBRA battery is Na-the β "-Al of conducts sodium ions 2o 3ceramic electrolyte, it reaches 10 at about 300 DEG C ionic conductivities -1the S/cm order of magnitude realizes sodium ion-conductive, and by the critical material of both positive and negative polarity active material isolation.Na-β "-Al 2o 3electrolytical resistance value accounts for 50% of whole ZEBRA cell resistance.The research in past shows, by by columned Na-β "-Al 2o 3the pipe of trilobes changed system into by pipe, reduce electrolytical resistance (J.L.Sudworth to a certain extent, The sodium/nickel chloride (ZEBRA) battery, Journal of Power Sources100 (2001) 149-163.).But, be but that the thickness of electrolytic tube is reduced to 10 ~ 50 μm from 1 ~ 2mm to the optimal optimization method of resistance.The research report of this respect is fewer, only has very few several sections.Such as Canadian Mali adopts slip casting to prepare porous beta "-Al 2o 3fine and close the β "-Al of substrate support 2o 3pipe, (A.Mali, A.Petric, Fabrication of a thin walled β "-alumina electrolyte cells; Journal of Power Sources196 (2011) 5191-5196.); average specific resistance have dropped 1.6 times, and except because except electrolytical thickness reduces, the improvement of the wetability that the capillary force of perforated substrate brings also is the reason that resistance reduces.Based on this, in order to optimize Na-β "-Al 2o 3the performance of electrolyte ceramics barrier film, can by following three kinds of approach: one is the surface area increasing electrolyte ceramics barrier film; Two is the thickness reducing electrolyte ceramics barrier film; Three is the wetabilitys improving electrolyte ceramics barrier film.
For ZEBRA battery, sodium and Na-β "-Al 2o 3wetability missionary society between electrolyte causes sodium and Na-β "-Al 2o 3interface produce serious polarization, electric current is assembled in a large number in polarization place and finally destroys Na-β "-Al 2o 3pottery, makes battery failure.Research finds, to Na-β "-Al 2o 3it is improve sodium and Na-β "-Al that modification is carried out on electrolyte ceramics surface 2o 3the effective means of wetability between electrolyte.A lot of material, comprises metal, oxide, carbide, nitride powder and porous nano metal etc., studied for modifying Na-β "-Al 2o 3on solid electrolyte surface.Wherein, at Na-β "-Al 2o 3deng coated one deck on solid electrolyte plumbous or bismuth (UK Patent Application 2067005), low melting point Na ion conductor amido sodium (PCT/GB90/01584, WO91/06133) and all reach good effect at its Surface coating one deck porous nano metal (British patent 1530274 and 1511152) etc.Porous material is because having larger specific area, and comparatively granular materials can improve wetability more, simultaneously can as anode capillary layer, but porous material and Na-β "-Al 2o 3deng adhesion difference between solid electrolyte be perplex always its application subject matter.For this problem, researcher before generally adopts physical deposition methods, as flame spray method and plasma sputtering etc., carries out the Surface coating of porous material.But this class methods cost is higher, generally needs to operate under a high vacuum, the needs of large-scale application can not be met.
Summary of the invention
In the face of prior art Problems existing, the object of this invention is to provide Na-the β "-Al that a kind of modified perforated membrane supports 2o 3electrolyte ceramics barrier film, this perforated membrane and Na-β "-Al 2o 3electrolyte combines good, can realize sodium and Na-β "-Al 2o 3wetability between electrolyte is significantly improved, and then improves the performance of battery, to overcome the deficiencies in the prior art.
At this, the electrolyte ceramics barrier film that first the present invention provides a kind of modified perforated membrane for sode cell to support, described electrolyte ceramics barrier film comprises Na-β "-Al 2o 3compacted zone and support described Na-β "-Al 2o 3the modified perforated membrane of compacted zone, the basic components of described modified perforated membrane is Na-β "-Al 2o 3and/or α-Al 2o 3, modified component is Ni, Co and/or its oxide.
Electrolyte ceramics barrier film for sode cell provided by the invention, to be two-layerly made up of inside and outside, and internal layer is fine and close Na-β "-Al 2o 3layer, skin is the perforated substrate of metal or modified metal oxide, modified perforated membrane and Na-β "-Al 2o 3electrolyte combines good, can effectively avoid contingent coming off in battery operation and cause the problems such as inefficacy, and in perforated membrane, modified metal medium is good to electron conduction, can not increase the internal resistance of cell.
Preferably, described Na-β "-Al 2o 3the thickness of compacted zone can be 15 ~ 30 μm.The thickness of described modified perforated membrane can be 0.5 ~ 0.6mm.
Preferably, in described modified perforated membrane, the weight percentage of modified component can be 1 ~ 2wt%.
Preferably, the ionic conductivity of described electrolyte ceramics barrier film at 300 DEG C can be 0.12 ~ 0.13S/cm.
The present invention also provides a kind of method preparing above-mentioned electrolyte ceramics barrier film, and described method comprises:
(1) Na-β "-Al 2o 3powder, with organic solvent and dispersant, ball milling 1 ~ 2 hour, then adds plastic agent, ball milling 1 hour, then adds binding agent, ball milling 2 ~ 3 hours, vacuumize the slurry that de-bubble obtains compacted zone;
(2) ceramic powder, mixes with organic solvent, dispersant and pore creating material, ball milling 1 ~ 2 hour, then adds plastic agent, ball milling 1 hour, then add binding agent, ball milling 2 ~ 3 hours, vacuumize the slurry that de-bubble obtains porous layer, described ceramic powder is Na-β "-Al 2o 3powder and/or α-Al 2o 3powder;
(3) matrix rotary pulling in the slurry of described compacted zone is applied repeatedly, the slurry rotary pulling coating of described porous layer is placed in again repeatedly after drying, 1000 ~ 1100 DEG C of pre-burnings 1 ~ 3 hour after drying, the demoulding, then within 20 ~ 30 minutes, obtain Na-the β "-Al of perforated membrane support at 1550 ~ 1600 DEG C of co-sinterings 2o 3electrolyte ceramics barrier film; And
(4) Na-the β "-Al described perforated membrane supported 2o 3electrolyte ceramics barrier film immerses in nickel nitrate or cobalt nitrate solution, and ultrasonic disperse, after 1 ~ 2 hour, obtains Na-the β "-Al of the perforated membrane support of the oxide of Ni or the modified oxide of Co for 1 ~ 3 hour 350 ~ 500 DEG C of heat treatments 2o 3electrolyte ceramics barrier film, or Na-the β "-Al obtaining the perforated membrane support that Ni or Co modifies in reducing atmosphere in 350 ~ 500 DEG C of heat treatments for 1 ~ 3 hour 2o 3electrolyte ceramics barrier film.
Preferably, described organic solvent can be ethanol and butanone, and described dispersant can be triethanolamine, and described binding agent can be polyvinyl butyral resin, and described plastic agent can be dibutyl phthalate and polyethylene glycol, and described pore creating material can be graphite or starch.
Preferably, in step (1), described Na-β "-Al 2o 3the weight ratio of powder, organic solvent, dispersant, plastic agent and binding agent can be 100:(100 ~ 200): (2 ~ 4): (6 ~ 12): (4 ~ 8).
Preferably, in step (2), the weight ratio of described ceramic split powder, organic solvent, dispersant, pore creating material, plastic agent and binding agent can be 100:(100 ~ 120): (2 ~ 4): (40 ~ 60): (12 ~ 18): (8 ~ 12).
The present invention has following beneficial effect:
(1) modified perforated membrane and Na-β "-Al 2o 3electrolytical bond strength is higher, can effectively avoid contingent coming off in cell operation and lose efficacy;
(2) perforated membrane of even air hole distribution can make sodium be evenly dispersed in Na-β "-Al 2o 3electrolytical surface, is conducive to the mass transfer promoting sodium;
(3) metal medium in perforated membrane is good to electron conduction, can not increase the internal resistance of battery;
(4) processing method is simple, and cost is lower.
Accompanying drawing explanation
Fig. 1 is Na-the β "-Al of the modified perforated membrane support that the present invention designs 2o 3electrolyte ceramics barrier film schematic diagram;
Fig. 2 is Na-the β "-Al of modified perforated membrane support prepared by the embodiment of the present invention 1 2o 3the SEM photo of electrolyte ceramics barrier film section;
Fig. 3 is Na-the β "-Al of Ni modification prepared by the embodiment of the present invention 2 2o 3na-the β "-Al that perforated membrane supports 2o 3the ac impedance spectroscopy of electrolyte ceramics barrier film in air atmosphere when 300 DEG C.
Embodiment
Below, the present invention is further illustrated with the following embodiments.Should be understood that embodiment only unrestricted the present invention for illustration of the present invention.
In order to optimize Na-the β "-Al of ZEBRA battery 2o 3electrolytical performance, the present invention has prepared Na-the β "-Al that a kind of modified perforated membrane supports 2o 3electrolyte ceramics barrier film, such as, see Fig. 1, it illustrates Na-the β "-Al that the modified perforated membrane that the present invention designs supports 2o 3electrolyte ceramics barrier film schematic diagram, Na-the β "-Al that this modified perforated membrane supports 2o 3electrolyte ceramics barrier film is the tubular structure that one end is closed, and to be two-layerly made up of inside and outside, skin is the perforated substrate of metal or modified metal oxide, and internal layer is Na-the β "-Al of densification 2o 3layer.But should be understood that Na-β "-Al of the present invention 2o 3electrolyte membrance is not limited to tubular type, also can be flat.The basic components of porous layer can be Na-β "-Al 2o 3and/or α-Al 2o 3, modified component is Ni, Co and/or its oxide.In order to reduce resistance, improve the efficiency of ZEBRA battery, the thickness of compacted zone below 30 μm, such as 15 ~ 30 μm.The thickness of porous layer can be 0.5-0.6mm, and in porous layer, the weight percentage of modified component can be 1 ~ 2wt%.Na-β "-Al of the present invention 2o 3electrolyte ceramics barrier film has excellent ionic conductivity, and at 300 DEG C, its ionic conductivity is 0.12 ~ 0.13S/cm.
Na-β "-Al of the present invention 2o 3electrolyte ceramics barrier film adopts the preparation of rotary pulling cladding process, comprises the processes such as batch mixing, degasification, rotary pulling coating, the demoulding, heat treatment:
(1) in the ceramic powder of porous layer, add organic solvent, dispersant, pore creating material ball milling mixing 1 ~ 2h, then add plastic agent ball milling 1h, then add binding agent continuation ball milling 2 ~ 3h, after vacuumizing process, obtain the slurry of porous layer; Fine and close Na-β "-Al 2o 3preparation method and the said process of layer slurry are similar, and just do not add pore creating material, the ceramic powder of porous layer can be Na-β "-Al 2o 3and/or α-Al 2o 3powder;
(2) fine and close Na-β "-Al can not be immersed with the tubular substrate of slurry reaction (as glass tube) 2o 3in the slurry of layer, rotary pulling coating repeatedly, in one example, flood and lift out lentamente from slurry after ten seconds and rotate, and stood upside down to rotate again and shape to slurry after certain hour, repeats said process several again until required thickness after drying;
(3) fine and close Na-β "-Al step (2) obtained 2o 3layer to immerse in porous layer slurry rotary pulling coating repeatedly, such as, flood and lifts out lentamente from slurry after ten seconds and rotate, and is stood upside down to rotate to slurry again and shape, and repeat number is secondary, by Na-β "-Al after drying after certain hour 2o 3the double-deck biscuit of densification/porous takes off from tubular substrate, at 1000 ~ 1100 DEG C of pre-burning 1 ~ 3h, then at 1550 ~ 1600 DEG C of co-sintering 20 ~ 30min, obtains Na-the β "-Al that perforated membrane supports 2o 3electrolyte ceramics barrier film;
(4) by Na-β "-Al that the perforated membrane that obtains in step (3) supports 2o 3electrolyte ceramics barrier film oral area seals, be immersed in the nitrate solution of respective metal ion, ultrasonic disperse a period of time, in corresponding heat-treated or heat treatment in corresponding temperature, reducing atmosphere after drying, the β "-Al that the perforated membrane obtaining required metal oxide or metal-modified supports 2o 3electrolyte ceramics barrier film, wherein the nitrate solution of metal ion can select the nitrate of the metal ion such as nickel and cobalt.
Na-β "-Al 2o 3powder can be prepared according to prior art.
Na-the β "-Al of design preparation 2o 3electrolyte ceramics barrier film is preferably tubular type, but also can be flat; The selection tubular substrate (as glass tube) of tubular type, the flat matrix of flat selection (as nonwoven fabrics).
In an embodiment of the present invention, with absolute ethyl alcohol and butanone for solvent, taking triethanolamine as dispersant, with dibutyl phthalate and polyethylene glycol for plastic agent, take polyvinyl butyral as binding agent, with graphite or starch etc. for pore creating material.The content of organic additive is as shown in table 1 relative to the mass percent of porous layer and compacted zone powder:
Table 1: the addition of organic additive
In the number of times that the thickness of porous layer and compacted zone and microstructure can be applied by rotary pulling and slurry, the content of organic additive controls, and the component of porous layer can change by changing the composition of the ceramic powder in slurry.Such as can take different proportionings for the porosity demand that porous layer is different.For the thickness requirement that each layer is different, different rotary pulling coating number of times can be taked.After each rotary pulling coating, through drying at room temperature.Thus, method of the present invention can prepare the controlled electrolyte membrance of porous layer composition, microstructure, porous layer and dense layer thickness.
The present invention illustrates that following examples are to illustrate the present invention better further.Should understand; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The numerical value that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.
Embodiment 1
Weigh Na-β "-Al 2o 3powder 100g, graphite 50g, triethanolamine 4g, absolute ethyl alcohol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate and the polyethylene glycol of 18wt%, add the polyvinyl butyral resin of 12wt% after ball milling 1h again, continue ball milling 2h and obtain porous Na-β "-Al 2o 3the slurry of layer; Weigh Na-β "-Al 2o 3powder 100g, triethanolamine 2g, ethanol 65g, butanone 135g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add 6wt% dibutyl phthalate and polyethylene glycol, add the polyvinyl butyral resin of 4wt% after ball milling 1h again, continue ball milling 2h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.Glass tube is immersed in above-mentioned fine and close Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after the several seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations 3 times, after drying at room temperature, be immersed in porous Na-β "-Al again 2o 3in the slurry of layer, rotary pulling applies 3 times, and dry, the demoulding, at 1000 DEG C of pre-burning 2h, then at 1600 DEG C of co-sintering 20min, obtains porous/fine and close Na-β "-Al 2o 3composite membrane, closes the openend of this composite membrane, is immersed in the nickel nitrate solution of 1mol/L, ultrasonic disperse 2h, takes out dry, then at 400 DEG C of roasting 2h, obtains Na-the β "-Al that NiO modifies 2o 3na-the β "-Al that perforated membrane supports 2o 3electrolyte ceramics barrier film.
Na-the β "-Al that the NiO that this embodiment obtains modifies 2o 3na-the β "-Al that perforated membrane supports 2o 3as shown in Figure 2, wherein the thickness of compacted zone is 15 μm to electrolyte ceramics barrier film, and the thickness of porous layer is 0.5mm.Ionic conductivity at 300 DEG C is 0.12S/cm.
Embodiment 2
Weigh Na-β "-Al 2o 3powder 100g, starch 40g, triethanolamine 4g, absolute ethyl alcohol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate and the polyethylene glycol of 18wt%, add the polyvinyl butyral resin of 12wt% after ball milling 1h again, continue ball milling 2h and obtain porous Na-β "-Al 2o 3the slurry of layer; Weigh Na-β "-Al 2o 3powder 100g, triethanolamine 2g, ethanol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 3g and polyethylene glycol 3g, add polyvinyl butyral resin 4g again after ball milling 1h, continue ball milling 2h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.Glass tube is immersed in above-mentioned fine and close Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after the several seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations 3 times, after drying at room temperature, be immersed in porous Na-β "-Al again 2o 3in the slurry of layer, rotary pulling applies 3 times, and dry, the demoulding, at 1000 DEG C of pre-burning 2h, then at 1550 DEG C of co-sintering 30min, obtains porous/fine and close Na-β "-Al 2o 3composite membrane, closes the openend of this composite membrane, is immersed in 1mol/L nickel nitrate solution, ultrasonic disperse 2h, takes out dry, then in hydrogen atmosphere 500 DEG C of roasting 1h, obtain Na-the β "-Al that Ni modifies 2o 3na-the β "-Al that perforated membrane supports 2o 3electrolyte ceramics barrier film.
Na-the β "-Al that the Ni that this embodiment obtains modifies 2o 3na-the β "-Al that perforated membrane supports 2o 3in electrolyte ceramics barrier film, the thickness of compacted zone is 30 μm, and the thickness of porous layer is 0.5mm.As shown in Figure 3, its ionic conductivity is 0.13S/cm to impedance spectrum in 300 DEG C of air atmospheres.
Embodiment 3
Weigh α-Al 2o 3powder 100g, graphite 60g, triethanolamine 4g, absolute ethyl alcohol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate and the polyethylene glycol of 18wt%, add the polyvinyl butyral resin of 12wt% after ball milling 1h again, continue ball milling 2h and obtain porous α-Al 2o 3the slurry of layer; Weigh Na-β "-Al 2o 3powder 100g, triethanolamine 4g, ethanol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add 6wt% dibutyl phthalate and polyethylene glycol, add the polyvinyl butyral resin of 4wt% after ball milling 1h again, continue ball milling 2h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.Glass tube is immersed in above-mentioned fine and close Na-β " Al 2o 3in the slurry of layer, lift out lentamente from slurry after the several seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations 3 times, after drying at room temperature, be immersed in porous α-Al again 2o 3in the slurry of layer, rotary pulling applies 3 times, and dry, the demoulding, at 1000 DEG C of pre-burning 2h, then at 1600 DEG C of co-sintering 20min, obtains porous α-Al 2o 3/ fine and close Na-β "-Al 2o 3composite membrane, closes the openend of this composite membrane, is immersed in 1.5mol/L nickel nitrate solution, ultrasonic disperse 2h, takes out dry, then in hydrogen atmosphere 500 DEG C of roasting 1h, obtain the α-Al that Ni modifies 2o 3na-the β "-Al that perforated membrane supports 2o 3electrolyte ceramics barrier film.
α-the Al that the Ni that this embodiment obtains modifies 2o 3na-the β "-Al that perforated membrane supports 2o 3in electrolyte ceramics barrier film, the thickness of compacted zone is 24 μm, and the thickness of porous layer is 0.6mm.Ionic conductivity at 300 DEG C is 0.12S/cm.
Embodiment 4
Weigh Na-β "-Al 2o 3powder 100g, starch 60g, triethanolamine 4g, absolute ethyl alcohol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate and the polyethylene glycol of 18wt%, add the polyvinyl butyral resin of 12wt% after ball milling 1h again, continue ball milling 2h and obtain porous Na-β "-Al 2o 3the slurry of layer; Weigh Na-β "-Al 2o 3powder 100g, triethanolamine 2g, ethanol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 3g and polyethylene glycol 3g, add polyvinyl butyral resin 4g again after ball milling 1h, continue ball milling 2h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.Glass tube is immersed in above-mentioned fine and close Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after the several seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations 2 times, after drying at room temperature, be immersed in porous Na-β "-Al again 2o 3in the slurry of layer, rotary pulling applies 3 times, and dry, the demoulding, at 1000 DEG C of pre-burning 2h, then at 1600 DEG C of co-sintering 20min, obtains porous/fine and close Na-β "-Al 2o 3composite membrane, closes the openend of this composite membrane, is immersed in certain density cobalt nitrate solution, ultrasonic disperse 2h, takes out dry, then at 350 DEG C of roasting 4h, obtains Co 3o 4na-the β "-Al modified 2o 3na-the β "-Al that perforated membrane supports 2o 3electrolyte ceramics barrier film.
The Co that this embodiment is obtained 3o 4na-the β "-Al modified 2o 3na-the β "-Al that perforated membrane supports 2o 3in electrolyte ceramics barrier film, the thickness of compacted zone is 20 μm, and the thickness of porous layer is 0.6mm.Ionic conductivity at 300 DEG C is 0.13S/cm.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.

Claims (10)

1. for the electrolyte ceramics barrier film that the modified perforated membrane of sode cell supports, it is characterized in that, described electrolyte ceramics barrier film comprises Na-β "-Al 2o 3compacted zone and support described Na-β "-Al 2o 3the modified perforated membrane of compacted zone, the basic components of described modified perforated membrane is Na-β "-Al 2o 3and/or α-Al 2o 3, modified component is Ni, Co and/or its oxide.
2. electrolyte ceramics barrier film according to claim 1, is characterized in that, described electrolyte ceramics barrier film forms the tubular structure that one end is closed.
3. electrolyte ceramics barrier film according to claim 1 and 2, is characterized in that, described Na-β "-Al 2o 3the thickness of compacted zone is 15 ~ 30 μm.
4. the electrolyte ceramics barrier film according to any one of claims 1 to 3, is characterized in that, the thickness of described modified perforated membrane is 0.5 ~ 0.6mm.
5. the electrolyte ceramics barrier film according to any one of Claims 1 to 4, is characterized in that, in described modified perforated membrane, the weight percentage of modified component is 1 ~ 2wt%.
6. the electrolyte ceramics barrier film according to any one of Claims 1 to 5, is characterized in that, the ionic conductivity of described electrolyte ceramics barrier film at 300 DEG C is 0.12 ~ 0.13S/cm.
7. prepare a method for the electrolyte ceramics barrier film according to any one of claim 1 ~ 6, it is characterized in that, described method comprises:
(1) Na-β "-Al 2o 3powder, with organic solvent and dispersant, ball milling 1 ~ 2 hour, then adds plastic agent, ball milling 1 hour, then adds binding agent, ball milling 2 ~ 3 hours, vacuumize the slurry that de-bubble obtains compacted zone;
(2) ceramic powder, mixes with organic solvent, dispersant and pore creating material, ball milling 1 ~ 2 hour, then adds plastic agent, ball milling 1 hour, then add binding agent, ball milling 2 ~ 3 hours, vacuumize the slurry that de-bubble obtains porous layer, described ceramic powder is Na-β "-Al 2o 3powder and/or α-Al 2o 3powder;
(3) matrix rotary pulling in the slurry of described compacted zone is applied repeatedly, the slurry rotary pulling coating of described porous layer is placed in again repeatedly after drying, 1000 ~ 1100 DEG C of pre-burnings 1 ~ 3 hour after drying, the demoulding, then within 20 ~ 30 minutes, obtain Na-the β "-Al of perforated membrane support at 1550 ~ 1600 DEG C of co-sinterings 2o 3electrolyte ceramics barrier film; And
(4) Na-the β "-Al described perforated membrane supported 2o 3electrolyte ceramics barrier film immerses in nickel nitrate or cobalt nitrate solution, and ultrasonic disperse, after 1 ~ 2 hour, obtains Na-the β "-Al of the perforated membrane support of the oxide of Ni or the modified oxide of Co for 1 ~ 3 hour 350 ~ 500 DEG C of heat treatments 2o 3electrolyte ceramics barrier film, or Na-the β "-Al obtaining the perforated membrane support that Ni or Co modifies in reducing atmosphere in 350 ~ 500 DEG C of heat treatments for 1 ~ 3 hour 2o 3electrolyte ceramics barrier film.
8. method according to claim 7, is characterized in that, described organic solvent is ethanol and butanone, described dispersant is triethanolamine, described binding agent is polyvinyl butyral resin, and described plastic agent is dibutyl phthalate and polyethylene glycol, and described pore creating material is graphite or starch.
9. the method according to claim 7 or 8, is characterized in that, in step (1), and described Na-β "-Al 2o 3the weight ratio of powder, organic solvent, dispersant, plastic agent and binding agent is 100:(100 ~ 200): (2 ~ 4): (6 ~ 12): (4 ~ 8).
10. the method according to any one of claim 7 ~ 9, it is characterized in that, in step (2), the weight ratio of described ceramic powder, organic solvent, dispersant, pore creating material, plastic agent and binding agent is 100:(100 ~ 120): (2 ~ 4): (40 ~ 60): (12 ~ 18): (8 ~ 12).
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CN105742663B (en) * 2016-04-28 2017-12-26 南充市世进地暖科技有限公司 A kind of high energy sodium chlorine medium temperature thermoelectricity pool preparation method
CN108254990A (en) * 2017-03-21 2018-07-06 中国科学技术大学 A kind of composite solid electrolyte material and preparation method thereof, full-solid electrochromic device
CN108254990B (en) * 2017-03-21 2020-10-27 中国科学技术大学 Composite solid electrolyte material, preparation method thereof and all-solid-state electrochromic device
CN113113723A (en) * 2021-04-06 2021-07-13 国家纳米科学中心 Coating diaphragm and preparation method and application thereof

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