CN104282867A - Electrolyte ceramic membrane for sodium battery and preparation method of electrolyte ceramic membrane - Google Patents

Electrolyte ceramic membrane for sodium battery and preparation method of electrolyte ceramic membrane Download PDF

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CN104282867A
CN104282867A CN201310294462.4A CN201310294462A CN104282867A CN 104282867 A CN104282867 A CN 104282867A CN 201310294462 A CN201310294462 A CN 201310294462A CN 104282867 A CN104282867 A CN 104282867A
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slurry
barrier film
ball milling
porous
electrolyte ceramics
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CN104282867B (en
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温兆银
张敬超
张高校
吴相伟
吴梅芬
胡英瑛
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • 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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  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

The invention relates to an electrolyte ceramic membrane for a sodium battery and a preparation method of the electrolyte ceramic membrane. The electrolyte ceramic membrane comprises a Na-beta'-Al2O3 dense layer, and a first Na-beta'-Al2O3 porous layer and a second Na-beta'-Al2O3 porous layer which are respectively positioned on two sides of the Na-beta'-Al2O3 dense layer, wherein the thickness of the Na-beta'-Al2O3 dense layer is 15-30 Mu m. The electrolyte ceramic membrane for the sodium battery provided by the invention has the double-gradient structural design, the thickness of the electrolyte is reduced through the dense Na-beta'-Al2O3, the specific surface area is increased by utilizing porous materials on two sides, the wettability of materials (such as sodium and Na-beta'-Al2O3 covering the whole surface) is improved, the ohmic resistance of the battery is reduced, and mass transfer of liquid sodium in pores is facilitated.

Description

For the electrolyte ceramics barrier film and preparation method thereof of sode cell
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.
Summary of the invention
In the face of prior art Problems existing, the object of this invention is to provide a kind of Na-β "-Al with the design of two gradient-structure 2o 3electrolyte, reduces electrolytical thickness but increases specific area simultaneously on the one hand, improving the wetability of material, reduces Ohmic resistance, to overcome the deficiencies in the prior art.
At this, first the present invention provides a kind of electrolyte ceramics barrier film for sode cell, and described electrolyte ceramics barrier film comprises Na-β "-Al 2o 3compacted zone and lay respectively at described Na-β "-Al 2o 3one Na-β "-Al of the both sides of compacted zone 2o 3porous layer and the 2nd Na-β "-Al 2o 3porous layer, wherein said Na-β ' '-Al 2o 3the thickness of compacted zone is 15 ~ 30 μm.
Electrolyte ceramics barrier film for sode cell provided by the invention, has two gradient type structural design, and centre is Na-the β "-Al of one deck densification 2o 3, both sides are Na-the β "-Al of porous 2o 3, by Na-the β "-Al of densification 2o 3reduce while electrolyte thickness, utilize the porous material of both sides to increase specific area, improve material and (as cover sodium and Na-the β "-Al on whole surface 2o 3) between wetability, be conducive to reducing the Ohmic resistance of battery, and promote the mass transfer of Liquid Sodium in hole.
Preferably, the thickness of described electrolyte ceramics barrier film is 0.6 ~ 1mm.
Preferably, the ionic conductivity of described electrolyte ceramics barrier film at 300 DEG C can be 0.12S/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 obtained Na-β "-Al 2o 3the slurry of compacted zone;
(2) Na-β "-Al 2o 3powder, mixes with organic solvent, dispersant and pore creating material, ball milling 1 ~ 2 hour, then adds plastic agent, ball milling 1 hour, then adds binding agent, ball milling 2 ~ 3 hours obtained Na-β "-Al 2o 3the slurry of porous layer;
(3) by matrix at described Na-β "-Al 2o 3in the slurry of porous layer, rotary pulling coating repeatedly, is placed in described Na-β "-Al again after drying 2o 3in the slurry of compacted zone, rotary pulling coating repeatedly, after drying, directly obtains by Na-β "-Al 1000 ~ 1100 DEG C of pre-burnings after 1000 ~ 1100 DEG C of pre-burnings 1 ~ 3 hour or the demoulding for 1 ~ 3 hour 2o 3porous/dense composite film; And
(4) by described Na-β "-Al 2o 3porous/dense composite film is placed in described Na-β "-Al 2o 3in the slurry of porous layer, rotary pulling coating repeatedly, is burnt altogether at 1550 ~ 1600 DEG C after drying and within 15 ~ 30 minutes, is obtained described electrolyte ceramics barrier film.
Described Na-β "-Al 2o 3the slurry of compacted zone and/or Na-β "-Al 2o 3the slurry of porous layer is first used further to rotary pulling coating through vacuumizing de-bubble process.
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), described Na-β "-Al 2o 3the weight ratio of powder, organic solvent, dispersant, pore creating material, plastic agent and binding agent can be 100:(100 ~ 120): (2 ~ 4): (10 ~ 30): (12 ~ 18): (8 ~ 12).
Preferably, described matrix is glass tube or nonwoven fabrics.
The present invention has following beneficial effect:
(1) by controlling the content of organic additive and pore creating material in rotary pulling coating number of times or slurry, can to Na-β "-Al 2o 3thickness and the microstructure of electrolyte ceramics barrier film porous layer and compacted zone control;
(2) can by compacted zone Na-β "-Al 2o 3electrolyte ceramics membrane thicknesses controls at 15 ~ 30 μm, is conducive to the Ohmic resistance reducing battery;
(3) the present invention can use Na-β "-Al 2o 3powder, as the component of porous layer, also can change the composition of ceramic powder in slurry as required, as used α-Al 2o 3powder;
(4) the present invention only prepares three-decker with a kind of simple rotary pulling cladding process, neither needs the equipment of complex and expensive, does not also need strict control climate, simplify technique, reduce cost;
(5) the present invention adopt method simple, reproducible, be easy to large-scale production, be also applicable to the preparation of multi-gradient material.
Accompanying drawing explanation
Fig. 1 is two gradient type Na-the β "-Al of tubular type that the present invention designs 2o 3electrolyte ceramics barrier film schematic diagram;
Fig. 2 is two gradient type Na-β "-Al that the present invention designs 2o 3electrolyte ceramics barrier film preparation technology schematic flow sheet;
Fig. 3 is two gradient type Na-β "-Al prepared by the embodiment of the present invention 1 2o 3the SEM photo of electrolyte ceramics barrier film (pre-burning) section.
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 of a kind of pair of gradient type design 2o 3electrolyte ceramics barrier film is Na-the β "-Al of one deck densification in the middle of this ceramic diaphragm 2o 3, both sides are Na-the β "-Al of porous 2o 3, while reduction electrolyte thickness, increase specific area, improve the wetability between material, reach the object reducing Ohmic resistance.Such as, see Fig. 1, two gradient type Na-the β "-Al of its tubular type illustrating that the present invention designs 2o 3electrolyte ceramics barrier film schematic diagram, but should be understood that Na-β "-Al of the present invention 2o 3electrolyte ceramics barrier film is not limited to tubular type, also can be flat.In order to reduce resistance, improve the efficiency of ZEBRA battery, the thickness of compacted zone below 30 μm, such as 15 ~ 30 μm.Na-β "-Al 2o 3the thickness of electrolyte ceramics barrier film can be 0.6 ~ 1mm, a porous layer (Na-β "-Al of inner side 2o 3porous layer) and outside porous layer (the 2nd Na-β "-Al 2o 3porous layer) thickness can be identical, also can be different.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 0.10 ~ 0.12S/cm.
Na-β "-Al of the present invention 2o 3electrolyte ceramics barrier film adopts the preparation of rotary pulling cladding process, comprises the processes (see Fig. 2) such as batch mixing, degasification, rotary pulling coating, the demoulding, heat treatment:
(1) Na-β "-Al is taken 2o 3powder, with organic solvent, dispersant, ball milling 1 ~ 2h, then adds plastic agent, ball milling 1h, then adds binding agent, ball milling 2 ~ 3h, is mixed with fine and close Na-β "-Al 2o 3the slurry of layer; Porous Na-β "-Al 2o 3slurry preparation process and the said process of layer are similar, just add pore creating material when preparing burden;
(2) slurry prepared is carried out vacuumizing process 1 ~ 2min, remove the bubble in slurry;
(3) porous Na-β "-Al can not be immersed with the matrix of slurry reaction 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour and rotate again to slurry sizing, repeating said process after drying more for several times until required thickness;
(4) porous Na-β "-Al step (3) obtained 2o 3layer immerses fine and close Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour and rotate again to slurry sizing, and repeat number time, by porous/fine and close Na-β "-Al after drying 2o 3double-deck biscuit takes off from tubular substrate, at 1000 ~ 1100 DEG C of roasting 1 ~ 3h(to flat, direct at 1000 ~ 1100 DEG C of pre-burning 1 ~ 3h after dry, removing matrix and organic principle);
(5) by the porous after pre-burning/fine and close Na-β "-Al 2o 3composite membrane immerses porous Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour and rotate again to slurry sizing, and repeat number time, burn 15 ~ 30min altogether at 1550 ~ 1600 DEG C after drying.
Na-β "-Al 2o 3powder can be prepared according to prior art.
Na-the β "-Al of design preparation 2o 3electrolyte ceramics barrier film can be tubular type, also can be flat; The selection tubular substrate (as glass tube) of tubular type, flat selection matrix (as nonwoven fabrics) that is flat, that remove by roasting.
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 10g, triethanolamine 2g, absolute ethyl alcohol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate and the polyethylene glycol of 12wt%, add the polyvinyl butyral resin of 8wt% after ball milling 1h again, continue ball milling 3h 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 and the polyethylene glycol of 6wt%, add the polyvinyl butyral resin of 4wt% after ball milling 1h again, continue ball milling 3h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.The glass tube of external diameter 12mm is immersed in above-mentioned porous 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 and reach 13.1mm to tube wall external diameter 4 times, after drying at room temperature, be immersed in fine and close 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, by porous/fine and close Na-the β "-Al obtained 2o 3composite membrane continues to be immersed in porous Na-β "-Al 2o 3, at 1600 DEG C of sintering 20min after drying, obtain two gradient type Na-β "-Al in the slurry of layer for 3 times 2o 3electrolyte ceramics barrier film.
Fig. 3 be embodiment 1 prepare pre-burning after, burn till before two gradient type Na-β "-Al 2o 3the microphoto of electrolyte ceramics barrier film section, can find out, both sides are loose structure, and centre is finer and close.Two gradient type Na-β "-Al that this embodiment is obtained 2o 3in the middle of electrolyte ceramics barrier film, the thickness of compacted zone is 30 μm, and the thickness of inner side porous layer is 0.5mm, and the thickness of outside porous layer is 0.4mm.Ionic conductivity at 300 DEG C is 0.11S/cm.
Embodiment 2
Weigh Na-β "-Al 2o 3powder 100g, graphite 30g, triethanolamine 4g, ethanol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 9g and polyethylene glycol 9g, after ball milling 1h, add polyvinyl butyral resin 12g again, continue ball milling 3h and obtain porous Na-β "-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 dibutyl phthalate 6g and polyethylene glycol 6g, add polyvinyl butyral resin 8g again after ball milling 1h, continue ball milling 3h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.The glass tube of external diameter 12mm is immersed in above-mentioned porous Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations after dry and reach 13.6mm to tube wall external diameter 6 times, after drying at room temperature, be immersed in fine and close 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, by porous/fine and close Na-the β "-Al obtained 2o 3composite membrane continues to be immersed in porous Na-β "-Al 2o 3, at 1600 DEG C of sintering 30min after drying, obtain two gradient type Na-β "-Al in the slurry of layer for 2 times 2o 3electrolyte ceramics barrier film.
Two gradient type Na-β "-Al that this embodiment is obtained 2o 3in the middle of electrolyte ceramics barrier film, the thickness of compacted zone is 24 μm, and the thickness of inner side porous layer is 0.7mm, and the thickness of outside porous layer is 0.2mm.Ionic conductivity at 300 DEG C is 0.12S/cm.
Embodiment 3
Weigh Na-β "-Al 2o 3powder 100g, starch 25g, triethanolamine 3g, absolute ethyl alcohol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 9g and polyethylene glycol 9g, add polyvinyl butyral resin 12g again after ball milling 1h, continue ball milling 2h and obtain porous Na-β "-Al 2o 3the slurry of layer; Weigh Na-β "-Al 2o 3powder 100g, triethanolamine 3g, ethanol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 6g and polyethylene glycol 6g, add polyvinyl butyral resin 8g 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 1min.The glass tube of external diameter 10mm is immersed in above-mentioned porous Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations after dry and reach 11.3mm to tube wall external diameter 5 times, after drying at room temperature, be immersed in fine and close Na-β "-Al 2o 3in the slurry of layer, rotary pulling applies 2 times, and dry, the demoulding, at 1100 DEG C of pre-burning 1h.Continue to be immersed in porous Na-β "-Al 2o 3, at 1550 DEG C of sintering 30min after drying, obtain two gradient type Na-β "-Al in the slurry of layer for 2 times 2o 3electrolyte ceramics barrier film.
Two gradient type Na-β "-Al that this embodiment is obtained 2o 3in the middle of electrolyte ceramics barrier film, the thickness of compacted zone is 19 μm, and the thickness of inner side porous layer is 0.6mm, and the thickness of outside porous layer is 0.2mm.Ionic conductivity at 300 DEG C is 0.10S/cm.
Embodiment 4
Weigh Na-β "-Al 2o 3powder 100g, starch 12g, triethanolamine 4g, absolute ethyl alcohol 40g, butanone 80g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 6g and polyethylene glycol 6g, add polyvinyl butyral resin 8g again after ball milling 1h, continue ball milling 2h and obtain porous Na-β "-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 dibutyl phthalate 6g and polyethylene glycol 6g, add polyvinyl butyral resin 8g 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 1min.The glass tube of external diameter 10mm is immersed in above-mentioned porous Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations after dry and reach 11.1mm to tube wall external diameter 4 times, after drying at room temperature, be immersed in fine and close Na-β "-Al 2o 3in the slurry of layer, rotary pulling applies 2 times, and dry, the demoulding, at 1000 DEG C of pre-burning 1h.Continue to be immersed in porous Na-β "-Al 2o 3, at 1600 DEG C of sintering 20min after drying, obtain two gradient type Na-β "-Al in the slurry of layer for 2 times 2o 3electrolyte ceramics barrier film.
Two gradient type Na-β "-Al that this embodiment is obtained 2o 3in the middle of electrolyte ceramics barrier film, the thickness of compacted zone is 16 μm, and the thickness of inner side porous layer is 0.5mm, and the thickness of outside porous layer is 0.2mm.Ionic conductivity at 300 DEG C is 0.11S/cm.
Embodiment 5
Weigh Na-β "-Al 2o 3powder 100g, graphite 10g, triethanolamine 2g, absolute ethyl alcohol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate and the polyethylene glycol of 12wt%, add the polyvinyl butyral resin of 8wt% after ball milling 1h again, continue ball milling 3h 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 and the polyethylene glycol of 6wt%, add the polyvinyl butyral resin of 4wt% after ball milling 1h again, continue ball milling 3h and obtain fine and close Na-β "-Al 2o 3the slurry of layer; Gained slurry is vacuumized 1.5min.The nonwoven fabrics of length of side 40mm is immersed in above-mentioned porous 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 and reach 41.3mm to the length of side 5 times, after drying at room temperature, be immersed in fine and close Na-β "-Al again 2o 3in the slurry of layer, rotary pulling applies 3 times, at 1000 DEG C of pre-burning 2h after drying, by porous/fine and close Na-the β "-Al obtained 2o 3composite membrane continues to be immersed in porous Na-β "-Al 2o 3, at 1600 DEG C of sintering 30min after drying, obtain two gradient type Na-β "-Al in the slurry of layer for 2 times 2o 3electrolyte ceramics barrier film.
Two gradient type Na-β "-Al that this embodiment is obtained 2o 3in the middle of electrolyte ceramics barrier film, the thickness of compacted zone is 30 μm, and the thickness of inner side porous layer is 0.6mm, and the thickness of outside porous layer is 0.3mm.Ionic conductivity at 300 DEG C is 0.12S/cm.
Embodiment 6
Weigh Na-β "-Al 2o 3powder 100g, starch 25g, triethanolamine 3g, absolute ethyl alcohol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 9g and polyethylene glycol 9g, add polyvinyl butyral resin 12g again after ball milling 1h, continue ball milling 2h and obtain porous Na-β "-Al 2o 3the slurry of layer; Weigh Na-β "-Al 2o 3powder 100g, triethanolamine 3g, ethanol 35g, butanone 65g, after mixing on planetary ball mill ball milling 1h, in above-mentioned slurry, add dibutyl phthalate 6g and polyethylene glycol 6g, add polyvinyl butyral resin 8g 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 1min.The nonwoven fabrics of length of side 50mm is immersed in above-mentioned porous Na-β "-Al 2o 3in the slurry of layer, lift out lentamente from slurry after ten seconds and rotate, being stood upside down after certain hour to rotate again to slurry and shape.Repeat aforesaid operations after dry and reach 51.5mm to the length of side 6 times, after drying at room temperature, be immersed in fine and close Na-β "-Al 2o 3in the slurry of layer, rotary pulling applies 2 times, at 1100 DEG C of pre-burning 1h after drying.Continue to be immersed in porous Na-β "-Al 2o 3, at 1550 DEG C of sintering 30min after drying, obtain two gradient type Na-β "-Al in the slurry of layer for 2 times 2o 3electrolyte ceramics barrier film.
Two gradient type Na-β "-Al that this embodiment is obtained 2o 3in the middle of electrolyte ceramics barrier film, the thickness of compacted zone is 19 μm, and the thickness of inner side porous layer is 0.7mm, and the thickness of outside porous layer is 0.2mm.Ionic conductivity at 300 DEG C is 0.10S/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 (9)

1. for an electrolyte ceramics barrier film for sode cell, it is characterized in that, described electrolyte ceramics barrier film comprises Na-β "-Al 2o 3compacted zone and lay respectively at described Na-β "-Al 2o 3one Na-β "-Al of the both sides of compacted zone 2o 3porous layer and the 2nd Na-β "-Al 2o 3porous layer.
2. electrolyte ceramics barrier film according to claim 1, is characterized in that, the thickness of described electrolyte ceramics barrier film is 0.6 ~ 1mm, wherein said Na-β "-Al 2o 3the thickness of compacted zone is 15 ~ 30 μm.
3. electrolyte ceramics barrier film according to claim 1 and 2, is characterized in that, the ionic conductivity of described electrolyte ceramics barrier film at 300 DEG C is 0.10 ~ 0.12S/cm.
4. prepare a method for the electrolyte ceramics barrier film according to any one of claims 1 to 3, 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 obtained Na-β "-Al 2o 3the slurry of compacted zone;
(2) Na-β "-Al 2o 3powder, mixes with organic solvent, dispersant and pore creating material, ball milling 1 ~ 2 hour, then adds plastic agent, ball milling 1 hour, then adds binding agent, ball milling 2 ~ 3 hours obtained Na-β "-Al 2o 3the slurry of porous layer;
(3) by matrix at described Na-β "-Al 2o 3in the slurry of porous layer, rotary pulling coating repeatedly, is placed in described Na-β "-Al again after drying 2o 3in the slurry of compacted zone, rotary pulling coating repeatedly, after drying, directly obtains by Na-β "-Al 1000 ~ 1100 DEG C of pre-burnings after 1000 ~ 1100 DEG C of pre-burnings 1 ~ 3 hour or the demoulding for 1 ~ 3 hour 2o 3porous/dense composite film; And
(4) by described Na-β " Al 2o 3porous/dense composite film is placed in described Na-β "-Al 2o 3in the slurry of porous layer, rotary pulling coating repeatedly, is burnt altogether at 1550 ~ 1600 DEG C after drying and within 15 ~ 30 minutes, is obtained described electrolyte ceramics barrier film.
5. method according to claim 4, is characterized in that, described Na-β "-Al 2o 3the slurry of compacted zone and/or Na-β "-Al 2o 3the slurry of porous layer is first used further to rotary pulling coating through vacuumizing de-bubble process.
6. the method according to claim 4 or 5, 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.
7. the method according to any one of claim 4 ~ 6, 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).
8. the method according to any one of claim 4 ~ 7, is characterized in that, in step (2), and described Na-β "-Al 2o 3the weight ratio of powder, organic solvent, dispersant, pore creating material, plastic agent and binding agent is 100:(100 ~ 120): (2 ~ 4): (10 ~ 30): (12 ~ 18): (8 ~ 12).
9. the method according to any one of claim 4 ~ 8, is characterized in that, described matrix is glass tube or nonwoven fabrics.
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CN104916869A (en) * 2015-05-15 2015-09-16 清华大学 Porous-compact double-layer electrolyte ceramic sintered body, lithium ion battery and lithium-air battery
CN104916869B (en) * 2015-05-15 2017-04-05 清华大学 Porous densification bilayer electrolyte ceramic sintered bodies, lithium ion battery, lithium-air battery
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CN112117434B (en) * 2020-09-07 2022-05-10 中国科学院上海硅酸盐研究所 High-capacity electrode of solid sodium battery and preparation method and application thereof
CN112103555A (en) * 2020-10-21 2020-12-18 中国科学技术大学 All-solid-state lithium ion battery and preparation method thereof
CN112467199A (en) * 2020-11-27 2021-03-09 江苏科技大学 All-solid-state three-layer electrolyte and preparation method of all-solid-state battery

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