CN104098323A - Multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and preparation method thereof - Google Patents
Multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and preparation method thereof Download PDFInfo
- Publication number
- CN104098323A CN104098323A CN201310126715.7A CN201310126715A CN104098323A CN 104098323 A CN104098323 A CN 104098323A CN 201310126715 A CN201310126715 A CN 201310126715A CN 104098323 A CN104098323 A CN 104098323A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- multilayer composite
- plate
- preparation
- curtain coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention provides a multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and a preparation method thereof. A porous supporting layer, which is slightly thicker than a thin-wall solid electrolyte layer, is attached to the thin-wall solid electrolyte layer, wherein the porous supporting layer has an effect of reinforcement so that the solid electrolyte is prevented from cracking during usage and a safety performance of a sodium-sulfur battery is enhanced. Meanwhile, the supporting layer is in a porous structure, wherein pores provide channels for transportation of sodium ions, do not have an obvious blocking effect on the transportation of the sodium ions and not influent resistivity and ion flux, so that the multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte, which is composed of a thin compact layer and a thick porous supporting layer, not only has a high ion flux but also has enough strength, thereby enabling a manufactured sodium-sulfur battery to be high in energy density and meanwhile safety to be not influenced.
Description
Technical field
The present invention relates to chemical field, relate in particular to a kind of MULTILAYER COMPOSITE β "-Al
2o
3flat-plate-type solid ionogen and preparation method thereof.
Background technology
Sodium-sulfur cell the earliest by U.S.'s Ford (Ford) company in 1967 Invention Announce first.It is a kind of taking sodium Metal 99.5 as negative pole, sulphur is anodal, β "-Al
2o
3vitrified pipe is the secondary cell of electrolyte membrance.The good characteristic of sodium-sulfur cell self: the overload pulse power output characteristic that energy density is high, operation life is long, green non-pollution, maintenance cost are low and outstanding and rapidly kinetic characteristic etc., make it have broad application prospects in the field such as accumulator system, power system.Nowadays sodium-sulfur cell has been successfully used in the stable output of the renewable energy sources such as peak load shifting, emergency source of electric power, wind-power electricity generation and has improved the aspects such as power quality, relating to multiple industries such as industry, business, traffic, electric power, is the potential a kind of energy-storage battery of tool in various secondary cells.
Solid electrolyte, as the core material of sodium-sulfur cell, is the key factor that affects sodium-sulfur cell performance and life-span.What adopt due to traditional sodium-sulfur cell is central electrode design, and therefore solid electrolyte is often tubular structure.Because electrophoretic deposition (electrophoretic deposition) has original advantage aspect the complex-shaped structured material of preparation, therefore traditional sodium-sulfur cell solid electrolyte ceramic pipe adopts the method preparation of electrophoretic deposition, as U.S. Patent No. 3,896, described in 018.Adopt the sodium-sulfur cell of this structure solid electrolyte, its negative pole sodium Metal 99.5 is filled in Tube-type Solid-electrolyte, and this requires solid electrolyte to have enough mechanical strengths, thereby the thickness of Tube-type Solid-electrolyte is larger, between 0.5mm ~ 2mm.But the ionic flux of solid electrolyte and the thickness of solid electrolyte are inversely proportional to, solid electrolyte thickness is larger, its ionic flux is just lower, this will make sodium-sulfur cell energy density reduce, and actual energy density is below 150Wh/kg, far below theoretical energy density 760Wh/kg.Meanwhile, the solid electrolyte preparation process complexity of tubular structure, production efficiency is low; Due to its preparation technology's impact, caliber and pipe range be restriction to some extent all.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of MULTILAYER COMPOSITE β "-Al
2o
3flat-plate-type solid ionogen and preparation method thereof.
MULTILAYER COMPOSITE flat-plate-type solid ionogen of the present invention mainly adopts casting method preparation.Casting method can be prepared flat board (film) solid electrolyte of thickness within the scope of 5 μ m ~ 2mm, and gained solid electrolyte can be very thin.And adopt casting method to prepare flat-plate-type solid ionogen to have that equipment is simple, technical maturity is stable, can operate continuously, production efficiency advantages of higher, be applicable to very much suitability for industrialized production.
Object of the present invention realizes by following steps:
The configuration of step 1, tight zone casting slurry:
By the β of 15 ~ 25 vol% "-Al
2o
3ceramic powder, 50 ~ 65vol% solvent, 1 ~ 10vol% dispersion agent add and in the nylon ball grinder that agate ball is housed, carry out one time ball milling.Ratio of grinding media to material (1 ~ 3): 1, rotating speed 80 ~ 400rpm, Ball-milling Time 8 ~ 24h.
After one time ball milling completes, then add 10 ~ 21vol% binding agent and 5 ~ 12vol% softening agent to carry out secondary ball milling in ball grinder, obtain stable slurry; Ball-milling Time 4 ~ 12h.
The stable slurry that ball milling is obtained carries out degassed under vacuum condition.Vacuum tightness≤0.01Mpa is advisable, and the degassed time is 1 ~ 4h.
The configuration of step 2, porous support layer slurry:
The ceramic powder of 10 ~ 25 vol%, 3% ~ 12%vol% pore-creating agent, 45 ~ 60vol% solvent, 1 ~ 10vol% dispersion agent are added and in the nylon ball grinder that agate ball is housed, carry out one time ball milling.Ratio of grinding media to material (1 ~ 3): 1, rotating speed 80 ~ 400rpm, Ball-milling Time 8 ~ 24h.
After one time ball milling completes, then add 5 ~ 18vol% binding agent and 5 ~ 12vol% softening agent to carry out secondary ball milling in ball grinder, obtain stable slurry; Ball-milling Time 4 ~ 12h.
The stable slurry that ball milling is obtained carries out degassed under vacuum condition.Vacuum tightness≤0.01Mpa is advisable, and the degassed time is 1 ~ 4h.
Step 3, pour the supporting layer slurry preparing into casting machine, flow casting molding in base band; Make the raw band of supporting layer of even thickness by controlling scraper gap, hopper liquid level, curtain coating speed etc.; Drying, binder removal sintering obtain porous support layer again.
Step 4, pour the tight zone slurry preparing into casting machine, flow casting molding on supporting layer, makes the raw band of MULTILAYER COMPOSITE solid electrolyte of even thickness by controlling scraper gap, hopper liquid level, curtain coating speed etc.; Raw band drying, binder removal sintering obtain target MULTILAYER COMPOSITE flat-plate-type solid ionogen.
Step 5, prepare three layers of compound solid electrolyte as need, can proceed by operation steps 4 at the another side of supporting layer.
Wherein, curtain coating tight zone β used in the present invention "-AI
2o
3ceramics powder, particle diameter 20 ~ 150nm is advisable.
In the present invention, for preventing that delamination from appearring in tight zone in sintering process because percent thermal shrinkage is different with supporting layer, tight zone should select with supporting layer the material that thermal expansivity is identical or close.Therefore curtain coating porous support layer ceramics powder used is β-AI in the present invention
2o
3or β "-AI
2o
3, particle diameter 0.5 ~ 2.0 μ m is advisable.
Be applicable to solvent of the present invention and be any one in the binary azeotropic solvent systems such as second alcohol and water, ethanol and toluene, ethanol and normal hexane, ethanol and butanone, butanone and methyl alcohol, trieline and methyl alcohol.
Be applicable to dispersion agent of the present invention and be any one in triethyl phosphate, ammonium polymethacrylate, triolein, ethoxy castor oil, menhaden fish oil.
Be applicable to binding agent of the present invention and be any one in polyvinyl alcohol, polyvinyl butyral acetal, latex, polymethylmethacrylate, methylcellulose gum, carboxymethyl cellulose.
Be applicable to softening agent of the present invention and be any one in glycerine, polyoxyethylene glycol, dibutyl phthalate, o-phthalic acid dibutyl ester, butyl benzyl phthalate, tri-ethylene glycol.
Be applicable to pore-creating agent of the present invention and be any one in volatile salt, bicarbonate of ammonia, rice husk, ammonium chloride, carbon dust, saw dust, starch.
Be applicable to curtain coating process of the present invention: when scraper gap is 20 ~ 125 μ m, curtain coating supporting layer when the viscosity of casting slurry is 1000m ~ 2000mPas, curtain coating tight zone, scraper gap is that 125 μ m ~ 1.5mm, hopper liquid level are that 0.3 ~ 2.5cm, curtain coating speed are 0.5 ~ 1.0cm/s.
The base band adopting when curtain coating porous support layer in the present invention is the polyester film base band of silane coating releasing agent, and thickness is that 70 μ m ~ 650 μ m are advisable.
In the present invention when curtain coating tight zone, both can be on the porous support layer of sinter molding curtain coating, also can bring curtain coating in the supporting layer life without sintering.
In curtain coating process of the present invention, kiln temperature is 40 DEG C ~ 60 DEG C and is advisable, and the sintering temperature of solid electrolyte is 1450 DEG C ~ 1600 DEG C.
The electrolytical number of plies of MULTILAYER COMPOSITE flat-plate-type solid of the present invention is that 2 ~ 3 layers of dense layer thickness, 10 μ m ~ 115 μ m are advisable, and porous support layer thickness 115 μ m ~ 1.25mm are advisable.
Porous support layer described in the present invention, its aperture is that 10 μ m ~ 85 μ m are advisable.
MULTILAYER COMPOSITE flat-plate-type solid ionogen of the present invention, its complex method is except above-mentioned direct curtain coating is compound, curtain coating is prepared after the raw band of porous support layer and the raw band of tight zone respectively, by its on demand laminated, hot pressing is compound or it is compound to cold pressing.
The invention provides a kind of flat-plate-type solid ionogen of MULTILAYER COMPOSITE, this solid electrolyte is made up of thinner tight zone and thicker porous support layer, have intensity and higher ionic flux concurrently, overcome the lower shortcoming of ionic flux that tubular structure solid electrolyte brings, make the sodium-sulfur cell energy density that makes high, performance is more excellent.
For solving solid electrolyte ceramic pipe because wall thickness makes the problem that sodium-sulfur cell energy density is lower, the present invention proposes to adopt the flat-plate-type solid ionogen of MULTILAYER COMPOSITE to replace traditional Tube-type Solid-electrolyte.Because adopt flat solid electrolytical sodium-sulfur cell, solid electrolyte, without sustaining electrode weight, just separates electrode, and what solid electrolyte just can do like this is very thin, and ionic flux is high like this, makes that the sodium-sulfur cell energy density that makes is high, performance good.For making the resistivity of solid electrolyte low as far as possible, ionic flux is high as far as possible, and flat solid ionogen need do to obtain Bao Yuehao more.But flat solid ionogen is too thin, under the thermal stresses effect producing in sodium-sulfur cell use procedure, likely break, sodium-sulfur cell is short-circuited, reduce the safety performance of sodium-sulfur cell.For this reason, the present invention proposes on the solid electrolyte layer of thin-walled, to enclose the porous support layer that one deck is slightly thick.Porous support layer plays the effect of enhancing, prevents that solid electrolyte from breaking in the process using, and promotes the safety performance of sodium-sulfur cell; Meanwhile, because this supporting layer is vesicular structure, the passage that duct provides sodium ion transmission, can not play significant inhibition to the transmission of sodium ion, can not have a significant effect to resistivity, ionic flux yet.Therefore, this MULTILAYER COMPOSITE flat solid ionogen being made up of thinner tight zone and thicker porous support layer had both had higher ionic flux, had again enough intensity; Make prepared sodium-sulfur cell energy density high, security simultaneously can be not influenced yet.
Preparing the electrolytical method of flat-plate-type solid has a lot, and electrophoretic deposition equally also can be for the preparation of flat-plate-type solid ionogen.Flat-plate-type solid ionogen prepared by casting method and electrophoretic deposition all has the features such as good uniformity, thickness be controlled, but electrophoretic deposition is prepared flat-plate-type solid, electrolytical influence factor is a lot, and the factor such as characteristic, pH value, additive types, deposition process temperature and the substrate surface state of suspension of electric current, voltage, dispersion medium and support pottery itself all will impact the electrolytical preparation of flat-plate-type solid.And casting method for the preparation of flat-plate-type solid ionogen have that equipment is simple, technical maturity is stable, can operate continuously, production efficiency advantages of higher, be applicable to suitability for industrialized production.
Embodiment
Now in conjunction with embodiment, the present invention is described as follows.Here it should be noted that embodiment not for example; just for the present invention is further illustrated; and can not be interpreted as limiting the scope of the present invention, all contents according to the present invention are made the improvement of unsubstantiality and adjust the row that all belong to the present invention's protection it.
Embodiment 1
Take the β that accounts for total amount 15vol% by formula "-Al
2o
3ceramics powder, the ethanol/water azeotropic solvent (wherein ethanol: the ratio of water is 95:5(wt%) of 65%vol), the triethyl phosphate of 5%vol.Take and get the β that accounts for total amount 25vol% by formula "-Al
2o
3ceramics powder, 12vol% volatile salt, the ethanol/water azeotropic solvent (wherein ethanol: the ratio of water is 95:5(wt%) of 45%vol), the triethyl phosphate of 5%vol.Load weighted raw material is poured into respectively and in nylon ball grinder, carried out one time ball milling, ratio of grinding media to material 2:1, rotating speed 400rpm, Ball-milling Time 12h.After one time ball milling completes, add 10vol% polyvinyl alcohol, 5vol% glycerine and 8vol% polyvinyl alcohol, 5vol% glycerine respectively again in ball grinder, ball milling 4h again, obtains stable casting slurry.By the casting slurry of gained degassed 2h under the vacuum condition of-0.01MPa.After degassed completing, pour casting slurry into casting machine and carry out curtain coating composite molding, scraper gap is respectively 20 μ m and 900 μ m.The composite solid electrolyte obtaining of curtain coating obtains target MULTILAYER COMPOSITE flat-plate-type solid ionogen through binder removal, sintering (1475 DEG C of sintering temperatures) after being dried.
Embodiment 2
Take the β that accounts for total amount 25vol% by formula "-Al
2o
3ceramics powder, the ethanol/toluene azeotropic solvent (wherein ethanol: the ratio of toluene is 68:32(wt%) of 50vol%), the menhaden fish oil of 10%vol.Take the β-Al that accounts for total amount 20vol% by formula
2o
3ceramics powder, 6vol% rice husk, the ethanol/toluene azeotropic solvent (wherein ethanol: the ratio of toluene is 68:32(wt%) of 45vol%), the menhaden fish oil of 10%vol.Load weighted raw material is poured into respectively and in nylon ball grinder, carried out one time ball milling, ratio of grinding media to material 2:1, rotating speed 400rpm, Ball-milling Time 24h.After one time ball milling completes, add 10vol% polyvinyl butyral acetal, 5vol% dibutyl phthalate and 12vol% polyvinyl butyral acetal, 7vol% dibutyl phthalate respectively again in ball grinder, ball milling 12h again, obtains stable casting slurry.By the casting slurry of gained degassed 4h under the vacuum condition of-0.01MPa.After degassed completing, pour casting slurry into casting machine and carry out curtain coating composite molding, scraper gap is respectively 50 μ m and 650 μ m.The composite solid electrolyte obtaining of curtain coating obtains target MULTILAYER COMPOSITE flat-plate-type solid ionogen through binder removal, sintering (1475 DEG C of sintering temperatures) after being dried.
Embodiment 3
Take the β that accounts for total amount 20vol% by formula "-Al
2o
3ceramics powder, butanone/methanol azeotropic solvent (wherein butanone: the ratio of methyl alcohol is 86:14(wt%) of 55%vol), the triolein of 3%vol.Take the β that accounts for total amount 20vol% by formula "-Al
2o
3ceramics powder, 5vol% saw dust, butanone/methanol azeotropic solvent (wherein butanone: the ratio of methyl alcohol is 86:14(wt%) of 50%vol), the triolein of 5%vol.Load weighted raw material is poured into respectively and in nylon ball grinder, carried out one time ball milling, ratio of grinding media to material 2:1, rotating speed 400rpm, Ball-milling Time 18h.After one time ball milling completes, add 16vol% polyvinyl butyral acetal, 6vol% divinyl ethylene glycol and 15vol% polyvinyl butyral acetal, 5vol% divinyl ethylene glycol again in ball grinder, ball milling 6h again, obtains stable casting slurry.By the casting slurry of gained degassed 2h under the vacuum condition of-0.01MPa.After degassed completing, pour casting slurry into casting machine and carry out curtain coating composite molding, scraper gap is respectively 35 μ m and 850 μ m.The composite solid electrolyte obtaining of curtain coating obtains target MULTILAYER COMPOSITE flat-plate-type solid ionogen through binder removal, sintering (1475 DEG C of sintering temperatures) after being dried.
Claims (15)
1. the plate β of MULTILAYER COMPOSITE "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that this solid electrolyte by tight zone and porous support layer is compound forms, and adopts casting method preparation, comprises the following steps:
The configuration of step 1, tight zone casting slurry:
By the β of 15 ~ 25 vol% "-Al
2o
3ceramic powder, 50 ~ 65vol% solvent, 1 ~ 10vol% dispersion agent add and in the nylon ball grinder that agate ball is housed, carry out one time ball milling; Ratio of grinding media to material (1 ~ 3): 1, rotating speed 80 ~ 400rpm, Ball-milling Time 8 ~ 24h;
After one time ball milling completes, then add 10 ~ 21vol% binding agent and 5 ~ 12vol% softening agent to carry out secondary ball milling in ball grinder, obtain stable slurry; Ball-milling Time 4 ~ 12h;
The stable slurry that ball milling is obtained carries out degassed under vacuum condition, and vacuum tightness≤0.01Mpa is advisable, and the degassed time is 1 ~ 4h;
The configuration of step 2, porous support layer slurry:
The ceramic powder of 10 ~ 25 vol%, 3% ~ 12%vol% pore-creating agent, 45 ~ 60vol% solvent, 1 ~ 10vol% dispersion agent are added and in the nylon ball grinder that agate ball is housed, carry out one time ball milling; Ratio of grinding media to material (1 ~ 3): 1, rotating speed 80 ~ 400rpm, Ball-milling Time 8 ~ 24h;
After one time ball milling completes, then add 5 ~ 18vol% binding agent and 5 ~ 12vol% softening agent to carry out secondary ball milling in ball grinder, obtain stable slurry, Ball-milling Time 4 ~ 12h; The stable slurry that ball milling is obtained carries out degassed under vacuum condition, and vacuum tightness≤0.01Mpa is advisable, and the degassed time is 1 ~ 4h;
Step 3, pour the supporting layer slurry preparing into casting machine, flow casting molding in base band; Make the raw band of supporting layer of even thickness by controlling scraper gap, hopper liquid level, curtain coating speed etc.; Drying, binder removal sintering obtain porous support layer again;
Step 4, pour the tight zone slurry preparing into casting machine, flow casting molding on supporting layer, makes the raw band of MULTILAYER COMPOSITE solid electrolyte of even thickness by controlling scraper gap, hopper liquid level, curtain coating speed etc.; Raw band drying, binder removal sintering obtain target MULTILAYER COMPOSITE flat-plate-type solid ionogen;
Step 5, prepare three layers of compound solid electrolyte as need, can proceed by operation steps 4 at the another side of supporting layer.
2. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described curtain coating tight zone β used "-AI
2o
3ceramics powder, particle diameter 20 ~ 150nm is advisable.
3. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described curtain coating porous support layer ceramics powder used is β-AI
2o
3or β "-AI
2o
3, particle diameter 0.5 ~ 2.0 μ m is advisable.
4. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described solvent is any one in the binary azeotropic solvent systems such as second alcohol and water, ethanol and toluene, ethanol and normal hexane, ethanol and butanone, butanone and methyl alcohol, trieline and methyl alcohol.
5. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described dispersion agent is any one in triethyl phosphate, ammonium polymethacrylate, triolein, ethoxy castor oil, menhaden fish oil.
6. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described binding agent is any one in polyvinyl alcohol, polyvinyl butyral acetal, latex, polymethylmethacrylate, methylcellulose gum, carboxymethyl cellulose.
7. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described softening agent is any one in glycerine, polyoxyethylene glycol, dibutyl phthalate, o-phthalic acid dibutyl ester, tri-ethylene glycol.
8. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described pore-creating agent is any one in volatile salt, bicarbonate of ammonia, rice husk, ammonium chloride, carbon dust, saw dust, starch.
9. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, when when the viscosity that it is characterized in that described casting slurry is 1000m ~ 2000mPas, curtain coating tight zone, scraper gap is 20 ~ 125 μ m, curtain coating supporting layer, scraper gap is that 125 μ m ~ 1.5mm, hopper liquid level are that 0.3 ~ 2.5cm, curtain coating speed are 0.5 ~ 1.0cm/s.
10. the plate β of a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, the base band adopting while it is characterized in that described curtain coating porous support layer is the polyester film base band of silane coating releasing agent, thickness is that 70 μ m ~ 650 μ m are advisable.
The plate β of 11. a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, while it is characterized in that curtain coating tight zone, both can be on the porous support layer of sinter molding curtain coating, also can bring curtain coating in the supporting layer life without sintering.
The plate β of 12. a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that in described curtain coating process that kiln temperature is 40 DEG C ~ 60 DEG C and is advisable, and the sintering temperature of solid electrolyte is 1450 DEG C ~ 1600 DEG C.
The plate β of 13. a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that the electrolytical number of plies of described MULTILAYER COMPOSITE flat-plate-type solid is 2 ~ 3 layers, and dense layer thickness 10 μ m ~ 115 μ m are advisable, and porous support layer thickness 115 μ m ~ 1.25mm are advisable.
The plate β of 14. a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, is characterized in that described porous support layer, and its aperture is that 10 μ m ~ 85 μ m are advisable.
The plate β of 15. a kind of MULTILAYER COMPOSITE as claimed in claim 1 "-Al
2o
3solid electrolyte and preparation method thereof, it is characterized in that described MULTILAYER COMPOSITE flat-plate-type solid ionogen, its complex method is except direct curtain coating is compound, and curtain coating is prepared after the raw band of porous support layer and the raw band of tight zone respectively, by its on demand laminated, hot pressing is compound or it is compound to cold pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310126715.7A CN104098323A (en) | 2013-04-12 | 2013-04-12 | Multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310126715.7A CN104098323A (en) | 2013-04-12 | 2013-04-12 | Multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104098323A true CN104098323A (en) | 2014-10-15 |
Family
ID=51666912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310126715.7A Pending CN104098323A (en) | 2013-04-12 | 2013-04-12 | Multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104098323A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761241A (en) * | 2014-01-03 | 2015-07-08 | 深圳光启创新技术有限公司 | Organic ceramic slurry suitable for casting technology |
| CN105174408A (en) * | 2015-09-14 | 2015-12-23 | 佛山市迭蓓丝生物科技有限公司 | Solid electrolyte, and preparation method and application thereof |
| CN105330265A (en) * | 2015-11-16 | 2016-02-17 | 中国科学院上海硅酸盐研究所 | Method for mass production of beta''-Al2O3 diaphragms |
| CN105990614A (en) * | 2015-02-13 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Sodium-metal chloride battery with plate structure |
| CN106182343A (en) * | 2016-08-17 | 2016-12-07 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery solid electrolyte ceramic pipe forming method |
| CN112010647A (en) * | 2020-09-07 | 2020-12-01 | 南京医科大学 | Self-supporting ceramic diaphragm and preparation method and application 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 |
| CN112909331A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Ultrathin sulfide electrolyte composite flexible film and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462868A (en) * | 2009-01-05 | 2009-06-24 | 中国科学院上海硅酸盐研究所 | Method for preparing beta-alumina ceramic membrane |
| CN101791818A (en) * | 2010-03-04 | 2010-08-04 | 中国电子科技集团公司第五十五研究所 | Method for preparing aluminium oxide ceramics green ceramic chip by tape casting |
| CN102424568A (en) * | 2011-09-02 | 2012-04-25 | 厦门大学 | Method for preparing tungsten-containing alumina ceramic heating substrate |
| CN102718498A (en) * | 2012-07-04 | 2012-10-10 | 珠海微晶新材料科技有限公司 | Coating preparation method for flakey aluminum oxide ceramic |
-
2013
- 2013-04-12 CN CN201310126715.7A patent/CN104098323A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462868A (en) * | 2009-01-05 | 2009-06-24 | 中国科学院上海硅酸盐研究所 | Method for preparing beta-alumina ceramic membrane |
| CN101791818A (en) * | 2010-03-04 | 2010-08-04 | 中国电子科技集团公司第五十五研究所 | Method for preparing aluminium oxide ceramics green ceramic chip by tape casting |
| CN102424568A (en) * | 2011-09-02 | 2012-04-25 | 厦门大学 | Method for preparing tungsten-containing alumina ceramic heating substrate |
| CN102718498A (en) * | 2012-07-04 | 2012-10-10 | 珠海微晶新材料科技有限公司 | Coating preparation method for flakey aluminum oxide ceramic |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761241A (en) * | 2014-01-03 | 2015-07-08 | 深圳光启创新技术有限公司 | Organic ceramic slurry suitable for casting technology |
| CN104761241B (en) * | 2014-01-03 | 2018-10-19 | 深圳光启创新技术有限公司 | A kind of organic group ceramic slurry of suitable casting technique |
| CN105990614A (en) * | 2015-02-13 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Sodium-metal chloride battery with plate structure |
| CN105174408A (en) * | 2015-09-14 | 2015-12-23 | 佛山市迭蓓丝生物科技有限公司 | Solid electrolyte, and preparation method and application thereof |
| CN105330265A (en) * | 2015-11-16 | 2016-02-17 | 中国科学院上海硅酸盐研究所 | Method for mass production of beta''-Al2O3 diaphragms |
| CN105330265B (en) * | 2015-11-16 | 2019-02-26 | 中国科学院上海硅酸盐研究所 | One kind being suitable for volume production β "-Al2O3The method of diaphragm |
| CN106182343A (en) * | 2016-08-17 | 2016-12-07 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery solid electrolyte ceramic pipe forming method |
| CN106182343B (en) * | 2016-08-17 | 2018-11-27 | 上海电气钠硫储能技术有限公司 | A kind of sodium-sulphur battery solid electrolyte ceramic pipe forming method |
| CN112909331A (en) * | 2019-12-04 | 2021-06-04 | 中国科学院宁波材料技术与工程研究所 | Ultrathin sulfide electrolyte composite flexible film and preparation method and application thereof |
| CN112010647A (en) * | 2020-09-07 | 2020-12-01 | 南京医科大学 | Self-supporting ceramic diaphragm and preparation method and application 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104098323A (en) | Multilayer composite [beta]"-Al2O3 flat-plate-type solid electrolyte and preparation method thereof | |
| JP5742941B2 (en) | All-solid battery and method for manufacturing the same | |
| KR101118933B1 (en) | Negative electrode for lithium secondary cell, lithium secondary cell employing the negative electrode, film deposition material used for forming negative electrode, and process for producing negative electrode | |
| JP6596194B2 (en) | Solid ion capacitor | |
| CN214706016U (en) | Energy device with lithium | |
| JP5201984B2 (en) | Method for manufacturing electrolyte impregnated electrode of molten carbonate fuel cell using wet method | |
| JP5285292B2 (en) | All solid lithium ion secondary battery | |
| JP5811191B2 (en) | All-solid battery and method for manufacturing the same | |
| JP2012099225A (en) | All-solid lithium ion secondary battery and method of manufacturing the same | |
| WO2017146133A1 (en) | Stacked green sheet, continuous stacked green sheet, stacked sintered body, continuous stacked sintered body, and all-solid secondary battery, and method for producing stacked green sheet, method for producing continuous stacked green sheet, and method for producing all-solid secondary battery | |
| JP2018063850A (en) | Laminate green sheet, all-solid type secondary battery, and method for fabricating the same | |
| CN104466188A (en) | Multilayer composite positive pole piece, method for preparing pole piece and lithium ion battery applying multilayer composite positive pole piece | |
| WO2017145657A1 (en) | All-solid secondary battery, method for producing all-solid secondary battery, stacked green sheet for all-solid secondary battery, stacked green sheet with current collector foil for all-solid secondary battery, and continuous stacked green sheet for all-solid secondary battery | |
| CN108134132B (en) | A kind of dynamic lithium battery microcapsules thin-film ceramics solid electrolyte and preparation method | |
| KR101222722B1 (en) | Interconnecting plate for solid oxide fuel cell and manufacturing method thereof, and solid oxide fuel cell using said interconnecting plate | |
| JP2011134617A (en) | All-solid battery | |
| KR20100047703A (en) | An electrolyte-filled and reinforced matrix for molten carbonate fuel cell and method for producing the same | |
| CN109585914A (en) | The preparation method of oxide solid electrolyte sheet and the solid state battery prepared using this method | |
| JP6192540B2 (en) | All-solid battery and method for manufacturing the same | |
| KR101089248B1 (en) | SAPARATOR USING POROUS SiOC THIN FILM AND FABRICATION METHOD THEREOF | |
| JP2009181875A (en) | Laminate for lithium ion secondary battery and method of manufacturing the same | |
| KR101008063B1 (en) | Wet-based?method of electrolyte filled electrodes for molten carbonate fuel cell | |
| KR20140075526A (en) | an electrode having conductive material integral structure and a secondary battery using thereof | |
| JP2018063808A (en) | Laminate green sheet, all-solid type secondary battery, and fabricating methods thereof | |
| JP2016207326A (en) | Electrode composite manufacturing method and lithium battery manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141015 |