CN106033825B - A kind of anode-supported type sodium nickel-based battery and preparation method thereof - Google Patents
A kind of anode-supported type sodium nickel-based battery and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
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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
- H01M10/24—Alkaline accumulators
- H01M10/28—Construction or manufacture
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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
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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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
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- 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
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Abstract
The present invention provides a kind of sodium nickel-based batteries of anode-supported type.For the sodium nickel-based battery using anode as strength support, it is then the NaAlCl of the film layer positioned at supporter side, positive electrode active materials Ni, NaCl particle and melting that anode, which uses the supporter of multi-pore structure, electrolyte,4Distribution is filled in the hole, and the hole forms the channel for being connected to electrolyte layer.Compared with prior art, the present invention can realize electrolyte thin membranization, effectively reduce the thickness of electrolyte layer, to reduce the operating temperature of sodium nickel-based battery, while improve battery performance.
Description
Technical field
The present invention relates to sodium nickel-based battery technical fields, and in particular to a kind of the sodium nickel-based battery and its system of anode-supported type structure
Preparation Method.
Background technology
Sodium nickel (Zero Emission Battery Research Activities, ZEBRA) battery is because of its unique peace
Full property (can such as bear high speed impact, excessive charge and discharge and other kinds extreme environment) is in electric vehicle, steamer, communication base
The every field such as stand have important application.Therefore, it although ZEBRA battery energy densities are not high, is still weighed extensively
Depending on.
ZEBRA battery compositions are relatively simple, mainly by β "-Al2O3Electrolyte is constituted with positive electrode, wherein positive electrode
Predominantly NaCl and Ni.Under conditions of charging, the NaCl in anode is reacted with Ni, forms Na and NiCl, the Na ions of generation
Through β "-Al2O3Electrolyte rests on cathode, forms high-temperature fusion Na metals.Then, under conditions of electric discharge, high-temperature fusion Na
The Na ions that metal is formed penetrate β "-Al2O3Electrolyte reaches anode, and is reacted with the NiCl in anode, forms NaCl and Ni.
Current problem is that sodium nickel-based battery operating temperature is higher, up to 300 DEG C, is unfavorable for its application in energy storage field.
For this purpose, reducing the operating temperature of sodium nickel-based battery, it is made to be reduced to 200 DEG C, it is even lower, become research tendency.
In order to reduce the operating temperature of sodium nickel-based battery, electrolyte thin membranization is crucial.Existing sodium nickel-based battery is electrolyte branch
Support formula, there are two types of structures, and one is tubular structure, another kind is plank frame.Electrolyte-supported tubular structure manufacturing technology
Difficulty is big, of high cost, and electrolyte thickness is higher, usually 1.5~2mm.Electrolyte-supported is board-like, overcomes tubular type knot
Big, the of high cost deficiency of structure manufacture difficulty, and electrolyte thickness is reduced, energy density has significantly excellent with operating temperature
Gesture.However, in order to meet the needs of intensity, existing electrolyte-supported plank frame sodium nickel-based battery need to using thicker electrolyte as
Support, electrolyte thickness usually still require more than 200 μm or more, generally 200~500 μm.If being capable of similar fuel cell one
The electrolyte thickness of this structure sodium nickel-based battery is reduced to some tens of pm magnitude even more thin, then the energy of sodium nickel-based battery by sample
Density and operating temperature are expected to advanced optimize.But such sodium nickel-based battery works as electrolysis still using electrolyte as strength support
Matter is reduced to, the problem that will unavoidably intensity deficiency occur.
Invention content
In view of the above technical problems, the present invention is intended to provide a kind of new structural sodium nickel-based battery, realizes electrolyte
Ultra-thin membranization reduce its operating temperature to improve the performance of sodium nickel-based battery.
In order to achieve the above technical purposes, current inventor provides a kind of sodium nickel-based batteries of anode-supported, i.e., are made with anode
It is supported for battery strength, by electrolyte layer filming, the technical solution is specific as follows：
A kind of anode-supported type sodium nickel-based battery, including anode and electrolyte layer, it is characterized in that：The sodium nickel-based battery is by just
Pole supports；The anode includes supporter and positive electrode, and supporter is in multi-pore structure, and positive electrode is distributed in the hole
In；The electrolyte layer is the film layer positioned at positive electrode surface, and the hole forms the channel for being connected to electrolyte layer.
The positive electrode includes Ni, NaCl and the NaAlCl of melting4。
The support body material includes mainly NiO, β "-Al2O3Or NiO and β "-Al2O3Mixture.Described
Support body material can also include pore creating material.The pore creating material include but not limited to graphite, carbon dust and other similar to pore-creating
The mixing of one or more of agent material.
The electrolyte layer includes mainly β "-Al2O3Deng.
When the support body material includes NiO, preferably, support body material NiO is reduced to Ni, support at this time
Body material Ni can be used as positive electrode Ni simultaneously.
The sodium nickel-based battery is anode-supported type, and the support body thickness is preferably greater than electrolyte layer thickness.
Preferably, the support body thickness is more than 0.1mm；It is further preferred that the support body thickness is 0.5
~1.5mm.
Preferably, the electrolyte layer thickness is less than 100 μm；It is further preferred that the electrolyte layer thickness
It is 1~50 μm；It is highly preferred that the electrolyte layer thickness is 2~10 μm.
The present invention also provides a kind of methods preparing above-mentioned anode-supported type sodium nickel-based battery, include the following steps：
(1) using support body material as raw material, pore creating material is added wherein, is uniformly mixed, using the methods of hot pressing, curtain coating system
At with certain thickness formed body；
The pore creating material is unlimited, including graphite, carbon dust and other similar to pore creating material etc..
The Content of Pore-forming Agents can adjust as needed, preferably, the pore creating material quality accounts for support body material
The 30~80% of quality.
(2) formed body made from step (1) is pre-sintered, pore creating material volatilization obtains having the pre- of multi-pore structure
Supporter, concrete dynamic modulus therein can be connected to form at least one channel for running through pre- supporter thickness.
Preferably, the pre-sintering temperature is 1000 DEG C~1200 DEG C.
(3) electrolyte is used coating, print by a side surface of the pre- supporter through-thickness made from step (2)
Electrolyte layer is made in the methods of brush, curtain coating, is then sintered, and be supported half electricity of support type that body is constituted with electrolyte layer
Pond；
Preferably, the sintering temperature is 1300~1600 DEG C.
(4) by the NaAlCl of Ni, NaCl particle and melting4Mixing, obtains mixture；The support type that step (3) is obtained
Half-cell immerses the mixture, and mixture is made to be filled in supporter hole, forms anode-supported type sodium nickel-based battery；Alternatively, will
The mixture is cast into supporter hole, forms anode-supported type sodium nickel-based battery.
When the support body material includes NiO, preferably, by the branch of support type half-cell made from step (3)
Support body is put under atmosphere furnace and restores, and NiO is made to be reduced to W metal, which can replace the Ni in step (4) in mixture
Particle.
Positive electrode consumption when in view of working condition in battery, the invention also provides a kind of preferred battery knots
Structure, supporter is the two parts being separated from each other, referred to as the first supporter and the second supporter in the structure；First supporter and
Two supporters are located at substrate surface；Electrolyte thin film layer is arranged in the first supporter two sides opposite with the second supporter；The
The opposite two sides of one supporter and the second supporter form concave structure with substrate surface.In the battery structure, it can incite somebody to action
Positive electrode is filled in concave structure, and after positive electrode consumes in battery work, positive electrode can pass through pore channel
It is supplemented, to be conducive to the job stability of battery.In addition, supporter is two parts in the structure, and it is symmetrical,
Be conducive to the payment of laminate stress when the addition and hot operation of electrolyte solution.
The base material is unlimited.Base material can be selected as electrolyte layer, at this point, supporter bottom and side
Face is electrolyte layer, increases reactivity area, is conducive to the energy density and the sealing that improve battery.
In conclusion the present invention, by the strength support using anode as sodium nickel-based battery, anode uses the branch of multiple-void structure
Support body, electrolyte are then the film layers positioned at supporter side, positive electrode active materials Ni, NaCl particle and melting
NaAlCl4Distribution is filled in the hole, and the hole forms the channel for being connected to electrolyte layer.Under conditions of charging,
NaCl in supporter hole reacts to form Na and NiCl with Ni, and the Na ions of generation enter electrolyte layer by the channel, thoroughly
It crosses electrolyte and rests on cathode, form high-temperature fusion Na metals.Under conditions of electric discharge, high-temperature fusion Na metals formed Na from
Son reaches anode through electrolyte, is reacted with NiCl by the channel, forms NaCl and Ni.Compared with prior art, of the invention
It can realize electrolyte thin membranization, effectively reduce the thickness of electrolyte layer, to reduce the operating temperature of sodium nickel-based battery, very
To may be decreased room temperature, its energy density performance is improved.
Description of the drawings
Fig. 1 is the structural schematic diagram of anode and electrolyte layer in 1 anode-supported type sodium nickel-based battery of the embodiment of the present invention.
Fig. 2 is the structural schematic diagram of anode and electrolyte layer in 4 anode-supported type sodium nickel-based battery of the embodiment of the present invention.
Specific implementation mode
Present invention is further described in detail for embodiment below in conjunction with the accompanying drawings, it should be pointed out that implementation as described below
Example is intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.
Reference numeral in Fig. 1 is：Anode 1, electrolyte layer 2, supporter 3, hole 4.
Reference numeral in Fig. 2 is：First electrolyte layer 2-1, the second electrolyte layer 2-2, the first supporter 3-1, second
Supporter 3-2, hole 4, concave structure 5, pedestal 6.
Embodiment 1：
In the present embodiment, it is the structural representation of its anode and electrolyte layer that sodium nickel-based battery, which uses anode-supported structure, Fig. 1,
Figure.Anode 1 includes supporter 3 and positive electrode, and support body material is β "-Al2O3, positive electrode Ni, NaCl and melting
NaAlCl4.Supporter 3 is in multi-pore structure, and positive electrode is distributed in the hole 4.Electrolyte 2 is to be located at positive electrode surface side
Film layer, hole 4 forms at least one channel for being connected to electrolyte layer 2.Electrolyte layer is β "-Al2O3。
The preparation method of the sodium nickel-based battery of the anode-supported type structure includes the following steps：
(1) with support body material β "-Al2O3For raw material, pore creating material graphite is added wherein, and graphite quality accounts for supporter material
Expect the 30~80% of quality, is uniformly mixed, thickness is made as the band of 0.1~1.5mm in the method for then using hot pressing；
(2) band made from step (1) is pre-sintered, pre-sintering temperature is 1000 DEG C~1200 DEG C, and pore creating material is waved
Hair obtains the pre- supporter of multi-pore structure, and wherein porosity communication forms at least one channel for running through pre- supporter thickness；
(3) the electrolyte β "-that the pre- supporting body surface side print thickness made from step (2) is 1~50 μm
Al2O3, then it is sintered, sintering temperature is 1300~1600 DEG C, and be supported half electricity of support type that body is constituted with electrolyte layer
Pond；
(4) by the NaAlCl of Ni, NaCl particle and melting4Mixing, obtains mixture；The support type that step (3) is obtained
Half-cell immerses the mixture, and mixture is made to be filled in supporter hole, forms anode-supported type sodium nickel-based battery；
(5) external assembling is carried out, monomer sodium nickel-based battery is formed.
It charging to sodium nickel-based battery obtained above, the NaCl in supporter hole reacts to form Na and NiCl with Ni,
The Na ions of generation enter electrolyte layer by pore channel, rest on cathode through electrolyte, form high-temperature fusion Na metals.
When electric discharge, the Na ions that high-temperature fusion Na metals are formed reach anode through electrolyte, are reacted with NiCl by pore channel, shape
At NaCl and Ni.
Embodiment 2：
In the present embodiment, it is the structural representation of its anode and electrolyte layer that sodium nickel-based battery, which uses anode-supported structure, Fig. 1,
Figure.Anode 1 includes supporter 3 and positive electrode, and support body material is β "-Al2O3With the mixture of YSZ, positive electrode Ni,
The NaCl and NaAlCl of melting4.Supporter 3 is in multi-pore structure, and positive electrode is distributed in the hole 4.Electrolyte 2 is position
Film layer in positive electrode surface side, hole 4 form at least one channel for being connected to electrolyte layer 2.Electrolyte layer is
β"-Al2O3。
The preparation method of the sodium nickel-based battery of the anode-supported type structure includes the following steps：
(1) with support body material β "-Al2O3It is raw material with YSZ, adds pore creating material graphite wherein, graphite quality accounts for support
The 30~80% of body quality of materials are uniformly mixed, and thickness is made as the band of 0.5~1.5mm in the method for then using hot pressing；
(2) band made from step (1) is pre-sintered, pre-sintering temperature is 1000 DEG C~1200 DEG C, and pore creating material is waved
Hair obtains the pre- supporter of multi-pore structure, and wherein porosity communication forms at least one channel for running through pre- supporter thickness；
(3) the electrolyte β "-that the pre- supporting body surface side print thickness made from step (2) is 2~10 μm
Al2O3, then it is sintered, sintering temperature is 1300~1600 DEG C, and be supported half electricity of support type that body is constituted with electrolyte layer
Pond；
(4) by the NaAlCl of Ni, NaCl particle and melting4Mixing, obtains mixture；The support type that step (3) is obtained
Half-cell immerses the mixture, and mixture is made to be filled in supporter hole, forms anode-supported type sodium nickel-based battery；
(5) external assembling is carried out, monomer sodium nickel-based battery is formed.
It charging to sodium nickel-based battery obtained above, the NaCl in supporter hole reacts to form Na and NiCl with Ni,
The Na ions of generation enter electrolyte layer by pore channel, rest on cathode through electrolyte, form high-temperature fusion Na metals.
When electric discharge, the Na ions that high-temperature fusion Na metals are formed reach anode through electrolyte, are reacted with NiCl by pore channel, shape
At NaCl and Ni.
Embodiment 3：
In the present embodiment, it is the structural representation of its anode and electrolyte layer that sodium nickel-based battery, which uses anode-supported structure, Fig. 1,
Figure.Anode 1 include supporter 3 and positive electrode, support body material be NiO reduzate W metal, positive electrode Ni,
The NaCl and NaAlCl of melting4.Supporter 3 is in multi-pore structure, and positive electrode is distributed in the hole 4.Electrolyte 4 is position
Film layer in positive electrode surface side, hole 4 form at least one channel for being connected to electrolyte layer 2.Electrolyte layer is
β"-Al2O3。
The preparation method of the sodium nickel-based battery of the anode-supported type structure includes the following steps：
(1) using support body material NiO as raw material, pore creating material graphite is added wherein, and graphite quality accounts for support body material matter
The 30~80% of amount are uniformly mixed, and thickness is made as the band of 0.5~1.5mm in the method for then using hot pressing；
(2) band made from step (1) is pre-sintered, pre-sintering temperature is 1000 DEG C~1200 DEG C, and pore creating material is waved
Hair obtains the pre- supporter of multi-pore structure, and wherein porosity communication forms at least one channel for running through pre- supporter thickness；
(3) the electrolyte β "-that the pre- supporting body surface side print thickness made from step (2) is 1~50 μm
Al2O3, then it is sintered, sintering temperature is 1300~1600 DEG C, and be supported half electricity of support type that body is constituted with electrolyte layer
Pond；
(4) the support body material NiO of porous structure is put under atmosphere furnace and is fully restored, it is made to be reduced to W metal, this
When support body material Ni can be used as positive electrode Ni simultaneously；
(5) by the NaAlCl of NaCl particles and melting4Mixing, obtains mixture；Half electricity of the support type that step (3) is obtained
The mixture is immersed in pond, and mixture is made to be filled in supporter hole, forms anode-supported type sodium nickel-based battery；
(6) external assembling is carried out, monomer sodium nickel-based battery is formed.
Charge to sodium nickel-based battery obtained above, the NaCl in supporter hole reacted with supporter Ni to be formed Na with
The Na ions of NiCl, generation enter electrolyte layer by pore channel, rest on cathode through electrolyte, form high-temperature fusion Na
Metal.When electric discharge, the Na ions that high-temperature fusion Na metals are formed reach anode through electrolyte, anti-with NiCl by pore channel
It answers, forms NaCl and Ni.
Embodiment 4：
In the present embodiment, it is the structural representation of its anode and electrolyte layer that sodium nickel-based battery, which uses anode-supported structure, Fig. 2,
Figure.In the structure, supporter is the two parts being separated from each other, referred to as the first supporter 3-1 and the second supporter 3-2；First
Support body 3-1 and the second supporter 3-2 are located at 6 surface of substrate；Two be away from each other of first supporter 3-1 and the second supporter 3-2
Electrolyte thin film layer is arranged in side, i.e., as shown in Fig. 2, the first electrolyte thin film layer 2-1 is arranged in the side of the first supporter 3-1,
The second electrolyte thin film layer 2-2 is arranged in the side of second supporter 3-2；First supporter 3-1 is opposite with the second supporter 3-2's
The surface of two sides and substrate 5 form a concave structure 5.First supporter 3-1 is in multi-pore structure, positive electrode distribution
In the hole 4.Second supporter 3-2 is in multi-pore structure, and positive electrode is distributed in the hole 4.First supporter 3-1's
Hole forms at least one channel for being connected to the first electrolyte layer 2-1.The hole of second supporter 3-2 forms at least one and connects
Pass to the channel of the second electrolyte layer 2-2.
The material of first electrolyte layer 2-1 and the second electrolyte layer is β "-Al2O3.First supporter 3-1 and second
The material of support body 3-2 is β "-Al2O3.Positive electrode is Ni, NaCl and the NaAlCl of melting4.The material of pedestal 6 is β "-
Al2O3。
In the present embodiment, it includes the first supporter 3-1 and first to be made respectively using the step (1) to (4) in embodiment 1
The anode-supported type sodium nickel-based battery of electrolyte layer 2-1, and the anode comprising the second supporter 3-2 and the second electrolyte layer 2-2
Then this two parts is fixed on 5 surface of pedestal by support type sodium nickel-based battery, the first supporter 3-1 is made to be deposited with the second supporter 3-2
It is being spaced, and two opposite sides of the first supporter 3-1 and the second supporter 3-2 form a spill knot with pedestal
Structure, first the second electrolyte layers of electrolyte layer 2-1 2-2 are located at two be away from each other of the first supporter 3-1 and the second supporter 3-2
A side.
When working condition, positive electrode is filled in the concave structure, is used for after positive electrode consumes, positive electrode
It can be supplemented by pore channel, to be conducive to the job stability of battery.In addition, supporter is two in the structure
Point, and it is symmetrical, be conducive to the payment of laminate stress when the addition and hot operation of electrolyte solution.
In this implementation, the material identical of base material and the first electrolyte layer 2-1 and the second electrolyte layer, is β "-
Al2O3, to increase reactivity area, be conducive to the energy density and the sealing that improve battery.
Above-described embodiment has carried out system detailed description to technical solution of the present invention, it should be understood that the upper example is only
For specific embodiments of the present invention, it is not intended to restrict the invention.All any modifications made in spirit of the present invention, benefit
It fills or equivalent replacement etc., should all be included in the protection scope of the present invention.
Claims (16)
1. a kind of preparation method of anode-supported type sodium nickel-based battery, the anode-supported type sodium nickel-based battery includes anode and electrolyte
Layer, it is characterized in that：The sodium nickel-based battery is by anode-supported；The anode includes supporter and positive electrode, it is described just
Pole material includes Ni, NaCl and the NaAlCl of melting4；Supporter is in multi-pore structure, and positive electrode is distributed in the hole；
The electrolyte layer is the film layer positioned at positive electrode surface, and the hole forms at least one and is connected to the logical of electrolyte layer
Road；
The preparation method of the anode-supported type sodium nickel-based battery includes the following steps：
(1) using support body material as raw material, pore creating material is added wherein, is uniformly mixed, tool is made using hot pressing or the tape casting
There is certain thickness formed body；
(2) formed body made from step (1) is pre-sintered, pore creating material volatilization obtains the pre- support with multi-pore structure
Body, concrete dynamic modulus therein are connected to form at least one channel for running through pre- supporter thickness；
(3) side surface of the pre- supporter through-thickness made from step (2) by electrolyte using coating, printing or
Electrolyte layer is made in person's the tape casting, is then sintered, the support type half-cell that the body that is supported is constituted with electrolyte layer；
(4) by the NaAlCl of Ni, NaCl particle and melting4Mixing, obtains mixture；The support type half-cell that step (3) is obtained
The mixture is immersed, mixture is made to be filled in supporter hole, forms anode-supported type sodium nickel-based battery；Alternatively, by the mixing
Body is cast into supporter hole, forms anode-supported type sodium nickel-based battery.
2. the preparation method of anode-supported type sodium nickel-based battery as described in claim 1, it is characterized in that：The support body material
Including NiO, β "-Al2O3Or NiO and β "-Al2O3Mixture.
3. the preparation method of anode-supported type sodium nickel-based battery as described in claim 1, it is characterized in that：The electrolyte layer material
Material includes β "-Al2O3。
4. the preparation method of anode-supported type sodium nickel-based battery as described in claim 1, it is characterized in that：The support body thickness
More than electrolyte layer thickness.
5. the preparation method of anode-supported type sodium nickel-based battery as described in claim 1, it is characterized in that：The support body thickness
More than 0.1mm.
6. the preparation method of anode-supported type sodium nickel-based battery as claimed in claim 5, it is characterized in that：The support body thickness
For 0.5~1.5mm.
7. the preparation method of anode-supported type sodium nickel-based battery as described in claim 1, it is characterized in that：The electrolyte thickness
Degree is less than 100 μm.
8. the preparation method of anode-supported type sodium nickel-based battery as claimed in claim 7, it is characterized in that：The electrolyte thickness
Degree is 1~50 μm.
9. the preparation method of anode-supported type sodium nickel-based battery as described in claim 1, it is characterized in that：The electrolyte thickness
Degree is 2~10 μm.
10. the preparation method of the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：The support body material further includes pore creating material.
11. the preparation method of the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：The pore creating material includes the mixing of one or both of graphite, carbon dust.
12. the preparation method of the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：The supporter is the two parts being separated from each other, referred to as the first supporter and the second supporter；First supporter and second
Supporter is located at substrate surface；The two sides setting electrolyte thin film layer of first supporter and the second supporter being away from each other；The
The surface of the opposite two sides and substrate of one supporter and the second supporter forms concave structure.
13. the preparation method of the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：The pore creating material quality accounts for the 30~80% of support body material quality.
14. the preparation method of the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：The pre-sintering temperature is 1000 DEG C~1200 DEG C.
15. the preparation method of the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：The sintering temperature is 1300~1600 DEG C.
16. the method for the preparation anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 9, feature
It is：When the support body material includes NiO, the support body material NiO of support type half-cell made from step (3) is carried out
Reduction, makes it be reduced to W metal, which replaces the Ni particles in mixture in step (4).
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| CN102746022A (en) * | 2011-12-29 | 2012-10-24 | 西安建筑科技大学 | Preparation method for Al2O3 ceramic material having controllable bimodal porous structure |
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| CN104282868A (en) * | 2013-07-12 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Electrolyte ceramic membrane supported by modified porous membrane and preparation method of electrolyte ceramic membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1667860A (en) * | 2005-04-07 | 2005-09-14 | 天津大学 | Fuel battery structure and process for preparing same |
| CN1913208A (en) * | 2006-07-17 | 2007-02-14 | 昆明理工大学 | Middle-temp. solid oxide fuel cell system material and its cell and preparation method |
| CN102746022A (en) * | 2011-12-29 | 2012-10-24 | 西安建筑科技大学 | Preparation method for Al2O3 ceramic material having controllable bimodal porous structure |
| CN103342544A (en) * | 2013-07-03 | 2013-10-09 | 镇江市江南矿山机电设备有限公司 | Method for preparing porous alumina ceramic |
| CN104282868A (en) * | 2013-07-12 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Electrolyte ceramic membrane supported by modified porous membrane and preparation method of electrolyte ceramic membrane |
| CN103474687A (en) * | 2013-09-10 | 2013-12-25 | 中国科学院上海硅酸盐研究所 | Method for preparing a high-performance slab solid oxide fuel single battery |
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