CN106033825A - Positive electrode support type sodium nickel battery and preparation method thereof - Google Patents

Positive electrode support type sodium nickel battery and preparation method thereof Download PDF

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Publication number
CN106033825A
CN106033825A CN201510117305.5A CN201510117305A CN106033825A CN 106033825 A CN106033825 A CN 106033825A CN 201510117305 A CN201510117305 A CN 201510117305A CN 106033825 A CN106033825 A CN 106033825A
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supporter
sodium nickel
anode
based battery
positive electrode
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CN106033825B (en
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官万兵
王建新
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/26—Selection of materials as electrolytes
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a positive electrode support type sodium nickel battery. According to the positive electrode support type sodium nickel battery, a positive electrode is adopted as a strength support, and adopts a support body having a porous structure, an electrolyte is a thin film layer positioned at one side of the support body, positive electrode active materials such as Ni, NaCl particles and molten NaAlCl4 are distributed and filled in the pores, and the pores form channels communicating to the electrolyte layer. Compared with the battery in the prior art, the battery of the present invention has the following advantages that the thinning of the electrolyte can be achieved and the thickness of the electrolyte layer is effectively reduced so as to reduce the working temperature of the sodium nickel battery and improve the battery performance.

Description

A kind of anode-supported type sodium nickel-based battery and preparation method thereof
Technical field
The present invention relates to sodium nickel-based battery technical field, be specifically related to sodium nickel-based battery and the preparation side thereof of a kind of anode-supported type structure Method.
Background technology
Sodium nickel (Zero Emission Battery Research Activities, ZEBRA) battery is because the safety of its uniqueness is (as can Bear high speed impact, excessive discharge and recharge and other kinds extreme environment etc.) each at electric automobile, steamer, communication base station etc. Individual field has important application.Therefore, although ZEBRA battery energy density is the highest, but the most in widespread attention.
ZEBRA battery composition is relatively simple, mainly by β "-Al2O3Electrolyte is constituted with positive electrode, wherein positive electrode Predominantly NaCl and Ni.Under conditions of charging, NaCl with Ni in positive pole reacts, and forms Na and NiCl, produces Na ion permeable β "-Al2O3Electrolyte rests on negative pole, forms high-temperature fusion Na metal.Subsequently, at the bar of electric discharge Under part, Na ion permeable the β "-Al that high-temperature fusion Na metal is formed2O3Electrolyte arrive positive pole, and with the NiCl in positive pole Reaction, forms NaCl and Ni.
Current problem is, sodium nickel-based battery operating temperature is higher, reaches 300 DEG C, is unfavorable for its application in energy storage field. To this end, reduce the operating temperature of sodium nickel-based battery so that it is be reduced to 200 DEG C, 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-supported formula, Its structure has two kinds, and one is tubular structure, and another kind is plank frame.Electrolyte-supported tubular structure manufacturing technology difficulty Greatly, cost is high, and electrolyte thickness is higher, and usually 1.5～2mm.Electrolyte-supported is board-like, overcomes tubular type knot The deficiency that structure manufacture difficulty is big, cost is high, and reduce electrolyte thickness, energy density all has the most excellent with operating temperature Gesture.But, in order to meet the needs of intensity, existing electrolyte-supported plank frame sodium nickel-based battery need to be made with thicker electrolyte For supporting, electrolyte thickness the most still requires more than more than 200 μm, generally 200～500 μm.If able to similar fuel Battery is the same, the electrolyte thickness of this structure sodium nickel-based battery is reduced to some tens of pm magnitude the thinnest, then sodium nickel-based battery Energy density and operating temperature be expected to optimize further.But, such sodium nickel-based battery still using electrolyte as strength support, When electrolyte is reduced to, unavoidably will appear from the problem that intensity is not enough.
Summary of the invention
For above-mentioned technical problem, it is desirable to provide the sodium nickel-based battery of a kind of new structure, it achieves the super of electrolyte Filming, thus improve the performance of sodium nickel-based battery, reduce its operating temperature.
In order to realize above-mentioned technical purpose, current inventor provides the sodium nickel-based battery of a kind of anode-supported, i.e. using positive pole as electricity Pond strength support, by dielectric substrate filming, this technical scheme is specific as follows:
A kind of anode-supported type sodium nickel-based battery, including positive pole and dielectric substrate, is characterized in that: described sodium nickel-based battery is by positive pole Support；Described positive pole includes supporter and positive electrode, and supporter is multi-pore structure, and positive electrode is distributed in this hole In；Described dielectric substrate is in the thin layer of positive electrode surface, and described hole forms the passage being communicated to dielectric substrate.
Described positive electrode includes Ni, NaCl and melted NaAlCl4。
Described support body material mainly includes NiO, β "-Al2O3, or NiO Yu β "-Al2O3Mixture.Described Support body material can also include pore creating material.Described pore creating material includes but not limited to graphite, carbon dust and other similar pore-creating One or more mixing in agent material.
Described electrolyte layer mainly includes β "-Al2O3Deng.
When described support body material includes NiO, as preferably, support body material NiO is reduced to Ni, now props up Support material Ni can be simultaneously as positive electrode Ni.
Described sodium nickel-based battery is anode-supported type, and described supporter thickness is preferably greater than dielectric substrate thickness.
As preferably, described supporter thickness is more than 0.1mm；It is further preferred that described supporter thickness is 0.5～1.5mm.
As preferably, described dielectric substrate thickness is less than 100 μm；It is further preferred that described dielectric substrate thickness It is 1～50 μm；It is highly preferred that described dielectric substrate thickness is 2～10 μm.
Present invention also offers a kind of method preparing above-mentioned anode-supported type sodium nickel-based battery, comprise the steps:
(1) with support body material as raw material, add pore creating material, mix homogeneously wherein, use the method such as hot pressing, curtain coating Make and there is certain thickness molded body；
Described pore creating material does not limits, including graphite, carbon dust and other similar pore creating materials etc..
Described Content of Pore-forming Agents can adjust as required, and as preferably, described pore creating material quality accounts for support body material quality 30～80%.
(2) molded body that step (1) prepares being carried out presintering, pore creating material volatilizees, and obtains having the pre-of multi-pore structure Supporter, concrete dynamic modulus therein can connect and form at least one passage running through pre-supporter thickness.
As preferably, described 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 prepared in step (2) The methods such as brush, curtain coating make dielectric substrate, are then sintered, support type half electricity that the body that is supported is constituted with dielectric substrate Pond；
As preferably, described sintering temperature is 1300～1600 DEG C.
(4) by Ni, NaCl granule and melted NaAlCl4Mixing, obtains mixture；Step (3) obtained props up Support type half-cell immerses this mixture, makes mixture be filled in supporter hole, forms anode-supported type sodium nickel-based battery；Or Person, is cast into this mixture in supporter hole, forms anode-supported type sodium nickel-based battery.
When described support body material includes NiO, as preferably, by propping up of support type half-cell prepared for step (3) Support body is put into and is reduced under atmosphere furnace, makes NiO be reduced to W metal, and this W metal can substitute for mixture in step (4) In Ni granule.
In view of the positive electrode consumption in battery during duty, the invention allows for a kind of preferably battery structure, should In structure, supporter is two parts separated from one another, the referred to as first supporter and the second supporter；First supporter and second Support body is positioned at substrate surface；The opposing two sides of the first supporter and the second supporter arrange electrolytic thin-membrane layer；First The relative two sides of support body and the second supporter form concave structure with substrate surface.In this battery structure, can be by positive pole Material is filled in concave structure, and after battery operated middle positive electrode consumes, positive electrode can be carried out by pore channel Supplement, thus the job stability of beneficially battery.It is it addition, supporter is two parts in this structure and symmetrical, Be conducive to interpolation and the payment of laminate stress during hot operation of electrolyte solution.
Described base material does not limits.Base material can be chosen as electrolyte layer, now, bottom supporter and side It is dielectric substrate, adds reactivity area, be conducive to improving energy density and the sealing of battery.
In sum, the strength support using positive pole as sodium nickel-based battery, positive pole are used the supporter of multiple-void structure by the present invention, Electrolyte is then in the thin layer of supporter side, positive electrode active materials Ni, NaCl granule and melted NaAlCl4 Distribution is filled in this hole, and this hole forms the passage being communicated to dielectric substrate.Under conditions of charging, supporter NaCl with Ni in hole reacts formation Na and NiCl, and the Na ion of generation enters dielectric substrate by this passage, thoroughly Cross electrolyte and rest on negative pole, form high-temperature fusion Na metal.Under conditions of electric discharge, high-temperature fusion Na metal is formed Na ion permeable electrolyte arrive positive pole, reacted with NiCl by this passage, formation NaCl and Ni.With prior art Comparing, the present invention is capable of electrolyte thin membranization, effectively reduces the thickness of dielectric substrate, thus reduces sodium nickel-based battery Operating temperature, in some instances it may even be possible to be reduced to room temperature, improve its energy density performance.
Accompanying drawing explanation
Fig. 1 is positive pole and the structural representation of dielectric substrate in the embodiment of the present invention 1 anode-supported type sodium nickel-based battery.
Fig. 2 is positive pole and the structural representation of dielectric substrate in the embodiment of the present invention 4 anode-supported type sodium nickel-based battery.
Detailed description of the invention
The present invention is described in further detail by embodiment below in conjunction with the accompanying drawings, it should be pointed out that embodiment described below purport It is being easy to the understanding of the present invention, and it is not being played any restriction effect.
Reference in Fig. 1 is: positive pole 1, dielectric substrate 2, supporter 3, hole 4.
Reference in Fig. 2 is: the first dielectric substrate 2-1, the second dielectric substrate 2-2, the first supporter 3-1, second Supporter 3-2, hole 4, concave structure 5, base 6.
Embodiment 1:
In the present embodiment, sodium nickel-based battery uses anode-supported structure, and Fig. 1 is the structural representation of its positive pole and dielectric substrate. Positive pole 1 includes supporter 3 and positive electrode, and support body material is β "-Al2O3, positive electrode is Ni, NaCl and melts The NaAlCl melted4.Supporter 3 is in multi-pore structure, and positive electrode is distributed in this hole 4.Electrolyte 2 is just in The thin layer of side, surface, pole, hole 4 forms at least one passage being communicated to dielectric substrate 2.Electrolyte layer is β"-Al2O3。
The preparation method of the sodium nickel-based battery of this anode-supported type structure comprises the steps:
(1) with support body material β "-Al2O3For raw material, adding pore creating material graphite wherein, graphite quality accounts for supporter material The 30～80% of material quality, mix homogeneously, then use the method for hot pressing to make band that thickness is 0.1～1.5mm；
(2) band that step (1) prepares being carried out presintering, pre-sintering temperature is 1000 DEG C～1200 DEG C, and pore creating material is waved Sending out, obtain the pre-supporter of multi-pore structure, wherein porosity communication forms at least one passage running through pre-supporter thickness；
(3) electrolyte the β "-Al that pre-supporting body surface side print thickness is 1～50 μm prepared in step (2)2O3, Then being sintered, sintering temperature is 1300～1600 DEG C, the support type half-cell that the body that is supported is constituted with dielectric substrate；
(4) by Ni, NaCl granule and melted NaAlCl4Mixing, obtains mixture；Step (3) obtained props up Support type half-cell immerses this mixture, makes mixture be filled in supporter hole, forms anode-supported type sodium nickel-based battery；
(5) carry out outside assembling, form monomer sodium nickel-based battery.
Being charged above-mentioned prepared sodium nickel-based battery, NaCl with Ni in supporter hole reacts formation Na and NiCl, The Na ion produced enters dielectric substrate by pore channel, rests on negative pole through electrolyte, forms high-temperature fusion Na Metal.During electric discharge, high-temperature fusion Na metal formed Na ion permeable electrolyte arrive positive pole, by pore channel with NiCl reacts, and forms NaCl and Ni.
Embodiment 2:
In the present embodiment, sodium nickel-based battery uses anode-supported structure, and Fig. 1 is the structural representation of its positive pole and dielectric substrate. Positive pole 1 includes supporter 3 and positive electrode, and support body material is β "-Al2O3With the mixture of YSZ, positive electrode is Ni, NaCl and melted NaAlCl4.Supporter 3 is in multi-pore structure, and positive electrode is distributed in this hole 4.Electricity Solving matter 2 and be in the thin layer of positive electrode surface side, hole 4 forms at least one passage being communicated to dielectric substrate 2.Electricity Solving matter layer material is β "-Al2O3。
The preparation method of the sodium nickel-based battery of this anode-supported type structure comprises the steps:
(1) with support body material β "-Al2O3Being raw material with YSZ, add pore creating material graphite wherein, graphite quality accounts for and props up The 30～80% of support material quality, mix homogeneously, then use the method for hot pressing to make band that thickness is 0.5～1.5mm；
(2) band that step (1) prepares being carried out presintering, pre-sintering temperature is 1000 DEG C～1200 DEG C, and pore creating material is waved Sending out, obtain the pre-supporter of multi-pore structure, wherein porosity communication forms at least one passage running through pre-supporter thickness；
(3) electrolyte the β "-Al that pre-supporting body surface side print thickness is 2～10 μm prepared in step (2)2O3, Then being sintered, sintering temperature is 1300～1600 DEG C, the support type half-cell that the body that is supported is constituted with dielectric substrate；
(4) by Ni, NaCl granule and melted NaAlCl4Mixing, obtains mixture；Step (3) obtained props up Support type half-cell immerses this mixture, makes mixture be filled in supporter hole, forms anode-supported type sodium nickel-based battery；
(5) carry out outside assembling, form monomer sodium nickel-based battery.
Being charged above-mentioned prepared sodium nickel-based battery, NaCl with Ni in supporter hole reacts formation Na and NiCl, The Na ion produced enters dielectric substrate by pore channel, rests on negative pole through electrolyte, forms high-temperature fusion Na Metal.During electric discharge, high-temperature fusion Na metal formed Na ion permeable electrolyte arrive positive pole, by pore channel with NiCl reacts, and forms NaCl and Ni.
Embodiment 3:
In the present embodiment, sodium nickel-based battery uses anode-supported structure, and Fig. 1 is the structural representation of its positive pole and dielectric substrate. Positive pole 1 includes supporter 3 and positive electrode, and support body material is the reduzate W metal of NiO, positive electrode be Ni, NaCl and melted NaAlCl4.Supporter 3 is in multi-pore structure, and positive electrode is distributed in this hole 4.Electrolyte 4 thin layers being in positive electrode surface side, hole 4 forms at least one passage being communicated to dielectric substrate 2.Electrolyte Layer material is β "-Al2O3。
The preparation method of the sodium nickel-based battery of this anode-supported type structure comprises the steps:
(1) with support body material NiO as raw material, adding pore creating material graphite wherein, graphite quality accounts for support body material matter The 30～80% of amount, mix homogeneously, then use the method for hot pressing to make band that thickness is 0.5～1.5mm；
(2) band that step (1) prepares being carried out presintering, pre-sintering temperature is 1000 DEG C～1200 DEG C, and pore creating material is waved Sending out, obtain the pre-supporter of multi-pore structure, wherein porosity communication forms at least one passage running through pre-supporter thickness；
(3) electrolyte the β "-Al that pre-supporting body surface side print thickness is 1～50 μm prepared in step (2)2O3, Then being sintered, sintering temperature is 1300～1600 DEG C, the support type half-cell that the body that is supported is constituted with dielectric substrate；
(4) the support body material NiO of loose structure is put into fully reduce under atmosphere furnace so that it is be reduced to W metal, this Time support body material Ni can be simultaneously as positive electrode Ni；
(5) by NaCl granule and melted NaAlCl4Mixing, obtains mixture；The support type that step (3) is obtained Half-cell immerses this mixture, makes mixture be filled in supporter hole, forms anode-supported type sodium nickel-based battery；
(6) carry out outside assembling, form monomer sodium nickel-based battery.
Above-mentioned prepared sodium nickel-based battery is charged, the NaCl in supporter hole and supporter Ni react formation Na with NiCl, the Na ion of generation enters dielectric substrate by pore channel, rests on negative pole through electrolyte, forms high temperature melting Melt Na metal.During electric discharge, the Na ion permeable electrolyte that high-temperature fusion Na metal is formed arrives positive pole, is led to by hole Road reacts with NiCl, forms NaCl and Ni.
Embodiment 4:
In the present embodiment, sodium nickel-based battery uses anode-supported structure, and Fig. 2 is the structural representation of its positive pole and dielectric substrate. In this structure, supporter is two parts separated from one another, the referred to as first supporter 3-1 and the second supporter 3-2；First Support body 3-1 and the second supporter 3-2 is positioned at substrate 6 surface；First supporter 3-1 and the second supporter 3-2 deviates from mutually Two sides electrolytic thin-membrane layer is set, i.e. as in figure 2 it is shown, the side of the first supporter 3-1 arranges the first electrolytic thin-membrane Layer 2-1, the side of the second supporter 3-2 arranges the second electrolytic thin-membrane layer 2-2；First supporter 3-1 and the second supporter The relative two sides of 3-2 form a concave structure 5 with the surface of substrate 5.First supporter 3-1 is multi-pore structure, Positive electrode is distributed in this hole 4.Second supporter 3-2 is multi-pore structure, and positive electrode is distributed in this hole 4. The hole of the first supporter 3-1 forms at least one passage being communicated to the first dielectric substrate 2-1.Second supporter 3-2's Hole forms at least one passage being communicated to the second dielectric substrate 2-2.
The material of the first dielectric substrate 2-1 and the second dielectric substrate is β "-Al2O3.First supporter 3-1 and second supports The material of body 3-2 is β "-Al2O3.Positive electrode is Ni, NaCl and melted NaAlCl4.The material of base 6 is β"-Al2O3。
In the present embodiment, use the step (1) to (4) in embodiment 1 to prepare respectively and comprise the first supporter 3-1 and the The anode-supported type sodium nickel-based battery of one dielectric substrate 2-1, and comprise the second supporter 3-2's and the second dielectric substrate 2-2 Then these two parts are fixed on base 5 surface by anode-supported type sodium nickel-based battery, make the first supporter 3-1 and second support There is interval in body 3-2, and two relative sides of the first supporter 3-1 and the second supporter 3-2 form one with base Individual concave structure, first dielectric substrate 2-1 the second dielectric substrate 2-2 is positioned at the first supporter 3-1 and the second supporter 3-2 Deviate from mutually two sides.
During duty, being filled in by positive electrode in this concave structure, after consuming when positive electrode, positive electrode can To be supplemented by pore channel, thus the job stability of beneficially battery.It addition, supporter is two in this structure Point, and symmetrical, the beneficially payment of laminate stress when the interpolation of electrolyte solution and hot operation.
In this enforcement, the material of base material and the first dielectric substrate 2-1 and the second dielectric substrate is identical, is β "-Al2O3, Thus add reactivity area, be conducive to improving energy density and the sealing of battery.
Above-described embodiment has carried out system detailed description to technical solution of the present invention, it should be understood that upper described example is only this The specific embodiment of invention, is not limited to the present invention.All made in spirit of the present invention any amendment, supplement Or equivalent etc., should be included within the scope of the present invention.

Claims (10)

1. an anode-supported type sodium nickel-based battery, including positive pole and dielectric substrate, is characterized in that: described sodium nickel-based battery By anode-supported；Described positive pole include supporter and positive electrode, described positive electrode include Ni, NaCl and Melted NaAlCl4；Supporter is multi-pore structure, and positive electrode is distributed in this hole；Described dielectric substrate is Being positioned at the thin layer of positive electrode surface, described hole forms at least one passage being communicated to dielectric substrate.
2. anode-supported type sodium nickel-based battery as claimed in claim 1, is characterized in that: described support body material includes NiO、β"-Al2O3, or NiO Yu β "-Al2O3Mixture；
As preferably, described electrolyte layer includes β "-Al2O3。
3. anode-supported type sodium nickel-based battery as claimed in claim 1, is characterized in that: described support body material includes During NiO, support body material NiO being reduced to Ni, this support body material Ni is simultaneously as positive electrode Ni.
4. anode-supported type sodium nickel-based battery as claimed in claim 1, is characterized in that: described supporter thickness is more than Dielectric substrate thickness.
5. anode-supported type sodium nickel-based battery as claimed in claim 1, is characterized in that: described supporter thickness is more than 0.1mm；It is preferably 0.5～1.5mm.
6. anode-supported type sodium nickel-based battery as claimed in claim 1, is characterized in that: described dielectric substrate thickness is little In 100 μm；It is preferably 1～50 μm；More preferably 2～10 μm.
7. the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 6, is characterized in that: institute The support body material stated also includes pore creating material；As preferably, described pore creating material includes one or both in graphite, carbon dust Mixing.
8. the anode-supported type sodium nickel-based battery as described in any claim in claim 1 to 6, is characterized in that: institute The supporter stated is two parts separated from one another, the referred to as first supporter and the second supporter；First supporter and second Support body is positioned at substrate surface；The two sides deviated from mutually of the first supporter and the second supporter arrange electrolytic thin-membrane layer；The The relative two sides of one supporter and the second supporter form concave structure with the surface of substrate.
9. the method preparing anode-supported type sodium nickel-based battery as claimed in claim 7, comprises the steps:
(1) with support body material as raw material, add pore creating material, mix homogeneously wherein, use hot pressing or the tape casting Make and there is certain thickness molded body；
As preferably, described pore creating material includes one or both the mixture in graphite, carbon dust；
As preferably, described pore creating material quality accounts for the 30～80% of support body material quality；
(2) molded body that step (1) prepares being carried out presintering, pore creating material volatilizees, and obtains having multi-pore structure Pre-supporter, concrete dynamic modulus therein connection forms at least one passage running through pre-supporter thickness；
As preferably, described pre-sintering temperature is 1000 DEG C～1200 DEG C；
(3) step (2) prepare pre-supporter through-thickness a side surface by electrolyte use coating, Printing or the tape casting make dielectric substrate, are then sintered, the support type half that the body that is supported is constituted with dielectric substrate Battery；
As preferably, described sintering temperature is 1300～1600 DEG C；
(4) by Ni, NaCl granule and melted NaAlCl4Mixing, obtains mixture；Step (3) is obtained Support type half-cell immerses this mixture, makes mixture be filled in supporter hole, forms anode-supported type sodium nickel-based battery； Or, this mixture is cast in supporter hole, forms anode-supported type sodium nickel-based battery.
10. the method preparing anode-supported type sodium nickel-based battery as claimed in claim 9, is characterized in that: when described props up When support material includes NiO, the support body material NiO of support type half-cell step (3) prepared reduces, Making it be reduced to W metal, this W metal replaces the Ni granule in step (4) in mixture.
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CN111200124A (en) * 2019-09-29 2020-05-26 浙江安力能源有限公司 Sodium-nickel battery positive electrode material and preparation method thereof

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