AU2020338256A1 - Electrochemical energy storage device - Google Patents
Electrochemical energy storage device Download PDFInfo
- Publication number
- AU2020338256A1 AU2020338256A1 AU2020338256A AU2020338256A AU2020338256A1 AU 2020338256 A1 AU2020338256 A1 AU 2020338256A1 AU 2020338256 A AU2020338256 A AU 2020338256A AU 2020338256 A AU2020338256 A AU 2020338256A AU 2020338256 A1 AU2020338256 A1 AU 2020338256A1
- Authority
- AU
- Australia
- Prior art keywords
- cell
- electrochemical cell
- tube
- electrolyte
- electrochemical
- 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
- 238000012983 electrochemical energy storage Methods 0.000 title abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 5
- 229910018965 MCl2 Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
- H01M10/3954—Sodium-sulfur cells containing additives or special arrangement in the sulfur compartment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
- H01M10/3963—Sealing means between the solid electrolyte and holders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention proceeds from an electrochemical energy storage device, in particular an electrochemical cell (10), based on the redox system Na/MCl2 comprising a ceramic electrolyte (12) that conducts Na+ ions and a salt as liquid electrolyte, wherein a cathode space (11) is arranged outside an electrolyte tube and an anode space (13) is arranged within an electrolyte tube. The invention proposes that the electrochemical energy storage device, in particular the electrochemical cell, comprises a cell housing (19) which has a semi-spherical cell bottom (23).
Description
Electrochemical energy storage device
Prior art
The present invention relates to an electrochemical cell for the reversible storage of electrical energy using the redox reaction
2 NaCl + M <-+ MC12 + 2 Na
where M is one of the transition metals such as for example nickel or iron in conjunction with a ceramic electrolyte made from P"-alumina. This electrolyte is generally tubular with a closed end. These cells have an open-circuit voltage of 2.58 V and, according to the prior art, a capacity in the range from 20 Ah to a little over 100 Ah. This capacity is determined by the internal volume of the electrolyte and the power by its surface area. Thus, the ratio of power to energy for large tube diameters decreases proportionally to 1/r.
EP 2 541 646 Al describes a current design of the electrochemical cell here with a is cloverleaf-shaped electrolyte, a complex shim structure which surrounds the electrolyte, and an anode space for liquid sodium between the ceramic electrolyte and the housing.
US 2017/0104244 Al describes an electrochemical cell of the same type. The current collector for the positive electrode is arranged centrally and is surrounded by the cathode mass. The amount the cathode mass and hence the cell capacity is limited by the size of the ceramic electrolytes and reduced by the volume of the current collector.
WO 94/23467 A2 describes the active components of this type of electrochemical cell.
US 4,722,875 A discloses an electrochemical cell which is based on the known redox system has an impregnated mixture which forms a cathode of the electrochemical cell and is separated from an alkali metal anode by a solid-state electrolyte separator.
GB 2 182 194 A and US 3,966,492 A likewise already disclose electrochemical cells.
The publication T. Oshima, M. Kajita, A. Okuno, Development of Sodium-Sulfur Batteries, Int. J. Apple. Ceram. Technol., 1 [3] 269-76 (2004) discloses that NaS battery cells also use an Na+ ion-conductive ceramic and that in this cell type the negative electrode is arranged inside the ceramic tube and the sulfur electrode is arranged outside the ceramic tube. The reasons for this arrangement are firstly the need for a sodium safety cartridge which can only be arranged inside the ceramic tube and secondly the installation of the sulfur cathode in the form of preformed shells. These differences made it nonobvious to arrange the cathode outside of the ceramic electrolyte for the NaNiCl2 system, since this would be accompanied by a reduction in power. As a result, cells with a high power requirement are designed with an internal cathode and cells with a high energy requirement are designed with an external cathode.
The object of the invention is in particular that of providing a device for the storage of is large amounts of electrical energy using the abovementioned redox reaction, which has a capacity of 200 Ah to more than 300 Ah and the same time allows complete discharge in fewer than or equal to 10 hours.
The object is achieved according to the invention by the features of patent claim 1, while advantageous configurations and developments of the invention can be gathered from the dependent claims.
Advantages of the invention
The invention proceeds from an electrochemical energy storage device, in particular an electrochemical cell, based on the redox system Na/MCl2, having an Na+ ion conducting ceramic electrolyte and a salt as liquid electrolyte, wherein a cathode space is arranged outside of an electrolyte tube and an anode space is arranged inside an electrolyte tube.
It is proposed that the electrochemical energy storage device, in particular the electrochemical cell, comprises a cell housing which has a hemispherical cell base. This form of the cell housing advantageously contributes to enabling a high capacity of the electrochemical energy storage device, in particular the electrochemical cell.
The ceramic electrolyte is the most cost-intensive component of the cell. By arranging the cathode outside of the electrolyte tube, significantly more active mass can be accommodated in relation to the tube, as a result of which the costs related to the energy content are reduced.
The process of the vacuum impregnation of the active mass with liquid salt as liquid electrolyte is greatly facilitated by a second opening the bottom of the cell housing, since as a result gas can escape at the top while the liquid is flowing in at the bottom.
The ratio of the volume of the active cathode mass to the volume of the active anode mass is approximately 2:1, for which reason it is actually unfavorable to arrange the cathode in the limited interior space of the electrolyte tube since this allows only cells of comparatively low capacity to be produced. It is therefore the object of the invention to enable significantly greater capacities while using the same electrochemical system.
When producing a cell, the active mass of the cathode in the form of a granular is material is filled into the cathode space and then vacuum impregnated with a salt melt as liquid electrolyte. The cathode space is tubular with a closed end, for which reason the filling process and the impregnation process can only be effected from the upper end. Because of the frequently occurring formation of bubbles when the granular material meets the liquid salt, the impregnation process is significantly 2o hindered. This disadvantage of the known solution is also intended to be overcome according to the invention.
Drawings
Figure 1 shows a cross section through a cell 10 according to the invention. It comprises a cathode space 11 arranged outside of the ceramic electrolyte 12, an anode space 13 located inside the ceramic electrolyte 12, and a shim tube 14 which forms a capillary gap 15 with respect to the ceramic electrolyte. The shim tube extends from the start of the cylindrical part of the ceramic electrolyte tube 16 up to the top, where it narrows to a relatively small diameter 14. As a result, the capillary gap widens and the sodium cannot rise any higher. The anode space 13 of a more or less charged cell is filled with liquid sodium to a greater or lesser level. This sodium rises in the capillary gap up to the diameter constriction of the shim tube, and as a result the glass seal 16 between the electrolyte tube and the ceramic support ring 17 is not wetted with liquid sodium, which has the effect of prolonging the lifetime of the seal. The shim tube 14 is intimately bonded to the cell cover 18 for example by friction welding. The cell cover serves at the same time as the negative pole of the cell. The cell housing 19 is produced from a metal the electrical potential of which must not be lower than that of nickel. An annular cover 20 closes the cell housing. In the annular cover there is an opening 21 into which the active mass in the form of a dry granular material is filled. At the round end of the cell housing there is a second opening 22 which serves for the vacuum impregnation of the active mass. After the filling and impregnation process has been completed, both openings 21, 22 are hermetically sealed. The cell base 23 is hemispherical in design, for which reason this part of the cell also contributes to the capacity.
Reference sign
electrochemical cell 11 cathode space 12 ceramic electrolyte 13 anode space 14 shim tube capillary gap 16 glass seal between the electrolyte tube and the ceramic support ring 17 support ring made from non-ion-conducting ceramic 18 cell cover 19 cell housing annular cover 21 filling opening 22 impregnation opening 23 hemispherical cell base
Claims (9)
1. An electrochemical cell (10), based on the redox system Na/MCl2, having an Na+ ion-conducting ceramic electrolyte (12) and a salt as liquid electrolyte, wherein a cathode space (11) of the electrochemical cell (10) is arranged outside of an electrolyte tube of the electrochemical cell (10) and an anode space (13) of the electrochemical cell (10) is arranged inside the electrolyte tube, characterized by a cell housing (19) which has a hemispherical cell base (23).
2. The electrochemical cell (10) as claimed in claim 1, characterized in that the hemispherical cell base (23) of the cell housing (19) of the electrochemical cell (10) has a filling opening (21) for vacuum impregnation of an active mass, the filling opening being configured to be closed after an impregnating liquid has solidified.
3. The electrochemical cell (10) as claimed in claim 1 or 2, characterized in that an annular cover (20) arranged at the top of the cell housing (19) has a filling hole which is configured for filling active mass in and for evacuating during an impregnation process.
4. The electrochemical cell (10) as claimed in claim 3, characterized in that the annular cover (20) arranged at the top of the cell housing (19) is formed such that it is simultaneously a cell closure and a sealing ring of a glass seal (16) of the electrochemical cell.
5. The electrochemical cell (10) as claimed in any of the preceding claims, characterized in that the cell housing (19) of the electrochemical cell (10) serves as a current collector of a positive electrode, and an annular cover (20) arranged at the top of the cell housing (19) forms a positive pole of the electrochemical cell (10).
6. The electrochemical cell (10) as claimed in any of the preceding claims, characterized in that in the interior of the ceramic electrolyte (12) there is arranged a shim tube (14) which forms an annular capillary gap (15) with an electrolyte tube.
7. A shim tube (14) in an electrochemical cell (10) as claimed in claim 6, characterized in that the shim tube (14) at the upper end approximately 10 mm below a glass seal (16) has a reduced diameter so that liquid sodium cannot rise higher.
8. A shim tube (14) in an electrochemical cell (10) as claimed in claim 6, characterized in that the shim tube (14) is formed from a material having good electrical conductivity, so that the shim tube (14) with low electrical resistance serves as current collector for the negative pole.
9. A shim tube (14) in an electrochemical cell (10) as claimed in claim 8, characterized in that the shim tube (14) is connected to a cell cover (18) in a manner with good metallic conductivity, so that the cell cover (18) forms a negative pole of the electrochemical cell (10).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01074/19A CH716540A1 (en) | 2019-08-27 | 2019-08-27 | Electrochemical energy storage device. |
| CH1074/19 | 2019-08-27 | ||
| PCT/EP2020/073992 WO2021037991A1 (en) | 2019-08-27 | 2020-08-27 | Electrochemical energy storage device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2020338256A1 true AU2020338256A1 (en) | 2022-03-17 |
Family
ID=67988830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2020338256A Pending AU2020338256A1 (en) | 2019-08-27 | 2020-08-27 | Electrochemical energy storage device |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP4022699A1 (en) |
| AU (1) | AU2020338256A1 (en) |
| BR (1) | BR112022003552A2 (en) |
| CH (1) | CH716540A1 (en) |
| WO (1) | WO2021037991A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966492A (en) * | 1975-08-20 | 1976-06-29 | Ford Motor Company | Sodium sulfur battery or cell with improved ampere-hour capacity |
| GB8523444D0 (en) * | 1985-09-23 | 1985-10-30 | Lilliwyte Sa | Electrochemical cell |
| IT1269906B (en) | 1993-04-02 | 1997-04-16 | Programme 3 Patent Holding | Electrochemical cell |
| US20130004828A1 (en) * | 2011-06-30 | 2013-01-03 | General Electric Company | Electrochemical cells, and related devices |
| US20170104244A1 (en) | 2015-10-07 | 2017-04-13 | General Electric Company | Positive electrode composition for overdischarge protection |
-
2019
- 2019-08-27 CH CH01074/19A patent/CH716540A1/en unknown
-
2020
- 2020-08-27 WO PCT/EP2020/073992 patent/WO2021037991A1/en unknown
- 2020-08-27 AU AU2020338256A patent/AU2020338256A1/en active Pending
- 2020-08-27 BR BR112022003552A patent/BR112022003552A2/en unknown
- 2020-08-27 EP EP20767486.2A patent/EP4022699A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CH716540A1 (en) | 2021-03-15 |
| WO2021037991A1 (en) | 2021-03-04 |
| BR112022003552A2 (en) | 2022-05-24 |
| EP4022699A1 (en) | 2022-07-06 |
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