CN104505558A - Gas-liquid dual-channel cathode lithium air cell - Google Patents
Gas-liquid dual-channel cathode lithium air cell Download PDFInfo
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- CN104505558A CN104505558A CN201410702680.1A CN201410702680A CN104505558A CN 104505558 A CN104505558 A CN 104505558A CN 201410702680 A CN201410702680 A CN 201410702680A CN 104505558 A CN104505558 A CN 104505558A
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- gas
- liquid
- flow field
- lithium
- binary channels
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
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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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a gas-liquid dual-channel cathode lithium air cell which comprises a shell, wherein the shell is formed by enclosing of a stainless steel shell body with openings in the upper and lower parts and two insulating shell bodies transversely arranged in the upper and lower openings of the stainless steel shell body; a lithium anode, a diaphragm A, a non-aqueous electrolyte, a diaphragm B, a porous cathode gas diffusion electrode and a dual-channel cathode flow field plate are sequentially vertically arranged from left to right in the shell; the dual-channel cathode flow field plate is internally provided with a gas flow field channel and a liquid flow field channel, the dual-channel cathode flow field plate is provided with a gas inlet valve and a gas discharge valve which are communicated with the gas flow field channel, and a liquid inlet valve and a liquid discharge valve communicated with the liquid flow field channel respectively, the gas inlet valve is connected with a gas cylinder, the liquid inlet valve and the liquid discharge valve are connected with a peristaltic pump, and the peristaltic pump is connected with a liquid tank. The gas-liquid dual-channel cathode lithium air cell has the advantages of preventing discharge products, namely lithium oxide or lithium peroxide, from blocking an electrode duct to avoid termination of discharge, improving cell circulating efficiency and increasing cell circulating times.
Description
Technical field
The present invention relates to a kind of gas-liquid binary channels negative electrode lithium-air battery, particularly a kind of gas phase discharges, liquid phase charging binary channels negative electrode lithium-air battery.
Background technology
Air cell is that one lithium metal makes negative pole, using oxygen as the mechanism of new electrochemical power sources of anode reactant, and becomes with its relatively high theoretical specific capacity and specific energy characteristic the power conversion system received much concern at present.Its operation principle is, discharge process: become lithium cation after the lithium metal of anode release electronics, lithium ion through electrolyte, at negative electrode and oxygen and be combined from the electronics that external circuit flows through and generate lithia (Li
2or lithium peroxide (Li O)
2o
2), and stay negative electrode; Charging process: by wire supplies electrons, lithium ion arrives negative terminal surface through organic electrolyte, to react generation lithium metal in negative terminal surface, and side of the positive electrode reaction generates oxygen, and the electronics of generation is supplied to wire.
Because lithia is not readily dissolved in organic electrolyte, therefore discharging product can only deposit on the oxygen electrode having negative oxygen ion, discharging product blocks oxygen electrode duct and guiding discharge stops, and the lithia that reaction generates does not have electrochemical reversibility, thus the cycle performance of lithium oxygen battery is caused to decline.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of gas-liquid binary channels negative electrode lithium-air battery, avoids discharging product lithia or lithium peroxide blocking electrode duct guiding discharge to stop, improves circulating battery efficiency, increase circulating battery number of times.
Technical solution of the present invention is:
A kind of gas-liquid binary channels negative electrode lithium-air battery, comprise housing, described housing is by upper, the Stainless Steel Shell of lower open mouth, be horizontally placed on the upper of Stainless Steel Shell, two insulation shells in end opening surround, its special character is, erect successively from left to right in housing and be equipped with lithium anode, barrier film A, non-aqueous electrolyte, barrier film B, porous cathode gas-diffusion electrode and binary channels cathode flow field plate, gas flow field channels and liquid flow field passage is provided with in described binary channels cathode flow field plate, binary channels cathode flow field plate is respectively equipped with the gas inlet valve and gas drain tap that communicate with gas flow field channels and the liquid liquid flowing valve communicated with liquid flow field passage and liquid draining valve, described gas inlet valve is connected with gas cylinder, described liquid liquid flowing valve and liquid draining valve are connected with peristaltic pump, described peristaltic pump is connected with flow container.
The material of described binary channels cathode flow field plate is graphite cake.
Described gas flow field channels and liquid flow field passage are snakelike tubulose.
Gas flow field channels and liquid flow field passage be arranged in parallel.
The length of described gas flow field channels is 50mm ~ 60mm, and width is 5mm, and groove depth is 1mm.
The length of described liquid flow field passage is 55mm ~ 58mm, and width is 3mm, and groove depth is 1mm.
The solute of described non-aqueous electrolyte is lithium sulfite or trifluoroacetic acid lithium, and solvent is at least one in ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, acetonitrile, glutaronitrile.
Described porous cathode gas-diffusion electrode, in diffusion layer, polytetrafluoroethylene mass content is 8 % ~ 12%, and regulating course thickness is 0.5 mg/cm
2~ 1.0 mg/cm
2.
Gas in described gas cylinder is air or oxygen, and flow is 10 mL/min ~ 500 mL/min, and pressure is 0.1 MPa ~ 0.5 MPa.
In described flow container, liquid is sulfurous acid or trifluoroacetic acid, and flow velocity is 0.1 mL/h ~ 10 mL/h, and pressure is 0.1 MPa ~ 0.3 MPa.
Beneficial effect of the present invention:
Rational in infrastructure, binary channels cathode flow field plate is set, discharging product lithia or the lithium peroxide of porous cathode gas-diffusion electrode is deposited in discharge process, the sulfurous acid that can pass into liquid flow field passage or trifluoroacetic acid substance reaction generate the lithium sulfite or trifluoroacetic acid lithium that are soluble in electrolyte, lithium ion arrives lithium anode surface through lithium cation through non-aqueous electrolyte, by external circuit supplies electrons, to react generation lithium metal at lithium anode surface, thus solve discharging product lithia or lithium peroxide is not readily dissolved in organic electrolyte, the problem that blocking electrode duct guiding discharge stops, improve circulating battery efficiency, increase circulating battery number of times.After testing, this structure lithium-air battery first discharge specific capacity >=2300mAh/g, cycle-index 50 times, specific energy decay 16.8% ~ 17%.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
Fig. 2 is vertical view of the present invention;
Fig. 3 is the structural representation of binary channels cathode flow field plate in Fig. 1.
1-housing, 101-Stainless Steel Shell, 102-insulation shell, 2-lithium anode, 3-barrier film A, 4-non-aqueous electrolyte, 5-porous cathode gas-diffusion electrode, 6-binary channels cathode flow field plate, 601-gas flow field channels, 602-liquid flow field passage, 601A-gas inlet valve, 601B-gas exhaust valve, 602A-liquid liquid flowing valve, 602B-liquid draining valve, 7-gas cylinder, 8-flow container, 9-peristaltic pump, 10-barrier film B.
Embodiment
Embodiment 1
As shown in Figure 1, this gas-liquid binary channels negative electrode lithium-air battery, comprise the housing 1 surrounded by upper and lower uncovered Stainless Steel Shell 101, two insulation shells 102 be horizontally placed in the upper and lower mouth of stainless steel case 101, erect successively from left to right in housing 1 and be equipped with lithium anode 2, barrier film A3, non-aqueous electrolyte 4, barrier film B10, porous cathode gas-diffusion electrode 5 and binary channels cathode flow field plate 6, the material of described binary channels cathode flow field plate 6 is graphite cake; The solute of described non-aqueous electrolyte 4 is lithium sulfite, and solvent is ethylene carbonate; PTFE(polytetrafluoroethylene in the diffusion layer of described porous cathode gas-diffusion electrode 5) mass content is 8 %, regulating course thickness is 0.5 mg/cm
2; The gas flow field channels 601 be arranged in parallel and liquid flow field passage 602 is provided with in described binary channels cathode flow field plate 6, described gas flow field channels 601 and liquid flow field passage 602 are snakelike tubulose, the length of described gas flow field channels 601 is 50mm, and width is 5mm, and groove depth is 1 mm; The length of described liquid flow field passage 602 is 55mm, and width is 3 mm, and groove depth is 1 mm; Described binary channels cathode flow field plate 6 is respectively equipped with the gas inlet valve 601A communicated with gas flow field channels 601 and gas drain tap 601B and the liquid liquid flowing valve 602A communicated with liquid flow field passage 602 and liquid draining valve 602B, described gas inlet valve 601A is connected with gas cylinder 7 by pipeline, described liquid liquid flowing valve 602A is connected a peristaltic pump 9 with liquid draining valve 602B by pipeline, described peristaltic pump 9 is connected with flow container 8 by pipeline, gas in described gas cylinder 7 is air, flow is 10 mL/min, and pressure is 0.1 MPa; In described flow container 8, liquid is sulfurous acid, and flow velocity is 0.1 mL/h, and pressure is 0.1 MPa.
After testing, this structure lithium-air battery first discharge specific capacity is 2300mAh/g, cycle-index 50 times, specific energy decay 17%.
Embodiment 2
As shown in Figure 1, this gas-liquid binary channels negative electrode lithium-air battery, comprise the housing 1 surrounded by upper and lower uncovered Stainless Steel Shell 101, two insulation shells 102 be horizontally placed in the upper and lower mouth of stainless steel case 101, erect successively from left to right in housing 1 and be equipped with lithium anode 2, barrier film A3, non-aqueous electrolyte 4, barrier film B10, porous cathode gas-diffusion electrode 5 and binary channels cathode flow field plate 6, the material of described binary channels cathode flow field plate 6 is graphite cake; The solute of described non-aqueous electrolyte 4 is trifluoroacetic acid lithium, and solvent is acetonitrile; PTFE(polytetrafluoroethylene in the diffusion layer of described porous cathode gas-diffusion electrode 5) mass content is 12%, regulating course thickness is 1.0 mg/cm
2; The gas flow field channels 601 be arranged in parallel and liquid flow field passage 602 is provided with in described binary channels cathode flow field plate 6, described gas flow field channels 601 and liquid flow field passage 602 are snakelike tubulose, the length of described gas flow field channels 601 is 60mm, and width is 5mm, and groove depth is 1 mm; The length of described liquid flow field passage 602 is 58mm, and width is 3 mm, and groove depth is 1 mm; Described binary channels cathode flow field plate 6 is respectively equipped with the gas inlet valve 601A communicated with gas flow field channels 601 and gas drain tap 601B and the liquid liquid flowing valve 602A communicated with liquid flow field passage 602 and liquid draining valve 602B, described gas inlet valve 601A is connected with gas cylinder 7 by pipeline, described liquid liquid flowing valve 602A is connected a peristaltic pump 9 with liquid draining valve 602B by pipeline, described peristaltic pump 9 is connected with flow container 8 by pipeline, gas in described gas cylinder 7 is oxygen, flow velocity is 10 mL/h, and pressure is 0.3 MPa.
After testing, this structure lithium-air battery first discharge specific capacity is 2312mAh/g, cycle-index 50 times, specific energy decay 16.8%.
Embodiment 3
As shown in Figure 1, this gas-liquid binary channels negative electrode lithium-air battery, comprise the housing 1 surrounded by upper and lower uncovered Stainless Steel Shell 101, two insulation shells 102 be horizontally placed in the upper and lower mouth of stainless steel case 101, erect successively from left to right in housing 1 and be equipped with lithium anode 2, barrier film A3, non-aqueous electrolyte 4, barrier film B10, porous cathode gas-diffusion electrode 5 and binary channels cathode flow field plate 6, the material of described binary channels cathode flow field plate 6 is graphite cake; The solute of described non-aqueous electrolyte 4 is lithium sulfite, and solvent is dimethyl carbonate; PTFE(polytetrafluoroethylene in the diffusion layer of described porous cathode gas-diffusion electrode 5) mass content is 10%, regulating course thickness is 0.8mg/cm
2; The gas flow field channels 601 be arranged in parallel and liquid flow field passage 602 is provided with in described binary channels cathode flow field plate 6, described gas flow field channels 601 and liquid flow field passage 602 are snakelike tubulose, the length of described gas flow field channels 601 is 55mm, and width is 5mm, and groove depth is 1 mm; The length of described liquid flow field passage 602 is 56mm, and width is 3 mm, and groove depth is 1 mm; Described binary channels cathode flow field plate 6 is respectively equipped with the gas inlet valve 601A communicated with gas flow field channels 601 and gas drain tap 601B and the liquid liquid flowing valve 602A communicated with liquid flow field passage 602 and liquid draining valve 602B, described gas inlet valve 601A is connected with gas cylinder 7 by pipeline, described liquid liquid flowing valve 602A is connected a peristaltic pump 9 with liquid draining valve 602B by pipeline, described peristaltic pump 9 is connected with flow container 8 by pipeline, gas in described gas cylinder 7 is oxygen, flow is 255 mL/min, and pressure is 0.3MPa; In described flow container 8, liquid is sulfurous acid, and flow velocity is 5mL/h, and pressure is 0.2 MPa.
After testing, this structure lithium-air battery first discharge specific capacity is 2310mAh/g, cycle-index 50 times, specific energy decay 16.9%.
This structure lithium-air battery operation principle is:
When the cell is discharged: the liquid liquid flowing valve 602A on closing liquid flow field channel 602 and liquid draining valve 602B, open the gas inlet valve 601A in gas flow field channels 601 and gas drain tap 601B, pass into air or oxygen.Now, lithium anode 2 becomes lithium cation after discharging electronics, lithium cation through non-aqueous electrolyte 4, the oxygen permeated in porous cathode gas-diffusion electrode 5 and gas flow field channels 601 and be combined from the electronics that external circuit flows through and generate lithia (Li
2or lithium peroxide (Li O)
2o
2), and depositing porous cathode gas-diffusion electrode 5.
When battery charges: close the gas inlet valve 601A in gas flow field channels 601 and gas drain tap 601B, open the liquid liquid flowing valve 602A on liquid flow field passage 602 and liquid draining valve 602B, pass into sulfurous acid or trifluoroacetic acid.Now, be deposited on the discharging product lithia of porous cathode gas-diffusion electrode 5 or lithium peroxide and the sulfurous acid passed into or trifluoroacetic acid substance reaction and generate the lithium sulfite or trifluoroacetic acid lithium that are soluble in electrolyte, lithium ion arrives lithium anode 2 surface through lithium cation through non-aqueous electrolyte 4, by external circuit supplies electrons, react on lithium anode 2 surface generation lithium metal.
Claims (10)
1. a gas-liquid binary channels negative electrode lithium-air battery, comprise housing, described housing is by upper, the Stainless Steel Shell of lower open mouth, be horizontally placed on the upper of Stainless Steel Shell, two insulation shells in end opening surround, it is characterized in that, erect successively from left to right in housing and be equipped with lithium anode, barrier film A, non-aqueous electrolyte, barrier film B, porous cathode gas-diffusion electrode and binary channels cathode flow field plate, gas flow field channels and liquid flow field passage is provided with in described binary channels cathode flow field plate, binary channels cathode flow field plate is respectively equipped with the gas inlet valve and gas drain tap that communicate with gas flow field channels and the liquid liquid flowing valve communicated with liquid flow field passage and liquid draining valve, described gas inlet valve is connected with gas cylinder, described liquid liquid flowing valve and liquid draining valve are connected with peristaltic pump, described peristaltic pump is connected with flow container.
2. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, is characterized in that, the material of described binary channels cathode flow field plate is graphite cake.
3. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, it is characterized in that, described gas flow field channels and liquid flow field passage are snakelike tubulose.
4. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, it is characterized in that, gas flow field channels and liquid flow field passage be arranged in parallel.
5. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, is characterized in that, the length of described gas flow field channels is 50mm ~ 60mm, and width is 5mm, and groove depth is 1mm.
6. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, is characterized in that, the length of described liquid flow field passage is 55mm ~ 58mm, and width is 3mm, and groove depth is 1mm.
7. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, it is characterized in that, the solute of described non-aqueous electrolyte is lithium sulfite or trifluoroacetic acid lithium, and solvent is at least one in ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, acetonitrile, glutaronitrile.
8. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, it is characterized in that, described porous cathode gas-diffusion electrode, in diffusion layer, polytetrafluoroethylene mass content is 8 % ~ 12%, and regulating course thickness is 0.5 mg/cm
2~ 1.0 mg/cm
2.
9. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, it is characterized in that, the gas in described gas cylinder is air or oxygen, and flow is 10 mL/min ~ 500 mL/min, and pressure is 0.1 MPa ~ 0.5 MPa.
10. gas-liquid binary channels negative electrode lithium-air battery according to claim 1, it is characterized in that, in described flow container, liquid is sulfurous acid or trifluoroacetic acid, and flow velocity is 0.1 mL/h ~ 10 mL/h, and pressure is 0.1 MPa ~ 0.3 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410702680.1A CN104505558B (en) | 2014-11-29 | 2014-11-29 | A kind of gas-liquid binary channels negative electrode lithium-air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410702680.1A CN104505558B (en) | 2014-11-29 | 2014-11-29 | A kind of gas-liquid binary channels negative electrode lithium-air battery |
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| Publication Number | Publication Date |
|---|---|
| CN104505558A true CN104505558A (en) | 2015-04-08 |
| CN104505558B CN104505558B (en) | 2016-05-18 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013536A (en) * | 2010-10-28 | 2011-04-13 | 清华大学 | Liquid flow type lithium-air battery |
| CN102157763A (en) * | 2011-03-09 | 2011-08-17 | 哈尔滨工业大学 | Lithium/air battery |
| CN102280674A (en) * | 2011-06-27 | 2011-12-14 | 清华大学 | Gas charging mode lithium-oxygen battery and charging method thereof |
-
2014
- 2014-11-29 CN CN201410702680.1A patent/CN104505558B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013536A (en) * | 2010-10-28 | 2011-04-13 | 清华大学 | Liquid flow type lithium-air battery |
| CN102157763A (en) * | 2011-03-09 | 2011-08-17 | 哈尔滨工业大学 | Lithium/air battery |
| CN102280674A (en) * | 2011-06-27 | 2011-12-14 | 清华大学 | Gas charging mode lithium-oxygen battery and charging method thereof |
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| CN104505558B (en) | 2016-05-18 |
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