CN105845847B - A kind of controllable composite anode structure lithium-oxygen battery - Google Patents
A kind of controllable composite anode structure lithium-oxygen battery Download PDFInfo
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- CN105845847B CN105845847B CN201610180048.4A CN201610180048A CN105845847B CN 105845847 B CN105845847 B CN 105845847B CN 201610180048 A CN201610180048 A CN 201610180048A CN 105845847 B CN105845847 B CN 105845847B
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- lithium
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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
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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
- H01M12/02—Details
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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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
- Y02E60/10—Energy storage using batteries
Abstract
A kind of controllable composite anode structure lithium-oxygen battery, including battery case, it is equipped with composite anode successively in battery case, membrane, electrolyte, membrane, cathode gas diffusion electrode, the gas piping and gas valve connected with air chamber is equipped in Stainless Steel Shell, it is located at composite anode one end in stainless steel case body and is equipped with visualization housing, it is corresponded in described two insulation shells and replacement port I and replacement port II is respectively equipped at composite anode, sealing-plug is equipped in replacement port II, the battery case is equipped with the controllable chamber of anode of built-in multi-disc composite anode, it is fitted on the controllable chamber of anode and I corresponding draw back plate of replacement port.Advantage is：Battery structure is reasonable, can carry out supply replacement to composite anode by anode control chamber so that lithium-oxygen battery can be with continuous work, so as to extend the service life of battery, discharge capacity >=2350mAh/kg, cycle-index are more than 95 times the lithium-oxygen battery for the first time, and stream time was more than 120 days.
Description
Technical field
The present invention relates to a kind of controllable composite anode structure lithium-oxygen batteries.
Background technology
Lithium-oxygen battery is a kind of by the use of lithium metal as cathode, using the oxygen in air as the battery of anode reactant.It puts
Electric process：Become lithium cation (Li after the lithium metal release electronics of anode+), Li+Through electrolyte, cathode and oxygen,
And the electronics come is flowed through from external circuit and combines generation lithia (Li2) or lithium peroxide (Li O2O2), and cathode is stayed in, lithium
The open-circuit voltage of oxygen cell is 2.91V.
Lithium-oxygen battery has higher energy density than lithium ion battery, because its cathode (based on porous carbon) is very light,
And oxygen obtains from environment and does not have to be stored in battery.Oxygen is unrestricted as lithium-oxygen battery cathode reactant, the battery
Capacity be only dependent upon lithium electrode, be 5,210Wh/kg (including oxygen quality) or 11,140Wh/kg (not including oxygen than energy
Gas), compared with other metal-air batteries, lithium-oxygen battery compares energy with higher.Therefore, lithium-oxygen battery has with it
Higher theoretical specific capacity and than energy and the characteristics such as environmentally friendly and as the energy transfer medium system being concerned at present.
But in lithium-oxygen battery discharge process, due to cathode side oxygen easily through electrolyte permeability to anode, oxidized metal lithium and lose
Discharge capability is carried out with the long-time of electric discharge, and guiding discharge terminates, and influences the service life of lithium-oxygen battery.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of controllable composite anode structure lithium-oxygen batteries, overcome anode metal
Lithium is corroded by inside battery oxygen or water, ultimately results in discharge off, so as to cause lithium-oxygen battery than energy and cycle performance
The problem of relatively low.
The present invention technical solution be：
A kind of controllable composite anode structure lithium-oxygen battery, including by Stainless Steel Shell and be located in stainless steel case body two
The battery case that insulation shell surrounds is equipped with composite anode, membrane, electrolyte, membrane, cathode gas successively in battery case
Diffusion electrode, air chamber is left on the interior cathode gas diffusion electrode right side that is located at of stainless steel case body, and is set in Stainless Steel Shell
There is the gas piping and gas valve connected with air chamber, be characterized in that：It is located at composite anode in stainless steel case body
One end is equipped with visualization housing, for observing the in vivo composite anode corrosion condition of battery case；In described two insulation shells pair
It answers and replacement port I and replacement port II is respectively equipped at composite anode, sealing-plug is equipped in replacement port II, is set on the battery case
There is the controllable chamber of anode of built-in multi-disc composite anode, be fitted on the controllable chamber of anode and I corresponding draw back plate of replacement port.
In the draw back plate upper end there is card edge, positioned after the draw back plate insertion controllable chamber of anode by card edge.
Spring is equipped in the controllable chamber of the anode, for multi-disc composite anode to be pushed against draw back plate.
It is square lithium-aluminium alloy piece that the composite anode is vertically arranged by the square foam nickel sheet that is vertically arranged, right side, horizontal embedding
Enter lithium-aluminium alloy and the circular metal lithium piece composition of nickel foam center, wherein, lithium-aluminium alloy piece, foam nickel sheet and lithium metal
The thickness ratio of piece is 1:1:2, foam nickel sheet is the good conductor of electronics, can play the role of afflux, and lithium-aluminium alloy piece has anti-corruption
Erosion, the effect of protection metal lithium sheet, the structure composite anode can effectively inhibit the corrosion of metal lithium sheet, improve the ratio of battery
Energy, cycle performance and working life.
5~10 composite anodes are housed in the controllable chamber of anode.
The nickel foam is identical with the size of lithium-aluminium alloy, and the diameter of the lithium metal and the length of side ratio of nickel foam are 1:
2~1:3.
The material of the visualization housing is organic glass.
The length of side of the visualization housing is 20mm~30mm.
The cathode diffusion electrode is divided into diffusion layer and Catalytic Layer two parts, and wherein catalyst is by mass ratio in Catalytic Layer
For 4:2:What 4 manganese dioxide, lanthana and pallium-on-carbon formed.
Beneficial effects of the present invention：
Battery structure is reasonable, is observed by visualizing housing, after the lithium metal corrosion of composite anode, can pass through sun
Pole control chamber carries out supply replacement to composite anode so that lithium-oxygen battery can will not be because of lithium metal with continuous work, lithium-oxygen battery
Corrode and be stopped, so as to extend the service life of battery, lithium-oxygen battery discharge capacity >=2350mAh/kg for the first time is followed
Ring number is more than 95 times, and stream time was more than 120 days.
Description of the drawings
Fig. 1 is the structure diagram of the controllable anode lithium-oxygen battery of the present invention；
Fig. 2 is the left view of composite anode in Fig. 1.
In figure；The controllable chamber of 1- anodes, 2- composite anodes, 201- foam nickel sheet, 202- lithium-aluminium alloy pieces, 203- lithium metals
Piece, 3- membranes, 4- electrolyte, 5- cathode gas diffusion electrodes, 6- draw back plates, 601- cards edge, 7- battery cases, 701- insulation shells
Body, 702- Stainless Steel Shells, 8- visualization housings, 9- gas valves, 10- gas pipings, 11- springs, 12- replacement ports I, 13-
Replacement port II, 14- sealing-plugs.
Specific embodiment
Embodiment 1
As shown in the figure, the controllable composite anode structure lithium-oxygen battery, including by upper and lower open Stainless Steel Shell 702 and
The battery case 7 that two insulation shells 701 being horizontally placed in the upper and lower mouth of Stainless Steel Shell 702 surround, in battery case 7
It has been vertically arranged composite anode 2, membrane 3, electrolyte 4, membrane 3, cathode gas diffusion electrode 5, Stainless Steel Shell successively from left to right
It is located at 5 right side of cathode gas diffusion electrode in 702 and leaves air chamber, and is equipped in Stainless Steel Shell 702 and air chamber
The gas piping 10 of connection and gas valve 9, it is 20mm that 2 one end of composite anode is located in Stainless Steel Shell 702 embedded with the length of side
~30mm, the visualization housing that material is organic glass, for observing 2 corrosion condition of composite anode in battery case 7, this reality
Apply example by visualize housing 8 be the length of side for the square of 20cm exemplified by；Composite anode 2 is corresponded in described two insulation shells 701
Place is respectively equipped with replacement port I 12 and replacement port II 13, and sealing-plug 14 is equipped in replacement port II 13, is set on the battery case 7
There is the controllable chamber 1 of anode of built-in 5~10 composite anodes 2, the present embodiment is exemplified by being equipped with 7 composite anodes, in anode
Be fitted on controllable chamber 1 with I 12 corresponding draw back plate 6 of replacement port, there is card in 6 upper end of draw back plate along 601, draw back plate 6 is inserted
It is positioned after entering the controllable chamber 1 of anode by card along 601, spring 11 is equipped in the controllable chamber 1 of the anode, for multi-disc to be answered
Heyang pole 2 is pushed against on draw back plate 6；
The square lithium-aluminium alloy piece that square foam nickel sheet 201 that the composite anode 2 is vertically arranged by left side, right side are vertically arranged
202nd, the circular metal lithium piece 203 of horizontal embedded lithium-aluminium alloy piece 202 and 201 center of foam nickel sheet forms, wherein, foam
Nickel sheet 201 is identical with the size of lithium-aluminium alloy piece 202, and the diameter of metal lithium sheet 203 and the length of side ratio of foam nickel sheet 201 are 1:
2, the thickness ratio of lithium-aluminium alloy piece 202, foam nickel sheet 201 and metal lithium sheet 203 is 1:1:2, foam nickel sheet 201 is the good of electronics
Conductor can play the role of afflux, and lithium-aluminium alloy piece 202 has anticorrosive, protection metal lithium sheet 203, which answers
Heyang pole 2 can effectively inhibit the corrosion of metal lithium sheet 203, improve ratio energy, cycle performance and the working life of battery.
The cathode gas diffusion electrode 5 divides for diffusion layer and Catalytic Layer two parts, wherein in Catalytic Layer catalyst be by
Mass ratio is 4:2:What 4 manganese dioxide, lanthana and pallium-on-carbon formed.
During work, 203 corrosion condition of metal lithium sheet of composite anode 2 is observed, it is necessary to replace compound by visualizing housing 8
During anode 2, sealing-plug 14 being removed, lifting draw back plate 6, the composite anode 2 in the controllable chamber 1 of anode is in the effect of 11 pressure of spring
Under, it moves to the left, the composite anode 2 of the leftmost side is moved to makes battery case with I 12 correspondence position of replacement port, pressure draw back plate 6
Composite anode 2 in body 7 is forced out by replacement port II 13, and the composite anode 2 in the controllable chamber 1 of anode is all pressed into battery case
In 7, sealing-plug 14 is packed into, makes battery case 7 closed.
Embodiment 2
As shown in the figure, the structure and composite anode structure of the controllable composite anode structure lithium-oxygen battery be with embodiment 1, wherein
The diameter of the lithium metal of composite anode and the length of side ratio of nickel foam are 1:3.
Embodiment 3
As shown in the figure, the structure and composite anode structure of the controllable composite anode structure lithium-oxygen battery be with embodiment 1, wherein
The diameter of the lithium metal of composite anode and the length of side ratio of nickel foam are 1:2.5.
The foam nickel sheet of the controllable composite anode structure lithium-oxygen battery composite anode of 1~embodiment of the embodiment of the present invention 3, lithium
Aluminum alloy sheet and metal lithium sheet thickness are respectively 0.1mm, 0.1mm, 0.2mm；
The material of membrane is microporous polypropylene membrane Celgard 2400.
Electrolyte is LiPF6EC/EMC/DMC solution (EC is ethylene carbonate, and EMC is methyl ethyl carbonate, and DMC is carbon
Dimethyl phthalate)；
Cathode gas diffusion electrode is regular air electrode, it is divided into diffusion layer and Catalytic Layer two parts；
Carbon paper is placed on 80 DEG C of electric hot plates, regulating course slurry will be prepared successively using spray gun and existed with Catalytic Layer slurry
Carbon paper surface is sprayed under the pressure of 0.2MPa, in 60 DEG C of dry 2h, then therefrom takes the disk of diameter 38mm as air electricity
It is extremely spare；The air electrode removed is placed in 60 DEG C of drying box dry 12h and obtains cathode gas diffusion electrode；
Regulating course slurry：It weighs 100mg carbon dusts to insert in small beaker, then adds in cohering for 250mg mass fractions 10%
Agent solution, 1000mg ethyl alcohol and 1000mg water, ultrasonic disperse 2h are spare；
Catalytic Layer slurry：80mg carbon dusts, 8mg manganese dioxide, 4mg lanthanas and 8mg pallium-on-carbons are weighed respectively inserts small burning
In cup, then add in 200mg mass fractions 10% coheres agent solution, 800mg ethyl alcohol and 800mg water, ultrasonic disperse 2h, standby
With.
The chemical property of the controllable composite anode structure lithium-oxygen battery of 1~embodiment of embodiment 3
| Discharge capacity for the first time | Cycle-index | Stream time | |
| Embodiment 1 | 2500mAh/kg | 97 times | 125 days |
| Embodiment 2 | 2450mAh/kg | 96 times | 122 days |
| Embodiment 3 | 2530mAh/kg | 98 times | 127 days |
It these are only specific embodiments of the present invention, be not intended to limit the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification within the spirit and principles of the invention, being made,
Equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of controllable composite anode structure lithium-oxygen battery, including by Stainless Steel Shell and be located in stainless steel case body two absolutely
The battery case that edge housing surrounds is equipped with composite anode, membrane, electrolyte, membrane, cathode gas expansion successively in battery case
Electrode is dissipated, is located in stainless steel case body on the right side of cathode gas diffusion electrode and leaves air chamber, and be equipped in Stainless Steel Shell
The gas piping and gas valve connected with air chamber, it is characterized in that：It is set in stainless steel case body positioned at composite anode one end
There is visualization housing, for observing the in vivo composite anode corrosion condition of battery case；It is corresponded in described two insulation shells compound
Replacement port I and replacement port II are respectively equipped at anode, sealing-plug is equipped in replacement port II, the battery case is equipped with built-in
The controllable chamber of anode of multi-disc composite anode is equipped with spring, for multi-disc composite anode to be pushed away in the controllable chamber of the anode
It leans against on draw back plate, is fitted on the controllable chamber of anode and I corresponding draw back plate of replacement port.
2. controllable composite anode structure lithium-oxygen battery according to claim 1, it is characterized in that：Have in the draw back plate upper end
There is card edge, positioned after the draw back plate insertion controllable chamber of anode by card edge.
3. controllable composite anode structure lithium-oxygen battery according to claim 1, it is characterized in that：The composite anode is by being vertically arranged
Square foam nickel sheet, the right side square lithium-aluminium alloy piece, horizontal embedded lithium-aluminium alloy piece and the foam nickel sheet center that are vertically arranged
The circular metal lithium piece composition of position, wherein, the thickness ratio of lithium-aluminium alloy piece, foam nickel sheet and metal lithium sheet is 1:1:2.
4. controllable composite anode structure lithium-oxygen battery according to claim 1, it is characterized in that：In the controllable chamber of anode
Equipped with 5~10 composite anodes.
5. controllable composite anode structure lithium-oxygen battery according to claim 3, it is characterized in that：The foam nickel sheet and lithium aluminium
The size of alloy sheet is identical, and the diameter of the metal lithium sheet and the length of side ratio of foam nickel sheet are 1:2~1:3.
6. controllable composite anode structure lithium-oxygen battery according to claim 1, it is characterized in that：The material of the visualization housing
Matter is organic glass.
7. controllable composite anode structure lithium-oxygen battery according to claim 1, it is characterized in that：The side of the visualization housing
The mm of a length of 20 mm~30.
8. controllable composite anode structure lithium-oxygen battery according to claim 1, it is characterized in that：The cathode gas diffusion electricity
Pole is divided into diffusion layer and Catalytic Layer two parts, wherein in Catalytic Layer catalyst be by mass ratio be 4:2:4 manganese dioxide aoxidizes
Lanthanum and pallium-on-carbon composition.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610180048.4A CN105845847B (en) | 2016-03-25 | 2016-03-25 | A kind of controllable composite anode structure lithium-oxygen battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610180048.4A CN105845847B (en) | 2016-03-25 | 2016-03-25 | A kind of controllable composite anode structure lithium-oxygen battery |
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| CN105845847A CN105845847A (en) | 2016-08-10 |
| CN105845847B true CN105845847B (en) | 2018-05-25 |
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| CN107658529A (en) * | 2017-07-27 | 2018-02-02 | 李勇 | A kind of aluminium-air cell and preparation method thereof |
| CN109830701A (en) * | 2019-01-29 | 2019-05-31 | 渤海大学 | A kind of preparation method and application of lithium-oxygen battery cathode parent lithium-cobalt manganese composition metal base organic frame catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101267057A (en) * | 2008-05-08 | 2008-09-17 | 复旦大学 | High ratio energy chargeable full-solid lithium air battery |
| CN101533935A (en) * | 2009-04-14 | 2009-09-16 | 黄穗阳 | A high-energy safe rechargeable lithium-oxygen battery |
| CN102723539A (en) * | 2012-05-04 | 2012-10-10 | 赵军辉 | Lithium-oxygen battery capable of improving battery energy density and method for manufacturing lithium-oxygen battery |
| CN104600399A (en) * | 2014-12-11 | 2015-05-06 | 渤海大学 | Electrolyte solution supply type lithium oxygen battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050187783A1 (en) * | 2004-02-20 | 2005-08-25 | Black & Decker Inc. | System for personalized combo kit of tools and accessories |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101267057A (en) * | 2008-05-08 | 2008-09-17 | 复旦大学 | High ratio energy chargeable full-solid lithium air battery |
| CN101533935A (en) * | 2009-04-14 | 2009-09-16 | 黄穗阳 | A high-energy safe rechargeable lithium-oxygen battery |
| CN102723539A (en) * | 2012-05-04 | 2012-10-10 | 赵军辉 | Lithium-oxygen battery capable of improving battery energy density and method for manufacturing lithium-oxygen battery |
| CN104600399A (en) * | 2014-12-11 | 2015-05-06 | 渤海大学 | Electrolyte solution supply type lithium oxygen battery |
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