CN107482284B - Lithium oxygen battery - Google Patents
Lithium oxygen battery Download PDFInfo
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- CN107482284B CN107482284B CN201710469830.2A CN201710469830A CN107482284B CN 107482284 B CN107482284 B CN 107482284B CN 201710469830 A CN201710469830 A CN 201710469830A CN 107482284 B CN107482284 B CN 107482284B
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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
- 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
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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
The invention relates to a lithium oxygen battery, which comprises a shell, a porous lithium negative electrode, a porous positive electrode and a diaphragm with electrolyte, wherein the porous lithium negative electrode and the porous positive electrode are arranged in the shell, the diaphragm with the electrolyte is arranged between the porous lithium negative electrode and the porous positive electrode, the lithium oxygen battery is characterized by also comprising a porous negative electrode current collector and a porous positive electrode current collector, the porous negative electrode current collector, the porous lithium negative electrode, the diaphragm with the electrolyte, the porous positive electrode and the porous positive electrode current collector are sequentially stacked, the shell close to the side of the porous positive electrode and the side of the porous lithium negative electrode are stainless steel shells, and a plurality of through holes for oxygen supply to enter are respectively arranged on the stainless steel shells close to the side of the porous positive electrode and the. According to the method, the metal lithium cathode is protected by introducing oxygen, so that the oxygen can preferentially react with the metal lithium, a layer of compact SEI film rich in lithium oxide and lithium peroxide is generated on the surface of the metal lithium, the corrosion of electrolyte to the metal lithium cathode is inhibited, and the cycling stability and the coulombic efficiency of the lithium cathode are obviously improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium oxygen battery.
Background
With the continuous progress of science and technology, lithium batteries used as energy storage devices are rapidly developed, and organic system lithium oxygen batteries are a powerful competitor for next-generation high-energy batteries due to the great theoretical specific energy density of the lithium oxygen batteries. For practical use, such a battery requires a metallic lithium negative electrode having high coulombic efficiency (coulombic efficiency refers to the ratio of dissolved lithium to deposited lithium in the deposition-dissolution process of lithium metal) and high cycle stability.
The existing organic electrolyte of the lithium oxygen battery is unstable to a lithium cathode, and can corrode metal lithium in the battery cycle and cause the decomposition of the electrolyte. This process results in low coulombic efficiency and poor cycling stability of the lithium metal negative electrode, accelerating the failure of the entire battery.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a lithium oxygen battery that protects a lithium negative electrode to achieve high coulombic efficiency and more stable cycle.
The invention relates to a lithium oxygen battery, which comprises a shell, a porous lithium cathode, a porous anode and a diaphragm, wherein the porous lithium cathode and the porous anode are arranged in the shell, the diaphragm is arranged between the porous lithium cathode and the porous anode and provided with electrolyte, the lithium oxygen battery also comprises a porous cathode current collector and a porous anode current collector, the porous cathode current collector, the porous lithium cathode, the diaphragm provided with the electrolyte, the porous anode and the porous anode current collector are sequentially stacked, the shell close to the porous anode side and the porous lithium cathode side is a stainless steel shell, and a plurality of through holes for oxygen supply to enter are respectively arranged on the stainless steel shell close to the porous anode side and the porous lithium cathode side.
Furthermore, the aperture of the through hole of the porous lithium cathode is 0.1-1.0mm, and the density of the through hole is 30-240 holes/cm2。
Further, the porous lithium negative electrode includes metallic lithium or a lithium silicon alloy.
Further, the porous current collector is a metal mesh or a perforated metal film or foam metal.
Furthermore, the porous lithium negative electrode is a metal lithium sheet, the porous negative current collector is foam copper, the porous positive electrode is prepared by mixing a binder and a positive electrode material according to the proportion of 1:4-19 and then performing a rolling film method or a coating method, and the positive current collector is an aluminum mesh.
Further, the binder is polytetrafluoroethylene or polyvinylidene fluoride.
Further, the positive electrode material is Ketjen black or carbon nanotubes or SuperP.
By the scheme, the invention at least has the following advantages:
the invention protects the metallic lithium cathode by introducing oxygen gas because oxygen gas has a higher reduction potential (about 2.9V, pair L i)+potential/L i) in the insulating casing, a through hole for oxygen to enter the negative electrode is formed at the negative electrode, so that oxygen can preferentially react with the lithium metal to form a film on the surface of the lithium metalA layer of compact SEI film rich in lithium oxide and lithium peroxide is generated, and the SEI film can effectively prevent the direct contact of the metal lithium and the electrolyte, inhibit the corrosion of the electrolyte to the metal lithium cathode and further play a role in protecting the metal lithium cathode. Therefore, the high-cycle-reversibility metal lithium negative electrode is realized under the condition that the components of the electrolyte are not changed, the problems of additive exhaustion and side reaction of the additive on the positive electrode in the conventional method for protecting the negative electrode by using the additive are effectively solved, and the low-cost metal lithium negative electrode protection scheme is beneficial to promoting the large-scale use of the lithium oxygen battery in the future.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic view of a lithium oxygen cell according to the present invention;
FIG. 2 is a charge-discharge cycle diagram of a lithium oxygen battery of the present invention;
fig. 3 is a graph of cycle curves for a lithium-lithium symmetric battery according to the present invention;
fig. 4 is a graph of the cycling profile of a lithium metal anode in an oxygen atmosphere in accordance with the present invention;
fig. 5 is a coulombic efficiency versus cycle number plot for a lithium metal anode in an oxygen atmosphere in accordance with the present invention;
fig. 6 is a graph of cycling curves for a lithium metal anode under oxygen-free conditions;
fig. 7 is a coulombic efficiency versus cycle number plot for a lithium metal anode in the absence of oxygen.
Wherein:
1 is a case, 101 is a positive electrode stainless steel case, 102 is a negative electrode stainless steel case, 103 is an insulating case, 2 is a porous lithium negative electrode, 3 is a porous positive electrode, 4 is a separator with an electrolytic solution, 5 is a porous negative electrode current collector, 6 is a porous positive electrode current collector, and 7 is a through hole.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example one
Referring to fig. 1, the lithium oxygen battery according to the present invention includes a case 1, a porous lithium negative electrode 2 disposed in the case 1, a porous positive electrode 3, and a separator 4 having an electrolyte disposed between the porous lithium negative electrode 2 and the porous positive electrode 3, in this embodiment, the electrolyte is preferably added by dropping the electrolyte, and the electrolyte may be ether solvents including tetraglyme, triglyme, and the like. The lithium salt can be selected from lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imide, lithium trifluoromethanesulfonate, lithium nitrate and the like. The molar ratio of the solvent to the lithium salt is 1-8: 1. In this example, the molar ratio of tetraethylene glycol dimethyl ether to lithium trifluoromethanesulfonate was preferably 4: 1. The lithium oxygen battery also comprises a porous negative current collector 5 and a porous positive current collector 6, wherein the porous negative current collector 5, the porous lithium negative electrode 2, the diaphragm 4 with electrolyte, the porous positive electrode 3 and the porous positive current collector 6 are sequentially stacked. The shell of the application comprises an insulating shell 103 and a stainless steel shell, the shell close to the porous positive electrode side and the porous lithium negative electrode side is respectively a positive stainless steel shell 101 and a negative stainless steel shell 102, the rest is the insulating shell 103, and a plurality of through holes 7 for oxygen supply to enter are formed in the positive stainless steel shell 101 and the negative stainless steel shell 102. In the embodiment, a plurality of through holes with the diameter of 2mm are preferably formed in the negative stainless steel shell 102 for oxygen to enter the battery, and 7 through holes with the diameter of 2mm are preferably formed in the positive stainless steel shell.
Specifically, the aperture of the through hole of the porous lithium negative electrode is 0.1-1.0mm, and the density of the through hole is 30-240 holes/cm2The aperture of the through hole is preferably 0.4mm, and the density of the through hole is 60 holes/cm2. The porous lithium negative electrode includes a lithium-containing negative electrode such as lithium metal or lithium silicon alloy, in this embodiment, the porous lithium negative electrode is preferably a lithium metal sheet, the porous current collector includes, but is not limited to, a conductive material such as copper, iron, nickel and the like, which is stable for the negative electrode, such as a metal mesh, a metal film with holes or a foamed metal, and in this embodiment, the porous current collector is preferably a porous negative electrode current collectorIs a copper foam.
The porous positive electrode is prepared by mixing a binder and a positive electrode material in a ratio of 1:4-19 and then performing a rolling membrane method or a coating method, wherein the binder is polytetrafluoroethylene or polyvinylidene fluoride, the positive electrode material is ketjen black or carbon nano tubes or SuperP, in the embodiment, 12% by mass of polytetrafluoroethylene emulsion and 12% by mass of SuperP are preferably mixed in a mass ratio of 3:17 and stirred into slurry, and then a membrane punching sheet, namely the porous positive electrode, is rolled, in the embodiment, the porous positive electrode current collector is preferably an aluminum net, and therefore the punching sheet is pressed on the aluminum net.
Specifically, the lithium oxygen battery is placed in a bottle filled with pure oxygen for electrochemical performance test, and the result shown in fig. 2 is obtained. The diameter of the electrode plate used in the test is 12mm, and the mass of the electrode plate is 5.06 mg. The current used during the circulation is 0.2mA/cm2The charge-discharge cut-off capacity is 1mAh/cm2. The first circle of the lithium-oxygen battery has the discharge potential of about 2.7V and the charge potential of below 4.5V basically, which is equivalent to the positive electrode of the carbon material lithium-oxygen battery reported in the general literature, and the battery structure can not change the charge and discharge potential. In addition, the charging and discharging curve of the lithium oxygen battery is basically kept stable after 20 cycles, which shows that the lithium oxygen battery has better cycling stability.
Example two
The remaining structure of the lithium oxygen cell was the same as in example one, except that:
the porous positive electrode in the first embodiment is replaced by a porous metal lithium sheet, and the porous positive electrode current collector is replaced by an aluminum mesh current collector and a foam copper current collector, so that the lithium-oxygen battery is converted into a lithium-lithium battery.
The modified lithium-lithium battery is placed in a bottle filled with pure oxygen for charge and discharge tests, and a reference battery which is not provided with a through hole for oxygen to enter the battery at the negative electrode and the positive electrode participates in the tests, so that the result shown in figure 3 is obtained. At a current density of 0.2mA/cm2In the case of (2), the time for deposition and dissolution of lithium metal was controlled to 5 hours. The overpotential of the battery without oxygen protection increases with the cycle, and after 50 hours of the cycleThe temperature reaches more than 0.4V. Indicating that as cycling proceeds, a large amount of by-products are generated on the lithium metal surface, causing the internal resistance of the cell to increase. Correspondingly, under the condition of oxygen protection, the over-potential of the deposition and dissolution process of the metallic lithium is kept quite stable, and the charge-discharge potential is still kept about 0.1V after 300 hours of circulation. Indicating that the internal impedance of the battery is kept stable and the generation of side reaction products is inhibited.
EXAMPLE III
The remaining structure of the lithium oxygen cell is the same as that of the example two except that: the lithium-lithium battery was converted to a lithium-copper battery by replacing the porous metal lithium sheet and the copper foam current collector on one side of the lithium-oxygen battery described in example two with a copper mesh. In the embodiment, a certain amount of metal lithium is deposited on the copper mesh, then the deposited lithium is dissolved, and the coulombic efficiency of lithium in the circulation process can be known by calculating the ratio of the dissolved lithium to the deposited lithium. In the experiment, the diameter of the electrode plate used by people is 12mm, and the amount of deposited metal lithium is 1mAh/cm2The cut-off potential of the charge is 1.0V. The lithium oxygen cell of this example was placed in a bottle filled with pure oxygen and tested, resulting in the cycle profile shown in fig. 4. It can be seen that the lithium metal maintains a high coulombic efficiency throughout the cycle except for the first turn, and that the overpotential during the cycle remains substantially constant. In addition, as shown in fig. 5, the coulombic efficiency of the lithium-copper battery is still over 98% after 200 cycles, and the average coulombic efficiency of the first 200 cycles is over 98%.
And other test conditions are unchanged, the modified lithium-copper battery is sealed to prevent oxygen from entering the battery, and charging and discharging tests are carried out. The results obtained under otherwise identical test conditions are shown in FIG. 6. It can be seen that the coulombic efficiency of the cell during cycling was below 50%, indicating that there was a significant amount of metallic lithium deposited on the copper electrode that failed to return to the metallic lithium electrode during charging. The rapidly increasing charge and discharge overpotential during cycling indicates the formation of a number of electrochemically inert byproducts due to the reaction of the lithium deposited on the copper electrode with the electrolyte. In addition, it can be seen from fig. 7 that the efficiency of the cell decreased to 0% after only 10 cycles, at which time the cell had completely failed.
In conclusion, the lithium oxygen battery designed by the application can remarkably improve the cycling stability and the coulombic efficiency of the lithium metal cathode based on the protection of the lithium cathode by oxygen.
The working principle of the invention is as follows:
the lithium oxygen battery designed by the application has higher reduction potential (about 2.9V, to L i) by using oxygen+Potential of/L i), a through hole for oxygen to enter the negative electrode is arranged at the position of the negative electrode of the insulating shell, so that oxygen can preferentially react with the metal lithium, and a layer of compact SEI film rich in lithium oxide and lithium peroxide is generated on the surface of the metal lithium, and the SEI film can effectively prevent the metal lithium from directly contacting with the electrolyte and inhibit the electrolyte from corroding the metal lithium negative electrode, thereby playing a role in protecting the metal lithium negative electrode, remarkably improving the cycling stability and the coulombic efficiency of the lithium negative electrode, and effectively solving the problem of failure of the lithium oxygen battery caused by poor cycling performance of the lithium oxygen battery negative electrode.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A lithium oxygen battery comprises a shell, a porous lithium negative electrode, a porous positive electrode and a diaphragm, wherein the porous lithium negative electrode and the porous positive electrode are arranged in the shell, the diaphragm is arranged between the porous lithium negative electrode and the porous positive electrode and provided with electrolyte, the lithium oxygen battery is characterized by further comprising a porous negative electrode current collector and a porous positive electrode current collector, the porous negative electrode current collector, the porous lithium negative electrode, the diaphragm provided with the electrolyte, the porous positive electrode and the porous positive electrode current collector are sequentially stacked, the shells close to the porous positive electrode side and the porous lithium negative electrode side are stainless steel shells, and a plurality of through holes for oxygen supply to enter are respectively arranged on the stainless steel shells close to the porous positive electrode side and the porous lithium negative electrode side; the aperture of the through hole of the porous lithium cathode is 0.1-1.0mm, the density of the through holes is 30-240 holes/cm2；
The porous lithium negative electrode includes metallic lithium or a lithium silicon alloy.
2. The lithium oxygen cell of claim 1, wherein the porous current collector is a metal mesh or a perforated metal film or a metal foam.
3. The lithium oxygen battery of claim 1, wherein the porous lithium negative electrode is a lithium metal sheet, the porous negative electrode current collector is a copper foam, the porous positive electrode is prepared by mixing a binder and a positive electrode material in a ratio of 1:4-19 and then performing a rolling film method or a coating method, and the positive electrode current collector is an aluminum mesh.
4. The lithium oxygen cell of claim 3, wherein the binder is polytetrafluoroethylene or polyvinylidene fluoride.
5. The lithium-oxygen battery as claimed in claim 3, wherein the positive electrode material is Ketjen black or carbon nanotubes or SuperP.
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| CN201710469830.2A CN107482284B (en) | 2017-06-20 | 2017-06-20 | Lithium oxygen battery |
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| CN201710469830.2A CN107482284B (en) | 2017-06-20 | 2017-06-20 | Lithium oxygen battery |
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| CN108511855A (en) * | 2018-03-26 | 2018-09-07 | 南开大学 | A kind of Li/Na-O of Li/Na composite metal negative poles2Secondary cell |
| CN109742489B (en) * | 2019-02-02 | 2020-08-04 | 北京师范大学 | Lithium-oxygen/air battery and preparation method thereof |
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| CN101567472B (en) * | 2008-04-25 | 2012-09-05 | 中国科学院物理研究所 | Electrolyte solution and preparation method and application thereof |
| US9269997B2 (en) * | 2010-06-08 | 2016-02-23 | Ramot At Tel Aviv University Ltd. | Rechargeable alkali metal-air battery |
| CN102315420B (en) * | 2010-07-05 | 2014-09-10 | 中国科学院上海硅酸盐研究所 | Metal cathode structure with protection layer and preparation method thereof |
| CN102263311A (en) * | 2011-06-27 | 2011-11-30 | 清华大学 | Bipolar-structured lithium-air battery |
| CN102376936B (en) * | 2011-10-22 | 2013-05-22 | 清华大学 | Lithium oxygen battery with porous cathode structure |
| US9214707B2 (en) * | 2012-09-21 | 2015-12-15 | Robert Bosch Gmbh | Metal/oxygen battery with precipitation zone |
| CN104218275B (en) * | 2013-05-31 | 2018-03-27 | 华为技术有限公司 | A kind of lithium-air battery and preparation method thereof |
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