CN114744204A - Lithium metal battery cathode and preparation method thereof - Google Patents
Lithium metal battery cathode and preparation method thereof Download PDFInfo
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- CN114744204A CN114744204A CN202210291223.2A CN202210291223A CN114744204A CN 114744204 A CN114744204 A CN 114744204A CN 202210291223 A CN202210291223 A CN 202210291223A CN 114744204 A CN114744204 A CN 114744204A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a lithium metal battery cathode and a preparation method thereof, belonging to the technical field of battery energy sources. The negative electrode of the lithium metal battery used in the invention is a composite current collector decorated with a lithium-philic layer; firstly, a cleaned copper foil is placed in a muffle furnace for oxidation by adopting an air oxidation method, an oxide layer is formed on the surface of a current collector, the oxidized copper current collector is modified by utilizing a thermal diffusion method by virtue of the volatility of lithium oxide, and finally a composite current collector is obtained.
Description
Technical Field
The invention belongs to the technical field of energy batteries, and particularly relates to a lithium metal battery cathode and a preparation method thereof.
Background
In recent years, energy and environmental problems have become increasingly serious to the human society. In order to reduce the consumption of fossil fuels, the automotive industry is gradually moving towards electric vehicles. However, since the current lithium ion battery is mainly oriented to 3C electronic products, when the current lithium ion battery is applied to the electric vehicle industry, the capacity problem of the lithium ion battery brings mileage anxiety to users of electric vehicles. For this reason, the low energy density of lithium ion batteries based on conventional graphite negative electrodes is limited (299W h kg)-1) The demand of people for larger energy density of energy storage products cannot be met, and the research on the lithium metal cathode gets the attention of researchers again.
Lithium metal has the lowest redox potential-3.04V (vs SHE) and 3862 mA h g-1The lithium metal battery is considered to be one of the most promising next-generation high energy density batteries because of the ultrahigh theoretical specific capacity of the negative electrode, and has attracted much attention. However, lithium negative electrodes have many problems during charge and discharge due to the inherent characteristics of lithium metal: uneven deposition of lithium, corrosion of the electrodes, dead lithium and volume expansion due to the formation of lithium dendrites; these problems can lead to severe capacity loss and even explosion of lithium metal batteries after long-term operation. Early research and research on lithium metal batteries focused on the reversibility of the lithium negative electrode, but the above problems have prevented the practical use of lithium metal batteries.
Disclosure of Invention
The invention provides a lithium metal battery negative electrode and a preparation method thereof, wherein the negative electrode is a lithium-philic layer constructed on the surface of a copper foil current collector, so that lithium metal is favorably deposited on the surface of an electrode, the formation of lithium dendrite is inhibited, and the service life of the battery is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
the negative electrode of the lithium metal battery is a composite current collector with a copper foil current collector surface modified with a lithium-philic compound, wherein the lithium-philic compound is LiCuO, and the thickness of the surface modified layer is 300nm-1 mu m.
A preparation method of a lithium metal battery negative electrode comprises the following steps:
(1) placing the copper foil in HCl with a certain concentration for cleaning;
(2) repeatedly cleaning the copper foil obtained in the step (1) with distilled water, and then cleaning with ethanol;
(3) drying the copper foil cleaned in the step (2), and then placing the copper foil in an air atmosphere for high-temperature oxidation;
(4) weighing a certain amount of lithium source, placing the weighed lithium source in an inert gas atmosphere, evaporating lithium at high temperature, modifying a lithium-philic layer on the surface of the oxidized copper foil, and cooling to obtain a modified copper current collector.
In the above step, the thickness of the copper foil in the step (1) is 5-20 μm, and the HCl concentration is 0.1-1 mol/L;
in the step (3), the heating rate of the high-temperature oxidation is 0.5-10 ℃/min, the temperature is 200 ℃ and 300 ℃, and the heat preservation time is 1-3 h;
in the step (4), the lithium source is one of lithium oxide, lithium hydroxide and lithium carbonate; the mass of the lithium source relative to the size of the copper foil is 0.1-10 mg/cm2(ii) a The high-temperature heating rate is 1-10 ℃/min, the temperature is 500-.
Has the advantages that: the invention provides a lithium metal battery cathode and a preparation method thereof, which comprises the steps of firstly, placing a cleaned copper foil in a muffle furnace for oxidation by adopting an air oxidation method, forming an oxide layer on the surface of a current collector, modifying the oxidized copper current collector by utilizing a thermal diffusion method by virtue of the volatility of lithium oxide, finally obtaining a composite current collector, and assembling a battery to test the electrochemical performance of the composite current collector. According to the invention, the lithium-philic layer is constructed on the surface of the copper current collector, the affinity of the surface of the composite current collector and lithium metal is greatly improved, the nucleation overpotential of the lithium metal on an electrode is reduced, a stable lithium deposition layer is obtained, and meanwhile, in the battery cycle process, the polarization condition of the electrode is improved, the reversibility of electrode reaction in the battery is improved, the stability of an electrode interface is improved, and the coulomb efficiency and the service life of the lithium metal battery are improved.
Drawings
FIG. 1 is a surface topography of a LiCuO/Cu composite current collector in an embodiment of the invention, (a) a topography under low magnification, (b) a topography under high magnification;
FIG. 2 is a diagram of the results of an XRD test of a LiCuO/Cu composite current collector in an example of the present invention;
FIG. 3 is a graph of the results of XPS testing of LiCuO/Cu composite current collectors in an embodiment of the present invention;
FIG. 4 is a time-voltage plot of lithium deposition on Cu and LiCuO/Cu in an example of the invention: 1 mA cm-2；
FIG. 5 is a graph of the cycling performance of cells of various capacities and current densities according to an example of the present invention, (a) 1 mA cm -21 mA h cm-2, (b) 0.5 mA cm-2 0.5 mA h cm-2；
FIG. 6 is a topographic map of lithium deposition on the surface of the copper current collector after different cycles in the embodiment of the present invention (1 mA cm)-2 1 mA h cm-2)，(a) Cu 1 th，(b) Cu 25 th，(c) Cu 50 th，(d) Cu2O 1 th，(e) Cu2O 25 th，(f) Cu2O 50 th，(g) LiCuO/Cu 1 th，(h) LiCuO/Cu 25 th，(i) LiCuO/Cu 50 th。
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
a lithium metal battery negative electrode is characterized in that a lithium-philic layer is constructed on the surface of a copper foil current collector, LiCuO is introduced to the surface of the current collector, as shown in figure 1, LiCuO is successfully introduced to the surface of the modified copper current collector, and the LiCuO/Cu composite current collector is successfully prepared after heat treatment by combining figures 1, 2 and 3, wherein the thickness of a surface modification layer is 300nm-1 mu m.
Example 1
The preparation method of the lithium metal battery negative electrode comprises the following steps:
(1) weighing a certain amount of concentrated hydrochloric acid, and putting the concentrated hydrochloric acid into distilled water to dilute the concentrated hydrochloric acid to 1 mol/L;
(2) placing the copper foil in diluted hydrochloric acid for cleaning, removing impurities and grease on the surface of the copper foil, then repeatedly washing for 3 times by using secondary water, then washing for 3 times by using absolute ethyl alcohol, and drying by using a blower after cleaning;
(3) directly placing the copper foil obtained in the step (2) in a muffle furnace for heating treatment, heating to 250 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 2 h;
(4) weighing 20mg of lithium oxide as a lithium source and placing the lithium oxide in a porcelain boat;
(5) cutting the oxidized copper foil into 3 cm by 6 cm, placing on a porcelain boat, and fixing;
(6) and (4) placing the porcelain boat in the step (5) in a high-temperature reaction furnace, introducing nitrogen as protective gas, heating to 600 ℃ at the heating rate of 10 ℃/min, and preserving heat for 4h to obtain the composite current collector with the surface containing LiCuO.
Example 2
The negative electrode is a LiCuO lithium-philic layer which is modified on the surface of a copper foil current collector.
The preparation method of the negative electrode of the lithium metal battery comprises the following steps:
(1) weighing a certain amount of concentrated hydrochloric acid, and putting the concentrated hydrochloric acid into distilled water to dilute the concentrated hydrochloric acid to 1 mol/L;
(2) placing the copper foil in diluted hydrochloric acid for cleaning, removing impurities and grease on the surface of the copper foil, then repeatedly washing for 3 times by using secondary water, then washing for 3 times by using absolute ethyl alcohol, and drying by using a blower after cleaning;
(3) directly placing the copper foil obtained in the step (2) in a muffle furnace for heating treatment, heating to 200 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 3 h;
(4) weighing 50mg of lithium hydroxide as a lithium source and placing the lithium hydroxide in a porcelain boat;
(5) cutting the oxidized copper foil into 3 cm by 6 cm, placing on a porcelain boat, and fixing;
(6) and (5) placing the ceramic boat in the step (5) in a high-temperature reaction furnace, introducing nitrogen as protective gas, heating to 700 ℃ at a heating rate of 10 ℃/min, and preserving heat for 2h to obtain the composite current collector with the surface containing LiCuO.
Example 3
The negative electrode is a LiCuO lithium-philic layer which is modified on the surface of a copper foil current collector.
The preparation method of the negative electrode of the lithium metal battery comprises the following steps:
(1) weighing a certain amount of concentrated hydrochloric acid, and putting the concentrated hydrochloric acid into distilled water to dilute the concentrated hydrochloric acid to 1 mol/L;
(2) placing the copper foil in diluted hydrochloric acid for cleaning, removing impurities and grease on the surface of the copper foil, then repeatedly washing for 3 times by using secondary water, then washing for 3 times by using absolute ethyl alcohol, and drying by using a blower after cleaning;
(3) directly placing the copper foil obtained in the step (2) in a muffle furnace for heating treatment, heating to 300 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 1 h;
(4) weighing 100mg of lithium carbonate as a lithium source and placing the lithium carbonate in a porcelain boat;
(5) cutting the oxidized copper foil into 3 cm by 6 cm, placing on a porcelain boat, and fixing;
(6) and (5) placing the porcelain boat in the step (5) in a high-temperature reaction furnace, introducing nitrogen as protective gas, heating to 900 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h to obtain the composite current collector with the surface containing LiCuO.
Comparative example 1
Assembling the copper foil without any treatment into a battery for testing;
comparative example 2
The cuprous oxide copper foil current collector is the same as the step (1), the step (2) and the step (3) of the embodiment 1, namely, the unmodified cuprous oxide copper foil current collector is used as a negative electrode, the metal lithium foil is used as a positive electrode, and a standard 2032 button cell assembled battery is assembled by a PE diaphragm in an argon glove box (H2O < 0.01 PPM, O2 < 0.01 PPM) for testing;
the conditions of each assembled battery are consistent and are 1 mA cm-2Current density of comparative example 1 unmodified Cu current collector, Cu of comparative example 22Electrodeposition was carried out on the O current collector and the LiCuO/Cu composite current collector of example 2, and as shown in fig. 4, it was found that the nucleation overpotential of the LiCuO/Cu composite current collector was significantly smaller than that of the two-group control, indicating that there was good affinity between LiCuO and lithium metal, which was advantageousThe lithium is uniformly nucleated on the surface of the current collector.
Fig. 5 reflects the significant improvement in coulombic efficiency and cycle life of lithium-copper half cells assembled using the LiCuO/Cu composite current collector as the negative electrode of the lithium metal battery. The battery has a battery capacity of 0.5 mA h cm-2The current density is 0.5 mA cm-2Under the condition of stable circulation for 200 circles, when the current density and the capacity are improved, the current density is 1 mA cm-2，1 mA h cm-2Under the condition, the coulombic efficiency is still over 85 percent after 125 cycles of circulation, and the graph shows that the coulombic efficiency and the cycle life are far better than those of the control group.
Fig. 6 is a diagram of lithium deposition morphology at the 1 st, 25 th and 50 th cycles of the assembled battery, and it can be clearly observed from the diagram that the comparative battery has a very obvious lithium dendrite structure, and the lithium dendrite structure becomes more and more obvious with the extension of the cycle period, while the battery using the LiCuO/Cu composite current collector as the negative electrode has no lithium dendrite structure, so that the morphology of the metal lithium of the battery is kept flat all the time during the 50 cycles of the battery.
The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the protection scope of the invention.
Claims (9)
1. The negative electrode of the lithium metal battery is characterized in that the negative electrode is a composite current collector with a copper foil current collector surface modified with a lithium-philic compound.
2. The lithium metal battery negative electrode of claim 1, wherein the thickness of the lithiophilic compound surface modification layer is 300nm to 1 μm.
3. The lithium metal battery anode of claim 1 or 2, wherein the lithium-philic compound is LiCuO.
4. A preparation method of a lithium metal battery cathode is characterized by comprising the following steps:
(1) placing the copper foil in HCl with a certain concentration for cleaning;
(2) repeatedly cleaning the copper foil obtained in the step (1) with distilled water, and then cleaning with ethanol;
(3) drying the copper foil cleaned in the step (2), and then placing the copper foil in an air atmosphere for high-temperature oxidation;
(4) weighing a certain amount of lithium source, placing the weighed lithium source in an inert gas atmosphere, evaporating lithium at high temperature, modifying a lithium-philic layer on the surface of the oxidized copper foil, and cooling to obtain the modified copper current collector.
5. The method of claim 4, wherein the HCl concentration in step (1) is 0.1 to 1 mol/L.
6. The method for preparing the negative electrode of the lithium metal battery as claimed in claim 4, wherein the temperature rise rate of the high-temperature oxidation in the step (3) is 0.5-10 ℃/min, the temperature is 200-300 ℃, and the holding time is 1-3 h.
7. The method for preparing a negative electrode for a lithium metal battery according to claim 4, wherein the mass of the lithium source in the step (4) is 0.1 to 10 mg/cm with respect to the size of the copper foil2。
8. The method of manufacturing a negative electrode for a lithium metal battery according to claim 4 or 7, wherein the lithium source in the step (4) is one of lithium oxide, lithium hydroxide, and lithium carbonate.
9. The method for preparing the negative electrode of the lithium metal battery as claimed in claim 4, wherein the temperature rise rate of the high temperature in the step (4) is 1-10 ℃/min, the temperature is 500-.
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| CN202210291223.2A CN114744204A (en) | 2022-03-23 | 2022-03-23 | Lithium metal battery cathode and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518254A (en) * | 2019-09-09 | 2019-11-29 | 厦门大学 | A kind of lithium metal battery negative current collector and its preparation method and application |
| CN112713260A (en) * | 2019-10-25 | 2021-04-27 | 广州汽车集团股份有限公司 | Flexible lithium metal battery cathode, preparation method thereof and lithium metal battery |
| CN112750982A (en) * | 2020-12-30 | 2021-05-04 | 复旦大学 | Laminated lithium metal battery negative electrode material, preparation method thereof and lithium metal secondary battery |
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- 2022-03-23 CN CN202210291223.2A patent/CN114744204A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110518254A (en) * | 2019-09-09 | 2019-11-29 | 厦门大学 | A kind of lithium metal battery negative current collector and its preparation method and application |
| CN112713260A (en) * | 2019-10-25 | 2021-04-27 | 广州汽车集团股份有限公司 | Flexible lithium metal battery cathode, preparation method thereof and lithium metal battery |
| CN112750982A (en) * | 2020-12-30 | 2021-05-04 | 复旦大学 | Laminated lithium metal battery negative electrode material, preparation method thereof and lithium metal secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| ZHONGZHENG ZUO 等: "The Lithiophilcity of Collector by LiCuO particles decorate Cu form to Restrain Lithium dendrite Growth", pages 1 - 19 * |
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