CN113594426A - Surface alloyed metal lithium foil and preparation method thereof, metal lithium cathode and lithium battery - Google Patents
Surface alloyed metal lithium foil and preparation method thereof, metal lithium cathode and lithium battery Download PDFInfo
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- CN113594426A CN113594426A CN202010360946.4A CN202010360946A CN113594426A CN 113594426 A CN113594426 A CN 113594426A CN 202010360946 A CN202010360946 A CN 202010360946A CN 113594426 A CN113594426 A CN 113594426A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/40—Alloys based on alkali metals
- H01M4/405—Alloys based on 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a surface alloyed metal lithium foil, a preparation method thereof, a metal lithium cathode and a lithium battery. A surface alloyed lithium metal foil comprising: a metallic lithium foil phase; and an alloying layer on at least one surface of the lithium metal foil phase, the alloying layer being formed in situ by an alloying reaction of lithium metal on the surface. Because the alloying layer and the metal lithium are integrated and can change along with the volume change of the metal lithium negative electrode, the separation of the alloying layer and the metal lithium phase can not occur, and therefore, the lithium battery has better cycle performance.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to a lithium metal negative electrode material for a lithium battery and a preparation method and application thereof.
Background
Due to high energy density, the lithium battery is widely applied to the fields of portable electronic equipment, power grid energy storage, electric trips and the like. However, after decades of development, the energy density of a commercial lithium ion battery using graphite as a negative electrode has developed to the bottleneck, and the requirements of the application field on the energy density and the endurance energy are difficult to meet. Therefore, development of a novel negative electrode material is required to improve the energy density of the battery.
The metallic lithium has a specific capacity of 3.86Ah/g, a potential of-3.04V relative to a hydrogen standard electrode and a density of 0.534g/cm3It is recognized in the industry as the "final" material for the negative electrode of lithium batteries. However, when the lithium metal is used as the negative electrode of the lithium secondary battery, lithium dendrites are formed by uneven deposition on the surface of the negative electrode of the lithium ion battery in the charging process, and the lithium dendrites may pierce through the diaphragm to cause short circuit of the battery, so that the battery explodes and safety accidents occur; the dendritic crystal is melted off in the discharging process to form dead lithium, and the electrochemical activity is lost, so that a large amount of active lithium is consumed and the cycle performance of the battery is reduced.
In order to solve the problems of the lithium negative electrode in the using process, the technical scheme reported at present is to coat protective layers on the surface of the metal lithium, wherein the protective layers can be made of organic materials (CN107305950B), inorganic materials (CN104617259B) or a mixture of organic and inorganic materials. The deposition uniformity of lithium ions is improved through the coating layer, and the formation of dendritic crystals is inhibited; in addition, the coating layer avoids the contact between the negative electrode lithium and the electrolyte, and avoids the direct fusion and the generation of dead lithium.
Disclosure of Invention
The inventors of the present application found that: the existing technology for coating a protective layer on the surface of metal lithium is to dissolve a coating substance in a solvent, then coat the coating substance on the surface of the metal lithium, after the solvent is removed, the coating substance forms a film on the surface layer of the metal lithium, the film is only simply attached to the surface of the metal lithium, no firm acting force exists between the two layers of substances, and in the long-term circulation process, the deposition/dissolution of lithium ions may cause interface separation, so that the protective layer fails, and the circulation performance of the battery cannot be maintained for a long time.
In view of the above problems, the inventors propose a surface-alloyed lithium metal foil and a negative electrode made of the same, in which a lithium alloy layer is formed in situ on the surface of lithium metal, thereby effectively suppressing dendrites and reducing dead lithium; on the other hand, the alloy is formed on the surface of the metal lithium through reaction and is integrated with the metal lithium cathode, so that interface separation cannot occur in the circulation process, and the battery has better circulation performance.
The invention adopts the following technical scheme:
one aspect of the present invention provides a surface-alloyed lithium metal foil, including a lithium metal foil phase and an alloying layer on at least one surface of the lithium metal foil phase, the alloying layer being formed in situ by an alloying reaction of lithium metal on the surface.
According to one embodiment, the alloying layer comprises LiM, wherein M represents at least one selected from the group consisting of a fourth main group element, a third main group element, a second main group element and a transition metal element.
According to one embodiment, the fourth main group element comprises Si, Sn; the third main group element comprises Al, In; the second main group elements comprise Mg, Ga, Sr; the transition metal elements include Ti and Zn.
According to one embodiment, the molar ratio of Li to M in LiM is 1:1 to 1: 5.
According to one embodiment, the thickness of the alloyed layer is in the range of 5 to 10000nm, preferably 10 to 200 nm.
Another aspect of the present invention provides a method of preparing the above-described surface-alloyed lithium metal foil, the method comprising:
step 1: preparing a metal lithium foil;
step 2: compounding M elementary substance foil on at least one surface of the metal lithium foil under pressure to enable metal lithium and M to generate alloying reaction;
or immersing the lithium metal foil in a solution of MX to react MX with lithium metal, taking out the reacted lithium metal foil, drying,
wherein M represents at least one selected from the group consisting of a fourth main group element, a third main group element, a second main group element and a transition metal element, and X represents a sixth main group element or a seventh main group element.
According to one embodiment, the sixth main group element comprises O, S; the seventh main group element comprises F, Cl and Br.
According to one embodiment, the pressure of the pressure recombination is in the range of 0.01 to 100MPa, preferably 3 to 70MPa, and the pressure temperature of the pressure recombination is in the range of 10 to 80 ℃, for example, the ambient temperature. The pressure compounding time can be within the range of 10-300 s, and preferably 20-200 s.
According to one embodiment, MX is a mixture of two or more compounds.
According to one embodiment, the solvent of the MX solution comprises tetrahydrofuran, n-hexane or dimethyl carbonate.
According to one embodiment, MX is reacted with lithium metal at a temperature in the range of 0 to 30s and for a time in the range of 5 to 500s, preferably 30 to 300 s.
In a further aspect of the invention, a lithium metal negative electrode is provided, which is made from the above surface alloyed lithium metal foil.
In yet another aspect, the present invention provides a lithium ion battery comprising the above-described metallic lithium negative electrode.
The invention has at least one of the following advantages:
(1) the alloying layer and the metal lithium are integrated, and can change along with the volume change of the metal lithium cathode, so that the separation of the alloying layer and the metal lithium phase can not occur, and the lithium ion battery has better cycle performance;
(2) the composition and thickness of the alloy layer can be adjusted to adapt to different application environments.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Further, the following examples are exemplary in terms of various product structure parameters, various reaction participants and process conditions, but through a lot of experiments, the inventors of the present invention have verified that other different structure parameters, other types of reaction participants and other process conditions listed above are applicable and can achieve the claimed technical effects.
Example 1 pressure compounding
And (3) stacking the 2-micron aluminum foil and the 50-micron lithium foil in order, placing the stacked aluminum foil and the 50-micron lithium foil in a flat press, regulating the pressure to 20MPa, keeping the pressure for 120s, taking out the compounded pole piece, and finding that the aluminum foil layer disappears to indicate that the surface alloying reaction is finished.
The electrode sheet was cut into a sheet having a width of 45 mm and a length of 58 mm, and used as a negative electrode (A).
The positive electrode adopts lithium cobaltate, a binder polyvinylidene fluoride (PVDF) and a conductive agent Acetylene Black (AB), and the mass ratio is 90: 5: 5, dispersing the mixture into N-methylpyrrolidone (NMP), uniformly stirring, coating the mixture on an aluminum foil, and drying the aluminum foil to be used as the positive electrode (B).
A, a separator and B were stacked in this order, and the stack was sealed in an aluminum plastic film, and an electrolyte (1M lithium hexafluorophosphate (LiFP6), Ethylene Carbonate (EC), dimethyl carbonate (DMC), 10 wt% fluoroethylene carbonate (FEC) was added).
The battery is activated for 3 circles by using 0.1C, and then is charged and discharged by using 1C multiplying power, and the battery still has a retention rate of 90% after 500 circles of circulation. The battery was disassembled and the negative electrode still maintained metallic luster.
Example 2 solution reaction alloying
Preparation of reaction solution (C): 1g of tin chloride was dissolved in 50g of tetrahydrofuran.
A 30 micron lithium sheet with a diameter of 16 mm was soaked in C for 30 s. Surface-alloyed metallic lithium (D) was obtained as a negative electrode.
The anode adopts elemental sulfur, a binder PVDF and a conductive agent AB, and the mass ratio is 70: 10: 20, dispersing into NMP, stirring uniformly, coating on aluminum foil, drying and using as the positive electrode (E).
Placing D, diaphragm and E in turn in button cell case, injecting electrolyte (1M lithium bistrifluoromethanesulfonimide (LiTFSI), 1, 3-Dioxolane (DOL): ethylene glycol dimethyl ether (DME), 0.2 wt% lithium nitrate (LiNO)3) To constitute a battery.
The battery is activated by 0.05C, and then is cycled for 1000 circles by 0.3C, and the capacity retention rate of 80 percent still exists. After the battery was disassembled, it was found that the negative electrode still exhibited metallic luster.
Comparative example 1 surface coating protective layer
Preparing a solution with a protective layer coated on the surface: polyacrylonitrile solution (F) was prepared by dissolving 1g of polyacrylonitrile in 30g of dimethyl carbonate.
And dropping the solution F on the surface of a lithium foil with the thickness of 50 micrometers by a dropper, then carrying out blade coating on the surface of the lithium foil by using a flat scraper, drying the lithium foil obtained by blade coating, and then cutting the lithium foil into a lithium metal negative electrode (G) with the width of 45 millimeters and the length of 58 millimeters to obtain a surface-coated protective layer.
The positive electrode (B) in example 1 was used.
And sequentially visiting G, the diaphragm and B, encapsulating the membrane in an aluminum plastic film, and injecting an electrolyte (1M LiFP6, EC: DMC, 10 wt% FEC addition).
The battery is activated for 3 circles by using 0.1C, then the battery is charged and discharged by adopting 1C multiplying power, and the battery capacity is rapidly attenuated after 200 circles of circulation. The battery is disassembled, the surface of the negative electrode loses metallic luster, and is in black and gray, and the pulverization is serious.
It should be understood that the above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A surface alloyed lithium metal foil, comprising:
a metallic lithium foil phase; and
an alloying layer on at least one surface of the lithium metal foil phase, the alloying layer being formed in situ by an alloying reaction of lithium metal on the surface.
2. The surface-alloyed metallic lithium foil of claim 1, wherein the alloying layer comprises LiM, wherein M represents at least one element selected from the group consisting of a fourth main group element, a third main group element, a second main group element, and a transition metal element.
3. The surface alloyed metallic lithium foil of claim 2, wherein the fourth main group element comprises Si, Sn; the third main group element comprises Al, In; the second main group elements comprise Mg, Ga, Sr; the transition metal elements include Ti and Zn.
4. The surface-alloyed lithium metal foil according to claim 2, wherein the molar ratio of Li to M in LiM is 1:1 to 1: 5.
5. The surface alloyed metallic lithium foil of claim 1, wherein the alloyed layer has a thickness in a range of 5nm to 10000 nm.
6. A method of making the surface alloyed lithium metal foil of any one of claims 1-5, characterized in that the method comprises:
step 1: preparing a metal lithium foil;
step 2: compounding M elementary substance foil on at least one surface of the metal lithium foil under pressure to enable metal lithium and M to generate alloying reaction;
or immersing the lithium metal foil in a solution of MX to react MX with lithium metal, taking out the reacted lithium metal foil, drying,
wherein M represents at least one selected from the group consisting of a fourth main group element, a third main group element, a second main group element and a transition metal element, and X represents a sixth main group element or a seventh main group element.
7. The method according to claim 6, wherein the pressure of the pressure recombination is in the range of 0.01 to 100MPa, and the temperature is in the range of 10 to 80 ℃.
8. The method of claim 6, wherein the solvent for the MX solution comprises tetrahydrofuran, n-hexane, or dimethyl carbonate.
9. A lithium metal anode made from the surface alloyed lithium metal foil according to any one of claims 1-5.
10. A lithium battery comprising the lithium metal negative electrode of claim 9.
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| CN202010360946.4A CN113594426A (en) | 2020-04-30 | 2020-04-30 | Surface alloyed metal lithium foil and preparation method thereof, metal lithium cathode and lithium battery |
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| CN202010360946.4A CN113594426A (en) | 2020-04-30 | 2020-04-30 | Surface alloyed metal lithium foil and preparation method thereof, metal lithium cathode and lithium battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114784259A (en) * | 2022-05-28 | 2022-07-22 | 浙江锋锂新能源科技有限公司 | Lithium metal battery cathode material, preparation method thereof and lithium metal battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068964A (en) * | 2016-12-29 | 2017-08-18 | 中国电子科技集团公司第十八研究所 | Lithium aluminum alloy surface modified lithium cathode and solid-state battery thereof |
| CN109638235A (en) * | 2018-11-09 | 2019-04-16 | 清华大学 | Metallic lithium surface guard method and equipment, cathode pole piece and lithium battery |
| US20200099046A1 (en) * | 2018-09-25 | 2020-03-26 | Toyota Motor Engineering & Manufacturing North America, Inc. | Nano-alloy interphase for lithium metal solid state batteries |
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- 2020-04-30 CN CN202010360946.4A patent/CN113594426A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068964A (en) * | 2016-12-29 | 2017-08-18 | 中国电子科技集团公司第十八研究所 | Lithium aluminum alloy surface modified lithium cathode and solid-state battery thereof |
| US20200099046A1 (en) * | 2018-09-25 | 2020-03-26 | Toyota Motor Engineering & Manufacturing North America, Inc. | Nano-alloy interphase for lithium metal solid state batteries |
| CN109638235A (en) * | 2018-11-09 | 2019-04-16 | 清华大学 | Metallic lithium surface guard method and equipment, cathode pole piece and lithium battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114784259A (en) * | 2022-05-28 | 2022-07-22 | 浙江锋锂新能源科技有限公司 | Lithium metal battery cathode material, preparation method thereof and lithium metal battery |
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Application publication date: 20211102 |