CN107689442B - Metal lithium composite material with coating layer structure, preparation method and application thereof - Google Patents
Metal lithium composite material with coating layer structure, preparation method and application thereof Download PDFInfo
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- 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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a metal lithium composite material with a coating layer structure and a preparation method thereof. The lithium metal composite material with the coating structure comprises a lithium metal material and an organic-inorganic composite coating layer coated on the surface of the lithium metal material, wherein the organic-inorganic composite coating layer comprises a silica inorganic network and polyelectrolyte. The invention also discloses application of the metal lithium composite material with the coating layer structure in preparation of a negative electrode material, a negative electrode or a battery. The metal lithium composite material with the coating layer provided by the invention is used as a negative electrode material, particularly a secondary negative electrode, can obviously improve the cycle performance of a battery such as a lithium battery, inhibit the formation of dendritic crystals, improve the safety of the battery, provide higher specific capacity and good cycle performance, and meanwhile, the preparation process of the provided metal lithium composite material is simple and easy to implement, good in controllability, low in cost and suitable for large-scale production.
Description
Technical Field
The application belongs to the field of energy batteries, and particularly relates to a metal lithium composite material with a coating layer structure, a preparation method and an application thereof, such as an application in preparing a secondary battery cathode and a secondary battery.
Background
Lithium secondary batteries play an important role in energy storage devices due to their characteristics of high energy density, good cycle performance, environmental friendliness, and the like. The lithium battery adopting the metal lithium as the cathode material has the characteristics of high operating voltage, high mass specific capacity, large specific energy and the like. However, when the lithium metal is simply used as the battery negative electrode, lithium ions are deposited on the lithium metal negative electrode in the charging and discharging processes to form dendrites, so that the specific surface is enlarged, and the lithium metal is easy to react with the electrolyte continuously to generate an SEI (solid electrolyte interface) film, which causes the impedance of the negative electrode to be larger and larger, and influences the specific capacity and the cycle performance of the battery. In severe cases, the membrane may be punctured to cause internal short circuit and overheating, so that the electrolyte may be decomposed and even burned, which is dangerous, and thus, the use of the membrane may be limited.
In order to protect the metallic lithium negative electrode, many researches have been made, and mainly focused on surface modification of the lithium negative electrode by an electrolyte additive (e.g., lithium nitrate), but such a single modification effect has a limited effect, and problems such as capacity loss, increase in internal resistance, and deterioration in performance are easily caused.
There have also been many researchers attempting to protect lithium negative electrodes by a pre-formed lithium protective layer. For example, lithium phosphorus oxynitride (LiPON, US patent 5314765), lithium silicate, lithium borate, lithium silicon sulfide, lithium sulfur phosphide (CN, 1208856C), alumina (CN, 103094522), silica (CN, 104617259 a) inorganic protective layer, or polypyrrole (CN, 103985840 a) organic protective layer, which is a conductive polymer, can achieve certain effects, but the protective effect is still very limited, the inorganic protective layer has strong rigidity and is easily damaged by dendrites, and the organic protective layer is difficult to be well attached to the surface of lithium metal and is easily detached.
Disclosure of Invention
The invention mainly aims to provide a metal lithium composite material with a coating layer structure, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the embodiment of the invention provides a lithium metal composite material with a coating structure, which comprises a lithium metal material and an organic-inorganic composite coating layer coated on the surface of the lithium metal material, wherein the organic-inorganic composite coating layer comprises a silica inorganic network and polyelectrolyte, and the content of the polyelectrolyte in the organic-inorganic composite coating layer is 0-100 wt%, preferably more than 0 and less than 100%.
Preferably, the silica inorganic network is mainly formed by carrying out in-situ sol-gel reaction on small molecular silane on the surface of the lithium metal material.
Preferably, the silica inorganic network forms a chemical bond with the lithium metal material, such as a Si-S-Li chemical bond.
Embodiments of the present invention also provide a method for preparing the lithium metal composite material with a cladding layer structure, including: and reacting the metallic lithium material with a mixed solution containing micromolecular silane and polyelectrolyte to form an organic-inorganic composite coating layer on the surface of the metallic lithium material.
The embodiment of the invention also provides application of the metal lithium composite material with the coating layer structure in preparation of a negative electrode material, a negative electrode or a battery.
Wherein the negative electrode may be a secondary battery negative electrode.
Wherein the battery may be a secondary battery.
Preferably, the secondary battery includes a lithium battery.
Compared with the prior art, the metal lithium composite material with the coating layer provided by the invention is used as a negative electrode material, particularly a secondary negative electrode, can obviously improve the cycle performance of a battery such as a lithium battery, inhibit the formation of dendritic crystals, improve the safety of the battery, provide higher specific capacity and good cycle performance, and meanwhile, the preparation process of the provided metal lithium composite material is simple and easy to implement, good in controllability, low in cost and suitable for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the comparison of the cut-off voltage of 1mAh charging and discharging for a half-cell of a lithium plate composed of the metallic lithium-carbon nanotube microsphere and the metallic lithium-carbon nanotube microsphere with a coating layer in example 1 of the present invention;
FIG. 2 is a comparative graph of 1mAh charging and discharging of a lithium half cell in 100 cycles in example 1 of the present invention, wherein the lithium-carbon nanotube microspheres and the lithium-carbon nanotube microspheres with a coating layer form a charging and discharging comparison;
FIG. 3 is an SEM image of a lithium sheet having a coating layer in example 2 of the present invention;
FIG. 4 is a graph showing the voltage change of 1mAh charging and discharging of a lithium plate half cell by the lithium plate having a coating layer in example 2 of the present invention;
fig. 5 is a graph comparing the cycle performance of the lithium sheet having a coating layer in example 2 of the present invention with that of an unprotected lithium sheet in a lithium sulfur battery.
Detailed Description
An aspect of an embodiment of the present invention provides a lithium metal composite material having a coating layer structure, which is characterized by comprising a lithium metal material and an organic-inorganic composite coating layer coated on a surface of the lithium metal material, wherein the organic-inorganic composite coating layer comprises a silica inorganic network and polyelectrolyte.
Further, the content of polyelectrolyte in the organic-inorganic composite coating layer is 0-100 wt%, preferably more than 0 and less than 100 wt%, and preferably 30-70 wt%. When the content of polyelectrolyte is 0, the organic-inorganic composite coating layer is an inorganic coating layer.
Preferably, the organic-inorganic composite coating layer is formed by doping a silica inorganic network and polyelectrolyte.
Preferably, the silica inorganic network is mainly formed by carrying out in-situ sol-gel reaction on small molecular silane on the surface of the lithium metal material.
Preferably, the silica inorganic network forms a chemical bond with the lithium metal material, such as a Si-S-Li chemical bond.
Further, the small molecule silane comprises mercaptosilane and a small molecule silane precursor.
For example, the mercaptosilane includes mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane, but is not limited thereto.
For example, the small molecule silane precursor includes tetraethoxysilane, trimethoxychlorosilane, aminopropyltrimethoxysilane, or aminopropyltriethoxysilane, but is not limited thereto.
Preferably, the small molecule silane consists of mercaptopropyl trimethoxysilane and tetraethoxy silane.
Preferably, the mass ratio of the mercaptopropyl trimethoxysilane to the tetraethoxy silane is 10-50%: 1.
further, the polyelectrolyte is selected from polyelectrolytes having certain lithium ion conductivity characteristics (lithium ion conductivity greater than 0.00005S/cm). For example, the polyelectrolyte may be selected from sulfonate-based polymers (e.g., lithium perfluorosulfonate polymer), acetate-based polymers (e.g., polystyrene lithium acetate), phosphate-based polymers (e.g., polystyrene lithium phosphate), or polyether-based polymers (e.g., polyethylene oxide (PEO)), but is not limited thereto. Preferably, the polyelectrolyte is a lithium perfluorosulfonate polymer.
Preferably, the thickness of the organic-inorganic composite coating layer is 1-1000 nm.
Further, the form of the lithium metal material includes a granular form or a flake form, but is not limited thereto, and may be, for example, other regular or irregular forms.
Further, the metallic lithium material includes a bulk material composed of metallic lithium or a composite material composed of metallic lithium and other metallic or non-metallic materials, such as a composite material of metallic lithium and carbon, and the like. Of course, in these composites at least a portion of the lithium metal should be exposed.
In the embodiment of the invention, micromolecular silane and polyelectrolyte can be subjected to in-situ sol-gel reaction on the surface of the metallic lithium material to generate the organic-inorganic composite membrane coating, the functional groups of the silane are connected between the surface of the metallic lithium and the coating through chemical bonds, the organic-inorganic composite material has better mechanical property and can respond to the volume change of the lithium cathode in the charging and discharging process, and the introduction of the polyelectrolyte with high lithium ion transference number can further reduce the impedance of the cathode surface. The coating layer structure can effectively control the reaction of the metal lithium and the electrolyte, reduce the impedance of the surface of the negative electrode and improve the specific capacity and the cycle performance of the lithium secondary battery.
An aspect of an embodiment of the present invention also provides a method of preparing a lithium metal composite having a clad structure, which includes: and reacting the metallic lithium material with a mixed solution containing micromolecular silane and polyelectrolyte to form an organic-inorganic composite coating layer on the surface of the metallic lithium material.
For example, the lithium metal can be reacted with a mixed solution of small molecule silane and polyelectrolyte for a period of time and then dried in a vacuum oven.
For example, if the metallic lithium material is metallic lithium particles, the metallic lithium particles are immersed in the mixed solution for reaction for a period of time, then the solvent is removed by suction filtration, and washed with the solvent several times, and finally the resulting material is dried in a vacuum oven.
For example, if the lithium metal material is a lithium metal sheet, the mixed solution may be drawn down to form a film on the surface of the lithium sheet by using a drawing method, and then the residual solvent may be removed by using a vacuum oven.
Preferably, the solute content in the mixed solution is 0.1-5 wt%.
Preferably, the molar ratio of the polyelectrolyte to the small molecule silane in the mixed solution is 0-10: 1, preferably wherein the amount of polyelectrolyte is greater than 0.
Preferably, the solvent in the mixed solution includes n-hexane or n-methylpyrrolidone, but is not limited thereto.
An aspect of the embodiments of the present invention also provides a use of the lithium metal composite material with a cladding structure in preparing a negative electrode material, a negative electrode or a battery.
Further, the negative electrode may be a secondary battery negative electrode.
Further, the battery may be a secondary battery.
Preferably, the secondary battery includes a lithium battery, such as a lithium metal-oxide battery, a lithium metal-polymer battery, a rechargeable lithium ion battery, a lithium sulfur battery, or a lithium air battery, etc., but is not limited thereto.
For example, a negative electrode for a secondary battery may include the lithium metal composite having a clad structure.
For example, a secondary battery may include the lithium metal composite having a clad structure or the negative electrode of the secondary battery.
Among them, the secondary battery includes a lithium battery such as a metallic lithium-oxide battery, a metallic lithium-polymer battery, a rechargeable lithium ion battery, a lithium sulfur battery, or a lithium air battery, etc., but is not limited thereto.
The metal lithium composite material with the coating layer structure can be applied to various lithium batteries, and can be applied to metal lithium-oxide batteries, metal lithium-polymer batteries, rechargeable lithium ion batteries and lithium-sulfur batteries. One area of interest is the use of rechargeable lithium ion batteries in portable electronic devices, and hybrid vehicles, where it is desirable to provide the highest specific capacity and good cycle performance of secondary lithium batteries and to ensure safety advances, while metallic lithium, as the most ideal negative electrode material, cannot be used directly due to dendrites generated during charging and discharging, low safety, the invention produces a metallic lithium composite material that can suppress the formation of dendrites, improve the safety of the battery, and provide higher specific capacity and good cycle performance.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
Example 1: the preparation method comprises the steps of soaking the metal lithium-carbon nanotube microspheres (see CN105374991A) in a small molecular silane solution, wherein the concentration of mercaptopropyl trimethoxy silane in the small molecular silane solution is 1%, the concentration of tetraethoxy silane in the small molecular silane solution is 2%, and a solvent is n-hexane. And after reaction and stirring for 3 minutes, carrying out suction filtration to remove residual reactants and solvent, washing with n-hexane, carrying out suction filtration twice, and drying to obtain the material, namely the metal lithium composite material with the silane protective layer. The metal lithium composite material is assembled into a half cell of a pair of lithium sheets, and the electrolyte is LiPF with the concentration of 1M6The cell voltage change was recorded at 1mAh charge-discharge cycles with the cut-off voltage for charge-discharge as shown in FIG. 1. Compared with the pole piece made of the metal lithium-carbon nanotube microsphere without protection treatment, the polarization degree of the metal lithium composite material with the protective layer is better controlled, especially within 150 cycles. The comparison of the charge and discharge curves at 100 cycles is shown in FIG. 2.
Example 2: soaking a lithium metal sheet in small molecular silane
In the mixed solution, the concentration of mercaptopropyl trimethoxy silane is 1 percent, the concentration of tetraethoxy silane is 2 percent,
the concentration is 2%, and the solvent is nitrogen methyl pyrrolidone. After reacting for 5 minutes, washing away residual reactants by using a solvent, and drying in a vacuum oven to obtain the metal lithium composite material with the organic-inorganic composite protective layer. The SEM photograph of the reacted lithium sheet is shown in fig. 3, and it can be seen that there is a distinct insulating protective layer on the surface, in which the particles are aggregated inorganic silicon particles.
The lithium metal composite and the common lithium sheet were combined to form a half cell, and subjected to DOL/DME (1:1, v%) with an electrolyte of 1M LiTFSI, and a charge-discharge cycle of 1mAh, and the voltage change of the cell was recorded, as shown in FIG. 4.
The lithium metal composite material is used as the cathode of a lithium-sulfur battery, and the anode is sulfur carbonComposite material (with sulfur proportion of 60% and surface density of 2 mg/cm)2) The electrolyte was 1M DOL/DME (1:1, v%) from LiTFSI, and was subjected to charge-discharge cycling at 0.1C of theoretical capacity, with the specific discharge capacity change shown in FIG. 5 and compared to the unprotected lithium plate.
The composition and/or structure parameters of the various products, the various reaction participants and the process conditions used in the foregoing embodiments are typical examples, 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.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (24)
1. The lithium metal composite material with the coating structure is characterized by comprising a lithium metal material and an organic-inorganic composite coating layer coated on the surface of the lithium metal material, wherein the organic-inorganic composite coating layer is formed by doping a silica inorganic network and polyelectrolyte, and the content of the polyelectrolyte in the organic-inorganic composite coating layer is more than 0 and less than 100 percent;
the silicon dioxide inorganic network is mainly formed by carrying out in-situ sol-gel reaction on micromolecular silane on the surface of a metal lithium material, wherein the micromolecular silane comprises mercaptosilane and a micromolecular silane precursor, so that a Si-S-Li chemical bond is formed between the silicon dioxide inorganic network and the metal lithium material;
the polyelectrolyte is selected from polyelectrolytes with the lithium ion conductivity of more than 0.00005S/cm.
2. The lithium metal composite with a clad structure as claimed in claim 1, wherein: the mercaptosilane includes mercaptopropyltrimethoxysilane or mercaptopropyltriethoxysilane.
3. The lithium metal composite with a clad structure as claimed in claim 1, wherein: the small molecule silane precursor comprises tetraethoxysilane, trimethoxychlorosilane, aminopropyltrimethoxysilane or aminopropyltriethoxysilane.
4. The lithium metal composite with a cladding structure according to any one of claims 1 to 3, wherein: the micromolecular silane consists of mercaptopropyl trimethoxysilane and tetraethoxy silane.
5. The lithium metal composite with a cladding structure according to claim 4, wherein: the mass ratio of the mercaptopropyl trimethoxysilane to the tetraethoxysilane is 10-50%: 1.
6. the lithium metal composite with a clad structure as claimed in claim 1, wherein: the content of polyelectrolyte in the organic-inorganic composite coating layer is 30-70 wt%.
7. The lithium metal composite having a clad structure according to claim 1 or 6, wherein: the polyelectrolyte is selected from sulfonate polymers, acetate polymers, phosphate polymers or polyether polymers.
8. The lithium metal composite with a cladding structure according to claim 7, wherein: the polyelectrolyte is a lithium perfluorosulfonate polymer.
9. The lithium metal composite with a clad structure as claimed in claim 1, wherein: the thickness of the organic-inorganic composite coating layer is 1-1000 nm.
10. The lithium metal composite with a clad structure as claimed in claim 1, wherein: the form of the metallic lithium material includes a granular form or a flake form.
11. The lithium metal composite with a clad structure as claimed in claim 1, wherein: the metallic lithium material includes a bulk material composed of metallic lithium or a composite material composed of metallic lithium and other metallic or non-metallic materials.
12. A method for preparing a lithium metal composite having a clad structure according to any one of claims 1 to 11, characterized by comprising: and reacting the metallic lithium material with a mixed solution containing micromolecular silane and polyelectrolyte to form an organic-inorganic composite coating layer on the surface of the metallic lithium material.
13. The method of manufacturing according to claim 12, wherein: the content of solute in the mixed solution is 0.1-5 wt%.
14. The production method according to claim 12 or 13, characterized in that: the molar ratio of the polyelectrolyte to the micromolecular silane in the mixed solution is 0-10: 1.
15. the method of manufacturing according to claim 12, wherein: the solvent in the mixed solution comprises n-hexane or N-methyl pyrrolidone.
16. Use of the lithium metal composite having a coating layer structure of any one of claims 1 to 11 for preparing a negative electrode material, a negative electrode or a battery.
17. Use according to claim 16, characterized in that: the negative electrode is a secondary battery negative electrode.
18. Use according to claim 16, characterized in that: the battery is a secondary battery.
19. Use according to claim 18, characterized in that: the secondary battery includes a lithium battery.
20. Use according to claim 19, characterized in that: the lithium battery includes a lithium metal-oxide battery, a lithium metal-polymer battery, a rechargeable lithium ion battery, a lithium sulfur battery, or a lithium air battery.
21. A negative electrode for a secondary battery, comprising the lithium metal composite having a clad structure according to any one of claims 1 to 11.
22. A secondary battery characterized by comprising the lithium metal composite having a clad structure according to any one of claims 1 to 11 or the secondary battery negative electrode according to claim 21.
23. The secondary battery according to claim 22, characterized in that: the secondary battery includes a lithium battery.
24. The secondary battery according to claim 23, characterized in that: the lithium battery includes a lithium metal-oxide battery, a lithium metal-polymer battery, a rechargeable lithium ion battery, a lithium sulfur battery, or a lithium air battery.
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| CN108878781B (en) * | 2018-07-25 | 2020-10-09 | 江苏合志锂硫电池技术有限公司 | Lithium metal cathode, preparation method thereof and lithium ion battery |
| CN110265661B (en) * | 2019-06-13 | 2021-01-05 | 北京科技大学 | Organic-inorganic composite coating film on surface of metal lithium cathode and preparation method thereof |
| CN113020589A (en) * | 2021-02-26 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Stable metal lithium powder and preparation method and application thereof |
| CN113078287B (en) * | 2021-03-29 | 2022-07-29 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN113422106B (en) * | 2021-07-09 | 2022-10-14 | 中国科学院过程工程研究所 | All-solid-state lithium ion battery and preparation method and application thereof |
| CN114373891A (en) * | 2021-12-31 | 2022-04-19 | 远景动力技术(江苏)有限公司 | Composite lithium negative electrode and application thereof |
| CN115360356B (en) * | 2022-10-24 | 2023-01-24 | 浙江金羽新能源科技有限公司 | Modified lithium cladding structure and preparation method and application thereof |
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