CN111435756A - Lithium battery and preparation method and application thereof - Google Patents
Lithium battery and preparation method and application thereof Download PDFInfo
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- CN111435756A CN111435756A CN201911379851.0A CN201911379851A CN111435756A CN 111435756 A CN111435756 A CN 111435756A CN 201911379851 A CN201911379851 A CN 201911379851A CN 111435756 A CN111435756 A CN 111435756A
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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
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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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
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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium battery and a preparation method and application thereof. The lithium cell is including the lithium metal negative pole piece, solid-state electrolyte layer and the positive plate that stack in proper order, wherein: and one surface of the solid electrolyte layer, which is close to the lithium metal negative plate, is provided with a metal coating, the metal coating is formed by adopting a physical vapor deposition method, the metal coating is connected with the lithium metal negative plate, and a coating metal and lithium metal form an alloy layer at the joint of the metal coating and the lithium metal negative plate. This lithium cell not only can prevent electrolyte layer and negative pole reaction and reduce interfacial impedance through forming metal coating on solid electrolyte layer and protect the negative pole, can also effectively restrain the production of lithium dendrite, has advantages such as long cycle life, rate performance are good, the security is high and long service life.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium battery and a preparation method and application thereof.
Background
With the rapid development of consumer electronics, electric vehicles, and the like, the demands for energy density, safety, reliability, and service life of batteries are also increasing dramatically. Lithium metal has an extremely high theoretical specific capacity (about 3860mAh/Kg) and a lowest potential (-3.04V), so that the lithium metal secondary battery is the preferred system of the next generation of high energy density energy storage devices. However, in the conventional liquid system battery, electrolyte is used as a medium for conducting ions, and potential safety hazards of leakage, flammability and even explosion exist, so people begin to develop a solid battery system, and the electrolyte and a diaphragm are replaced by solid electrolyte for ion transmission.
However, the current solid-state battery development has great challenges, and many problems to be solved are still needed, such as the solid-solid interface contact problem between the solid-state electrolyte layer and the positive plate or the negative plate, and the instability problem between the solid-state electrolyte and the lithium metal negative electrode, which can seriously affect the rate capability and the cycling stability of the battery; in addition, the solid electrolyte layer has many voids, which are easily penetrated by lithium dendrites during cycling, resulting in micro short circuits of the battery and reduced cycle life of the battery. Therefore, how to improve the overall performance of the battery is still under further study.
Disclosure of Invention
The invention is mainly based on the following problems:
in order to solve the solid-solid interface contact problem of the solid electrolyte layer and the positive plate or the negative plate and the unstable problem of the solid electrolyte and the lithium metal negative electrode, the most common method is to add a polymer soft layer capable of conducting ions between the electrolyte layer and the negative electrode so as to achieve the purposes of reducing the interface impedance, separating the solid electrolyte layer and the lithium metal negative electrode layer and preventing the two layers from directly contacting and reacting. However, this also means that a new impedance is introduced, namely the impedance of the polymer soft layer itself, and when the soft layer is thicker, the impedance is also larger, and the impedance is increased, so that the rate capability and the capacity performance of the battery are obviously reduced. For this purpose, the soft layer thickness is optionally reduced, but when the soft layer thickness is reduced, lithium dendrites grow out and easily pierce the polymer soft layer during the charge-discharge cycle of the battery, resulting in a micro short circuit phenomenon of the battery. In addition, the polymer soft layer only plays a role in isolating the electrolyte layer and the negative electrode to prevent reaction and reduce interface impedance, and does not play a positive role in the deposition of lithium ions in the charge and discharge process, so that lithium dendrites still appear in the battery structure in the charge and discharge cycle process.
In view of the above, the present invention is directed to a lithium battery, and a method for manufacturing the same and an application of the same, so as to achieve the purposes of preventing a reaction between an electrolyte layer and a negative electrode and reducing an interface impedance, and promoting uniform deposition of lithium ions and reducing generation of lithium dendrites during charging and discharging.
To achieve the above object, according to a first aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery includes: a lithium metal negative plate, a solid electrolyte layer and a positive plate which are sequentially stacked,
wherein: and one surface of the solid electrolyte layer, which is close to the lithium metal negative plate, is provided with a metal coating, the metal coating is formed by adopting a physical vapor deposition method, the metal coating is connected with the lithium metal negative plate, and a coating metal and lithium metal form an alloy layer at the joint of the metal coating and the lithium metal negative plate.
Further, the thickness of the metal coating is 5-500 nm.
Further, the metal purity of the metal coating is 99.99-99.999%.
Further, the metal plating layer includes at least one selected from gold, silver, indium, zinc, tin, magnesium, aluminum, gallium, cadmium, bismuth, lead, and antimony.
Further, the lithium battery is a lithium ion battery, a lithium metal battery, a lithium air battery or a lithium sulfur battery.
Compared with the prior art, the lithium battery provided by the invention has at least the following advantages: on one hand, the metal coating is formed by adopting a physical vapor deposition method, so that the metal coating can be uniformly and compactly distributed on the surface of the solid electrolyte layer, the metal purity of the metal coating is extremely high, other impurities are not generated, and the uniform deposition of lithium ions cannot be influenced in the charging and discharging process; in addition, the formed metal plating layer has better structural stability with the solid electrolyte, because a plurality of gaps exist in the solid electrolyte layer, and the plating metal can be embedded into the solid electrolyte layer in the physical vapor deposition process, so that the metal plating layer and the solid electrolyte layer are tightly combined. On the other hand, when the battery is assembled, the metal in the metal coating layer reacts with the lithium metal cathode when in direct contact and forms a layer of alloy on the surface of the lithium metal, so that the metal coating layer completely or partially exists in the form of an alloy protective layer, the metal coating layer and the lithium metal cathode are integrated, the metal coating layer is respectively and tightly connected with the solid electrolyte layer and the lithium metal cathode, the interface impedance between the lithium metal cathode and the solid electrolyte layer can be greatly reduced, the alloy protective layer can enable the surface potential of the cathode to be uniformly distributed, the uniform deposition of lithium ions is promoted in the charging and discharging process, the generation of lithium dendrites is effectively inhibited, compared with a polymer soft layer, the alloy protective layer has enough mechanical strength and toughness, the expansion and contraction of the volume of the lithium metal cathode can be inhibited, the lithium dendrites are more effectively blocked, even a small amount of lithium dendrites are generated, effective blocking can be performed, and thus, a significant improvement in the cycle performance of the battery can be achieved. The lithium battery provided by the embodiment of the invention can prevent the reaction between the electrolyte layer and the negative electrode, reduce the interface impedance, effectively inhibit the generation of lithium dendrites, and has the advantages of long cycle life, good rate capability, high safety, long service life and the like.
The invention also aims to provide a method for preparing the lithium battery, so that the process flow is simplified, and the prepared lithium battery has the advantages of long cycle life, good rate capability, high safety, long service life and the like.
To achieve the above object, according to a second aspect of the present invention, a method of manufacturing a lithium battery is provided. According to an embodiment of the invention, the method comprises:
(1) forming a metal coating on the surface of the solid electrolyte layer by adopting a physical vapor deposition method;
(2) and (2) assembling the lithium metal negative plate, the positive plate and the solid electrolyte layer obtained in the step (1), wherein the metal coating is attached to the lithium metal negative plate so as to enable the coating metal to react with the lithium metal negative plate and form an alloy layer at the attachment part, and thus the lithium battery is obtained.
Further, the step (1) is carried out in a dry environment with the dew point not higher than minus 40 ℃.
Further, in the step (1), the physical vapor deposition method is a vacuum evaporation method, an ion sputtering method, a magnetron sputtering coating method, an arc plasma coating method or a molecular beam epitaxy method.
Further, the vacuum evaporation method is performed under the following conditions: the temperature of the evaporation substrate plate is 20-150 ℃, the evaporation rate is 0.001-0.05 nm/s, and the vacuum degree in the evaporation chamber is 10-3～10-5Pa。
Compared with the prior art, the method for preparing the lithium battery has the following advantages: on one hand, the metal coating formed by the physical vapor deposition method can be uniformly and compactly distributed on the surface of the solid electrolyte layer, and the metal purity of the metal coating is extremely high without other impurities, so that the uniform deposition of lithium ions cannot be influenced in the charging and discharging processes; in addition, the formed metal plating layer has better structural stability with the solid electrolyte, because a plurality of gaps exist in the solid electrolyte layer, and the plating metal can be embedded into the solid electrolyte layer in the physical vapor deposition process, so that the metal plating layer and the solid electrolyte layer are tightly combined. On the other hand, when the battery is assembled, the metal in the metal coating layer reacts with the lithium metal cathode when in direct contact and forms a layer of alloy on the surface of the lithium metal, so that the metal coating layer completely or partially exists in the form of an alloy protective layer, the metal coating layer and the lithium metal cathode are integrated, the metal coating layer is respectively and tightly connected with the solid electrolyte layer and the lithium metal cathode, the interface impedance between the lithium metal cathode and the solid electrolyte layer can be greatly reduced, the alloy protective layer can enable the surface potential of the cathode to be uniformly distributed, the uniform deposition of lithium ions is promoted in the charging and discharging process, the generation of lithium dendrites is effectively inhibited, compared with a polymer soft layer, the alloy protective layer has enough mechanical strength and toughness, the expansion and contraction of the volume of the lithium metal cathode can be inhibited, the lithium dendrites are more effectively blocked, even a small amount of lithium dendrites are generated, effective blocking can be performed, and thus, a significant improvement in the cycle performance of the battery can be achieved. The method is simple in process, the price of the metal of the coating is relatively low, the manufacturing cost can be reduced, large-scale production can be realized, the prepared lithium battery can prevent the reaction of the electrolyte layer and the negative electrode, reduce the interface impedance, effectively inhibit the generation of lithium dendrites, has the advantages of long cycle life, good rate performance, high safety, long service life and the like, and can be widely applied to the fields of new energy automobiles and the like.
Another object of the present invention is to provide a vehicle to further improve the competitiveness of the vehicle. In order to achieve the above object, according to a third aspect of the present invention, a vehicle is provided, which has the above lithium battery or the lithium battery obtained by the above preparation method according to an embodiment of the present invention. Compared with the prior art, the vehicle has higher safety and longer service life.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural view of a lithium battery according to an embodiment of the present invention.
Fig. 2 is a flow chart of a method of manufacturing a lithium battery according to one embodiment of the present invention.
Fig. 3 is a cycle performance test chart of the assembled full cell of example 1 of the present invention.
Fig. 4 is a cycle performance test chart of a full cell assembled according to comparative example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
According to a first aspect of the invention, a lithium battery is provided. According to an embodiment of the present invention, as shown in fig. 1, the lithium battery includes: the lithium metal negative plate a, the solid electrolyte layer b and the positive plate c are stacked in sequence, wherein: and one surface of the solid electrolyte layer b close to the lithium metal negative electrode sheet a is provided with a metal plating layer d, the metal plating layer d is formed by adopting a physical vapor deposition method, the metal plating layer d is connected with the lithium metal negative electrode sheet a, and a plating metal and lithium metal form an alloy layer e at the connection position of the metal plating layer d and the lithium metal negative electrode sheet a. The metal coating d exists partially or completely in an alloy form, so that the interface impedance in a solid battery system can be effectively reduced, the charge distribution on the surface of an electrode can be balanced in the charging and discharging process, lithium is uniformly deposited, the growth of lithium dendrites is inhibited, and the cycle life of the battery can be effectively prolonged. Therefore, the lithium battery can prevent the reaction between the electrolyte layer and the negative electrode, reduce the interface impedance, effectively inhibit the generation of lithium dendrites, and has the advantages of long cycle life, good rate capability, high safety, long service life and the like.
The lithium battery according to the above embodiment of the present invention will be described in detail.
According to an embodiment of the present invention, the type of physical vapor deposition method used in forming the metal coating layer in the present invention is not particularly limited, and those skilled in the art can select the method according to actual needs, for example, vacuum evaporation, ion sputtering, magnetron sputtering, arc plasma coating, or molecular beam epitaxy may be used. For another example, when the vacuum evaporation method is selected, the conditions of the vacuum evaporation method may be: the evaporation rate can be 0.001-0.05 nm/s, and the vacuum degree in the evaporation chamber can be 10-3～10-5Pa, which can be carried out in a dry environment with the dew point not higher than minus 40 ℃; for another example, the film can be formed by ion sputtering in a dry environment with a dew point of not higher than-40 degrees centigradeAnd (5) plating a metal layer. According to the invention, the uniformity and compactness of the metal coating can be further improved by controlling the conditions, the bonding strength of the metal coating and the solid electrolyte layer can be further improved, any other impurities are avoided from being introduced, and the purity of the metal coating is ensured, so that the lithium dendritic crystal can be further blocked, and the cycle performance of the battery can be improved. When the vacuum evaporation method is adopted, the temperature of the evaporation substrate plate is the temperature expected to raise the temperature of the lithium metal negative plate, and the evaporation rate refers to the deposition rate of the protective layer metal on the lithium metal negative plate.
According to another embodiment of the present invention, the thickness of the metal plating layer d may be 5 to 500nm, for example, 5nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 450nm, 10 to 400nm, 50 to 350nm, 80 to 200nm, etc., the inventors found that if the thickness of the metal plating layer is too small, an alloy layer formed when reacting with a lithium metal negative electrode is thin, which cannot effectively inhibit the volume change of the lithium metal negative electrode during the charging and discharging process, easily causes the alloy protection layer to fail, is not favorable for the uniform deposition of lithium ions, and has an unobvious blocking effect on lithium dendrites; if the thickness of the metal coating is too large, the internal impedance of the battery is large, and the circulating rate performance of the battery is affected. According to the invention, by controlling the thickness of the metal coating, an alloy protective layer which is uniformly distributed and has a stable structure is formed on the surface of the lithium metal negative electrode, the alloy protective layer can inhibit the volume change of the lithium metal negative electrode and effectively block lithium dendrites, and the battery can be ensured to have lower internal resistance. Furthermore, the metal purity of the metal coating can be 99.99-99.999%, so that the influence of impurities in the metal coating on the uniform deposition of lithium ions in the charging and discharging process can be effectively avoided, and the generation of lithium dendrites can be further inhibited.
According to another embodiment of the present invention, the material of the metal plating layer in the present invention is not particularly limited, and those skilled in the art can select the material according to actual needs, for example, at least one of gold, silver, indium, zinc, tin, magnesium, aluminum, gallium, cadmium, bismuth, lead and antimony can be selected to form the metal plating layer.
According to another embodiment of the present invention, the type of the lithium battery in the present invention is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, the lithium battery can be a lithium ion battery, a lithium metal battery, a lithium air battery, a lithium sulfur battery, or the like, and is preferably an all-solid-state battery.
In summary, the lithium battery of the above embodiment of the invention has at least the following advantages: on one hand, the metal coating is formed by adopting a physical vapor deposition method, so that the metal coating can be uniformly and compactly distributed on the surface of the solid electrolyte layer, the metal purity of the metal coating is extremely high, other impurities are not generated, and the uniform deposition of lithium ions cannot be influenced in the charging and discharging process; in addition, the formed metal plating layer has better structural stability with the solid electrolyte, because a plurality of gaps exist in the solid electrolyte layer, and the plating metal can be embedded into the solid electrolyte layer in the physical vapor deposition process, so that the metal plating layer and the solid electrolyte layer are tightly combined. On the other hand, when the battery is assembled, the metal in the metal coating layer reacts with the lithium metal cathode when in direct contact and forms a layer of alloy on the surface of the lithium metal, so that the metal coating layer completely or partially exists in the form of an alloy protective layer, the metal coating layer and the lithium metal cathode are integrated, the metal coating layer is respectively and tightly connected with the solid electrolyte layer and the lithium metal cathode, the interface impedance between the lithium metal cathode and the solid electrolyte layer can be greatly reduced, the alloy protective layer can enable the surface potential of the cathode to be uniformly distributed, the uniform deposition of lithium ions is promoted in the charging and discharging process, the generation of lithium dendrites is effectively inhibited, compared with a polymer soft layer, the alloy protective layer has enough mechanical strength and toughness, the expansion and contraction of the volume of the lithium metal cathode can be inhibited, the lithium dendrites are more effectively blocked, even a small amount of lithium dendrites are generated, effective blocking can be performed, and thus, a significant improvement in the cycle performance of the battery can be achieved. The lithium battery provided by the embodiment of the invention can prevent the reaction between the electrolyte layer and the negative electrode, reduce the interface impedance, effectively inhibit the generation of lithium dendrites, and has the advantages of long cycle life, good rate capability, high safety, long service life and the like.
According to a second aspect of the invention, a method of making a lithium battery is provided. According to an embodiment of the invention, the method comprises: (1) forming a metal coating on the surface of the solid electrolyte layer by adopting a physical vapor deposition method; (2) and (2) assembling the lithium metal negative plate, the positive plate and the solid electrolyte layer obtained in the step (1), wherein the metal coating is attached to the lithium metal negative plate so as to enable the coating metal to react with the lithium metal negative plate and form an alloy layer at the attachment part, thus obtaining the lithium battery. The method is simple in process and suitable for large-scale production, the prepared lithium battery can prevent the reaction of the electrolyte layer and the negative electrode, reduce the interface impedance, effectively inhibit the generation of lithium dendrites, has the advantages of long cycle life, good rate capability, high safety, long service life and the like, and can be widely applied to the fields of new energy automobiles and the like.
According to an embodiment of the present invention, step (1) may be performed in a dry environment with a dew point of no higher than-40 ℃, so as to further avoid impurities introduced by chemical reaction of the plating metal. Further, the step (2) is preferably performed under vacuum drying conditions, whereby it can be ensured that the lithium metal negative electrode does not react with moisture in the air, and the metal purity of the formed alloy protective layer can be further ensured.
According to still another embodiment of the present invention, the type of the physical vapor deposition method used in the present invention is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, vacuum evaporation, ion sputtering, magnetron sputtering, arc plasma coating, molecular beam epitaxy, or the like may be selected. For another example, when the vacuum evaporation method is selected, the conditions of the vacuum evaporation method may be: the evaporation rate can be 0.001-0.05 nm/s, and the vacuum degree in the evaporation chamber can be 10-3～10-5Pa, which can be carried out in a dry environment with the dew point not higher than minus 40 ℃; for another example, the metal plating layer may be formed by ion sputtering in a dry environment having a dew point of not higher than minus 40 ℃. The uniformity of the metal coating can be further improved by controlling the above conditions in the present inventionAnd the tightness can further improve the bonding strength of the metal plating layer and the solid electrolyte layer, and simultaneously avoid introducing any other impurities, so that the purity of the metal plating layer is ensured, and the lithium dendritic crystal can be further blocked, and the cycle performance of the battery is improved.
According to another embodiment of the present invention, in a dry environment (e.g. dew point-40 ℃), the solid electrolyte layer is fixed on the evaporation mask plate at the position of the substrate plate of the evaporation chamber, the plating metal is fixed on the evaporation source in the evaporation boat (made of molybdenum, tungsten, tantalum, etc.), and the vacuum degree of the chamber reaches 10-3～10-5And after Pa, gradually increasing the evaporation arc current until the evaporation rate is stabilized at 0.001-0.05 nm/s, continuously evaporating metal on the surface of the solid electrolyte layer at the speed until the thickness of the plating layer reaches the expected thickness, stopping evaporation, and taking out the electrolyte layer after the electrolyte layer is cooled to room temperature to obtain the electrolyte layer with the uniform metal plating layer.
According to another embodiment of the present invention, the material for forming the metal plating layer is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, at least one of gold, silver, indium, zinc, tin, magnesium, aluminum, gallium, cadmium, bismuth, lead, and antimony may be selected to form the metal plating layer.
It should be noted that the features and methods described above for the lithium battery are also applicable to the method for preparing the lithium battery, and are not described in detail here.
In summary, the method for preparing the lithium battery has the following advantages: on one hand, the metal coating formed by the physical vapor deposition method can be uniformly and compactly distributed on the surface of the solid electrolyte layer, and the metal purity of the metal coating is extremely high without other impurities, so that the uniform deposition of lithium ions cannot be influenced in the charging and discharging processes; in addition, the formed metal plating layer has better structural stability with the solid electrolyte, because a plurality of gaps exist in the solid electrolyte layer, and the plating metal can be embedded into the solid electrolyte layer in the physical vapor deposition process, so that the metal plating layer and the solid electrolyte layer are tightly combined. On the other hand, when the battery is assembled, the metal in the metal coating layer reacts with the lithium metal cathode when in direct contact and forms a layer of alloy on the surface of the lithium metal, so that the metal coating layer completely or partially exists in the form of an alloy protective layer, the metal coating layer and the lithium metal cathode are integrated, the metal coating layer is respectively and tightly connected with the solid electrolyte layer and the lithium metal cathode, the interface impedance between the lithium metal cathode and the solid electrolyte layer can be greatly reduced, the alloy protective layer can enable the surface potential of the cathode to be uniformly distributed, the uniform deposition of lithium ions is promoted in the charging and discharging process, the generation of lithium dendrites is effectively inhibited, compared with a polymer soft layer, the alloy protective layer has enough mechanical strength and toughness, the expansion and contraction of the volume of the lithium metal cathode can be inhibited, the lithium dendrites are more effectively blocked, even a small amount of lithium dendrites are generated, effective blocking can be performed, and thus, a significant improvement in the cycle performance of the battery can be achieved. The method is simple in process, the price of the metal of the coating is relatively low, the manufacturing cost can be reduced, large-scale production can be realized, the prepared lithium battery can prevent the reaction of the electrolyte layer and the negative electrode, reduce the interface impedance, effectively inhibit the generation of lithium dendrites, has the advantages of long cycle life, good rate performance, high safety, long service life and the like, and can be widely applied to the fields of new energy automobiles and the like.
According to a third aspect of the present invention, a vehicle is provided. According to an embodiment of the present invention, the vehicle has the above lithium battery or the lithium battery obtained by the above preparation method. Compared with the prior art, the vehicle has higher safety and longer service life. It should be noted that the features and effects described above for the lithium battery and the method for manufacturing the lithium battery are also applicable to the vehicle, and are not described in detail herein.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Fixing a 10cm × 10cm solid electrolyte layer (prepared from solid electrolyte and binder) on a substrate plate of an evaporation mask plate in a dry room environment (dew point-40 deg.C), placing 0.4g metallic silver in an evaporation boat (made of molybdenum) and fixing on the evaporation source until the vacuum degree of the chamber reaches 10-3～10-5And after Pa, gradually increasing the evaporation arc current until the evaporation rate is stabilized at 0.01nm/s, continuously evaporating silver on the surface of the solid electrolyte layer at the speed, stopping evaporation when the thickness of the evaporation layer reaches 50nm, and taking out the electrolyte layer after the electrolyte layer is cooled to room temperature to obtain the electrolyte layer with a uniform metal silver layer.
The prepared solid electrolyte layer with the metal silver layer is used as a diaphragm to assemble a full cell, pure lithium foil is used as a negative electrode, and a positive electrode piece is composed of a positive active material, a solid electrolyte, conductive carbon and a binder. Cycling tests were performed at 0.05C and 0.1C rates, with the first three charge-discharge cycles using a rate of 0.05C, followed by a rate of 0.1C, and the data is shown in fig. 3.
Comparative example 1
The difference from example 1 is that the metallic silver layer was replaced by a polymer film obtained by dissolving PEO and L iTFSI in a mass ratio of 3:1 into anhydrous grade acetonitrile, coating the film on a coater with a blade gap of 400 μm, drying the solvent after film formation and then transferring to a vacuum drying oven to dry at 60 ℃ for 24 hours to obtain a polymer film having a thickness of 10 μm.
A full cell was assembled in which the positive electrode, negative electrode and solid electrolyte layer were the same as in example 1, and a polymer separator was interposed between the negative electrode and the solid electrolyte layer instead of the metallic silver layer. Cycling tests were performed under the same conditions, with the first three charge-discharge cycles using a 0.05C rate, followed by a 0.1C rate, and the data are shown in fig. 4.
Example 2
Under a dry environment (dew point-40 deg.C), adding 10cm × 10cm of solid electrolyteThe layer (solid electrolyte layer is prepared from solid electrolyte and binder) is fixed on the evaporation mask plate and placed on the substrate plate of the evaporation chamber, 0.4g of metal zinc is placed in the evaporation boat (made of molybdenum) and fixed on the evaporation source, and when the vacuum degree of the chamber reaches 10-3～10-5And after Pa, gradually increasing the evaporation arc current until the evaporation rate is stabilized at 0.01nm/s, continuously evaporating zinc on the surface of the solid electrolyte layer at the speed, stopping evaporation when the thickness of the evaporation layer reaches 100nm, and taking out the electrolyte layer after the electrolyte layer is cooled to room temperature to obtain the electrolyte layer with a uniform metal zinc layer.
Example 3
The difference from example 1 is that the thickness of the vapor deposition layer was 5 nm.
Example 4
The difference from example 1 is that the thickness of the evaporated layer was 500 nm.
The solid electrolyte layers with the metallic silver layers prepared in examples 2 to 4 were respectively used as separators to assemble a full cell, and the cycle performance of the full cell was tested under the same assembly conditions and test conditions as in example 1.
Results and conclusions:
as can be seen from fig. 3, the battery prepared in example 1 has stable cycle performance, and can normally perform charge and discharge cycles at the multiplying power of 0.05C and 0.1C; as can be seen from fig. 4, the full cell using the polymer film as the protective layer can be cycled at a rate of 0.05C, but the 0.1C cannot be normally cycled, and the polymer protective layer has a certain impedance, so that the impedance of the whole cell is increased, which may affect the rate performance of the cell. After the cycle performance of the batteries prepared in examples 2 to 4 is tested by the method in example 1, the cycle performance of the batteries prepared in examples 2 to 4 is similar to that of example 1, and the cycle performance of the batteries is stable.
It can be seen from the combination of examples 1 to 4 and comparative example 1 that the solid electrolyte layer prepared by the method of the above example of the present invention can significantly improve the cycle performance of the battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A lithium battery, comprising: lithium metal negative pole piece, solid-state electrolyte layer and positive plate that stack in proper order, wherein:
and one surface of the solid electrolyte layer, which is close to the lithium metal negative plate, is provided with a metal coating, the metal coating is formed by adopting a physical vapor deposition method, the metal coating is connected with the lithium metal negative plate, and a coating metal and lithium metal form an alloy layer at the joint of the metal coating and the lithium metal negative plate.
2. The lithium battery according to claim 1, wherein the metal plating layer has a thickness of 5 to 500 nm.
3. The lithium battery as claimed in claim 1, wherein the metal purity of the metal plating layer is 99.99 to 99.999%.
4. The lithium battery of claim 1, wherein the metal plating layer comprises at least one selected from the group consisting of gold, silver, indium, zinc, tin, magnesium, aluminum, gallium, cadmium, bismuth, lead, and antimony.
5. The lithium battery of claim 1, wherein the lithium battery is a lithium ion battery, a lithium metal battery, a lithium air battery, or a lithium sulfur battery.
6. A method of manufacturing a lithium battery according to any one of claims 1 to 5, comprising:
(1) forming a metal coating on the surface of the solid electrolyte layer by adopting a physical vapor deposition method;
(2) and (2) assembling the lithium metal negative plate, the positive plate and the solid electrolyte layer obtained in the step (1), wherein the metal coating is attached to the lithium metal negative plate so as to enable the coating metal to react with the lithium metal negative plate and form an alloy layer at the attachment part, and thus the lithium battery is obtained.
7. The method of claim 6, wherein step (1) is performed in a dry environment having a dew point of no more than-40 ℃.
8. The method according to claim 6, wherein in the step (1), the physical vapor deposition method is a vacuum evaporation method, an ion sputtering method, a magnetron sputtering coating method, an arc plasma coating method or a molecular beam epitaxy method.
9. The method according to claim 8, wherein the vacuum evaporation method is performed under the following conditions: the temperature of the evaporation substrate plate is 20-150 ℃, the evaporation rate is 0.001-0.05 nm/s, and the vacuum degree in the evaporation chamber is 10-3～10-5Pa。
10. A vehicle comprising a lithium battery according to any one of claims 1 to 5 or a lithium battery produced by the method according to any one of claims 6 to 9.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112086680A (en) * | 2020-09-23 | 2020-12-15 | 蜂巢能源科技有限公司 | All-solid-state electrolyte layer and preparation method and application thereof |
| CN112133955A (en) * | 2020-09-28 | 2020-12-25 | 蜂巢能源科技有限公司 | Cell structure of solid-state battery and preparation method thereof |
| CN112838217A (en) * | 2020-12-31 | 2021-05-25 | 上海电气集团股份有限公司 | Composite structure containing lithium cathode, preparation method thereof and solid-state battery |
| CN113140785A (en) * | 2021-04-20 | 2021-07-20 | 惠州亿纬锂能股份有限公司 | Modified solid electrolyte and preparation method and application thereof |
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| CN115036555A (en) * | 2022-07-12 | 2022-09-09 | 欣旺达电子股份有限公司 | Secondary battery and electric equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415123A (en) * | 1999-11-23 | 2003-04-30 | 分子技术股份有限公司 | Lithium anodes for electrochemical cells |
| DE102012200862A1 (en) * | 2012-01-23 | 2013-07-25 | Robert Bosch Gmbh | Battery production by spin coating |
| CN105489845A (en) * | 2015-12-30 | 2016-04-13 | 哈尔滨工业大学 | Method for preparing thin-layer lithium metal anode for all-solid-state lithium-ion battery based on PVD |
| US20180294476A1 (en) * | 2017-04-10 | 2018-10-11 | Nanotek Instruments, Inc. | Lithium Metal Secondary Battery Containing an Anode-Protecting Polymer Layer and Manufacturing Method |
-
2019
- 2019-12-27 CN CN201911379851.0A patent/CN111435756A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415123A (en) * | 1999-11-23 | 2003-04-30 | 分子技术股份有限公司 | Lithium anodes for electrochemical cells |
| DE102012200862A1 (en) * | 2012-01-23 | 2013-07-25 | Robert Bosch Gmbh | Battery production by spin coating |
| CN105489845A (en) * | 2015-12-30 | 2016-04-13 | 哈尔滨工业大学 | Method for preparing thin-layer lithium metal anode for all-solid-state lithium-ion battery based on PVD |
| US20180294476A1 (en) * | 2017-04-10 | 2018-10-11 | Nanotek Instruments, Inc. | Lithium Metal Secondary Battery Containing an Anode-Protecting Polymer Layer and Manufacturing Method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112086680A (en) * | 2020-09-23 | 2020-12-15 | 蜂巢能源科技有限公司 | All-solid-state electrolyte layer and preparation method and application thereof |
| CN112133955A (en) * | 2020-09-28 | 2020-12-25 | 蜂巢能源科技有限公司 | Cell structure of solid-state battery and preparation method thereof |
| CN112133955B (en) * | 2020-09-28 | 2021-12-07 | 蜂巢能源科技有限公司 | Cell structure of solid-state battery and preparation method thereof |
| CN112838217A (en) * | 2020-12-31 | 2021-05-25 | 上海电气集团股份有限公司 | Composite structure containing lithium cathode, preparation method thereof and solid-state battery |
| CN113140785A (en) * | 2021-04-20 | 2021-07-20 | 惠州亿纬锂能股份有限公司 | Modified solid electrolyte and preparation method and application thereof |
| CN113140784A (en) * | 2021-04-20 | 2021-07-20 | 惠州亿纬锂能股份有限公司 | Modified solid electrolyte and preparation method and application thereof |
| CN113594541A (en) * | 2021-07-13 | 2021-11-02 | 南京邮电大学 | Method for preparing LAGP-based solid electrolyte by plasma magnetic filtration technology |
| CN114171799A (en) * | 2021-11-19 | 2022-03-11 | 哈尔滨工业大学 | Method for improving wettability of lithium on surface of solid electrolyte and all-solid-state battery |
| CN114843615A (en) * | 2022-05-13 | 2022-08-02 | 电子科技大学 | All-solid-state thick film lithium battery with alloy interface layer and preparation method thereof |
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| CN115036555A (en) * | 2022-07-12 | 2022-09-09 | 欣旺达电子股份有限公司 | Secondary battery and electric equipment |
| WO2024011871A1 (en) * | 2022-07-12 | 2024-01-18 | 欣旺达电子股份有限公司 | Secondary battery and electrical device |
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Application publication date: 20200721 |