CN113346192A - Lithium ion battery composite diaphragm and preparation method and application thereof - Google Patents
Lithium ion battery composite diaphragm and preparation method and application thereof Download PDFInfo
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- CN113346192A CN113346192A CN202110550321.9A CN202110550321A CN113346192A CN 113346192 A CN113346192 A CN 113346192A CN 202110550321 A CN202110550321 A CN 202110550321A CN 113346192 A CN113346192 A CN 113346192A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery composite diaphragm and a preparation method and application thereof. The composite diaphragm comprises a diaphragm substrate, a lithium metal layer attached to the surface of the diaphragm substrate, and an outer protection layer attached to the surface of the lithium metal layer. According to the composite diaphragm provided by the invention, the metal lithium layer and the protective layer are deposited on the surface, close to the negative electrode, of the ceramic-attached diaphragm through a simple and easily large-scale technology, the surface treatment is carried out on the ceramic-attached diaphragm, and the introduction of the transition layer is added, so that the binding force between the ceramic-attached diaphragm and the metal lithium layer is effectively enhanced, the stability of the composite diaphragm in the battery assembling process is ensured, the reaction between metal lithium and oxygen and moisture can be reduced through the protective layer, the stability of the metal lithium layer in the air is increased, and after the battery is assembled, the loss of lithium elements in the battery circulating process can be effectively supplemented through the metal lithium layer.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery composite diaphragm and a preparation method and application thereof.
Background
With social development and technological progress, the general application of electronic products has become a major trend, lithium ion batteries are widely applied to power supplies of electronic products such as mobile communication, laptop computers, digital cameras and the like due to the remarkable advantages of high specific energy and long cycle life, in recent years, high energy density and excellent cycle stability become important research and development directions of lithium batteries, however, the instability of electrode materials caused by the high energy density makes the safety performance of the batteries greatly valued, and the cycle capacity retention rate for a long time is also a key factor for whether the lithium batteries can be widely applied. The conventional diaphragm is a porous polymer film, is not only a channel for ion migration, but also plays a role of a diaphragm between a positive electrode material and a negative electrode material, and the ceramic diaphragm is attached on the premise that the upper surface and the lower surface of the porous polymer film are coated with a ceramic surface mainly comprising oxides and a binder, so that the mechanical strength of an original film is increased, a battery is assembled, and the battery has excellent performances in the aspects of high temperature resistance, puncture resistance and the like.
CN106129315A discloses a lithium ion battery composite diaphragm and a preparation method thereof, and a lithium ion battery, and specifically discloses a lithium ion battery composite diaphragm which comprises a diaphragm substrate, wherein the diaphragm substrate is a polyolefin microporous membrane or a polyolefin microporous membrane with a ceramic layer coated on the surface, the surface of the diaphragm substrate is coated with a lithium supplement layer, and the lithium supplement layer contains lithium powder. According to the technical scheme, the composite diaphragm fills up lithium required for forming the SEI film by arranging the lithium supplement layer on the surface of the diaphragm, and supplements lithium ions consumed for forming the SEI film on the surface of the negative pole piece, however, a mixture of lithium powder and high molecular polymer in the lithium supplement layer has the following defects relative to a pure metal lithium layer: 1. the surface of the lithium metal powder is often provided with a thicker oxide layer, and the existence of the oxide layer not only reduces the amount of effective active lithium, but also increases the difficulty of utilizing the lithium metal in the lithium supplement process, and influences the energy density and the lithium supplement effect of the battery; 2. the existence of a large amount of non-conductive high molecular polymers not only influences the transmission of electrons of the lithium supplement layer, but also increases additional inactive mass, and further influences the energy density and the lithium supplement effect of the battery; 3. the lithium supplement layer is not added with a protective layer, is directly exposed and is easy to react with air oxygen and moisture, and the operation difficulty in the actual production is increased. There is therefore room for improvement.
CN112599928A discloses a composite separator with lithium supplementing effect, a preparation method thereof, and a lithium ion battery, including a base film, a first ceramic coating and a second ceramic coating respectively located on the upper surface and the lower surface of the base film, and a lithium supplementing gel coating located on the upper surface of the first ceramic coating and a gel coating located on the lower surface of the second ceramic coating. Mend lithium gel coating among this technical scheme and prevent that the silicon carbon negative pole from taking place excessive lithiation and appearing separating lithium, however, mend lithium gel coating thickness and be uncontrollable, can not realize the even accurate lithium of mending to silicon carbon negative pole piece, mend the lithium layer moreover and not increase the protective layer, directly expose easily with air oxygen and moisture reaction, consequently still there is the improvement space.
Therefore, a lithium ion battery composite diaphragm capable of improving the long-term cycling capacity stability of the battery for a long time is still lacked in the prior art.
Disclosure of Invention
Aiming at the improvement requirement of the prior art, the invention provides a lithium ion battery composite diaphragm which comprises a lithium metal layer and a protective layer, wherein the content of a lithium element in the battery is effectively improved by introducing the metal lithium layer, and the lithium ion battery composite diaphragm has important significance for improving the long-term circulation capacity stability of the battery; because the lithium element is more active, a protective layer is plated on the surface of the metal lithium layer, so that the corrosion of the external air to the metal lithium can be effectively isolated, and the metal lithium can form an alloy with the metal lithium, so that the active metal lithium can participate in electrochemical reaction.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a lithium ion battery composite separator including a separator substrate, a lithium metal layer attached to a surface of the separator substrate, and an outer protective layer attached to a surface of the lithium metal layer.
Preferably, the lithium ion separator further comprises an inner protective layer located between the separator substrate and the lithium metal layer.
Preferably, the outer protective layer is any one of metal aluminum, metal nickel, metal zinc, metal chromium, metal tin, metal silver and any two or more metal alloys, and preferably is metal aluminum.
Preferably, the inner protective layer is any one of metal aluminum, metal nickel, metal zinc, metal chromium, metal tin, metal silver and any two or more metal alloys.
Preferably, the separator substrate includes a polymer porous film substrate and a ceramic layer attached to a surface of the polymer porous film substrate, the ceramic layer is located on one side of the lithium metal layer, and the polymer porous film substrate includes at least one of Polyethylene (PE), polypropylene (PP), and a copolymer of ethylene and propylene (PE/PP), the ceramic layer includes a mixture of an oxide coating and a binder, and the oxide coating is at least one of alumina, silica, and titania.
Preferably, the thickness of the lithium metal layer is 0.05-10um, preferably 0.5-5 um; the thickness of the inner protective layer is 20-500nm, preferably 50-100 nm; the thickness of the outer protective layer is 0.05-5um, preferably 0.2-3 um.
According to another aspect of the invention, a method for preparing the composite diaphragm is provided, wherein a lithium metal layer and an outer protective layer are sequentially prepared on the surface of a diaphragm substrate through vacuum continuous plating equipment.
Preferably, the inner protective layer is further prepared, specifically, the inner protective layer, the lithium metal layer and the outer protective layer are sequentially prepared by a vacuum continuous plating device, and preferably, the vacuum continuous plating is one of a vacuum evaporation method, an electron beam evaporation method, a thermal evaporation method and a magnetron sputtering method.
Preferably, the diaphragm substrate is subjected to a surface pretreatment before vacuum continuous plating, and the surface pretreatment is preferably one of plasma treatment, ion implantation, ion plating, and laser surface treatment.
According to another aspect of the invention, a lithium ion battery is provided, which comprises a positive electrode, a negative electrode, an electrolyte and the composite separator, wherein the outer protective layer of the composite separator is positioned on one side of the negative electrode.
The invention has the following beneficial effects:
(1) according to the composite diaphragm provided by the invention, the metal lithium layer and the protective layer are deposited on the surface, close to the negative electrode, of the ceramic-attached diaphragm through a simple and easily-large-scale technology, the surface treatment is carried out on the ceramic-attached diaphragm, and the introduction of the transition layer effectively enhances the binding force between the ceramic-attached diaphragm and the metal lithium layer, and ensures the stability of the composite diaphragm in the battery assembling process.
(2) Compared with the commercialized ceramic-attached diaphragm, the composite diaphragm provided by the invention has the advantages that on the premise of ensuring high ionic conductivity, extremely low electronic conductivity and high chemical and electrochemical stability, due to the introduction of the metal lithium layer, the loss of lithium in the electrochemical cycle process of the battery is supplemented, the energy density and the cycle performance of the battery are effectively improved, the reaction between the metal lithium and oxygen and moisture can be reduced through the protective layer, the stability of the metal lithium layer in the air is improved, and the protective layer can form an alloy with the metal lithium, so that the active metal lithium can participate in the electrochemical reaction, and the loss of lithium elements in the battery cycle process is effectively supplemented.
Drawings
FIG. 1 is a schematic structural view of a composite separator of the present invention;
FIG. 2 is a schematic diagram of a route of a vacuum continuous plating apparatus;
FIG. 3 shows the first cycle of charge and discharge of a soft package battery assembled by a composite diaphragm and a common diaphragm;
FIG. 4 shows a 1C rate charge-discharge cycle of a soft package battery assembled by a composite diaphragm and a common diaphragm;
fig. 5 shows the 1C rate charge-discharge cycle of the composite diaphragm assembled soft-package battery under different conditions.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein: the device comprises a polymer porous membrane substrate 1, a ceramic layer 2, an inner protection layer 3, a lithium metal layer 4, an outer protection layer 5, a vacuum pump 6, an unreeling shaft 7, a first cooling roller 8, a second cooling roller 9, a third cooling roller 10, a first evaporation boat 11, a second evaporation boat 12, a third evaporation boat 13, a reeling shaft 14 and a visible window 15.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. 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.
In the embodiment of the vacuum continuous plating equipment for the composite diaphragm, as shown in fig. 2, a diaphragm substrate with a coiled material structure is taken as a substrate layer and wound on a roller of an unwinding shaft 7, a first cooling roller 8, a second cooling roller 9 and a third cooling roller 10 are sequentially arranged along the advancing direction of the diaphragm substrate and finally reach the roller of a winding shaft 14, and the vacuum continuous plating equipment is provided with a vacuum pump 6 for vacuumizing and can be observed through a window 15.
A first evaporation boat 11 is arranged below the first cooling roller 8 and used for carrying out first vacuum coating; similarly, a second evaporation boat 12 is arranged below the second cooling roller 9 and used for carrying out second vacuum coating; and a third evaporation boat 13 is arranged below the third cooling roller 10 and is used for carrying out third vacuum coating. Thus, 3 times of continuous vacuum coating was realized as the diaphragm substrate advanced. The membrane after vacuum coating is shown in figure 1, the membrane matrix comprises a polymer porous membrane substrate 1 and a ceramic layer 2, and an inner protective layer 3, a lithium metal layer 4 and an outer protective layer 5 are sequentially vacuum-plated on the ceramic layer 2.
The following are specific embodiments.
Example 1
The utility model provides a composite diaphragm, the diaphragm base member includes polymer porous membrane substrate and ceramic layer, and thickness distribution is 8um and 2um, and the inner protective layer is metallic nickel, and thickness is 50nm, and the thickness of lithium metal layer is 500nm, and the outer protective layer is metallic aluminum, and thickness is 1 um. The preparation method comprises the following steps:
the method comprises the following steps: taking a diaphragm substrate with a coiled material structure as a substrate layer, and winding the substrate layer on a roller;
step two: the roller equipment is arranged in a vacuum environment, and the vacuum degree is less than or equal to 10-3Pa；
Step three: carrying out plasma treatment on the surface of the diaphragm substrate to improve the surface adhesion;
step four: sequentially carrying out resistance heating melting evaporation on a nickel target material, a lithium target material and an aluminum target material in a vacuum environment to obtain gaseous metal nickel, metal lithium and metal aluminum;
step five: the gaseous metal nickel is contacted with the surface of the ceramic membrane to form a transition layer, then the metal lithium is attached to the outer surface of the metal nickel, and finally a protective layer is formed by the metal aluminum;
step six: performing rolling evaporation for multiple times through a roller to obtain a metal nickel transition layer with the thickness of 50nm, a metal lithium layer with the thickness of 500nm and a metal aluminum layer with the thickness of 1 um;
step seven: after the steps are completed, the required composite diaphragm can be obtained.
Example 2
The utility model provides a composite diaphragm, the diaphragm base member includes the porous membrane substrate of polymer and attaches the pottery layer, and thickness distribution is 8um and 4um, and the inner protective layer is nichrome, and thickness is 100nm, and the thickness on metal lithium layer is 1um, and the outer protective layer is aluminium zinc alloy, and its thickness is 1um, and the manufacturing method includes following step:
the method comprises the following steps: taking the ceramic-attached diaphragm of the coiled material structure as a substrate layer, and winding the substrate layer on a roller;
step two: the roller equipment is placed in a vacuum environment, and the vacuum degree is less than or equal to 10-3 Pa;
step three: ion implantation treatment is carried out on the surface of the ceramic diaphragm, so that the surface adhesive force is improved;
step four: in a vacuum environment, carrying out electron beam heating melting evaporation on a nickel-chromium target, a lithium target and an aluminum-zinc target in sequence to obtain gaseous nickel-chromium alloy, lithium metal and aluminum-zinc alloy;
step five: the gaseous nickel-chromium alloy is contacted with the surface of the ceramic membrane to form a transition layer, then the metal lithium is attached to the outer surface of the transition layer, and finally a protective layer is formed by the aluminum-zinc alloy;
step six: performing evaporation once through a roller to obtain a nickel-chromium alloy transition layer with the thickness of 100nm, a metal lithium layer with the thickness of 1um and an aluminum-zinc alloy protective layer with the thickness of 1um in sequence;
step seven: after the steps are completed, the required composite diaphragm can be obtained;
comparative example 1
This example does not include a metal layer, and is only the separator substrate in example 1, which includes a polymer porous film substrate and a ceramic layer, and the thickness distribution is 8um and 2 um.
Comparative example 2
Melting and uniformly stirring 1 part by weight of lithium powder, 1 part by weight of graphene, 10 parts by weight of polyethylene and 10 parts by weight of polytrimethylene carbonate, coating the slurry on the surface of the ceramic-attached diaphragm, wherein the coating thickness is 2 microns, and manufacturing the composite diaphragm.
Test example 1
The composite diaphragm prepared in example 1 and the diaphragm substrate prepared in comparative example 1 are respectively assembled into lithium batteries (NCM 523-graphite) of the same type, as shown in FIG. 3, the composite diaphragm battery shows 95% first-turn efficiency which is higher than 92% first-turn efficiency of a common ceramic diaphragm battery, FIG. 4 is a charge and discharge cycle diagram of the two batteries under 1C multiplying power, the composite diaphragm battery circulates 230 turns under 1C multiplying power, the capacity retention rate is 85%, the ceramic diaphragm battery circulates 230 turns under 1C multiplying power, the capacity retention rate is 78%, and the composite diaphragm shows excellent cycle stability due to the addition of a metal lithium layer. Fig. 5 shows that the composite diaphragm is placed in a room with 50% humidity for 24h, 48h and 72h, then the battery assembly is carried out on the composite diaphragm under different conditions, and the charge-discharge cycle test is carried out at the rate of 1C, and no obvious capacity difference can be seen, which indicates that the metal aluminum protective layer effectively isolates water and oxygen in the air from oxidizing the metal lithium layer.
Test example 2
The composite diaphragm prepared in the embodiment 2 and the diaphragm substrate prepared in the comparative embodiment 1 are respectively assembled into lithium batteries of the same model, the composite diaphragm battery shows 97% first-turn efficiency which is higher than 92% first-turn efficiency of the ceramic diaphragm battery, the capacity retention rate of the composite diaphragm battery is 90% after the composite diaphragm battery is cycled for 300 turns at 1C rate, the capacity retention rate of the ceramic diaphragm battery is 83% after the composite diaphragm battery is cycled for 300 turns at 1C rate, and the composite diaphragm assembled battery shows excellent cycling stability due to the addition of the metal lithium layer.
Test example 3
The composite diaphragm prepared in the example 2 and the composite diaphragm prepared in the comparative example 2 are respectively assembled into lithium batteries (NCM 523-graphite) of the same model, the composite diaphragm battery of the example 1 shows 95% first-turn efficiency, the first-turn efficiency of the composite diaphragm battery of the comparative example is lower than 90%, the capacity retention rate of the composite diaphragm battery of the example 1 is 85% after 230 turns of circulation under 1C multiplying power, the capacity retention rate of the composite diaphragm battery of the comparative example is 79% after 230 turns of circulation under 1C multiplying power, the mass of the composite diaphragm of the comparative example is increased by 18% compared with that of the composite diaphragm of the example 1, the composite diaphragm battery of the example 1 has higher energy density, after the composite diaphragm prepared in the comparative example is placed in a room with 50% humidity for 24h, the first-turn efficiency of the assembled battery is 85%, the first-turn efficiency of circulation under 1C multiplying power is 230 turns, the capacity retention rate is 80%, and the composite diaphragm without a protective layer can be seen, the stability in air is poor, because the oxidation of the surface lithium is severe, compared with the composite diaphragm of the embodiment 1, the lithium supplementing effect is also poor, and the composite diaphragm shows excellent lithium supplementing performance and cycling stability due to the addition of the surface metal aluminum layer protective layer.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The composite diaphragm of the lithium ion battery is characterized by comprising a diaphragm substrate, a lithium metal layer attached to the surface of the diaphragm substrate and an outer protection layer attached to the surface of the lithium metal layer.
2. The composite separator according to claim 1, further comprising an inner protective layer positioned between the separator substrate and the lithium metal layer.
3. The composite separator according to claim 1 or 2, wherein the outer protective layer is any one of metal aluminum, metal nickel, metal zinc, metal chromium, metal tin, metal silver, and any two or more metal alloys, preferably metal aluminum.
4. The composite separator of claim 2, wherein the inner protective layer is any one of metal aluminum, metal nickel, metal zinc, metal chromium, metal tin, metal silver, and any two or more metal alloys.
5. The composite separator according to claim 1, wherein the separator base comprises a polymeric porous membrane substrate and a ceramic layer attached to a surface of the polymeric porous membrane substrate, the ceramic layer being located on the lithium metal layer side, preferably, the polymeric porous membrane substrate comprises at least one of polyethylene, polypropylene, and a copolymer of ethylene and propylene, the ceramic layer comprises a mixture of an oxide coating and a binder, and the oxide coating is at least one of alumina, silica, and titania.
6. The composite separator according to claim 2, wherein the thickness of the lithium metal layer is 0.05-10um, preferably 0.5-5 um; the thickness of the inner protective layer is 20-500nm, preferably 50-100 nm; the thickness of the outer protective layer is 0.05-5um, preferably 0.2-3 um.
7. The method for preparing a composite separator according to any one of claims 1 to 6, wherein the lithium metal layer and the outer protective layer are sequentially prepared on the surface of the separator substrate by a vacuum continuous plating apparatus.
8. The method for preparing the composite separator according to claim 7, wherein an inner protective layer is further prepared, and specifically, the inner protective layer, the lithium metal layer and the outer protective layer are sequentially prepared by a vacuum continuous plating device, and preferably, the vacuum continuous plating is one of a vacuum evaporation method, an electron beam evaporation method, a thermal evaporation method and a magnetron sputtering method.
9. The method for preparing a composite separator according to claim 7, wherein the separator substrate is subjected to a surface pretreatment before the vacuum continuous plating, and preferably, the surface pretreatment is one of plasma treatment, ion implantation, ion plating and laser surface treatment.
10. A lithium ion battery, which is characterized by comprising a positive electrode, a negative electrode, an electrolyte and the composite separator of any one of claims 1 to 6, wherein the outer protective layer of the composite separator is positioned on the side of the negative electrode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114464953A (en) * | 2021-12-27 | 2022-05-10 | 国联汽车动力电池研究院有限责任公司 | Pre-sodium treatment method of diaphragm for sodium ion battery |
| CN116053708A (en) * | 2023-03-29 | 2023-05-02 | 安迈特科技(北京)有限公司 | Lithium supplementing composite diaphragm for lithium battery, lithium battery and preparation method of lithium battery |
| CN116053708B (en) * | 2023-03-29 | 2023-07-04 | 安迈特科技(北京)有限公司 | Lithium supplementing composite diaphragm for lithium battery, lithium battery and preparation method of lithium battery |
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| CN113346192B (en) | 2023-04-07 |
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