CN115621419A - Metal lithium polymer negative electrode for secondary battery and preparation method - Google Patents

Metal lithium polymer negative electrode for secondary battery and preparation method Download PDF

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CN115621419A
CN115621419A CN202211383773.3A CN202211383773A CN115621419A CN 115621419 A CN115621419 A CN 115621419A CN 202211383773 A CN202211383773 A CN 202211383773A CN 115621419 A CN115621419 A CN 115621419A
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lithium
polymer
film
metal
negative electrode
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解明
胡进
杨斌
熊红波
张宣宣
刘志宏
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Ningbo Rouchuang Nanometer Technology Co ltd
Roudian Wuhan Technology Co ltd
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Ningbo Rouchuang Nanometer Technology Co ltd
Roudian Wuhan Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0483—Processes of manufacture in general by methods including the handling of a melt
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 energy storage, and particularly relates to a metallic lithium polymer negative electrode for a secondary battery and a preparation method thereof, wherein the metallic lithium polymer negative electrode comprises: the lithium ion battery comprises a high molecular polymer substrate and an alloy layer growing on the surface of the high molecular polymer, wherein the alloy layer consists of a lithium-philic nano-scale film and a metallic lithium film. The invention deposits the lithium-philic nanometer film on the polymer film substrate by utilizing the atomic layer deposition, and then the metal lithium forms chemical bond combination with the substrate by means of the lithium-philic nanometer film. The composite has the characteristics of light weight and high strength, can be automatically shrunk when being heated, and can simultaneously realize high energy density and safety of the battery.

Description

Metal lithium polymer negative electrode for secondary battery and preparation method
Technical Field
The invention relates to the technical field of energy storage, in particular to a lithium metal polymer cathode for a secondary battery and a preparation method thereof.
Background
The lithium battery is widely applied to the fields of aerospace, computers, mobile communication equipment, robots, electric automobiles and the like due to the advantages of high energy density, long cycle life and wide applicable temperature range. With the development of society and the advancement of science and technology, the requirements on the energy density and the cycle life of a lithium battery are higher and higher, but the lithium ion battery which only uses graphite as a negative electrode at present cannot meet the social expectation, so that a novel positive and negative electrode material with higher specific capacity needs to be developed. For the negative electrode material, a novel negative electrode with higher gram capacity is adopted, so that the energy density of the battery energy can be effectively improved, and the industrial requirements are met. Lithium metal has a high specific capacity (3860 mAh/g, 10 times that of graphite negative electrodes) and a lowest redox potential (-3.04 VVS standard hydrogen potential). The lithium metal is adopted as the battery cathode, has wider prospect and is the most ideal battery cathode in the future.
Although the metallic lithium negative electrode has such advantages, many problems remain to be solved, the volume change of the metallic lithium during the cycle, and the lithium dendrite problem restrict the development of the metallic lithium negative electrode. In addition, the tensile strength of the lithium metal is low, the ductility is good, and the industrial production of continuous lithium metal strips is not facilitated. The current unsupported lithium metal strip cannot be made thin (to below 5 microns) and, in order to be thin, requires a substrate for support. At present, copper foil is widely used as a supporting material to be used as a lithium copper composite belt, but the density of copper is high, and the weight is sacrificed. In addition, the lithium metal battery is extremely unsafe and has great potential safety hazard.
Although the high molecular polymer material has the advantages of light weight and high tensile strength, the high molecular polymer material has low wettability with metal lithium, so that the bonding force between a lithium film and the high molecular polymer material is low, and the falling and the unevenness of the lithium film are easy to occur.
Therefore, there is still a need to develop a light-weight, ultra-thin metallic lithium polymer material that can be directly used for a negative electrode of a lithium battery.
Disclosure of Invention
The invention aims to provide a metal lithium polymer negative electrode which has light weight, thin thickness, high strength, high energy density and good safety and can be used for a negative electrode of a lithium battery.
Accordingly, an aspect of the present invention is directed to a lithium metal polymer anode useful for a secondary battery, comprising: the lithium ion battery comprises a non-conductive high polymer film substrate, a metal lithium film and an alloy layer connecting the substrate and the metal lithium film, wherein the alloy layer is a film layer formed after the metal lithium film reacts with lithium-philic nano-scale clusters on the substrate, and the high polymer film is thermoplastic resin which shrinks at the temperature of more than 100 ℃.
Preferably, the lithium metal polymer negative electrode has a uniform thickness of 1.0 to 200 μm with a thickness tolerance within ± 0.5 μm.
More preferably, the lithium metal polymer negative electrode has a thickness of 1 to 50 μm (most preferably 3 to 5 μm) with a thickness tolerance of ± 0.1 μm.
Preferably, the high molecular polymer in the high molecular polymer film includes: one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, butadiene rubber, ethylene propylene rubber, phenolic resin, epoxy resin, unsaturated polyester resin, cellulose acetate, nylon, terylene, polyformaldehyde, polycarbonate, polyamide, polyimide, polyarylether and polyaramide.
Optionally, the lithium-philic nanocluster material is selected from one or more of simple substances, fluorides and oxides of metals of Zn, cu, co, sn, co, ni, mn, mo, al and Au; or one or more selected from organic matters containing lithium-philic groups, wherein the lithium-philic groups comprise at least one of amino, nitro, pyrrole, pyridine, imidazole, fluorine, amine, nitrile, azide, azo and diazo groups;
preferably, the lithium-philic nanoclusters are deposited on a high polymer thin film substrate through an atomic layer, the metal lithium thin film comprises metal lithium or lithium alloy, the thickness of the metal lithium polymer negative electrode is 1-200 micrometers, the thickness tolerance is +/-0.5 mu m, and the density of the high polymer thin film is not more than that of a pure metal lithium thin film.
Optionally, the lithium-philic nanoclusters are grown in pores among fibers in the high molecular polymer film and on the surface of the high molecular polymer film.
Optionally, the lithium-philic nanoclusters are grown and coated on the surface of each fiber in the high molecular polymer film to form the lithium-philic nanoscale film.
Preferably, a conductive metal layer with the thickness not greater than 1 μm is further arranged between the lithium-philic nanocluster and the high polymer film, the conductive metal layer is deposited on the surface of the high polymer film in a molecular deposition mode, and the lithium-philic nanocluster grows on the surface of the conductive metal layer.
Preferably, the metal in the conductive metal layer is preferably copper, aluminum, silver, gold.
Further, before the lithium-philic nanoclusters are deposited on the high molecular polymer film substrate by adopting the atomic layer, the high molecular polymer film substrate is pretreated by ozone oxidation or electron radiation.
The lithium-philic nanoscale cluster can grow and wrap the surface of each fiber in the high polymer film to form a lithium-philic nanoscale film, and the metal lithium film can grow on the surface of the fiber wrapping the lithium-philic nanoscale film.
Optionally, the material of the metallic lithium film comprises pure metallic lithium or a lithium alloy, and when the material of the metallic lithium film is pure metallic lithium, the content of lithium element in the metallic lithium film is 99.95% -99.99%; when the material of the metal lithium film is lithium alloy, the lithium alloy is an alloy of metal lithium and one or more of silicon, magnesium, aluminum, indium, boron, tin, gallium, yttrium, silver, copper, lead, bismuth, sodium, carbon, germanium, titanium, chromium, cobalt, tungsten, iron, niobium, nickel, gold, barium, cadmium, cesium, calcium, manganese, nitrogen, platinum, sulfur, thallium, strontium, tellurium, zinc, antimony and zirconium, wherein the lithium content is 5-99.9%.
Preferably, the high molecular polymer thin film is formed by rolling an ultra-thin lithium foil or lithium alloy foil with a melting point of not more than 180 ℃.
Or, when the melting point of the high molecular polymer film is more than 180 ℃, the metallic lithium film is formed by coating molten metallic lithium or lithium alloy and then rolling.
A lithium metal battery comprises a positive pole piece, a negative pole piece, an isolating membrane and an electrolyte layer, wherein the negative pole piece is the metal lithium polymer negative pole.
The invention also provides a preparation method of the metal lithium polymer negative electrode, which comprises the following steps:
(1) Pretreating a high molecular polymer film substrate by ozone oxidation or electron radiation under vacuum; or depositing a conductive metal layer with the thickness not more than 1 mu m on the surface of the high molecular polymer film by a molecular deposition mode;
(2) Depositing a lithium-philic nano-scale film on the treated high molecular polymer film substrate or the conductive metal layer by utilizing an atomic layer deposition technology to obtain a substrate material;
(3) The lithium metal thin film is formed on the substrate after the lithium-philic nano-scale thin film is deposited on the substrate by coating molten lithium metal or lithium alloy and then rolling, or by rolling an ultrathin lithium foil or lithium alloy foil.
Preferably, the step (3) is specifically operated as follows:
heating solid lithium to a molten state in a molten lithium metal spray bath, and then continuously passing the base material of step (2) through the molten lithium metal spray bath, followed by rolling, to obtain a negative electrode material.
Alternatively, the temperature of the molten pool is in the range of 200 to 500 deg.C, preferably 200 to 250 deg.C.
Optionally, the ambient atmosphere requires: the entire lithium metal polymer composite is prepared in an inert atmosphere (e.g., argon) with the water content controlled to be less than 0.1ppm and the oxygen content controlled to be less than 0.1ppm.
Optionally, the molecular deposition means comprises magnetron sputtering or evaporation.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention utilizes the atomic layer deposition technology to deposit the lithium-philic nano-scale film on the ultrathin high molecular polymer film. Compared with other physical deposition means, the atomic layer deposition precursor can form stable chemical bonds with the high molecular polymer film, and the formed lithium-philic nano-scale film has strong bonding force with the high molecular polymer film matrix. And coating molten lithium or rolling the ultrathin lithium foil to enable the lithium-philic thin film to perform electrochemical reaction with lithium metal, thereby obtaining the ultralight ultrathin metal lithium polymer composite. The composite has the characteristics of light weight and high strength, and the metal lithium and the polymer substrate are not layered, so that the high energy density of the battery is realized. In addition, after the conductive metal layer is deposited on the surface of the high molecular polymer in an evaporation or sputtering mode, the electron transmission capability of the lithium metal polymer cathode can be enhanced.
When the existing copper foil lithium battery is used, when the internal thermal runaway of the battery is caused, and the temperature exceeds the melting point of the diaphragm, the diaphragm is shrunk and melted, so that the positive electrode and the negative electrode are in face-to-face contact to form a short circuit. A large amount of heat is released in a short time, so that an uncontrollable irreversible process, i.e. thermal runaway, occurs. After the copper foil is replaced by the polymer or the polymer/conductive metal layer substrate, when a diaphragm is punctured or the local temperature is too high and local melting and damage occur, the positive electrode and the negative electrode are in face-to-face contact for a short time to transmit electrons to form a short circuit, but along with the short circuit, the internal temperature of the battery is increased, so that the high molecular polymer is contracted, the positive electrode and the negative electrode in face contact are in point contact, the positive electrode and the negative electrode are not in contact any more to form an open circuit, further thermal runaway is avoided, and the safety of the lithium metal battery is improved.
Drawings
FIG. 1 is an SEM image of a PET film with a deposited lithium-philic zinc oxide film;
FIG. 2 is an SEM image of molten lithium metal forming a composite negative electrode on the surface of a composite structure of a PET film substrate;
FIG. 3 shows the results of charge-discharge cycle testing of three metal batteries made according to the present invention;
FIG. 4 is a diagram showing the effect of a soft battery pack containing a polymer/lithium foil negative electrode tab and a soft battery pack containing a polymer/copper foil/lithium foil negative electrode tab after needling;
fig. 5 is a diagram showing the needling effect of a soft battery pack containing a copper foil/lithium foil negative electrode sheet.
Detailed Description
The following examples of the present invention are described in detail, and it will be understood by those skilled in the art that the following examples are intended to illustrate the present invention, but should not be construed as limiting the present invention. Unless otherwise indicated, specific techniques or conditions are not explicitly described in the following examples, and those skilled in the art may follow techniques or conditions commonly employed in the art or in accordance with the product specifications.
In the following embodiments, the tabs are metal conductors leading out the positive and negative electrodes from the battery core;
in the operation of coating zinc oxide on the surface of the high molecular polymer film by using the atomic layer deposition technology ALD, the ALD reaction chamber parameters are set as follows: charging into DEZ (diethyl zinc) 10s, N 2 Purging for 30s, charging H 2 O 10s, N 2 And purging for 30s. Repeating for 10 times to form a coating layer of about 2 nm.
Example 1 a lithium metal battery was prepared by the following method:
(1) Preparation of composite structures
The non-conductive high molecular polymer film (thermoplastic resin) is put in a vacuum chamber for ozone oxidation pretreatment, the reaction temperature is 50 ℃, and the treatment time is 30min. And then coating zinc oxide on the surface of the high molecular polymer film by utilizing an atomic layer deposition technology ALD, wherein the reaction temperature is 80 ℃, and the number of coating turns is 10 (the thickness of the zinc oxide coated by 10 turns is about 1-2 nanometers, and after the zinc oxide is coated by ozone treatment and ALD, the whole thickness and weight are not affected basically), so that the high molecular polymer film subjected to lithium-philic treatment, namely the composite structure, is obtained.
The thickness of the polymer film used in this example was 5 μm with a thickness tolerance of. + -. 0.5. Mu.m, preferably. + -. 0.1. Mu.m. The high molecular polymer film used in the composite structure is PET (polyethylene terephthalate), or PI (polyimide), or PP (polypropylene), or PE (polyethylene). The densities of the four thermoplastic resins were: 1.37g/cm of PET, PI: 1.38-1.43 g/cm, and (PP): 0.9g/cm, PE: the thermal conductivity of the three thermoplastic resins is very low, for example, PE has a thermal conductivity of about 0.42w/mk. The melting point of PET is about 250 to 255 ℃, the melting point of PI is more than 300 ℃, the melting point of PE is about 120 ℃, and the melting point of PP is about 170 ℃.
(2) Preparation of negative pole piece
If the melting point of the high molecular polymer is not higher than 180 ℃, it is formed by rolling an ultra-thin lithium foil or lithium alloy foil on a base material. If the melting point of the high molecular polymer is higher than 180 ℃, if the high molecular polymer is aramid fiber, PI or PET, the production of the negative pole piece adopts a roll-to-roll continuous production method, and the production method comprises the steps of enabling the substrate material to continuously pass through a molten metal lithium spraying pool and then rolling to obtain the negative pole piece.
In this embodiment, when the high molecular polymer is PP, the specific preparation method of the negative electrode plate is as follows:
and (2) taking the high molecular polymer film subjected to lithium-philic treatment in the step (1) as a substrate material, and rolling an ultrathin lithium foil on the substrate material to attach lithium to the polymer substrate subjected to lithium-philic treatment to obtain a negative pole piece with the thickness of 50 microns.
When the high molecular polymer adopted in this embodiment is PET, the specific preparation method of the negative electrode sheet is as follows:
heating solid lithium to a molten state in a molten metal lithium spraying pool, taking the high polymer film subjected to lithium-philic treatment in the step (1) as a base material, continuously passing through the molten metal lithium spraying pool, rolling, attaching lithium in a high-temperature molten state to the polymer base subjected to lithium-philic treatment to obtain a negative pole piece with the thickness of 50 micrometers, wherein the temperatures of molten lithium and poured lithium are set to be 200 ℃. The environmental atmosphere requires: the whole preparation process of the negative pole piece is carried out in an argon atmosphere with the water content less than 0.1ppm and the oxygen content less than 0.1ppm. Fig. 1 is an SEM image of a deposited lithium-philic PET film of zinc oxide, and fig. 2 is an SEM image of molten lithium metal forming a composite anode on the surface of a composite structure.
(3) Preparation of positive pole piece
Lithium iron phosphate (LiFePO) as positive electrode active material 4 ) The conductive carbon black (Super P) and PVDF are mixed according to the weight ratio of 97.5. And uniformly coating the slurry on an aluminum foil of the positive current collector, and drying at 90 ℃ to obtain the positive pole piece. The loading capacity is 1mAh/cm 2 . After coating, the pole pieces were cut into disks 14mm in diameter for use.
(4) Preparation of the electrolyte
In a dry argon atmosphere, firstly, mixing Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) according to a volume ratio of 1:1, then adding lithium salt LiTFSI (lithium bistrifluoromethylenesulfonic imide) to dissolve and uniformly mix, and obtaining the electrolyte with the lithium salt concentration of 1M.
(5) Lithium metal battery preparation
And (3) placing a porous polyethylene film with the thickness of 15 mu m between the positive plate and the negative plate as an isolating film, soaking the electrolyte into the positive plate, the negative plate and the diaphragm of the battery, and assembling the prepared negative plate, positive plate and electrode solution into the button battery. When the tab is led out from the negative pole piece, the tab is welded through the substrate by an ultrasonic roll welding technology, or the tab is pressure-welded on the surface of the lithium metal.
When the high molecular polymer of the substrate in the negative plate is PET, the battery is subjected to a cyclic charge and discharge test at a multiplying power of 0.5C, and the result shows that: the battery can be stably cycled for 200 weeks, and the capacity retention rate is 80%.
A battery with a lithium foil/copper foil electrode as the negative electrode was prepared as described above except that: omitting the step (1), replacing the substrate material in the step (2) with copper foil with a thickness of 6 μm and a density of 8.960g/cm (the thermal conductivity of copper is 401W/m.K) for carrying out thin film transfer, so as to obtain a lithium foil/copper foil electro-negative electrode plate with a thickness of 50 μm, and obtaining a battery with a magnification of 0.5C (the current density is 5 mA/cm) 2 The current density of the lithium metal battery is 3700 to 3860mAh/gCalculation) charge-discharge cycle test results are shown in fig. 3, the cycle charge-discharge test of the battery is carried out, and the results show that: the battery can be stably cycled for 200 weeks, and the capacity retention rate is 78%.
As a modification of the above embodiment, after the substrate material is replaced by a PP film with a thickness of 10 μm and a copper-plated surface, a 50 μm PP film/copper foil/lithium foil electric negative electrode sheet can be prepared, and the PP film/copper foil/lithium foil electric negative electrode sheet is prepared by the following steps: before the zinc oxide is coated by adopting an atomic deposition method, a copper conducting layer with the thickness not more than 1 mu m is formed on the surface of the polymer PP by adopting an evaporation or magnetron sputtering method, then the zinc oxide is coated by adopting the atomic deposition method to obtain a substrate, and finally the ultrathin lithium foil or lithium alloy foil is rolled on the substrate material to form the zinc oxide coated substrate, so that the electron transmission capability of the substrate can be enhanced.
The obtained battery was used at a rate of 0.5C (current density of 5 mA/cm) 2 The current density of the lithium metal battery is calculated according to 3700 to 3860mAh/g), the charge-discharge cycle test result is shown in figure 3, and the charge-discharge cycle test of the battery is carried out, and the result shows that: the battery can be stably cycled for 200 weeks, and the capacity retention rate is 82%.
The lithium foil/copper foil and the negative electrode plate in the example 1 are respectively used as negative electrodes to prepare a soft package battery, and a needling test is carried out on the soft package battery, wherein the two figures on the left side in the figure 4 are the effect of the soft battery containing the PP polymer film/Li foil negative electrode plate prepared by the method in the example after needling is carried out on the soft package battery; the two right-hand diagrams in FIG. 4 are the effect diagrams of the soft battery pack containing the PP polymer film/Cu foil/Li foil negative electrode plate prepared by the method of the embodiment after needling, and no fire occurs; fig. 5 is a diagram showing the needling effect of the soft battery pack containing the Cu foil/Li foil negative electrode sheet manufactured by the prior art, and it can be seen that needling causes fire.
In the embodiment, the thickness of the metal lithium film on the surface of the negative electrode plate can be not more than 5 μm, the thickness of the substrate formed by the high polymer film can be not more than 10 μm, and the copper foil is used as the substrate in the prior art, although the thickness is smaller, the density of the copper foil is high, so that the specific capacity of the battery is not high.

Claims (12)

1. A metallic lithium polymer negative electrode useful for a secondary battery, comprising: the lithium ion battery comprises a non-conductive high polymer film substrate, a metal lithium film and an alloy layer connecting the substrate and the metal lithium film, wherein the alloy layer is a film layer formed after the metal lithium film reacts with lithium-philic nano-scale clusters on the substrate, and the high polymer film is thermoplastic resin which shrinks at the temperature of more than 100 ℃.
2. The lithium metal polymer negative electrode usable for a secondary battery according to claim 1, wherein the high molecular polymer in the high molecular polymer film comprises: one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, butadiene rubber, ethylene propylene rubber, phenolic resin, epoxy resin, unsaturated polyester resin, cellulose acetate, nylon, terylene, polyformaldehyde, polycarbonate, polyamide, polyimide, polyarylether and polyaramide.
3. The metallic lithium polymer negative electrode usable for a secondary battery according to claim 2, wherein the lithium-philic nanocluster material is selected from one or more of Zn, cu, co, sn, co, ni, mn, mo, al, elemental of Au metal, fluoride, nitride, or oxide; or one or more selected from organic matters containing lithium-philic groups, wherein the lithium-philic groups comprise at least one of amino groups, nitro groups, pyrrole groups, pyridine groups, imidazole groups, fluorine groups, amine groups, nitrile groups, azide groups, azo groups and diazo groups.
4. The metallic lithium polymer negative electrode for a secondary battery as claimed in claim 3, wherein the lithium-philic nanoclusters are deposited on a polymer thin film substrate by atomic layer deposition, the metallic lithium thin film comprises metallic lithium or lithium alloy, the metallic lithium polymer negative electrode has a thickness of 1 to 200 microns and a thickness tolerance of ± 0.5 μm.
5. The metallic lithium polymer negative electrode for a secondary battery according to claim 4, wherein the lithium-philic nanoclusters are grown in pores between individual fibers in the polymer thin film and on the surface of the polymer thin film.
6. The metallic lithium polymer negative electrode usable for a secondary battery according to claim 4, wherein the lithium-philic nanoclusters are grown and coated on the surface of each fiber in the polymer thin film to form a lithium-philic nanoscale thin film.
7. The metallic lithium polymer negative electrode for a secondary battery according to claim 4, wherein a conductive metal layer with a thickness of not more than 1 μm is further disposed between the lithium-philic nanocluster and the polymer thin film, the conductive metal layer is deposited on the surface of the polymer thin film by molecular deposition, and the lithium-philic nanocluster is grown on the surface of the conductive metal layer.
8. The metallic lithium polymer negative electrode for secondary batteries according to claim 6, wherein a high molecular polymer thin film substrate is further pretreated with ozone oxidation or electron irradiation before the lithium-philic nanoclusters are deposited on the high molecular polymer thin film substrate using the atomic layer.
9. The lithium metal polymer anode of any one of claims 5~8 useful in a secondary battery, wherein the material of said lithium metal film comprises pure lithium metal or lithium alloy, and when the material of said lithium metal film is pure lithium metal, the content of lithium element in said lithium metal film is 99.95% -99.99%; when the material of the metal lithium film is lithium alloy, the lithium alloy is an alloy of metal lithium and one or more of silicon, magnesium, aluminum, indium, boron, tin, gallium, yttrium, silver, copper, lead, bismuth, sodium, carbon, germanium, titanium, chromium, cobalt, tungsten, iron, niobium, nickel, gold, barium, cadmium, cesium, calcium, manganese, nitrogen, platinum, sulfur, thallium, strontium, tellurium, zinc, antimony and zirconium, wherein the lithium content is 5-99.9%.
10. The lithium metal polymer negative electrode usable for a secondary battery according to claim 9, wherein the high molecular polymer thin film is formed by rolling an ultra-thin lithium foil or lithium alloy foil when the melting point thereof is not more than 180 ℃; when the melting point of the high molecular polymer film is more than 180 ℃, the metal lithium film is formed by coating molten metal lithium or lithium alloy and then rolling.
11. A lithium metal battery comprising a positive electrode tab, a negative electrode tab, a separator and an electrolyte layer, wherein the negative electrode tab is the metallic lithium polymer negative electrode of claim 10.
12. The method of preparing a lithium metal polymer negative electrode for a secondary battery according to claim 10, comprising the steps of:
(1) Pretreating a high molecular polymer film substrate by ozone oxidation or electron radiation under vacuum; or depositing a conductive metal layer with the thickness not more than 1 mu m on the surface of the high molecular polymer film by a molecular deposition mode;
(2) Depositing a lithium-philic nano-scale film on the treated high-molecular polymer film substrate or the conductive metal layer by utilizing an atomic layer deposition technology to obtain a substrate material;
(3) The lithium metal thin film is formed on the substrate after the lithium-philic nano-scale thin film is deposited on the substrate by coating molten lithium metal or lithium alloy and then rolling, or by rolling an ultrathin lithium foil or lithium alloy foil.
CN202211383773.3A 2022-11-07 2022-11-07 Metal lithium polymer negative electrode for secondary battery and preparation method Pending CN115621419A (en)

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CN113073496A (en) * 2020-09-17 2021-07-06 江汉大学 Method for preparing conductive fiber paper with hydrophilic-hydrophobic lithium gradient structure and conductive fiber paper
CN113206257A (en) * 2021-04-23 2021-08-03 天津中能锂业有限公司 Primary lithium battery and preparation method thereof
CN113258044A (en) * 2021-04-23 2021-08-13 天津中能锂业有限公司 Ultra-light three-dimensional framework metal lithium complex and preparation method thereof

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JPH0837000A (en) * 1994-07-21 1996-02-06 Mitsubishi Cable Ind Ltd Negative electrode, its manufacturing method, and lithium secondary battery
US20130045427A1 (en) * 2011-08-19 2013-02-21 Nanoteck Instruments, Inc. Prelithiated current collector and secondary lithium cells containing same
CN108365200A (en) * 2018-02-11 2018-08-03 清华大学 A kind of preparation method of compound lithium an- ode
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CN113258044A (en) * 2021-04-23 2021-08-13 天津中能锂业有限公司 Ultra-light three-dimensional framework metal lithium complex and preparation method thereof

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