CN110993929B - Polymer protective film, metal negative electrode material, lithium ion battery and preparation method - Google Patents

Polymer protective film, metal negative electrode material, lithium ion battery and preparation method Download PDF

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CN110993929B
CN110993929B CN201911155374.XA CN201911155374A CN110993929B CN 110993929 B CN110993929 B CN 110993929B CN 201911155374 A CN201911155374 A CN 201911155374A CN 110993929 B CN110993929 B CN 110993929B
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negative electrode
protective film
electrode material
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metal negative
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CN110993929A (en
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孙佩佩
安黎
胡梦
张友为
孟凡星
张耀
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Xinwangda Power Technology Co ltd
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Sunwoda Electric Vehicle Battery 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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Abstract

The invention discloses a polymer protective film, a composite metal cathode material, a lithium ion battery and a preparation method thereof, wherein the material of the polymer protective film comprises an organic polymer, and the general formula of the organic polymer is as follows:
Figure DDA0002284663080000011
wherein R is independently selected from-O-ph, -OH and-OCH3N is a positive integer. The polymer protective film can relieve or even inhibit the growth of lithium dendrites, further improve the safety performance of the battery, and simultaneously can avoid electrode pulverization caused by direct contact of metal and electrolyte, so as to improve the cycle performance of the battery.

Description

Polymer protective film, metal negative electrode material, lithium ion battery and preparation method
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a polymer protective film, a composite metal negative electrode material, a lithium ion battery and a preparation method.
Background
With the rapid development of global economy and the continuous rising of energy demand, lithium ion batteries are distinguished from a plurality of energy storage devices because of the advantages of no memory effect, greenness, no pollution and the like. The commercial lithium ion battery at present has low energy density, the difference of the endurance mileage is larger compared with the traditional fuel vehicle, the theoretical specific capacity of the metal lithium is as high as 3860mAh/g, the reduction potential is the lowest, and if the lithium metal cathode material can be successfully applied to the power battery, the lithium ion battery has great significance for improving the endurance mileage of a new energy vehicle.
However, the lithium dendrite problem that limits commercialization of lithium metal negative electrodes has not been solved: firstly, the electrochemical property of the lithium metal cathode is more active, lithium dendrite is easily generated in the charging and discharging process, and a diaphragm is easily punctured, so that the safety accident of short circuit of the anode and the cathode is caused; secondly, the lithium metal negative electrode is directly contacted with the electrolyte, so that side reaction is easy to occur, a large amount of dead lithium is generated, and then the electrode is pulverized and the electrolyte is consumed.
Disclosure of Invention
The invention mainly solves the technical problem of providing a polymer protective film, a composite metal negative electrode material, a lithium ion battery and a preparation method thereof, which can relieve or even inhibit the growth of lithium dendrite so as to improve the safety performance of the battery, and simultaneously can avoid electrode pulverization caused by direct contact of metal and electrolyte so as to improve the cycle performance of the battery.
In order to solve the technical problems, the invention adopts a technical scheme that: providing a polymer protective film of a metal cathode material, wherein the material of the polymer protective film comprises an organic polymer, and the general formula of the organic polymer is as follows:
Figure BDA0002284663070000021
wherein R is independently selected from-O-ph, -OH and-OCH3N is a positive integer.
Wherein, the material of the polymer protective film also comprises a binder.
Wherein the mass ratio of the organic polymer to the binder is in the range of 1:1 to 20: 1.
Wherein the binder comprises at least one of polytetrafluoroethylene, polyolefins and polyvinylidene fluoride.
Wherein, the material of the polymer protective film also comprises ceramic powder.
Wherein the organic polymer has an areal density in the range of 0.8mg/cm2-1.4mg/cm2。
In order to solve the technical problem, the invention adopts another technical scheme that: provided is a composite metal anode material including: the polymer protective film comprises a metal negative electrode material and the polymer protective film coated on the outer surface of the metal negative electrode material.
Wherein the metal negative electrode material is lithium.
In order to solve the technical problem, the invention adopts another technical scheme that: provided is a method for preparing a composite metal anode material, comprising: providing a mixed solution comprising a solvent and an organic polymer uniformly dispersed in the solvent, the organic polymer having the general formula:
Figure BDA0002284663070000022
wherein R is independently selected from-O-ph, -OH and-OCH3N is a positive integer; and uniformly coating the mixed solution on the outer surface of the metal negative electrode material under the protection of inert gas, thereby obtaining the composite metal negative electrode material.
In order to solve the technical problem, the invention adopts another technical scheme that: the lithium ion battery comprises a negative electrode, and the material of the negative electrode comprises the composite metal negative electrode material or the composite metal negative electrode material prepared by the preparation method of the composite metal negative electrode material.
The invention has the beneficial effects that: different from the situation of the prior art, the polymer protective film of the composite metal cathode material has certain flexibility and fatigue resistance, can avoid direct contact between metal and electrolyte, avoid side reaction and further avoid pulverization of the cathode material; the aromatic structure of benzene ring of organic polymer in the polymer protective film has pi-pi conjugated bond, and the interaction of the aromatic structure and the conjugated bond can balance the charge on the surface of the metal negative electrode material, avoid overlarge local current, relieve and even inhibit the growth of lithium dendrite, and further improve the safety performance of the battery.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides a polymer protective film of a metal negative electrode material, which comprises an organic polymer, wherein the general formula of the organic polymer is as follows:
Figure BDA0002284663070000031
wherein R is independently selected from-O-ph, -OH and-OCH3N is a positive integer (ph is a benzene ring).
The polymer protective film of the composite metal cathode material has certain flexibility and fatigue resistance, can avoid direct contact between metal and electrolyte, avoids side reaction and further avoids pulverization of the cathode material; the aromatic structure of the benzene ring of the organic polymer in the polymer protective film has pi-pi conjugated bonds, and the interaction of the aromatic structure and the conjugated bonds can balance the charges on the surface of the metal negative electrode material, avoid overlarge local current, relieve or even inhibit the growth of lithium dendrites, and further improve the safety performance of the battery. When R is independently selected from-O-ph, the benzene ring in R also has an aromatic structure and a pi-pi conjugated bond, and the interaction of the aromatic structure and the pi-pi conjugated bond can further balance the charge on the surface of the metal negative electrode material, further avoid overlarge local current, further relieve and even inhibit the growth of lithium dendrites, and improve the cycle performance and the safety performance of the battery.
The boron atom of the organic polymer in the polymer protective film of the invention can be used as an anion receptor and PF due to the empty orbit6-Or F-Is complexed with, canThe ionization degree of metal ions is improved, hydrofluoric acid in the electrolyte can be captured, HF in the electrolyte can be captured, the HF is prevented from attacking a CEI film of the anode, and the cycle performance of the battery can be improved.
The organic polymer has certain adhesive property, and can be adhered to the outer surface of the metal negative electrode material after film forming. In some applications, there is a high requirement for the adhesion between the polymer protective film and the metal negative electrode material, and a single organic polymer may not be able to adhere firmly, so as to further adhere the organic polymer firmly to the metal negative electrode material and prevent it from falling off, in one embodiment, the material of the polymer protective film further includes a binder. The binder of lithium ion batteries is generally a high molecular compound. The function of the organic polymer adhesive is to ensure the uniformity and safety of the active component organic polymer, to bond the organic polymer to the metal cathode material, to prevent the organic polymer from falling off from the metal cathode material. Common binders include, but are not limited to: polytetrafluoroethylene PTFE, polyolefins, polyvinylidene fluoride PVDF, and the like.
In one application, the binder comprises polyvinylidene fluoride. The metal battery electrode material prepared from the polyvinylidene fluoride has good chemical stability, temperature stability, excellent mechanical property and processability.
The proportions of organic polymer and binder are determined according to the specific application, specific requirements, such as: adhesion requirements, activity requirements of the active ingredient organic polymer, capacity requirements, and the like. In one embodiment, the mass ratio of organic polymer to binder is in the range of 1:1 to 20:1, for example: 1:1, 5:1, 10:1, 15:1, 20:1, etc.
In one application, the material of the polymer protective film further comprises ceramic powder. The ceramic powder can improve the thermal stability of the battery and improve the liquid retention capacity of the electrolyte, so that the capacity retention rate and the safety of the battery are improved. Wherein, the ceramic powder comprises one or more of alumina, titanium oxide and montmorillonite.
The ratio of ceramic powder to organic polymer is determined according to the specific application, specific requirements, such as: active ingredient organic polymers activity requirements, capacity requirements, stability requirements, safety requirements, and the like. In one embodiment, the mass ratio of the ceramic powder to the organic polymer is in the range of 1:100 to 20:100, for example: 1:100, 5:100, 10:100, 15:100, 20:100, etc.
Wherein the organic polymer has an areal density in the range of 0.8mg/cm2-1.4mg/cm2The surface density range can simultaneously take the protection effect of the polymer protective film on the lithium metal cathode and ensure smaller impedance. When the surface density is too low, the safety performance of the battery is reduced to some extent; when the areal density is too high, the cell impedance is increased, which affects the cell performance. For example, the organic polymer has an areal density of 0.8mg/cm2、1.1mg/cm2、1.4mg/cm2And so on.
The invention also provides a composite metal anode material, which comprises: the polymer protective film comprises a metal negative electrode material and the polymer protective film coated on the outer surface of the metal negative electrode material. For a detailed description of the polymer protective film, reference is made to the above description, which is not repeated herein.
Wherein the metal negative electrode material is lithium.
The invention also provides a preparation method of the composite metal negative electrode material, which comprises the following steps:
step S101: providing a mixed solution, wherein the mixed solution comprises a solvent and the material of the polymer protective film uniformly dispersed in the solvent.
Step S102: and uniformly coating the mixed solution on the outer surface of the metal negative electrode material under the protection of inert gas to obtain the composite metal negative electrode material. Inert gases include, but are not limited to, argon, nitrogen, and the like. Nitrogen is cheap and readily available, and is generally used.
Wherein, providing the mixture in step S101 may include: sub-step S1011 and sub-step S1012.
Substep S1011: and dissolving the organic polymer in a solvent under the protection of inert gas to obtain an intermediate mixed solution.
Sub-step S1012: and adding the binder and/or the ceramic powder (the binder or the ceramic powder or the binder and the ceramic powder) into the intermediate mixed solution, and uniformly stirring to obtain a mixed solution.
In one application, the solvent includes one or more of ethanol, acetone, N-methyl pyrrolidone.
Wherein the mass ratio of organic polymer to solvent is in the range of 1:2 to 1:15, e.g., 1:2, 1:5, 1:8, 1:12, 1:15, etc.
The invention also provides a lithium ion battery which comprises a negative electrode, wherein the material of the negative electrode comprises the composite metal negative electrode material or the composite metal negative electrode material prepared by the preparation method of the composite metal negative electrode material. For a detailed description of the composite metal negative electrode material or the preparation method of the composite metal negative electrode material, reference is made to the above contents, which are not described in detail herein.
The lithium ion battery further includes a positive electrode material. The anode material comprises at least one of lithium iron phosphate, lithium manganate, lithium cobaltate and ternary materials.
Further, the positive electrode material is a ternary material. Further, the general formula of the positive electrode material is LiNi1-x- yCoxMnyO2Wherein x + y is less than 1, x is more than 0, and y is more than 0.
The lithium ion battery further includes an electrolyte. Further, the electrolyte includes a nonaqueous solvent and a lithium salt. Specifically, the non-aqueous solvent is one or a combination of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate; the lithium salt is one or a combination of more of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium difluoro (oxalato) borate and lithium tetrafluoroborate. Further, the concentration of the lithium salt is 0.5-2.0 mol/L.
The following specific example using metal lithium which is relatively commonly used as an example will describe in detail the performance of the composite metal negative electrode material prepared by the preparation method of the present invention applied to a lithium ion battery, and the performance of the composite metal negative electrode material applied to a lithium ion battery is described by the first coulombic efficiency, the capacity retention rate after 100 cycles, and the lithium dendrite. Wherein, coulombic efficiency (also called discharge efficiency) refers to the ratio of the battery discharge capacity to the charge capacity in the same cycle process, i.e. the percentage of the discharge capacity to the charge capacity. The first coulombic efficiency is the percentage of the discharge capacity to the charge capacity after 1 cycle. The capacity retention rate after 100 circles is the percentage ratio of the capacity after 100 circles of the charge-discharge cycle to the initial capacity.
Example 1:
(1) preparing a positive plate: adding a ternary cathode material NCM811, conductive carbon black and a binding agent polyvinylidene fluoride into a stirring tank according to the mass ratio of 93:4:3, adding a proper amount of N-methyl pyrrolidone, and fully and uniformly stirring to obtain cathode slurry with moderate viscosity and solid content; uniformly coating the positive electrode slurry on an aluminum foil, and drying, rolling and punching to obtain a positive electrode plate;
(2) lithium metal negative electrode sheet: under the protection of nitrogen at room temperature, dissolving 1g of poly (p-diphenylhydroxyborosiloxane) in 9g N-methylpyrrolidone, stirring for 1h at the rotation speed of 200r/min, adding 1g of polyvinylidene fluoride and 0.2g of alumina nanoparticles into the solution after the solution is completely dissolved, continuously stirring for 3h, and uniformly coating the obtained mixed solution on the surface of the metal lithium foil in a glove box, wherein the surface density of the organic polymer is 1.4mg/cm2After the solvent is volatilized, the lithium metal negative plate (namely the composite metal negative material) is obtained;
(3) electricity buckling (namely button cell) preparation: the lithium metal negative plate is used as a negative electrode, the obtained positive plate is used as a positive electrode, the polypropylene film is used as a diaphragm, and the concentration of the LiPF is 1mol/L6And (3) assembling the CR2032 type button cell in an argon atmosphere surrounding glove box by taking mixed solution of + EC/DEC/EMC (ethylene carbonate/diethyl carbonate/methyl ethyl carbonate with the volume ratio of 1:1:1) as electrolyte.
Example 2:
example 2 the charging was prepared in approximately the same manner as in example 1, except that the mass ratio of poly (p-diphenylsiloxane-co-hydroxyborane) to polyvinylidene fluoride was 10: 1.
Example 3:
example 3 was prepared in substantially the same manner as in example 1 except that the mass ratio of poly (p-diphenylsiloxane) to polyvinylidene fluoride was 20: 1.
Example 4:
example 4 was prepared in substantially the same manner as in example 1 except that the solvent for dissolving the polyparaphenylene boroxine was ethanol.
Example 5:
example 5 was prepared in substantially the same manner as in example 1 except that the mass ratio of poly (p-diphenylsiloxane) to N-methylpyrrolidone was 1: 15.
Example 6:
example 6 was carried out in substantially the same manner as in example 1 except that the solvent for dissolving the polyparaphenylene group oxyborone was a mixed solution of ethanol and acetone at a mass ratio of 1: 1.
Example 7:
example 7 was prepared in substantially the same manner as in example 1 except that the organic polymer had an areal density of 0.8mg/cm2。
Example 8:
example 8 was prepared in much the same manner as in example 1 except that the organic polymer was a polyparaphenylene borosiloxane.
Example 9:
example 9 the charging was prepared in substantially the same manner as in example 1, except that the organic polymer had an areal density of 1.1mg/cm2。
Example 10:
example 10 was prepared in substantially the same manner as in example 1 except that montmorillonite was used as the ceramic powder.
Example 11:
example 11 was prepared in substantially the same manner as in example 1 except that the amount of the added alumina nanoparticles was 0.01 g.
Example 12:
example 12 was prepared in substantially the same manner as in example 1 except that the amount of the added alumina nanoparticles was 0.1 g.
Example 13:
example 13 was prepared in substantially the same manner as in example 1, except that no inorganic nanoparticles were added to the polymeric protective film.
Comparative example 1:
comparative example 1 was prepared in substantially the same manner as in example 1 except that the negative electrode was directly formed of a lithium metal foil without coating any protective film.
Comparative example 2:
comparative example 2 was prepared in substantially the same manner as in example 1 except that a polyacrylonitrile organic polymer was used.
Comparative example 3:
comparative example 3 was prepared in substantially the same manner as in example 1, except that a polyacrylonitrile organic polymer was used and no alumina nanoparticles were added.
And (3) testing:
(1) first coulombic efficiency: the charging rates of the electrodes obtained in examples 1 to 13 and comparative examples 1 to 3 were set to 0.5mA/cm2Under the current density of the battery, the button battery is charged with constant current, the charge cut-off voltage is 4.25V, and the first charge specific capacity (C) is obtainedcc1) Then at 0.5mA/cm2Discharging to 3.0V at current density to obtain first discharge specific capacity (C)dc1) The results are shown in Table 1.
Wherein the first coulombic efficiency is the first specific discharge capacity (C)cc1) Specific first charge capacity (C)dc1)。
(2) And (3) testing discharge capacity:
the charging rates of the electrodes obtained in examples 1 to 13 and comparative examples 1 to 3 were set to 0.5mA/cm2Under the current density of the battery, the button battery is charged with constant current, the charge cut-off voltage is 4.25V, and the first charge specific capacity (C) is obtainedcc1) Then at 0.5mA/cm2Discharging to 3.0V at current density to obtain first discharge specific capacity (C)dc1) The battery was repeatedly charged and discharged as described above, and the cycle was repeated up to the 100 th cycle to obtain a specific discharge capacity C at the time of 100 cyclesdc100The results are shown in Table 1.
Wherein, the containerCapacity retention rate is the specific discharge capacity C in 100 cyclesdc100Specific first charge capacity (C)dc1)。
(3) Lithium dendrite test and pulverization:
after 100 cycles of the charging cycle prepared in examples 1 to 13 and comparative examples 1 to 3, the charging was disassembled in a glove box, the morphology of the negative electrode piece was observed under an optical microscope by the disassembled negative electrode piece, whether lithium dendrite was generated or not and whether the negative electrode piece was pulverized or not were checked, and the test results are shown in table 1.
TABLE 1
Figure BDA0002284663070000081
Figure BDA0002284663070000091
As can be seen from table 1 above: the metal lithium foils of examples 1 to 13 are coated with the polymer protective film, after 100 cycles, due to the protective effect of the polymer protective film, the situation that no lithium dendrite exists on the surface of the negative pole piece is observed under an optical microscope, the negative pole interface is good, and no pulverization occurs, while the metal lithium foils of comparative example 1 are directly used as the negative pole, no protective film is coated, and after 100 cycles, severe lithium dendrite occurs on the surface of the negative pole, and severe pulverization occurs; therefore, the polymer protective film has a good protective effect on the negative electrode material, can effectively avoid direct contact between the metal lithium foil and the electrolyte, avoid side reactions, avoid pulverization of the negative electrode material, and effectively avoid generation of lithium dendrites, so that the safety performance of the battery is improved, in addition, the first coulomb efficiency of the lithium battery in the embodiments 1 to 13 is 97% or more, the polymer protective film is coated on the surface of the metal lithium foil in advance, effective lithium ions can be prevented from being consumed, further, the irreversible capacity loss of the lithium battery is avoided from being increased, and the first inventory efficiency of the lithium battery can be ensured to be at a higher level.
The results of examples 1 to 12 and example 13 prove that the addition of the ceramic powder can improve the cycle performance of the lithium ion battery to a certain extent, and after 100 cycles, the capacity retention rate is reduced without adding the ceramic powder, so that the existence of the ceramic powder can improve the liquid retention capacity of the negative electrode to the electrolyte, and further improve the capacity retention rate of the battery.
The results of examples 1-13 and comparative examples 2-3 prove that improving the flexibility of the organic polymer protective film is beneficial to avoiding the cracking problem of the protective film caused by poor fatigue resistance of the organic polymer, further avoiding the direct contact of the electrolyte and the lithium metal cathode, avoiding the pulverization of the cathode pole piece and the lithium dendrite, and improving the battery
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. The polymer protective film of the metal negative electrode material is characterized in that the material of the polymer protective film comprises an organic polymer with a benzene ring aromatic structure, and the general formula of the organic polymer is as follows:
Figure FDA0002884380930000011
wherein R is independently selected from-O-ph, -OH and-OCH3N is a positive integer.
2. The polymer protective film of claim 1, wherein the material of the polymer protective film further comprises a binder.
3. The polymer protective film according to claim 2, wherein a mass ratio of the organic polymer to the binder is in a range of 1:1 to 20: 1.
4. The polymer protective film of claim 2, wherein the adhesive comprises at least one of polytetrafluoroethylene, polyolefins, and polyvinylidene fluoride.
5. The polymer protective film according to claim 1, wherein the material of the polymer protective film further comprises ceramic powder.
6. The polymer protective film according to claim 1, wherein the organic polymer has an areal density in the range of 0.8mg/cm2-1.4mg/cm2。
7. A composite metal anode material, comprising: a metal negative electrode material and the polymer protective film according to any one of claims 1 to 6 coated on an outer surface of the metal negative electrode material.
8. The composite metal anode material according to claim 7, wherein the metal anode material is lithium.
9. A preparation method of a composite metal negative electrode material is characterized by comprising the following steps:
providing a mixed solution, wherein the mixed solution comprises a solvent and an organic polymer with a benzene ring aromatic structure uniformly dispersed in the solvent, and the general formula of the organic polymer is as follows:
Figure FDA0002884380930000021
wherein R is independently selected from-O-ph, -OH and-OCH3N is a positive integer;
and under the protection of inert gas, uniformly coating the mixed solution on the outer surface of the metal negative electrode material to obtain the composite metal negative electrode material.
10. A lithium ion battery, comprising a negative electrode, wherein the material of the negative electrode comprises the composite metal negative electrode material according to any one of claims 7 to 8 or the composite metal negative electrode material prepared by the preparation method of the composite metal negative electrode material according to claim 9.
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