CN110212166B - Method for constructing double-layer protection interface on surface of lithium metal negative electrode - Google Patents
Method for constructing double-layer protection interface on surface of lithium metal negative electrode Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—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
- 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
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Abstract
The invention relates to a method for constructing a double-layer protection interface on the surface of a lithium metal negative electrode, which comprises the following steps: (a) carrying out esterification reaction on polyphosphoric acid and polyhydric alcohol to form polyphosphoric acid ester; (b) adding the polyphosphate into an organic solvent to prepare an ester treatment fluid; (c) and immersing the lithium metal sheet into the ester treatment liquid for etching reaction. Active lithium metal sheets are immersed into specific ester treatment liquid containing a certain mass content for etching reaction, so that an organic/inorganic double-layer interface protection layer can be formed on the metal surface through in-situ etching, the treated metal sheets are stably stored in the air, and the cycle performance and the safety performance of the lithium metal battery can be greatly improved when the lithium metal battery is used.
Description
Technical Field
The invention belongs to the field of lithium metal batteries, relates to a construction method of a lithium metal negative electrode protection layer, and particularly relates to a method for constructing a double-layer protection interface on the surface of a lithium metal negative electrode.
Background
In recent years, as electric vehicles, power grid energy storage, portable electronic products, and the like have been developed, research on high energy density batteries has been directly promoted. Lithium metal has the highest specific capacity (3860mAh g)-1) And the lowest redox potential (-3.04V vs SHE), and is therefore considered a potential candidate for replacing existing commercial lithium ion battery anode materials. However, lithium metal having high reactivity spontaneously reacts with an organic electrolyte to form an unstable solid electrolyte interface layer (SEI). The continuous electroplating/stripping process on the surface of the lithium metal can cause great volume change of the lithium metal, along with structural damage and fragmentation of an SEI film, and cracks are formed on the surface of the lithium metal, which can cause uneven distribution of lithium ion concentration in electrolyte, and large lithium ion concentration at the cracks, so that dendritic non-uniform lithium deposition is caused, and further growth of lithium dendrites is caused. Lithium dendrites tend to puncture the separator during growth, causing internal short circuits and causing safety problems. Further, of SEI filmsRepetitive cracking and growth of lithium dendrites expose the lithium simple substance to the organic electrolyte and continuously react with the electrolyte to form a new SEI layer. This results in rapid depletion of the electrolyte and severe lithium corrosion processes, and further affects the coulombic efficiency and lifetime of the battery. Therefore, artificially modifying the SEI layer remains a key to achieving high performance lithium metal negative electrodes.
In recent years, many strategies have been proposed to stabilize lithium metal anodes. By optimizing the composition of the electrolyte, such as additives, high concentration electrolytes, solid electrolytes, and the like, the stability of the in-situ formed SEI layer can be improved; however, the SEI layer has poor mechanical properties, and it is still difficult to avoid the problems described above, resulting in poor cycle stability; ex-situ coatings composed of organic polymers, inorganic ceramics and hybrids thereof have stronger mechanical strength compared to in-situ SEI layers. The incorporation of such ex-situ coatings on the surface of lithium metal can thus significantly ameliorate the brittleness problem faced by in-situ SEI. However, problems such as low ionic conductivity, insufficient mechanical strength of the polymer, poor interface contact of the ceramic, and the like remain inevitable problems in practical use of the lithium metal negative electrode. Therefore, the construction of the protective layer which has a reasonable structure, can provide a rapid lithium ion transmission channel, has high mechanical modulus and good morphology consistency has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for constructing a double-layer protective interface on the surface of a lithium metal negative electrode.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for constructing a double-layer protection interface on the surface of a lithium metal negative electrode comprises the following steps:
(a) carrying out esterification reaction on polyphosphoric acid and polyhydric alcohol to form polyphosphoric acid ester;
(b) adding the polyphosphate into an organic solvent to prepare an ester treatment fluid;
(c) and immersing the lithium metal sheet into the ester treatment liquid for etching reaction.
Optimally, it also comprises:
(d) and (c) cleaning the lithium metal sheet treated in the step (c) by using an anhydrous solvent, removing residual liquid on the surface of the lithium metal sheet, and drying the lithium metal sheet under a vacuum condition.
Preferably, in the step (a), the polyol is a mixture of one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, xylitol, sorbitol, sucrose, neopentyl glycol, pentaerythritol, polyoxypropylene glycol and polytetrahydrofuran glycol.
Optimally, in the step (a), the molar ratio of the polyphosphoric acid to the polyol is 1:1 to 6.
Further, in the step (a), the reaction temperature of the esterification reaction is 60-200 ℃ and the reaction time is 30 min-24 h.
Preferably, in the step (b), the organic solvent is a mixture of one or more selected from cyclohexane, tetrahydrofuran, N-methylpyrrolidone, acetone and dimethylformamide.
Further, in the step (b), the mass concentration of the polyphosphate in the ester treatment liquid is 0.1-10%.
Optimally, in the step (c), the etching reaction time is 30 min-8 h.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the method for constructing the double-layer protection interface on the surface of the lithium metal cathode, active lithium metal sheets are immersed into specific ester treatment liquid containing a certain mass content for etching reaction, so that an organic/inorganic double-layer interface protection layer can be formed on the metal surface through in-situ etching, the treated metal sheets are stably stored in the air, and the cycle performance and the safety performance of the metal sheets can be greatly improved when the metal sheets are used for a lithium metal battery.
Drawings
FIG. 1 is a scanning electron microscope image of a double-layer interface-protected lithium metal negative electrode prepared in example 1;
FIG. 2 is a scanning electron microscope cross-sectional view of a double-layer interface protection lithium metal cathode prepared in example 1;
FIG. 3 is a circular polarization curve of a lithium symmetric battery assembled by a double-layer interface protection lithium metal negative electrode prepared in example 1;
FIG. 4 is the assembly of the two-layer interface-protected lithium metal anode prepared in example 1 into L i/L iFePO4A post-battery charge-discharge curve;
FIG. 5 is L i/L iFePO assembled from the two-layer interface-protected lithium metal anode made in example 14A cycle comparison plot of the cell and the comparative cell;
FIG. 6 is L i/L iFePO assembled separately after the two-layer interface-protected lithium metal negative electrode of example 1 and the conventional lithium metal negative electrode of comparative example were stored in air for 30min4A cycle comparison graph of the battery;
FIG. 7 is a solid L i/L iFePO assembled from the bi-layer interface-protected lithium metal negative electrode of example 1 and the conventional lithium sheet of comparative example, respectively4A cycle comparison graph of the battery;
FIG. 8 is a cycle comparison of the assembly of the two-layer interface-protected lithium metal negative electrode made in example 1 into an L i/S cell and a comparative cell;
FIG. 9 is L i/L iCoO assembled from the two-layer interface-protected lithium metal negative electrode made in example 12A cycle comparison plot of the cell and the comparative cell;
fig. 10 comparative scanning electron microscope images of the two-layer interface protection lithium metal negative electrode prepared in example 1 and the conventional lithium sheet of comparative example after 100 cycles of charge and discharge.
Detailed Description
The invention discloses a method for constructing a double-layer protection interface on the surface of a lithium metal negative electrode, which comprises the following steps: (a) carrying out esterification reaction on polyphosphoric acid and polyhydric alcohol to form polyphosphoric acid ester; (b) adding the polyphosphate into an organic solvent to prepare an ester treatment fluid; (c) and immersing the lithium metal sheet into the ester treatment liquid for etching reaction. Active lithium metal sheets are immersed into specific ester treatment liquid containing a certain mass content for etching reaction, so that an organic/inorganic double-layer interface protection layer can be formed on the metal surface through in-situ etching, the treated metal sheets are stably stored in the air, and the cycle performance and the safety performance of the lithium metal battery can be greatly improved when the lithium metal battery is used; the treated lithium metal sheet can ensure that lithium is uniformly deposited in the double-layer interface protection, effectively inhibit the growth of lithium dendrites and relieve the volume change of lithium metal in the electroplating/stripping process.
The above method may further comprise step (d): and (c) cleaning the lithium metal sheet treated in the step (c) by using an anhydrous solvent, removing residual liquid on the surface of the lithium metal sheet, and drying the lithium metal sheet under a vacuum condition. In the step (a), the polyhydric alcohol is a mixture of one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, xylitol, sorbitol, sucrose, neopentyl glycol, pentaerythritol, polyoxypropylene glycol and polytetrahydrofuran glycol; most preferably pentaerythritol. In the step (a), the molar ratio of the polyphosphoric acid to the polyol is 1:1 to 6. In the step (a), the reaction temperature of the esterification reaction is 60-200 ℃ (preferably 100-150 ℃), and the reaction time is 30 min-24 h (preferably 6-12 h). In the step (b), the organic solvent is a mixture consisting of one or more selected from cyclohexane, tetrahydrofuran, N-methylpyrrolidone, acetone and dimethylformamide; the mass concentration of the polyphosphate in the ester treatment liquid is 0.1-10%. In the step (c), the etching reaction time is 30 min-8 h.
The present invention will be further described with reference to examples.
Example 1
The embodiment provides a method for constructing a double-layer protection interface on the surface of a lithium metal negative electrode, which comprises the following steps:
(a) and (3) synthesis of an organic phosphate precursor: adding 4.2g of polyphosphoric acid into a single-neck flask, heating to 120 ℃, then adding 1g of pentaerythritol, uniformly stirring, and reacting for 6 hours at the temperature of 100 ℃;
(b) preparing an ester treatment solution, namely adding 80mg of organic phosphate into 20m L tetrahydrofuran in a glove box filled with argon to uniformly disperse the organic phosphate to form the ester treatment solution;
(c) taking 1 metal lithium sheet, scraping a passivation layer on the surface of the metal lithium sheet by using a fine brush, completely immersing the metal lithium sheet into an ester treatment solution, and soaking for 1 hour at room temperature;
(d) and (3) taking the lithium sheet out, washing the lithium sheet for multiple times (3-5 times) by using cyclohexane, sucking residual ester treatment liquid and cyclohexane (more importantly, removing polyphosphate) by using dust-free paper, and drying the lithium sheet under a vacuum condition.
Example 2
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (a), the synthesis temperature of the organic phosphate precursor is 200 ℃.
Example 3
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (a), the synthesis time of the organic phosphate precursor is 12 h.
Example 4
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (b), the content of the organic phosphate ester added to the tetrahydrofuran solvent was 40 mg.
Example 5
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (b), the mass concentration of the polyphosphate in the ester treatment liquid is 0.1%.
Example 6
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (b), the mass concentration of the polyphosphate in the ester treatment liquid is 10%.
Example 7
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (c), the lithium sheet is soaked in the ester treatment liquid for reaction for 30 min.
Example 8
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (c), the lithium sheet is soaked in the ester treatment solution for 4 hours.
Example 9
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (c), the lithium sheet is soaked in the ester treatment solution for 8 hours.
Example 10
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in step (a), the molar ratio of polyphosphoric acid to pentaerythritol is 1: 1.
Example 11
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in step (a), the molar ratio of polyphosphoric acid to pentaerythritol is 1: 6.
Example 12
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (a), the polyhydric alcohol added to the polyphosphoric acid is propylene glycol (other glycols such as ethylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, polyoxypropylene glycol, and polytetrahydrofuran glycol have substantially the same effect as propylene glycol).
Example 13
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (a), the polyhydric alcohol added to the polyphosphoric acid is trimethylolethane (the use effect of triols such as other glycerol and trimethylolpropane is basically the same as that of trimethylolethane).
Example 14
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (a), xylitol is added into polyphosphoric acid (the using effect of sorbitol and sucrose is basically consistent with that of xylitol).
Comparative example 1
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in step (a), the molar ratio of polyphosphoric acid to pentaerythritol is 1: 8.
Comparative example 2
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: in the step (b), the mass concentration of the polyphosphate in the ester treatment liquid is too high, and is 15%.
Comparative example 3
This example provides a method for forming a double-layer protective interface on the surface of a lithium metal negative electrode, which is substantially the same as the operation steps in example 1, except that: step (a) is not carried out, and instead of the polyphosphate, the polyphosphate is used directly.
Examples of the experiments
This example provides a method for assembling various batteries using the lithium sheets prepared in the above examples as negative electrodes, specifically as follows:
(1) l iFePO4Powder: acetylene black: PVDF as a 8: 1:1, adding a proper amount of N-methyl pyrrolidone (NMP) as a dispersing agent, uniformly grinding the mixture in an agate mortar, coating the slurry on an aluminum foil current collector, drying for 12 hours in a vacuum drying box at 60 ℃, and finally cutting into pole pieces with the diameter of 13mm by using a slicing machine (the mass average of active substances in each pole piece is about 4 mg/cm)2) (ii) a The lithium metal sheets treated in examples 1 to 14 and comparative examples 1 to 3 and the likeLithium metal platelet (comparative) as L i/L iFePO4The negative electrode of the battery was charged with 1M lithium hexafluorophosphate (L iPF)6) Dissolving in Ethylene Carbonate (EC)/diethyl carbonate (DEC) mixed solution with the volume ratio of 1:1 to assemble L i/L iFePO4The cells were tested for electrochemical performance by exposing the dried lithium plates to air for 30min and then reassembling the dried lithium plates into L i/L iFePO by the same method4And (4) carrying out a battery performance test (the performance test data are shown in the table 1).
(2) L iFePO4Powder: acetylene black: PVDF as a 8: 1:1, adding a proper amount of N-methyl pyrrolidone (NMP) as a dispersing agent, uniformly grinding the mixture in an agate mortar, coating the slurry on an aluminum foil current collector, drying for 12 hours in a vacuum drying box at 60 ℃, and finally cutting into pole pieces with the diameter of 13mm by using a slicing machine (the mass average of active substances in each pole piece is about 4 mg/cm)2) L iPF was dissolved in a lithium sheet (in example 1) completely dried after the reaction as a negative electrode6PEO (carbon oxide) as a solid electrolyte, prepared into L i/L iFePO4And carrying out electrochemical performance test after the all-solid-state battery. The test results are shown in the attached figure.
(3) Mixing sulfur powder: acetylene black: PVDF as 7: 2: 1, adding a proper amount of N-methyl pyrrolidone (NMP) as a dispersing agent, uniformly grinding the mixture in an agate mortar, coating the slurry on an aluminum foil current collector, drying for 12 hours in a vacuum drying oven at 60 ℃, and finally cutting into pole pieces with the diameter of 13mm by using a slicing machine (the mass average of sulfur active substances in each pole piece is about 1.2 mg/cm)2) A lithium sheet (in example 1) completely dried after reaction is used as a negative electrode of an L i/S battery, and an electrolytic liquid system used is a mixed solution of 1M lithium bis (trifluoromethylsulfonyl) imide (L iTFSI) and 1, 3-dioxolane (DO L)/ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, so that the L i/S battery is assembled for electrochemical performance test.
(4) L iCoO2Powder: acetylene black: PVDF as a 8: 1:1, adding a proper amount of N-methyl pyrrolidone (NMP) as a dispersing agent, uniformly grinding the mixture in an agate mortar, and then coating the slurry and aluminum foilDrying on the current collector for 12h at 60 deg.C in a vacuum drying oven, cutting into pole pieces with diameter of 13mm (mass of active material in single pole piece is about 4mg/cm2 on average) with a slicer, and taking the completely dried lithium piece (in example 1) as L i/L iCoO2The negative electrode of the battery uses an electrolytic solution of 1M L iPF6Dissolving in EC/DEC mixed solution with the volume ratio of 1:1 to assemble into L i/L iCoO2The cell was tested for electrochemical performance. The test results are shown in the attached figure.
FIG. 1 and FIG. 2 are a scanning electron microscope image and an electron microscope cross-sectional view of a double-layered interface-protected lithium metal negative electrode prepared in example 1, respectively, and it can be seen that a polyphosphate generated by an esterification reaction between polyphosphoric acid and pentaerythritol is dispersed in a tetrahydrofuran solvent, a metal lithium sheet shows a uniform and flat surface after being soaked, and an organic/inorganic double-layered interface layer is simultaneously generated, so that lithium ions can be uniformly deposited on the surface of the lithium metal negative electrode in a cycle process of a L i | L i battery, and lithium dendrite growth is effectively inhibited4The charge and discharge curves measured are shown in FIG. 4, and FIG. 5 shows the L i/L iFePO assembly of the two-layer interface-protected lithium metal anodes prepared in example 1 and comparative example4The cycle comparison of the battery shows that the lithium sheet of the invention can maintain L i/L iFePO4Long term stable cycling of the cell the double layer interface protected lithium metal negative electrode of the present invention was stable in air and fig. 6 is a diagram of the reassembly of L i/L iFePO after exposing the double layer interface protected lithium metal negative electrode of example 1 and the conventional lithium sheet of the comparative example to air for 30min4The comparison of the battery cycles measured by the battery shows that the performance of the battery is severely attenuated due to the fact that the common lithium sheet is completely oxidized, the double-layer interface protects the lithium metal negative electrode from influencing the electrochemical performance after being exposed in the air for 30min, and the excellent cycle stability can be still maintained. FIG. 7 is a bilayer interface made in example 1Solid L i/L iFePO assembled separately from a lithium metal negative electrode and a conventional lithium sheet of comparative example4The comparison of the battery cycle shows that the double-layer interface protection lithium metal cathode of the invention has obvious effect on maintaining the cycle stability of the solid-state battery, and the L i/S and L i/L iCoO assembled by the double-layer interface protection lithium metal cathode prepared in example 1 are respectively shown in FIG. 8 and FIG. 92The cycling comparison of the cell to a corresponding comparative cell illustrates that the two-layer interface-protected lithium metal anode of the present invention can also remain based on sulfur and L iCoO2Cycling stability of the cell of the positive electrode material. In order to prove that the formed double-layer interface structure can still exist stably after the long-term process of the battery, the battery in example 1 is disassembled after being cycled for 100 times, and the appearance of the lithium metal surface is observed by using SEM. Similarly, the battery of the comparative example was disassembled after 100 cycles and analyzed for surface morphology. Fig. 10 is a comparison of the two morphologies, and it can be seen that the double-layer interface protection lithium metal negative electrode of the present invention can maintain the original flat structure after long-term cycling, and no formation of lithium dendrite is found on the surface. While the lithium sheet of the comparative example had a large amount of dendritic lithium formed on the surface after long-term cycling. An organic/inorganic double-layer interface layer is formed on the surface of the metal lithium, wherein the bottom inorganic layer has high Young modulus, so that the growth of lithium dendrites can be effectively inhibited; the upper organic layer has excellent viscoelasticity, and can relieve the volume change of lithium metal in the electroplating/stripping process. In addition, the organic/inorganic composite protective layer can make the treated lithium sheet stably exist in the air. When the lithium ion battery is used for the lithium metal battery, the cycle performance and the safety performance of the lithium metal battery can be greatly improved. The method has the advantages of simple preparation, cheap and easily-obtained raw materials, suitability for large-scale production and good application prospect.
The two-layer interface-protected lithium metal anodes prepared in examples 1-14 and comparative examples 1-3 were used as L i/L iFePO4The battery performance test of the battery negative electrode is carried out, the result is shown in table 1, and it can be seen that the battery negative electrode still maintains higher capacity after 150 circles, and has good cycle performance and safety performance.
TABLE 1 lithium metal anodes in examples 1-14, comparative examples 1-3 are identified as L i/L iFePO4Battery with a battery cellPerformance table of negative electrode
The above examples are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A method for constructing a double-layer protection interface on the surface of a lithium metal negative electrode is characterized by comprising the following steps:
(a) carrying out esterification reaction on polyphosphoric acid and polyhydric alcohol to form polyphosphoric acid ester;
(b) adding the polyphosphate into an organic solvent to prepare an ester treatment fluid;
(c) and immersing the lithium metal sheet into the ester treatment liquid for etching reaction.
2. The method for forming a double-layer protective interface on the surface of a lithium metal negative electrode according to claim 1, further comprising:
(d) and (c) cleaning the lithium metal sheet treated in the step (c) by using an anhydrous solvent, removing residual liquid on the surface of the lithium metal sheet, and drying the lithium metal sheet under a vacuum condition.
3. The method for constructing the double-layer protection interface on the surface of the lithium metal negative electrode as claimed in claim 1, wherein: in the step (a), the polyhydric alcohol is a mixture of one or more selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, xylitol, sorbitol, sucrose, pentaerythritol, polyoxypropylene glycol and polytetrahydrofuran glycol.
4. The method for constructing the double-layer protection interface on the surface of the lithium metal negative electrode as claimed in claim 1, wherein: in the step (a), the molar ratio of the polyphosphoric acid to the polyol is 1:1 to 6.
5. The method for constructing the double-layer protection interface on the surface of the lithium metal negative electrode as claimed in claim 1 or 4, wherein: in the step (a), the reaction temperature of the esterification reaction is 60-200 ℃, and the reaction time is 30 min-24 h.
6. The method for constructing the double-layer protection interface on the surface of the lithium metal negative electrode as claimed in claim 1, wherein: in the step (b), the organic solvent is a mixture of one or more selected from cyclohexane, tetrahydrofuran, N-methylpyrrolidone, acetone and dimethylformamide.
7. The method for constructing the double-layer protection interface on the surface of the lithium metal negative electrode as claimed in claim 1 or 6, wherein: in the step (b), the mass concentration of the polyphosphate in the ester treatment liquid is 0.1-10%.
8. The method for constructing the double-layer protection interface on the surface of the lithium metal negative electrode as claimed in claim 1, wherein: in the step (c), the etching reaction time is 30 min-8 h.
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