CN113437297A - Metallic lithium negative electrode, preparation method thereof and lithium battery - Google Patents

Metallic lithium negative electrode, preparation method thereof and lithium battery Download PDF

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CN113437297A
CN113437297A CN202010209024.3A CN202010209024A CN113437297A CN 113437297 A CN113437297 A CN 113437297A CN 202010209024 A CN202010209024 A CN 202010209024A CN 113437297 A CN113437297 A CN 113437297A
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lithium
metal
negative electrode
anode
inorganic particles
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CN113437297B (en
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张露露
郭姿珠
谢静
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BYD 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present disclosure relates to a lithium metal negative electrode, a method of preparing the same, and a lithium battery, the lithium metal negative electrode includes a negative electrode current collector and a negative electrode protective layer, the negative electrode protective layer contains an organic polymer and inorganic particles; the inorganic particles comprise an inner core and an outer shell, and the outer shell covers part of the outer surface of the inner core; the inner core contains halogenated lithium salt, and the outer shell contains one or more of transition metal oxide, magnesium oxide and aluminum oxide. Lithium batteries containing the lithium metal anodes of the present disclosure have good cycling stability and coulombic efficiency.

Description

Metallic lithium negative electrode, preparation method thereof and lithium battery
Technical Field
The disclosure relates to the field of lithium ion batteries, in particular to a metal lithium cathode, a preparation method thereof and a lithium battery.
Background
The battery taking the metal lithium as the negative electrode has higher energy density and attracts much attention compared with the traditional lithium ion battery, but the battery has the problems of short circuit, low coulombic efficiency and the like in the using process. The current research is directed to the use of a lithium negative electrode protective layer to solve the above problems. In 2019, professor francisco Ciucci, hong kong science and technology university, introduced a LiF protective layer (j.mater.chem.a,2019,7,17995) generated in situ during cycling by using FEC, and the lithium battery having the protective layer had high stability. However, when FEC is used as an additive, FEC is reduced during cycling to generate LiF in situ with lithium metal. In-situ generated LiF has a uniform and sustained protective effect, but the coulombic efficiency of the battery is low because its generation process consumes Li.
Disclosure of Invention
The purpose of the disclosure is to provide a lithium metal negative electrode, a preparation method thereof and a lithium battery, aiming at overcoming the problems of poor cycle performance and low coulombic efficiency of the existing lithium metal negative electrode battery.
In order to achieve the above object, a first aspect of the present disclosure provides a lithium metal anode including an anode current collector and an anode protective layer containing an organic polymer and inorganic particles; the inorganic particles comprise an inner core and an outer shell, wherein the outer shell covers part of the outer surface of the inner core; the inner core contains halogenated lithium salt, and the outer shell contains one or more of transition metal oxide, magnesium oxide and aluminum oxide.
Optionally, the surface area of the coated inner core is 60-80% based on the total surface area of the inner core.
Optionally, the inner core has a diameter of 10-20nm and the outer shell has a thickness of 3-7 nm.
Optionally, the inorganic particles are present in an amount of 15 to 20 wt%, based on the total weight of the negative electrode protective layer.
Optionally, the thickness of the negative electrode protection layer is 1-15 μm; the negative current collector is a metal lithium sheet, a lithium foil or a lithium-loaded copper foil.
Optionally, the halogenated lithium salt is selected from one or more of lithium fluoride, lithium chloride, lithium bromide and lithium iodide; the transition metal oxide is selected from one or more of zinc oxide, manganese oxide and iron oxide;
the organic polymer is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, perfluorosulfonic acid polymer, polyimide, styrene-butadiene rubber and poly (vinylidene fluoride-co-trifluoroethylene).
Optionally, the negative electrode protective layer further contains a lithium salt;
the lithium salt is selected from LiPF6、LiFSI、LiTFSI、LiNO3、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2And LiN (C)4F9SO2)(CF3SO3) One or more of them.
A second aspect of the present disclosure provides a method of preparing a lithium metal anode provided by the first aspect of the present disclosure, the method comprising:
s1, mixing nitrate and halogenated lithium salt of metal with a first solvent to obtain a first solution; wherein, the metal is selected from one or more of transition metal, magnesium and aluminum;
s2, reacting the first solution with a second solution containing urea at the temperature of 80-100 ℃, and performing first drying to obtain solid powder;
s3, calcining the solid powder in an inert atmosphere to obtain inorganic particles;
and S4, mixing the inorganic particles, the organic polymer and a second solvent, coating the obtained mixed slurry on the negative electrode current collector, and performing second drying to obtain the lithium metal negative electrode.
Alternatively, in step S1, the molar ratio of the metal nitrate to the lithium halide salt is 1: (30-70), wherein the nitrate salt of the metal is in moles of metal and the lithium halide salt is in moles of lithium;
in step S3, the calcination temperature is 500-900 ℃ and the calcination time is 1-5 hours;
in step S4, the inorganic particles are used in an amount of 15 to 20 parts by weight, relative to 100 parts by weight of the organic polymer.
Optionally, the nitrate of the transition metal is selected from one or more of zinc nitrate, manganese nitrate and ferric nitrate;
the halogenated lithium salt is selected from one or more of lithium fluoride, lithium chloride, lithium bromide and lithium iodide;
the first solvent is ethylene glycol and/or ethanol;
the second solvent is N, N-dimethylacetamide and/or N, N-dimethylformamide.
A third aspect of the present disclosure provides a lithium battery comprising an electrolyte, a positive electrode, and a metallic lithium negative electrode provided by the first aspect of the present disclosure.
Through the technical scheme, the negative electrode protection layer of the metal lithium negative electrode disclosed by the invention contains the inorganic particles, the inorganic particles are provided with an inner core containing halogenated lithium salt and an outer shell partially coated on the surface of the inner core, the halogenated lithium salt of the inner core can continuously participate in the formation of an SEI film, the loss of active lithium is avoided, and the battery with the metal lithium negative electrode disclosed by the invention has good cycle performance and coulombic efficiency.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is a schematic diagram of the structure of an inorganic particle of the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides, in a first aspect, a lithium metal anode comprising an anode current collector and an anode protective layer, the anode protective layer containing an organic polymer and inorganic particles; the inorganic particles comprise an inner core and an outer shell, and the outer shell covers part of the outer surface of the inner core; the inner core contains halogenated lithium salt, and the outer shell contains one or more of transition metal oxide, magnesium oxide and aluminum oxide.
The negative electrode protective layer is coated on the negative electrode current collector, can be a porous protective layer or a compact protective layer, and when the protective layer is a porous protective layer, the size and the porosity of the pore diameter are not particularly limited and can be selected according to actual needs. The outer shell covers part of the outer surface of the inner core, which means that the inner core is not completely covered by the outer shell, but the outer surface of the inner core is covered by the outer shell, and the outer shell can be continuous or discontinuous, and is not limited.
The lithium metal cathode comprises a cathode protective layer, wherein the surface of the core part of inorganic particles is coated by a shell, and the shell can prevent direct contact of electrolyte and halogenated lithium salt in the core to a certain extent, so that the rapid consumption of the halogenated lithium salt caused by the generation of an SEI film is greatly reduced, the effective components of the cathode protective layer are effectively reserved, and the halogenated lithium salt can continuously participate in the formation of the SEI film; meanwhile, the halogenated lithium salt participates in the formation of an SEI film, and the loss of active lithium in the battery can be effectively avoided. The negative electrode protection layer of the present disclosure can improve the cycling stability and coulombic efficiency of the battery.
In accordance with the present disclosure, the surface area of the coated core of the inorganic particles, which in one embodiment is 60 to 80%, preferably 65 to 75%, based on the total surface area of the core, has a significant effect on the properties of the negative electrode protective layer. Within the above range, the area of the coated core is suitable, so that direct contact between the halogenated lithium salt and the electrolyte can be effectively blocked, and the halogenated lithium salt can continuously participate in the generation process of the SEI film, so that the battery containing the negative electrode protection layer disclosed by the invention has better cycle stability and coulombic efficiency.
The diameter of the inner core and the thickness of the outer shell of the inorganic particles may vary over a wide range in accordance with the present disclosure. Preferably, the diameter of the inner core may be 10-20nm, and the thickness of the outer shell may be 3-7 nm; preferably, the inner core has a diameter of 10-15nm and the outer shell has a thickness of 3-5 nm. Wherein the diameter of the core and the thickness of the shell can be determined by observing Transmission Electron Microscope (TEM) images. In the above preferred ranges, it is possible to make the battery containing the anode protective layer of the present disclosure have more excellent cycle stability and coulombic efficiency.
According to the present disclosure, in the anode protective layer of the present disclosure, the content of the inorganic particles may vary within a wide range, and preferably, the content of the inorganic particles is 15 to 20 wt%, more preferably 18 to 20 wt%, based on the total weight of the anode protective layer.
The thickness of the negative electrode protective layer may vary within wide limits according to the present disclosure, and in one embodiment the thickness of the negative electrode protective layer is 1-15 μm, preferably 2-5 μm.
According to the present disclosure, the negative electrode current collector may be a metallic lithium sheet, a lithium foil or a lithium-loaded copper foil, the lithium-loaded copper foil has no particular requirement on the capacity of lithium, the thickness of the negative electrode current collector may vary within a wide range, for example, may be 5 to 12 μm, and a negative electrode protective layer is coated on the negative electrode current collector.
According to the present disclosure, a halogenated lithium salt refers to a lithium salt containing halogen selected from one or more of F, Cl, Br and I. In a preferred embodiment, the halogenated lithium salt is selected from one or more of lithium fluoride, lithium chloride, lithium bromide and lithium iodide; the transition metal in the transition metal oxide is well known to those skilled in the art, and may be, for example, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pt, or the like, preferably Zn, Mn, Fe. In a preferred embodiment, the transition metal oxide is selected from one or more of zinc oxide, manganese oxide and iron oxide. The present disclosure does not require the crystalline form of the halogenated lithium salt and the transition metal oxides, magnesium oxide and aluminum oxide.
Organic polymers are well known to those skilled in the art in light of this disclosure and may be selected from, for example, one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, perfluorosulfonic acid polymers, polyimide, styrene butadiene rubber, and poly (vinylidene fluoride-co-trifluoroethylene). Wherein poly (vinylidene fluoride)Alkene-co-trifluoroethylene) refers to a copolymer of vinylidene fluoride and trifluoroethylene, and the poly (vinylidene fluoride-co-trifluoroethylene) can be chosen from those having the production trade name Solven@200、Solvene@250 and Solven@300, or a plurality of the same. The crystal form of the organic polymer is not required, and for example, the organic polymer can be one or more of an organic polymer of an alpha crystal form, an organic polymer of a beta crystal form and an organic polymer of a gamma crystal form.
According to the present disclosure, in order to further enhance the protective effect of the negative electrode protective layer, the negative electrode protective layer may further contain a lithium salt. The lithium salt may be conventionally used by those skilled in the art and may be selected from, for example, LiPF6、LiFSI、LiTFSI、LiNO3、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2And LiN (C)4F9SO2)(CF3SO3) To compensate for the loss of active lithium and to further improve the cycling performance and coulombic efficiency of the battery.
A second aspect of the present disclosure provides a method of preparing a lithium metal anode provided by the first aspect of the present disclosure, the method comprising:
s1, mixing nitrate and halogenated lithium salt of metal with a first solvent to obtain a first solution; wherein, the metal is selected from one or more of transition metal, magnesium and aluminum;
s2, reacting the first solution with a second solution containing urea at the temperature of 80-100 ℃, and performing first drying to obtain solid powder;
s3, calcining the solid powder in an inert atmosphere to obtain inorganic particles;
and S4, mixing the inorganic particles, the organic polymer and a second solvent, coating the obtained mixed slurry on a negative electrode current collector, and performing second drying to obtain the lithium metal negative electrode.
The method comprises the steps of mixing a precursor substance (halogenated lithium salt) of a core and a precursor substance (metal nitrate) of a shell with a first solvent, wherein the nucleation energy of the halogenated lithium salt is low and can be firstly nucleated due to different nucleation energies and intermolecular forces of the metal nitrate and the halogenated lithium salt, the nucleation energy of the metal nitrate is high and can be adsorbed on a core outer layer formed by the halogenated lithium salt, and the metal nitrate on the outer layer reacts with ammonia water, and then is dried and calcined at high temperature to obtain the inorganic particles with the core-shell structure. The lithium metal cathode prepared by the method has good cycle performance and coulombic efficiency.
In one embodiment, in step S1, the nitrate of the metal is mixed with the first solvent, and then the lithium halide salt is added. The mixing temperature and time in step S1 are not particularly limited, and for example, it is preferable that the temperature is 10 to 60 ℃ and the time is 1 to 5 hours.
According to the present disclosure, in step S1, the molar ratio of the metal nitrate to the lithium halide salt may vary within a wide range, preferably 1: (30-70), more preferably 1: (40-60), more preferably 1: (45-55), wherein the nitrate of the metal is calculated by the mole number of the metal, and the halogenated lithium salt is calculated by the mole number of lithium.
In one embodiment, in step S2, the second solution containing urea is gradually dropped into the first solution, and the resulting mixture is washed with ethanol and/or deionized water and then subjected to first drying. The temperature of the first drying may be 60 to 100 ℃ and the time may be 1 to 10 hours. Wherein the mass concentration of urea in the second solution may vary within a wide range, preferably from 5 to 20 wt.%, more preferably from 10 to 15 wt.%, and the weight ratio of urea in the second solution to metal in the metal nitrate salt in the first solution may be 1: (0.5-4), preferably 1: (1-2).
According to the present disclosure, in step S3, the calcination temperature may be 500-900 ℃ for 1-5 hours, and preferably, the calcination temperature is 600-800 ℃ for 1-3 hours. The calcination may be carried out by means of equipment known to those skilled in the art, and may be, for example, a muffle furnace or a tube furnace. Inert atmospheres are well known to those skilled in the art and may be, for example, argon, nitrogen, helium.
According to the present disclosure, in step S4, the inorganic particles may be used in an amount of 15 to 20 parts by weight, preferably 18 to 20 parts by weight, with respect to 100 parts by weight of the organic polymer. The temperature of the second drying may be 60-100 deg.C, and the time may be 12-24 hours.
According to the present disclosure, the nitrate of the transition metal may be selected from one or more of zinc nitrate, manganese nitrate and iron nitrate, the nitrate of magnesium is magnesium nitrate, and the nitrate of aluminum is aluminum nitrate; the halogenated lithium salt can be one or more selected from lithium fluoride, lithium chloride, lithium bromide and lithium iodide; the first solvent may be ethylene glycol and/or ethanol; the second solvent may be N, N-dimethylacetamide and/or N, N-dimethylformamide. The amount of the first solvent is not particularly limited, as long as the metal nitrate can be dissolved and the halogenated lithium salt can be dispersed; the amount of the second solvent used is also not particularly limited as long as the inorganic particles and the organic polymer can be dispersed.
A third aspect of the present disclosure provides a lithium battery comprising an electrolyte, a positive electrode, and a metallic lithium negative electrode provided by the first aspect of the present disclosure.
Wherein the positive electrode comprises a positive electrode current collector and a positive electrode active material, and in one embodiment, the positive electrode active material is selected from the group consisting of LiFexMnyMzPO4(x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and x + y + z is 1, wherein M is at least one of Al, Mg, Ga, Ti, Cr, Cu, Zn and Mo), Li3V2(PO4)3、Li3V3(PO4)3、LiNi0.5-xMn1.5-yMx+yO4X is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 1.5, M is at least one of Li, Co, Fe, Al, Mg, Ca, Ti, Mo, Cr, Cu and Zn), and LiVPO4F、Li1+xL1－y－zMyNzO2(L, M, N represents Li, Co, Mn)At least one of Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B, -0.1-0.2 x, 0-1 y, 0-1 z, 0-1 y + z 1.0), Li2CuO2And Li5FeO4One or more of; preferably, the positive active material is selected from LiAl0.05Co0.15Ni0.80O2、LiNi0.80Co0.10Mn0.10O2、LiNi0.60Co0.20Mn0.20O2、LiCoO2、LiMn2O4、LiFePO4、LiMnPO4、LiNiPO4、LiCoPO4、LiNi0.5Mn1.5O4And Li3V3(PO4)3And the like.
According to the present disclosure, the electrolyte contains a solvent and a lithium salt, and the solvent may have one or more of the following groups: ether groups, nitrile groups, cyanide groups, fluorine ester groups, tetrazolyl groups, fluorosulfonyl groups, chlorosulfonyl groups, nitro groups, carbonate groups, dicarbonate groups, nitrate groups, fluoroamide groups, diketone groups, azole groups, and triazine groups. The lithium salt may be selected from LiPF6、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2And LiN (C)4F9SO2)(CF3SO3) One or more of them.
The specific preparation method of the lithium metal negative electrode battery is not particularly limited in the present disclosure, and a conventional preparation method of a lithium battery in the field may be adopted; the battery cell is obtained by sealing a battery cell in a battery shell; the preparation of the battery cell is a preparation method of the battery cell in the conventional lithium battery in the field, and is not particularly limited.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
The starting materials in the examples and comparative examples were obtained commercially.
Example 1
S1, mixing 0.05g of Al (NO)3)3Adding the mixture into 40mL of glycol, and stirring and dissolving the mixture at room temperature; then 0.3g LiF (diameter is 12nm) is added into the solution and stirred for 1 hour to obtain a first solution;
s2, dropwise adding 0.1g of urea solution (the mass concentration of urea is 10 wt%) into the first solution, heating to 100 ℃, stirring for 3 hours, sequentially washing the obtained solution with ethanol and deionized water until organic matters are washed clean, and then drying at 80 ℃ for 5 hours to obtain solid powder;
s3, calcining the obtained solid powder in a tube furnace at 700 ℃ for 2 hours under an argon atmosphere to obtain inorganic particles.
S4, dissolving PVDF in N, N-dimethylacetamide (DMAc), stirring until the PVDF is completely dissolved, enabling the concentration of the PVDF to be 10 wt%, adding a certain amount of inorganic particles, enabling the amount of the inorganic particles to be 19% of the total weight of the PVDF, continuing stirring, uniformly mixing to form stable and uniform slurry, coating the obtained slurry on a current collector lithium foil, and drying in an oven at 60 ℃ for 3 hours to obtain the lithium foil covered with a negative electrode protection layer, namely the metal lithium negative electrode A.
The ratio of the core to be coated in the inorganic particles and the thickness of the shell were measured by a Transmission Electron Microscope (TEM), and the measurement method was: clear particles are found in the visual field of a transmission electron microscope, the thickness of the shell and the coating proportion are automatically measured and read by a computer by selecting a scale, the measurement is continued by changing different visual fields, and the average value is obtained by measuring 50 particles in total, and the measurement result is shown in table 1. The schematic structure of the inorganic particles prepared in this example is shown in fig. 1.
Example 2
A lithium metal negative electrode B was produced in the same manner as in example 1, except that, in step S1, 0.02g of Al (NO) was added3)3Added to 40mL of ethylene glycol.
Example 3
A lithium metal negative electrode C was produced in the same manner as in example 1, except that, in step S1, 0.09g of Al (NO) was added3)3Added to 40mL of ethylene glycol.
Example 4
A lithium metal negative electrode D was produced in the same manner as in example 1, except that in step S3, the resulting solid powder was calcined in a tube furnace at 400 ℃ for 1 hour under an argon atmosphere.
Example 5
A lithium metal negative electrode E was prepared in the same manner as in example 1, except that, in step S4, PVDF was dissolved in N, N-dimethylacetamide (DMAc) and stirred until completely dissolved so that the concentration of PVDF was 10 wt%, a certain amount of inorganic particles was added, the inorganic particles were 10 wt% of the total weight of PVDF, and stirring was continued and uniformly mixed to form a stable and uniform slurry.
Example 6
Preparing a lithium metal negative electrode F by the same method as in example 1, except that in step S4, PVDF is dissolved in N, N-dimethylacetamide (DMAc) and stirred until the PVDF is completely dissolved, so that the concentration of the PVDF is 4 wt%, a certain amount of inorganic particles is added, the inorganic particles account for 19 wt% of the total weight of the PVDF, and the mixture is continuously stirred and uniformly mixed to form stable and uniform slurry; and coating the obtained slurry on a current collector lithium foil, and drying in an oven at 60 ℃ for 3 hours to obtain the lithium foil coated with the negative electrode protective layer, namely the metal lithium negative electrode F.
Example 7
S1, mixing 0.06g Fe (NO)3)3The mixture was added to 50mL of ethylene glycol and dissolved with stirring at room temperature. Adding 1.00g of LiBr (the diameter is 16nm) into the solution, and stirring for 1 hour to obtain a first solution;
s2, dropwise adding 0.1g of urea solution (the mass concentration of urea is 10 wt%) into the first solution, heating to 100 ℃, stirring for 4 hours, sequentially washing the obtained solution with ethanol and deionized water until organic matters are washed clean, and then drying at 90 ℃ to obtain solid powder;
s3, calcining the obtained solid powder in a tube furnace at 800 ℃ for 2.5 hours under an argon atmosphere to obtain inorganic particles.
S4, dissolving PVDF in N, N-dimethylacetamide (DMAc), stirring until the PVDF is completely dissolved, enabling the concentration of the PVDF to be 12 wt%, adding a certain amount of inorganic particles, wherein the inorganic particles account for 18 wt% of the total weight of the PVDF, continuously stirring, uniformly mixing to form stable and uniform slurry, then coating the obtained slurry on a current collector lithium foil, and drying in an oven at 80 ℃ to obtain a lithium foil covered with a negative electrode protection layer, namely a metal lithium negative electrode F.
Comparative example 1
Dissolving a certain amount of PVDF in N, N-dimethylacetamide (DMAc), wherein the concentration of the PVDF is 10%, stirring until the PVDF is completely dissolved, adding a certain amount of LiF (with the diameter of 12nm) particles, wherein the dosage of the LiF particles is 19% of the total weight of the PVDF, continuously stirring, uniformly mixing to form stable and uniform slurry, then coating the obtained slurry on a current collector lithium foil, and drying in a 60 ℃ oven to obtain the lithium foil covered with a negative electrode protective layer, namely a metal lithium negative electrode a.
Comparative example 2
Dissolving a certain amount of PVDF in N, N-dimethylacetamide (DMAc), stirring until the concentration of PVDF is 10%, completely dissolving the PVDF, and adding a certain amount of LiF (with the diameter of 12nm) particles and Al2O3The dosage of the LiF particles is 10 percent of the total weight of the PVDF, and the Al content is2O3The amount of the particles is 10% of the total weight of PVDF, the particles are continuously stirred and uniformly mixed to form stable and uniform slurry, then the obtained slurry is coated on a current collector lithium foil and dried in a 60 ℃ oven, and the lithium foil coated with a composite protective layer, namely the metal lithium cathode b, is obtained.
Comparative example 3
A lithium metal negative electrode c was produced in the same manner as in example 1, except that, in step S1, 0.1g of Al (NO) was added3)3Adding the mixture into 40mL of glycol, and stirring and dissolving the mixture at room temperature; then, 0.3g of LiF was added to the solution, and stirred for 1 hour to obtain a first solution.
Test example
(1) And (3) testing the cycle performance:
the lithium cathodes prepared in examples 1 to 7 and comparative examples 1 to 3 and the ternary cathode material were assembled into a cathode vs Li laminated battery, and the battery was subjected to a cyclic charge-discharge performance test at room temperature using a blue tester with a test parameter of 0.5C for constant current charging to 4.2V, and then 0.5C for constant current discharging to 3V, to evaluate the cycle life of the battery.
(2) And (3) rate performance test:
the slurries prepared in examples 1 to 7 and comparative examples 1 to 3 were coated on copper foils and dried in an oven at 60 c to obtain protective layer-coated copper foils.
Cutting the copper foil into pole pieces with the diameter of 17mm, adding two PE diaphragms with the diameter of 19mm, adding lithium foil with the diameter of 15mm, applying pressure of 0.1-1Mpa to compress the two PE diaphragms, and packaging the two PE diaphragms in a button cell shell to obtain the Li vs Cu cell. Using 1mA cm-2The lithium deposition was performed at a current density of (1), and the morphology and the site of the lithium metal deposition were observed by SEM. And (4) testing the coulombic efficiency of the battery by using cyclic charge and discharge, and calculating the average coulombic efficiency of every 10 cycles of charge and discharge cycles until 100 cycles.
The test results of the above tests are shown in table 2.
TABLE 1
Figure BDA0002422171650000121
Figure BDA0002422171650000131
TABLE 2
Lithium negative electrode numbering Average coulomb efficiency,% Capacity is maintained at 80% cycle number, circle
A 99.46 140
B 99.42 117
C 99.41 115
D 99.42 120
E 99.43 130
F 99.41 116
G 99.43 129
a 99.38 108
b 99.39 110
c 99.40 112
The method disclosed by the invention can be used for preparing the metal lithium cathode with higher stability, and the lithium battery containing the lithium cathode disclosed by the invention has good cycling stability and rate capability.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (11)

1. A lithium metal anode comprising an anode current collector and an anode protective layer, wherein the anode protective layer comprises an organic polymer and inorganic particles; the inorganic particles comprise an inner core and an outer shell, wherein the outer shell covers part of the outer surface of the inner core; the inner core contains halogenated lithium salt, and the outer shell contains one or more of transition metal oxide, magnesium oxide and aluminum oxide.
2. The lithium metal anode of claim 1, wherein the surface area of the coated core is 60-80% based on the total surface area of the core.
3. The lithium metal anode of claim 1, wherein the diameter of the core is 10-20nm and the thickness of the shell is 3-7 nm.
4. The lithium metal anode of claim 1, wherein the inorganic particles are present in an amount of 15 to 20 wt.%, based on the total weight of the anode protective layer.
5. The lithium metal anode of claim 1, wherein the anode protective layer has a thickness of 1 to 15 μ ι η; the negative current collector is a metal lithium sheet, a lithium foil or a lithium-loaded copper foil.
6. The lithium metal anode of claim 1, wherein the halogenated lithium salt is selected from one or more of lithium fluoride, lithium chloride, lithium bromide and lithium iodide; the transition metal oxide is selected from one or more of zinc oxide, manganese oxide and iron oxide;
the organic polymer is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, perfluorosulfonic acid polymer, polyimide, styrene-butadiene rubber and poly (vinylidene fluoride-co-trifluoroethylene).
7. The lithium metal anode of claim 1, wherein the anode protective layer further comprises a lithium salt;
the lithium salt is selected from LiPF6、LiFSI、LiTFSI、LiNO3、LiAsF6、LiClO4、LiBF6、LiN(CF3SO3)2、LiCF3SO3、LiC(CF3SO3)2And LiN (C)4F9SO2)(CF3SO3) One or more of them.
8. A method of preparing a lithium metal anode according to any one of claims 1 to 7, characterized in that the method comprises:
s1, mixing nitrate and halogenated lithium salt of metal with a first solvent to obtain a first solution; wherein, the metal is selected from one or more of transition metal, magnesium and aluminum;
s2, reacting the first solution with a second solution containing urea at the temperature of 80-100 ℃, and performing first drying to obtain solid powder;
s3, calcining the solid powder in an inert atmosphere to obtain inorganic particles;
and S4, mixing the inorganic particles, the organic polymer and a second solvent, coating the obtained mixed slurry on the negative electrode current collector, and performing second drying to obtain the lithium metal negative electrode.
9. The method according to claim 8, wherein in step S1, the molar ratio of the metal nitrate to the lithium halide salt is 1: (30-70), wherein the nitrate salt of the metal is in moles of metal and the lithium halide salt is in moles of lithium;
in step S3, the calcination temperature is 500-900 ℃ and the calcination time is 1-5 hours;
in step S4, the inorganic particles are used in an amount of 15 to 20 parts by weight, relative to 100 parts by weight of the organic polymer.
10. The method according to claim 8, wherein the nitrate of the transition metal is selected from one or more of zinc nitrate, manganese nitrate and iron nitrate;
the halogenated lithium salt is selected from one or more of lithium fluoride, lithium chloride, lithium bromide and lithium iodide;
the first solvent is ethylene glycol and/or ethanol;
the second solvent is N, N-dimethylacetamide and/or N, N-dimethylformamide.
11. A lithium battery comprising an electrolyte, a positive electrode and a lithium metal negative electrode according to any one of claims 1 to 7.
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