CN110783529A - Lithium metal cathode for secondary battery and preparation and application thereof - Google Patents

Lithium metal cathode for secondary battery and preparation and application thereof Download PDF

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CN110783529A
CN110783529A CN201810859419.0A CN201810859419A CN110783529A CN 110783529 A CN110783529 A CN 110783529A CN 201810859419 A CN201810859419 A CN 201810859419A CN 110783529 A CN110783529 A CN 110783529A
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bismuth
lithium
compound
current collector
negative electrode
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CN110783529B (en
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赖延清
洪波
董庆元
覃昭铭
范海林
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • 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
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    • 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 belongs to the field of lithium secondary battery cathode materials, and particularly discloses a lithium metal cathode for a secondary battery, which comprises a current collector, a lithium bismuth alloy substrate layer compounded on the current collector, and a lithium compound layer compounded on the surface of the lithium bismuth alloy substrate layer. The invention also discloses a preparation method of the metallic lithium cathode for the secondary battery, which comprises the steps of slurrying the bismuth compound, the conductive agent and the binder, then compounding the slurried bismuth compound, the conductive agent and the binder on the surface of the current collector, and then reacting the bismuth compound compounded on the current collector with metallic lithium to prepare the metallic lithium cathode for the secondary battery. The invention originally discovers that an effective lithium bismuth alloy is generated through the chemical reaction of the bismuth compound and metallic lithium; the method promotes the uniform growth of the metallic lithium in the bismuth framework, and simultaneously produces an effective SEI film, protects the metallic lithium, avoids the generation of lithium dendrites, thereby improving the charge-discharge coulombic efficiency and the cycle life of the metallic lithium cathode.

Description

Lithium metal cathode for secondary battery and preparation and application thereof
Technical Field
The invention belongs to the field of new energy devices, and particularly relates to a novel metal lithium cathode for a secondary battery.
Background
With the rise of new energy fields, battery materials are receiving more and more attention. Metallic lithium relies on a high theoretical specific capacity (3860mAh/g), a lowest electrode potential (-3.040V vs. SHE), and a low density (0.53 g/cm) 3) The lithium ion battery is an ideal negative electrode material in a lithium battery. However, lithium dendrites are growing and the safety hazards that arise from them limit their commercial applications. Because the activity of the metal lithium is high, lithium dendrite grows in the charge-discharge cycle process, the battery short circuit and the coulombic efficiency are low, and the application of the metal lithium is restricted. The main effective methods at present are: modification of electrolyte, application of 3D current collectors, solid electrolyte applications, artificial SEI films, and the like.
For example: yang et al also realize good lithium storage performance by preparing porous copper through dealloying Cu-Zn alloy as a 3D current collector, but only improve the specific surface area, so that more metal lithium is exposed in the electrolyte without the protection of an SEI film, and the excellent performance of a lithium cathode is not enough to be realized [1 ]. Also the design of artificial SEI films is as follows: y Cao et Al uniformly coat Al2O3 on the surface of the lithium metal by a molecular deposition technology, effectively protect the lithium metal and inhibit the growth of lithium dendrites, but the artificial SEI film has large internal resistance and more side reactions, so that the coulombic efficiency of the battery cannot be improved.
[1]YANG C-P，YIN Y-X，ZHANG S-F，et al.Accommodating lithium into 3Dcurrent collectors with a submicronskeleton towards long-life lithium metalanodes[J].2015，6(8058)
[2]CaoY，Meng X，Elam JW.Atomic Layer Deposition of LixAlyS Solid-StateElectrolytes for Stabilizing Lithium-Metal Anodes[J].Chemelectrochem，2016，3(6)：858-863.
Disclosure of Invention
In order to solve the technical defects of the conventional lithium negative electrode, the invention starts from an alloyed lithium metal negative electrode, modifies the lithium metal negative electrode, and keeps long cycle and high coulombic efficiency.
The second purpose of the invention is to provide a preparation method of the negative electrode.
The third purpose of the invention is to provide the application of the lithium metal negative electrode.
A lithium metal negative electrode for a secondary battery (also referred to as a lithium metal negative electrode for short in the invention) comprises a current collector, a lithium bismuth alloy substrate layer compounded on the current collector, and a lithium compound layer compounded on the surface of the lithium bismuth alloy substrate layer.
The lithium bismuth alloy is innovatively adopted as the substrate, the lithium compound layer is compounded on the substrate, the lithium metal negative electrode with the components and the structure can promote the uniform growth of the lithium metal in the bismuth framework, and is beneficial to avoiding the generation of lithium dendrites, meanwhile, an in-situ SEI film generated on the surface of the lithium bismuth alloy can stably exist in the electrolyte, the contact between the lithium metal negative electrode and the electrolyte is blocked, the occurrence of side reactions is effectively reduced, and therefore the charging and discharging coulomb efficiency and the cycle life of the lithium metal negative electrode are improved.
Preferably, the material of the lithium bismuth alloy substrate layer is Li 3Bi and/or LiBi.
Preferably, the lithium compound layer is at least one of an oxide, a sulfide, a chloride, a nitride, a phosphide and a fluoride of lithium.
More preferably, the lithium compound layer is Li 2O、LiCl、Li 2S、Li 3N、Li 3P, LiF.
The current collector is a metal current collector, preferably at least one of copper, stainless steel, nickel and titanium.
Preferably, the thickness of the current collector is 10 to 20 micrometers, and more preferably 15 micrometers.
Preferably, the thickness of the lithium bismuth alloy substrate layer is 5 micrometers to 40 micrometers. Preferably, the thickness of the lithium compound layer is 5 nm to 500 nm.
The lithium metal negative electrode for a secondary battery further contains additional components, such as a conductive agent, a binder, and the like, which are allowable to be added to conventional lithium metal negative electrodes. The conductive agent can be compounded in the lithium bismuth alloy substrate layer.
The lithium metal negative electrode for the secondary battery comprises a current collector and an active substance compounded on the current collector, wherein the active substance is a reaction product of a bismuth compound and lithium metal; among them, the compound of bismuth is preferably bismuth (Bi) trioxide 2O 3) Bismuth trichloride (BiCl) 3) Bismuth trisulfide (Bi) 2S 3) Bismuth disulfide (BiS) 2) Bismuth phosphide (Bi) 3P), bismuth fluoride (BiF), bismuth nitride (Bi) 3N).
Another innovation of the present invention is to provide a method for preparing a lithium bismuth alloy substrate in one step and in-situ compounding the lithium compound layer on the substrate. The preparation method of the metal lithium negative electrode for the secondary battery comprises the steps of slurrying a bismuth compound, a conductive agent and a binder, then compounding the slurried bismuth compound, the conductive agent and the binder on the surface of a current collector, and then reacting the bismuth compound compounded on the current collector with metal lithium to prepare the metal lithium negative electrode for the secondary battery.
According to the preparation method, a bismuth compound is adopted as an active ingredient, the bismuth compound is coated on a current collector in advance, then the bismuth compound and metal lithium are subjected to alloying reaction, and a lithium compound compounded on the alloy is formed in situ.
The conductive agent and the binder may employ additive components known in the art that may be used for a lithium metal negative electrode.
Preferably, the conductive agent is at least one of acetylene black, carbon fiber cloth, graphite, activated carbon, graphene, acetylene black, carbon nanotubes and ketjen black.
The binder is for example PVDF.
In the present invention, the conductive agent, the binder and the bismuth compound may be slurried with a solvent and then combined with the current collector by a conventional method, which may be a method well known in the art such as coating.
In the slurry, the proportion of the bismuth compound, the conductive carbon and the binder can be adjusted according to the requirement.
Preferably, in the slurry, the mass ratio of the bismuth compound, the conductive carbon and the binder is 10: 1.
Preferably, the coating thickness of the slurry after slurrying is 1-300 μm; preferably: 20 to 50 μm.
The bismuth compound is powdery, and the particle size of the bismuth compound is about 50-800 nm, preferably 50-300 nm. At the preferred particle size, it is helpful to produce a metallic lithium negative electrode having excellent properties, and it has been found that when the particle size of the bismuth compound is large (for example, larger than the upper limit required in the present invention), the bismuth compound does not sufficiently react with the metallic lithium; however, if the particles are small (for example, smaller than the lower limit required in the present invention), the binding force of the lithium bismuth alloy particles formed after the reaction is small, and the particles are easily pulverized.
Preferably, the bismuth compound is at least one of an oxide, a chloride, a sulfide, a bismuth phosphide, a bismuth fluoride and a bismuth nitride of bismuth.
Further preferably, the bismuth compound is at least one of bismuth trioxide, bismuth trichloride, bismuth trisulfide, bismuth disulfide, bismuth phosphide, bismuth fluoride and bismuth nitride; preferably at least one of bismuth trioxide, bismuth phosphide, bismuth trichloride and bismuth nitride.
More preferably, the bismuth compound is a mixture of bismuth fluoride and bismuth nitride. The invention further innovatively discovers that bismuth fluoride and bismuth nitride have excellent synergistic effect, and the combined use can unexpectedly and obviously improve the electrical property and the cycling stability.
Preferably, the bismuth compound is a mixture of bismuth fluoride and bismuth nitride in a mass ratio of 1-3: 1-3.
Preferably, the mass of the bismuth compound on the current collector is: 1mg/cm 2～6mg/cm 2To (c) to (d); prior to 3mg/cm 2～5mg/cm 2。
The method comprises the steps of uniformly mixing slurry of bismuth compounds, conductive carbon and a binder, coating the slurry on the surface of a current collector, drying the slurry, and filling metal lithium on the surface of the slurry to fully react the metal lithium with the bismuth compounds; the method for filling metallic lithium may be an existing method.
Preferably, the current collector combined with the bismuth compound is subjected to electrodeposition and/or lithium metal filling, and the lithium metal is reacted with the bismuth compound.
Preferably, the metallic lithium is filled into the bismuth compound current collector by electrodeposition. Compared with other methods for filling lithium, the method adopts electrochemical deposition, the lithium metal and bismuth compound are fully reacted, the reaction uniformity is better, the generated lithium bismuth alloy has strong binding force and high stability, and the surface is provided with an in-situ SEI film which can effectively protect the lithium bismuth alloy. The invention discovers that the performance of the prepared lithium metal negative electrode is further improved by innovatively adopting an electrodeposition method, for example, the cycle performance of the negative electrode is further improved.
By supplying metallic lithium to a current collector compounded with a bismuth compound, an alloying reaction proceeds, the reaction mechanism being, for example:
Bi+Li＝LiBi+Li 3Bi
Bi 2O 3+Li＝LiBi+Li 3Bi+Li 2O
BiCl 3+Li＝LiBi+Li 3Bi+LiCl
Bi 2S 3+Li＝LiBi+Li 3Bi+Li 2S
BiS 2+Li＝LiBi+Li 3Bi+Li 2S
Bi 3P+Li＝LiBi+Li 3Bi+Li 3P
BiF+Li＝LiBi+Li 3Bi+LiF
Bi 3N+Li＝LiBi+Li 3Bi+Li 3N
the dosage of the metallic lithium is not less than 80 percent of the theoretical molar ratio of the bismuth compound for complete reaction.
In the lithium metal negative electrode, the content of the filled lithium metal is not less than the lithium amount lost in the first charge and discharge.
Preferably, the method comprises the following steps: in the lithium metal negative electrode, the content of the lithium metal is 1 mAh-8 mAh.
The invention also discloses a lithium metal cathode prepared by the preparation method. The metal lithium negative electrode comprises a current collector, a lithium bismuth alloy substrate compounded on the current collector, and a lithium compound layer compounded on the surface of the lithium bismuth alloy substrate. The material of the lithium bismuth alloy substrate layer is Li 3Bi and/or LiBi. The lithium compound layer is at least one of lithium oxide, sulfide, chloride, nitride, phosphide and fluoride; preferably Li 2O、LiCl、Li 2S、Li 3N、Li 3P, LiF.
The invention also provides application of the metal lithium cathode, and the metal lithium cathode is used as a cathode to be assembled into a lithium ion battery, a lithium sulfur battery or a lithium air battery.
Preferably, the lithium metal negative electrode is used for assembling a button lithium ion battery.
In the invention, the bismuth compound can generate a stable lithium bismuth alloy with the lithium metal, so that the stability of the lithium metal is improved, the lithium metal is promoted to be stably deposited in the lithium bismuth alloy, the generation of lithium dendrite is avoided, and the cycling stability and the coulombic efficiency of the lithium cathode taking the lithium bismuth alloy as a framework are further improved. And a lithium compound (Li) formed by a chemical reaction between metallic lithium and a bismuth compound 2O、LiCl、Li 2S、Li 3P、LiF、Li 3N) is an effective SEI film, can stabilize the surface of the lithium bismuth alloy, inhibit the side reaction of the cathode and the electrolyte, protect the lithium metal cathode, and furtherThe method is favorable for obviously improving the cycle stability of the cathode.
The invention takes a bismuth compound as a substrate, and metal lithium deposited on the bismuth compound reacts with the bismuth compound through an electrochemical method to generate an effective lithium bismuth compound and a corresponding SEI film. Lithium bismuth is used as a current collector, and the surface of the lithium bismuth is effectively protected by an SEI film, so that the lithium metal cathode with high coulombic efficiency, long cycle and high capacity density is realized.
Has the advantages that:
the chemical reaction of the bismuth compound and the lithium is applied to generate a stable lithium bismuth alloy and a corresponding lithium-containing compound, wherein the lithium bismuth alloy can be used as a lithium deposition site, the lithium can be uniformly deposited on the lithium deposition site, the lithium-containing compound can be used as an SEI film effectively generated to separate the lithium from an electrolyte, the occurrence of side reactions is reduced, the double protection of the lithium deposition site and the SEI film is integrated, lithium dendrite generated by the nonuniform deposition of the lithium can be effectively avoided, and the high specific capacity characteristic of the lithium metal cathode in the charging and discharging process is maintained. The lithium secondary battery can effectively prevent the growth of lithium dendrites for a long time, and further improves the coulombic efficiency and the cycle life of the lithium secondary battery.
The invention innovatively adopts the preparation method, and can prepare the metallic lithium cathode in one step, and the inventor innovatively discovers that the electrical property of the metallic lithium cathode can be obviously prepared by adopting an electrodeposition method in the whole scheme of the invention.
Under the preparation method, the invention also innovatively discovers that the electrical property of the prepared lithium metal cathode can be further improved by combining bismuth fluoride and bismuth nitride.
Researches show that compared with the conventional metal lithium cathode, the cycle life of the cathode is prolonged by more than 3 times; compared with the cathode of the lithium bismuth alloy, the cycle performance is improved by nearly 2 times.
Drawings
FIG. 1 is an SEM photograph of metallic bismuth used in example 1;
FIG. 2 shows the metal bismuth used in example 1 smeared with acetylene black, binder in a mass ratio of 8: 1, at a current density of1mA/cm 2And the area capacity is 1mAh/cm 2Electrochemical performance of the copper foil under cycling is compared.
FIG. 3 shows bismuth trioxide (Bi) used in example 2 2O 3) SEM picture of (1);
FIG. 4 shows bismuth trioxide (Bi) used in example 2 2O 3) Smearing with acetylene black and adhesive in the mass ratio of 8: 1, and then coating at the current density of 1mA/em 2And the area capacity is 1mAh/cm 2Electrochemical performance of the copper foil under cycling is shown.
FIG. 5 shows bismuth trichloride (BiCl) used in example 3 3) Smearing with acetylene black and adhesive in the mass ratio of 8: 1, and then coating at the current density of 1mA/em 2And the area capacity is 1mAh/cm 2Electrochemical performance of the copper foil under cycling is shown.
FIG. 6 is a graph of the full cell electrochemical performance used in example 4;
FIG. 7 is a graph of the electrochemical performance of the half cell used in example 5;
FIG. 8 is a graph of the electrochemical performance of a half cell used in comparative example 1;
figure 9 is a graph of the electrochemical performance of the half cell used in example 6.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described above, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Performance testing
The method for testing the high-voltage cycle performance of the directionally-grown/dissolved lithium anode assembled battery comprises the following steps:
1. assembling the battery: mixing a bismuth compound serving as an active substance with acetylene black and PVDF according to the mass ratio of 8: 1, uniformly dispersing the mixture into slurry by using NMP, coating the slurry on a copper foil with the thickness of 10 microns, drying the copper foil in an oven at the temperature of 80 ℃ for 12 hours, punching the copper foil into a pole piece cathode with the diameter of 13mm, taking a metal lithium piece as a counter electrode, and adopting1M LiTFSI/DOL: DME (1: 1 by volume) contains 1% wt LiNO 3The electrolyte and the lithium cathode prepared by the invention are assembled into a 2025 button lithium ion battery, and a diaphragm adopts GF/D glass fiber to carry out charge-discharge cycle test. The charge-discharge cycle test was carried out with a compound of metallic bismuth of the same structure as the active material.
Example 1
In commercial Bi 2S 3The powder is an active substance (the micro morphology of the powder is shown in figure 1), the active substance, acetylene black and PVDF are mixed according to the mass ratio of 8: 1, NMP is used for uniformly dispersing the mixture into slurry, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, a lithium metal piece is used as a counter electrode, and a half cell is assembled. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests show that the lithium metal cathode is 1mA/cm by adopting the lithium ion battery provided by the invention 2Charge and discharge current density and 1mAh/cm 2The cycle life under the charge-discharge area capacity is more than 2 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 96.3%, and the stable cycle is more than 140 circles (figure 2).
Example 2
Compared with example 1, the difference is that the bismuth compound used is Bi 2O 3The method comprises the following specific operations:
with commercial bismuth oxide (Bi) 2O 3) The powder is used as an active substance (the micro morphology is shown in figure 3), the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, the mixture is uniformly dispersed into slurry by NMP, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is used as a counter electrode to assemble a half cell. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests have found that the lithium negative electrode with bismuth oxide according to the invention is used at 1mA/cm 2Charge and discharge current density and 1mAh/cm 2The cycle life under the charge-discharge area capacity is more than 3 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 96.7%, and the stable cycle is more than 140 circles (figure 4).
Example 3
Compared with example 1, the difference is that the bismuth compound used is BiCl 3The method comprises the following specific operations:
with commercial bismuth trichloride (BiCl) 3) The powder is used as an active substance (the micro morphology is shown in figure 3), the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, the mixture is uniformly dispersed into slurry by NMP, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is used as a counter electrode to assemble a half cell. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests have found that the lithium negative electrode with bismuth oxide according to the invention is used at 1mA/cm 2Charge and discharge current density and 1mAh/cm 2The cycle life under the charge-discharge area capacity is more than 3 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 97.0%, and the stable cycle is more than 150 circles (figure 5).
Example 4
Compared with example 1, the difference is that the bismuth compound used is BiN 3The method comprises the following specific operations:
with commercial bismuth nitride (BiN) 3) The powder is used as an active substance, the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, the mixture is uniformly dispersed into slurry by using NMP, the slurry is coated on a copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is used as a counter electrode to assemble a half cell. Assembling a half cell for lithium metal at a current density of 0.1mA/cm 2And then, constant-current deposition is carried out for about 10 hours according to the amount of bismuth nitride, and the complete reaction of bismuth nitride and metal lithium is realized, so that the excellent metal lithium cathode material with the lithium bismuth alloy as a substrate and the surface coated with the lithium nitride is prepared. The lithium bismuth alloy is matched with commercial mature lithium cobaltate to assemble a full cell, the capacity retention rate of 200 circles can reach 92.7 percent after stable circulation at 1C, and the lithium bismuth alloy corresponding to the traditional metal bismuth is used as a cathode, so that the effect of obviously improving the capacity retention rate of the lithium bismuth alloy is achieved.
Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests show that the bismuth oxide has the advantages ofAt a lithium negative electrode of 1mA/cm 2Charge and discharge current density and 1mAh/cm 2The cycle life at charge-discharge area capacity was more than 3 times that of the smooth copper foil lithium negative electrode (fig. 6).
Example 5
Compared with example 1, the difference is that the bismuth compounds used are bismuth fluoride (BiF) and bismuth nitride (Bi) 3N) the composite bismuth material comprises the following specific operations:
using bismuth fluoride (BiF) and bismuth nitride (Bi) 3N) ball-milling and uniformly mixing the active substances according to the mass ratio of 1: 1, mixing the active substances with acetylene black and PVDF according to the mass ratio of 8: 1, uniformly dispersing the mixture into slurry by using NMP, coating the slurry on a copper foil with the thickness of 10 microns, drying the slurry in an oven at the temperature of 80 ℃ for 12 hours, punching the slurry into a pole piece with the diameter of 13mm, and assembling a half cell by using a metal lithium piece as a counter electrode. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests show that the half cell for electrochemically depositing lithium by adopting the two preferable metal bismuth compounds can stably generate an SEI film with the thickness of 30 nanometers, and has good cycle performance at 1mA/cm 2Charge and discharge current density and 1mAh/cm 2The cycle life under the charge-discharge area capacity is more than 3 times of that of a smooth copper foil lithium negative electrode, the average coulombic efficiency is kept above 97.3%, and the stable cycle is more than 190 circles. (FIG. 7). Coulomb efficiency and cycle number are obviously improved, and performance can be improved by unexpected cooperation in composite use.
Comparative example 1
Elemental metal bismuth is adopted as an active substance, the active substance is mixed with acetylene black and PVDF according to the mass ratio of 8: 1, NMP is used for uniformly dispersing the mixture into slurry, the slurry is coated on copper foil with the thickness of 10 microns, the copper foil is dried in an oven at the temperature of 80 ℃ for 12 hours, a pole piece with the diameter of 13mm is punched, and a metal lithium piece is taken as a counter electrode to assemble a half-cell. Under the same structure, a lithium negative electrode with uncoated copper foil was used as a comparative sample. Tests show that the cycle performance of the half-cell for electrochemically depositing lithium by adopting metal bismuth is improved relative to that of copper foil at 1mA/cm 2Charge and discharge current density and 1mAh/cm 2The cycle life under the charge-discharge area capacity is more than 1.5 times of that of a smooth copper foil lithium negative electrode, and the average coulombic efficiencyThe concentration is kept above 95%, and the stable circulation is above 100 circles (figure 8). However, the lithium bismuth alloy negative electrode produced by using the compound without bismuth as an active material has excellent performance.
Example 6
Compared with the embodiment 1, the difference is that the performance of the lithium bismuth alloy cathode produced by wetting with molten lithium is as follows:
mixing bismuth oxide (Bi2O3) as an active substance with acetylene black and PVDF according to the mass ratio of 8: 1, uniformly dispersing the mixture into slurry by using NMP, coating the slurry on a copper foil with the thickness of 10 microns, drying the copper foil in an oven at the temperature of 80 ℃ for 12 hours, and punching the slurry into a pole piece with the diameter of 13mm, wherein the mass of the active substance bismuth oxide is 2mg/cm 210 microns thick; and (5) assembling the half cell by taking the metal lithium sheet as a counter electrode. Under the same structure, the bismuth oxide on the pole piece is completely converted into a metal lithium bismuth alloy (the lithium content is about 3mAh) by a molten lithium infiltration method. At 1mA/cm 2Charge and discharge current density and 1mAh/cm 2Cycling at charge-discharge area capacity. Tests show that the negative polarity of the lithium bismuth alloy prepared by soaking molten lithium is slightly improved, but the negative electrode prepared without the electrochemical deposition of the metal lithium has long service life which is only close to 100 cycles, and the coulombic efficiency is not as high as the negative electrode prepared with the electrochemical deposition of the metal lithium and is only 94%. (FIG. 9).

Claims (10)

1. A lithium metal negative electrode for a secondary battery is characterized by comprising a current collector, a lithium bismuth alloy substrate compounded on the current collector, and a lithium compound layer compounded on the surface of the lithium bismuth alloy substrate.
2. The lithium metal negative electrode according to claim 1, wherein the material of the lithium bismuth alloy substrate layer is Li 3Bi and/or LiBi.
3. The lithium metal negative electrode according to claim 1, wherein the lithium compound layer is at least one of an oxide, sulfide, chloride, nitride, phosphide and fluoride of lithium(ii) a Preferably Li 2O、LiCl、Li 2S、Li 3N、Li 3P, LiF.
4. The lithium metal negative electrode according to any one of claims 1 to 3, wherein the current collector is a metal current collector, preferably at least one of copper, stainless steel, nickel and titanium; the thickness of the current collector is preferably 10-20 microns;
preferably, the thickness of the lithium bismuth alloy substrate layer is 5 microns to 40 microns;
preferably, the thickness of the lithium compound layer is 5 nm to 500 nm;
preferably, the current collector comprises a current collector and an active material compounded on the current collector, wherein the active material is a reaction product of a bismuth compound and metallic lithium; wherein, the compound of bismuth is preferably at least one of bismuth trioxide, bismuth trichloride, bismuth trisulfide, bismuth disulfide, bismuth phosphide, bismuth fluoride and bismuth nitride.
5. A preparation method of a metal lithium negative electrode for a secondary battery is characterized in that a bismuth compound, a conductive agent and a binder are slurried and then compounded on the surface of a current collector, and then the bismuth compound compounded on the current collector is reacted with metal lithium to prepare the metal lithium negative electrode for the secondary battery.
6. The method for producing a metallic lithium negative electrode for a secondary battery according to claim 5, wherein the bismuth compound is at least one of an oxide, chloride, sulfide, bismuth phosphide, bismuth fluoride and bismuth nitride of bismuth;
preferably at least one of bismuth trioxide, bismuth trichloride, bismuth trisulfide, bismuth disulfide, bismuth phosphide, bismuth fluoride and bismuth nitride.
7. The method of manufacturing a lithium metal negative electrode for a secondary battery according to claim 6, wherein the bismuth compound is a mixture of bismuth fluoride and bismuth nitride; preferably a mixture of bismuth fluoride and bismuth nitride with the mass ratio of 1-3: 1-3.
8. The method of manufacturing a lithium metal anode for a secondary battery according to claim 5, wherein the mass of the bismuth compound on the current collector is: 1mg/cm 2～6mg/cm 2To (c) to (d);
the dosage of the metallic lithium is not less than 80 percent of the theoretical molar ratio of the bismuth compound for complete reaction.
9. The method for producing a lithium metal negative electrode for a secondary battery according to any one of claims 5 to 8, wherein lithium metal is electrochemically deposited and/or melt-filled on a current collector to which a bismuth compound is combined, and the lithium metal is reacted with the bismuth compound.
10. Use of the lithium metal negative electrode for a secondary battery according to any one of claims 1 to 4 or the lithium metal negative electrode for a secondary battery prepared by the preparation method according to any one of claims 5 to 9, wherein: and the negative electrode is assembled into a lithium ion battery, a lithium sulfur battery or a lithium air battery.
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