CN112103512A

CN112103512A - Negative current collector, and preparation method and application thereof

Info

Publication number: CN112103512A
Application number: CN202011074968.0A
Authority: CN
Inventors: 王兆翔; 刘泽鹏; 杨高靖; 张思蒙; 王雪锋; 陈立泉
Original assignee: Institute of Physics of CAS
Current assignee: Institute of Physics of CAS
Priority date: 2020-10-09
Filing date: 2020-10-09
Publication date: 2020-12-18

Abstract

The invention provides a negative current collector which comprises a current collector base material and an inducing layer covering the surface of the current collector base material, wherein the inducing layer is used for inducing metal deposition, and a preparation method and application thereof are also provided. The present invention is applicable to secondary batteries using various metals (lithium, sodium, magnesium, aluminum, potassium, zinc) as negative electrode (anode) active materials. The current collector (negative electrode) can effectively inhibit dendritic crystal growth on the negative electrode of the battery and side reaction between active metal and electrolyte, and improves the safety, the cycle efficiency and the cycle life of the secondary battery.

Description

Negative current collector, and preparation method and application thereof

Technical Field

The invention belongs to the technical field of battery materials, and particularly relates to a negative current collector, and a preparation method and application thereof.

Background

With the development of portable electronic devices and electric vehicles, the demand of people for energy storage devices with high energy density is increasingly urgent. Secondary batteries based on intercalation chemistry, such as lithium ion batteries, suffer from energy density bottlenecks due to limitations in the crystal structure of the lithium-storing host, among other reasons. Therefore, research and development have been focused on secondary batteries using various (light) metals as negative electrode (or anode) active materials, such as lithium secondary batteries (the negative electrode active material is metallic lithium, and the positive electrode (or cathode) active material is an oxide, fluoride, polyanion compound, sulfur, oxygen, etc.), sodium secondary batteries, zinc secondary batteries, potassium secondary batteries, magnesium secondary batteries, aluminum secondary batteries, and (all) solid-state metal batteries, etc., based on deposition and elution of active metals. In these cells, active metal ions (e.g., Li)⁺、Na⁺、K⁺、Mg²⁺、Zn²⁺、Al³⁺Etc.) move in the electrolyte between the positive and negative electrodes of the battery and deposition (during charging of the battery) and dissolution (during discharging of the battery) occur on the negative electrode side of the battery. These metal-based negative electrode materials based on electrochemical deposition and dissolution of metals generally have very high specific capacities, and metal secondary batteries constructed with appropriate positive electrode materials also have high operating voltages and very high energy densities. However, because the current density distribution of the battery cathode is not uniform in the deposition and dissolution processes, the deposition or dissolution of the active metal is often non-uniform, so that metal dendrites are generated in the deposition process to cause potential safety hazards of the battery, or the dendrites are broken off to lose electrical contact with surrounding active metal or current collectors in the dissolution process to form isolated islands, and the cycle life of the battery is shortened. In more severe cases, the metal dendrites can puncture the battery separator or penetrate the solid electrolyte to connect the positive and negative electrodes of the battery, causing short circuits in the battery, causing the battery to fail and even to explode due to combustion. The key to ensure the safety of various metal secondary batteries is to effectively prevent the growth of metal dendrites. On the other hand, the volume and surface area of the metal electrode vary greatly during the deposition and dissolution of the active metal, and side reactions between the active metal and the electrolyte, etc. reduce the energy conversion efficiency of the battery, the active material, and the likeThe rate of utilization, the cycle life of the battery, and the limited battery applications, it is desirable to protect the active metal on the negative electrode. A protective layer (naturally occurring or artificially prepared) covering the surface of the negative current collector or active metal negative electrode may also result in uneven deposition of the active metal, even on top of such a protective layer. In addition, the huge volume change generated during the metal deposition and dissolution causes the contact of the negative electrode/electrolyte interface of the battery to be poor, the internal resistance and polarization of the battery are increased, the energy conversion efficiency of the battery is reduced, and the service life of the battery is shortened.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a negative electrode current collector (or a negative electrode) of a metal secondary battery, and a preparation method and application thereof.

Before setting forth the context of the present invention, the terms used herein are defined as follows:

the term "active metal" refers to: a metal species participating in an electrochemical reaction in the corresponding cell.

The term "active metal inducing substance" means: a substance having an inducing or guiding effect on the deposition of the active metal.

The term "negative current collector" means: flakes of non-reactive metal species that allow reactive metals to adhere to their surfaces are generally required to have strong resistance to reduction, good mechanical ductility, and electrical conductivity.

The term "negative electrode" means: a sheet, consisting of a suitable current collector and an active material supported thereon, is located on the lower potential side of the cell.

The term "polymer electrolyte" refers to: mixing a polar high-molecular polymer (polyethylene oxide PEO, polymethyl ethylene carbonate PPC, polyacrylonitrile PAN and lithium salt (trifluoromethyl ammonium sulfonate lithium LiTFSI) and lithium hexafluorophosphate LiPF with a proper amount of solvent according to an atomic ratio of O to Li (or N to Li or O to Na or N to Na) of 8-14₆) Lithium perchlorate LiClO₄) Sodium salt sodium trifluoromethanesulfonate LiTFSI and sodium hexafluorophosphate NaPF₆Sodium perchlorate (NaClO)₄) Mixing and dissolving, and then evaporating the solvent to obtain powder with lithium (or sodium) ion conductivityA bulk, film-like or bulk material, wherein O is an oxygen (O) containing unit in PEO or PPC and N is a nitrogen (N) containing unit in PAN.

The term "ceramic electrolyte" refers to: inorganic solid electrolytes such as perovskite type, anti-perovskite type, NASICON type, garnet type, and sulfide type.

The term "adhesive, binder" means: substances capable of adhering together the electrode substance (active or inactive) and the current collector are generally polymeric materials, such as polyvinylidene fluoride (PVDF), PPA (polyacrylic acid).

The term "PVDF" refers to: polyvinylidene fluoride.

The term "PAN" refers to: polyacrylonitrile.

The term "PAA" refers to: polyacrylic acid.

The term "SBR" means: styrene butadiene rubber.

The term "CMC" means: carboxymethyl cellulose.

The term "NMP" refers to: n-methyl pyrrolidone.

The term "DMSO" refers to: dimethyl sulfoxide (DMSO).

The term "DMF" refers to: dimethylformamide (DMF).

The term "DMC" means: dimethyl carbonate.

The term "DEC" means: diethyl carbonate.

The term "AN" refers to: and (3) acetonitrile.

The term "DOL" means: dioxolane (dioxypentane).

The term "DME" means: dimethoxyethane.

In order to achieve the above object, a first aspect of the present invention provides a negative current collector, including a current collector base material and an inducing layer covering a surface of the current collector base material, where the inducing layer is configured to induce metal deposition;

wherein the material of the induction layer is A_xD_y(ratio x: y ═ 0.1 to 10.0), and the element a is selected from one or more of: boron, carbon, nitrogen, magnesium, aluminum, silicon, phosphorus, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickelCopper, zinc, strontium, yttrium, zirconium, niobium, molybdenum, silver, cadmium, indium, tin, antimony, barium, tungsten, iridium, platinum, gold, lead, bismuth, lanthanum, cerium, said element D being selected from one or more of carbon, boron, nitrogen, phosphorus, silicon, fluorine, hydrogen;

preferably, the element a is selected from one or more of: magnesium, aluminium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, niobium, molybdenum, silver, tin, antimony, barium, tungsten, gold, cerium, said element D being selected from one or more of the following: carbon, boron, nitrogen, phosphorus, silicon, fluorine;

more preferably, the element a is selected from one or more of the following: copper, iron, titanium and tungsten, wherein the element D is selected from one or more of the following elements: carbon, boron, nitrogen, phosphorus, fluorine.

The negative electrode current collector according to the first aspect of the present invention, wherein the inducing layer has a thickness of 10 to 2000nm, preferably 50 to 1500 nm.

The negative electrode current collector according to the first aspect of the present invention, wherein the surface of the inducing layer of the negative electrode current collector is further covered with a protective layer;

preferably, the thickness of the protective layer is 10-1000 nm, and more preferably 20-500 nm; and/or

The protective layer material is selected from one or more of the following: polymer electrolyte (PEO/LiPF)₆、PPC/LiPF₆、PAN/LiClO₄、PPC/NaTFSI、PEO/NaPF₆PEO/LiTFSI, PPC/LiTFSI), organic-inorganic composites (MgX)₂-Li_yMg (X ═ F, Cl, Br, I; y ═ 0.001-1000) complex, LiF/Mg_xLi (x ═ 0.001 to 1000) complex, Li-Li_xSn-PTMEG (x is 0.001-1000) complex) (PTMEG refers to polytetrahydrofuran or tetrahydrofuran polyether or polytetramethylene ether glycol).

The negative electrode current collector according to the first aspect of the present invention, wherein an active metal layer is further included between the inducing layer and the protective layer;

preferably, the material of the active metal layer is lithium or sodium; and/or

Preferably, the thickness of the active metal layer is 0.1 to 200 μm, and more preferably 0.2 to 100 μm.

A second aspect of the present invention provides the method for preparing the negative electrode current collector of the first aspect, including preparing an inducing layer on the surface of the current collector base material;

preferably, the method for preparing the inducing layer is selected from one or more of the following: vapor deposition, plasma ion implantation, magnetron sputtering deposition, pulsed laser deposition, thermal evaporation deposition, atomic layer deposition, molecular layer deposition, coating.

The production method according to the second aspect of the invention, wherein the method of producing the inducing layer is plasma-based ion implantation, the method comprising the steps of: placing a current collector base material containing an element A in a precursor atmosphere containing an element D, and combining the element D and the element A in the current collector base material on the surface of the current collector base material by a low-temperature plasma surface treatment technology to form an inducing layer A_xD_y(x:y＝0.1～10.0)；

Preferably, the precursor is selected from one or more of: methane, ethane, nitrogen, ammonia, silane, borane, phosphine, more preferably methane, nitrogen, ammonia, silane, and further preferably methane, nitrogen, ammonia; and/or

The partial pressure of the precursor gas is 80-100%, preferably 95-100%.

According to the preparation method of the second aspect of the invention, the temperature of the current collector base material is 300-1200 ℃, preferably 500-1200 ℃, and more preferably 600-1000 ℃; and/or

The implantation dose is 10¹⁵～10¹⁸ions/cm²。

According to the preparation method of the second aspect of the invention, when the current collector base material does not contain the element a, a plating layer of the element a is made on the surface of the current collector base material;

preferably, the thickness of the plating layer is 5nm to 500 nm.

The production method according to the second aspect of the invention, wherein the method of producing the inducing layer is coating, the method comprising the steps of: mixing and dispersing the inducing layer material and the bonding material in a diluent, coating the diluent on the surface of the current collector substrate material, and drying to obtain the inducing layer;

preferably, the bonding material is selected from one or more of the following: polyvinylidene fluoride (PVDF), Polyacrylonitrile (PAN), polyacrylic acid (PAA), Styrene Butadiene Rubber (SBR), carboxymethyl cellulose (CMC); the diluent is selected from one or more of the following: n-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethyl carbonate (DMC), diethyl carbonate (DEC), Acetonitrile (AN).

A third aspect of the invention provides a battery comprising the negative electrode current collector of the first aspect or the negative electrode current collector prepared according to the method of the second aspect;

preferably, the battery is selected from a secondary battery and/or a solid-state metal battery;

more preferably, the secondary battery is selected from one or more of the following: lithium secondary batteries, sodium secondary batteries, potassium secondary batteries, magnesium secondary batteries, aluminum secondary batteries, zinc secondary batteries; and/or the solid-state metal battery is an all-solid-state metal battery.

The invention relates to a negative current collector, a preparation method thereof, a metal secondary battery negative current collector (as an active material carrier) or a negative electrode (negative current collector + active material) using metal lithium (sodium, magnesium, aluminum, potassium and zinc) or alloy thereof as a negative electrode (anode), a preparation method thereof and application thereof.

Carbides are binary or multicomponent compounds of carbon with elements having a smaller or similar electronegativity than that of carbon. The carbide has the characteristics of metal bond and covalent bond, and is dominated by the metal bond. Carbides generally have a positive temperature coefficient of resistance and have conductive properties. The inventors found that the carbide has a strong affinity for light metals such as lithium, sodium, and potassium. Therefore, if the surface of the conventional current collector substrate is covered with carbides, the metal ions can penetrate other ion conductors (such as artificial or natural Solid Electrolyte Interface (SEI) films, solid electrolytes and the like) and the like under the induction of the carbides, so that electrons are reduced and deposited on the carbide surface. Therefore, the induction effect of the carbide on lithium can enable lithium to penetrate through other protective layers to be deposited on the surface of a current collector or an electrode covered with the carbide, so that the deposition of metal lithium in the protective layers is avoided, and the direct contact and reaction of the metal lithium and an electrolyte are also avoided, thereby improving the coulombic efficiency of a metal lithium cathode, prolonging the service life of the battery and the like. Some nitrides, borides, phosphides, silicides, fluorides, etc. also have properties similar to carbides, and can also have affinity for lithium, sodium, magnesium, aluminum, potassium, zinc, etc. Therefore, the current collector or the electrode containing these compounds can also induce metals such as lithium, sodium, magnesium, aluminum, potassium, and zinc.

The invention provides a metal secondary battery negative electrode current collector (negative electrode) capable of inducing metal deposition. The negative current collector (negative electrode) material consists of a solid or porous current collector matrix material and an inducing layer which is subjected to carbonization, nitridation, phosphorization, fluorination and other treatments, and the chemical general formula of the effective inducing substance is A_xD_yThe treatment method comprises the steps of directly carrying out carbonization, nitridation, phosphorization, fluorination and other treatments on a current collector substrate made of proper materials, or carrying out carbonization, nitridation, phosphorization, fluorination and other treatments after a proper metal coating is made on the current collector substrate, or plating a carbide, a nitride, a phosphide and a fluoride on a current collector substrate, and coating a coating containing an inducing substance on a common (solid or porous) current collector substrate. The negative electrode is formed by pasting or depositing active metal on a current collector containing an inducing layer. The present invention is applicable to secondary batteries using various metals (lithium, sodium, magnesium, aluminum, potassium, zinc) as negative electrode (anode) active materials. The current collector (negative electrode) can effectively inhibit dendritic crystal growth on the negative electrode of the battery and side reaction between active metal and electrolyte, and improves the safety, the cycle efficiency and the cycle life of the secondary battery.

The invention relates to a negative current collector (negative electrode) capable of inducing metal deposition, wherein the surface of the negative current collector is covered with a layer of carbide, nitride, boride, phosphide, fluoride or silicide. General formula writing A_xD_y(x is more than or equal to 0.1 and less than or equal to 10.0). The element D is selected from carbon (C), boron (B), nitrogen (N), phosphorus (P), silicon (Si),Fluorine (F), hydrogen (H), or a combination thereof; the element A is selected from one or the combination of the following elements: boron (B), carbon (C), nitrogen (N), magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), strontium (Sr), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), barium (Ba), tungsten (W), iridium (Ir), platinum (Pt), gold (Au), lead (Pb), bismuth (Bi), lanthanum (La), cerium (Ce), preferably magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), niobium (Nb), Molybdenum (Mo), silver (Ag), tin (Sn), antimony (Sb), barium (Ba), tungsten (W), gold (Au) and cerium (Ce).

According to a specific embodiment of the invention, the surface of the current collector foil material is subjected to carbonization, nitridation, boronization, phosphorization, silicification, fluorination and coating treatment to produce a layer of carbide, nitride, boride, phosphide, silicide and fluoride.

According to a specific embodiment of the present invention, the negative electrode current collector (negative electrode) is carbonized, nitrided, boronized, phosphated, siliconized, fluorinated, and coated by one or more of the following methods: (1) putting a current collector foil in a precursor atmosphere containing carbon, nitrogen, boron, phosphorus, silicon and fluorine elements, and heating the current collector foil through vapor deposition to enable the elements to permeate into the surface of the current collector to form a corresponding carbide, nitride, boride, phosphide, silicide and fluoride induction layer; (2) placing a current collector foil (made of A) in a plasma atmosphere containing an element D, and enabling the element D to permeate into the surface of the metal A to form a corresponding carbide, nitride, boride, phosphide, silicide and fluoride induction layer; (3) and plating a layer of the metal A in the first aspect on the surface of the current collector foil. Then placing the current collector foil in a plasma atmosphere containing an element D, and enabling the element D to permeate into the metal surface through heat treatment to form a corresponding carbide, nitride, boride, phosphide, silicide and fluoride induction layer; (4) transferring (plating) carbide, nitride, boride, phosphide, silicide and fluoride in the target material to the surface of the heated metal foil by methods such as magnetron sputtering, laser sputtering, thermal evaporation and the like to form corresponding carbide, nitride, boride, phosphide, silicide and fluoride induction layers; (5) and coating a layer of the inducing substance of the first aspect on the surface of the current collector foil.

And plating or sticking a layer of active metal on the surface of the negative current collector covered with the inducing layer.

According to a particular embodiment of the invention, the precursor compound is selected from one or more of the following: methane, ethane, ammonia, silane, borane, phosphine. Preferably methane, nitrogen, ammonia, silane, most preferably methane, nitrogen, ammonia.

According to an embodiment of the present invention, the surface of the negative electrode current collector substrate includes a metal coating layer of 5 to 500nm, preferably magnesium (Mg), aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), tin (Sn), antimony (Sb), barium (Ba), tungsten (W), and cerium (Ce), more preferably magnesium (Mg), aluminum (Al), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium (Nb), molybdenum (Mo), tungsten (W), and most preferably iron, titanium, copper, tungsten, and vanadium. The purity is 90.00-99.99%.

According to a particular embodiment of the invention, the partial pressure of the precursor gas is between 80% and 100%, preferably between 95% and 100%.

According to one embodiment of the present invention, a suitable grain size of carbide, nitride, boride, phosphide, silicide, fluoride and a binder material are mixed and applied to a metal foil to form an induction film of a suitable thickness.

According to an embodiment of the present invention, the temperature of the substrate during the carbonization, nitridation, boronization, phosphating, silicidation and fluorination processes is between 300 ℃ and 1200 ℃, preferably between 500 ℃ and 1200 ℃, and most preferably between 500 ℃ and 1000 ℃. The time for carbonization, nitridation, boronization, phosphorization, silicification and fluorination treatment is 1-120 minutes, or the passing speed is 1-100 cm/min. The heating rate in the carbonization, nitridation, boronization, phosphorization, silicification and fluorination treatment processes is 2-7 ℃/min, and preferably 5 ℃/min.

The negative electrode current collector of the present invention may have, but is not limited to, the following advantageous effects:

the present invention is applicable to secondary batteries using various metals (lithium, sodium, magnesium, aluminum, potassium, zinc) as negative electrode (anode) active materials. The current collector (negative electrode) can effectively inhibit dendritic crystal growth on the negative electrode of the battery and side reaction between active metal and electrolyte, and improves the safety, the cycle efficiency and the cycle life of the secondary battery.

Drawings

Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

fig. 1 illustrates a typical structure and principle of the negative electrode current collector according to the present invention.

Fig. 2 shows the structure and principle comparison of the negative electrode current collector (metal negative electrode) of the present invention and a general current collector (metal negative electrode).

Fig. 3 shows the topography of the flat plate current collector substrate (foil) of example 1.

Fig. 4 shows the cross-sectional morphology of the negative current collector prepared in example 5 by depositing an inducing layer on the surface of a current collector substrate.

Fig. 5 shows the cross-sectional morphology of the negative electrode current collector prepared by coating the current collector substrate with the inducing layer in example 10.

Fig. 6 shows the cycle performance (a) and the voltage curve segment (B) (corresponding to a half-cell constituted by metallic lithium/inducing layer current collector) of example 13, deposition/dissolution of metallic lithium on a current collector comprising an inducing layer.

FIG. 7 shows the surface topography of the sodium metal of example 14 rolled on the surface of the inducing layer.

FIG. 8 shows the surface morphology of the composite protective film formed on the surface of lithium metal after soaking in the electrolyte of example 19.

Fig. 9 shows the topography of the porous (foam or mesh) current collector substrate (foil) of example 20.

Fig. 10 shows the cross-sectional morphology of the negative current collector of example 25 with a protective layer overlaid on top of the current collector substrate and inducing layer.

FIG. 11 shows the surface topography of the composite protective film formed on the surface of the sodium metal after soaking in the electrolyte of example 29.

FIG. 12 shows example 30 using a conventional liquid electrolyte (room temperature) or polymer electrolyte (PEO/LiTFSI, 60 ℃) with LiFePO as a negative electrode covered with a protective layer current collector (with or without metallic lithium sandwiched between the inducing layer and the protective layer)₄Cycling performance curve for the positive cell.

Detailed Description

The invention is further illustrated by the following specific examples, which, however, are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

This section generally describes the materials used in the testing of the present invention, as well as the testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible. It will be apparent to those skilled in the art that the materials and methods of operation used in the present invention are well within the skill of the art, provided that they are not specifically illustrated.

The reagents and instrumentation used in the following examples are as follows:

comprises preparing carbon/nitrogen/boron/phosphide reagent, adhesive for bonding carbide, solid electrolyte and FeF₃The raw materials are all purchased from national medicine reagents company, liquid electrolyte (1M LiPF)₆EC/DMC), copper foil, and positive electrode sheet (LiNi)_0.85Co_0.1Al_0.05O₂、LiCoO₂、LiFePO₄、LiNi_0.5Co_0.2Mn_0.3O₂、LiNi_0.8Co_0.1Mn_0.1O₂、Li_1.2Mn_0.54Co_0.13Ni_0.13O₂) The lithium-ion battery is purchased from CATL, the metal lithium sheet, the stainless steel foil and the titanium foil are purchased from Tianjin lithium industry Limited, and the diaphragm is purchased from Shenzhencao Jingzhida technology Limited. Solid electrolyte (polymer, ceramic, composite electrolyte, semi-solid electrolyte, gel electrolyte, etc.), FeF₃Powder and electrode sheetAnd other unrecited materials for various metal secondary batteries are self-made.

Example 1

This example is for explaining a method of preparing the negative electrode current collector of the present invention.

The preparation method comprises the following steps: injecting carbon into the copper-based current collector by using a low-temperature plasma surface treatment technology to form Cu_xAnd a C inducing layer (x is 0.1-5.0). With CH₄As a carbon source, the temperature of the workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99% -99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, with CH₄The carbon source is a carbon source, the temperature of a workpiece is 600 ℃, the pressure of the back bottom is 2000Pa, the working pressure is 0.2Pa, the purity of a gas source is 99 percent, and the injection dosage is 10 percent¹⁶ions/cm²Forming an inducing layer Cu with a thickness of 30nm₂C。

Example 2

The preparation method comprises the following steps: injecting carbon into the surface of the stainless steel base current collector by using a low-temperature plasma surface treatment technology to form Fe_xAnd a C inducing layer (x is 0.1-5). Using CH₄As a carbon source, the temperature of the workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99-99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, with CH₄As carbon source, the workpiece temperature is 700 ℃, and the background pressure is 10⁴Pa, working pressure 0.2Pa, gas source purity 99.5%, and injection dosage 5X 10¹⁶ions/cm²Forming an inducing layer Fe with a thickness of 50nm₂C。

Example 3

The preparation method comprises the following steps: injecting nitrogen into the surface of the titanium-based current collector by using a low-temperature plasma surface treatment technology to form Ti_xAn N-inducing layer (x is 0.1 to 5). Using nitrogen (N)₂) Is a nitrogen source, the temperature of a workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99.00-99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, nitrogen (N) is used₂) Is a nitrogen source, the workpiece temperature is 1000 ℃, and the back pressure is 2 multiplied by 10⁴Pa, working pressure 0.3Pa, gas source purity 99%, and injection dosage 10¹⁶ions/cm²An inducing layer TiN with a thickness of 20nm was formed.

Example 4

The preparation method comprises the following steps: plating tungsten (W) on the surface by using a low-temperature plasma surface treatment technology, and injecting carbon into the surface of a copper-based current collector with the plating thickness of 20-100 nm to form W_xAnd a C (x is 0.1-5.0) inducing layer. Using CH₄As a carbon source, the temperature of the workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99.00-99.99 percent and injection dosage of 10 percent¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, with CH₄As carbon source, the workpiece temperature is 600 ℃, and the background pressure is 10⁴Pa, working pressure 0.35Pa, gas source purity 99%, and injection dosage 5X 10¹⁵ions/cm²An inducing layer WC was formed to a thickness of 50 nm.

Example 5

The preparation method comprises the following steps: titanium (Ti) is plated on the surface by using a low-temperature plasma surface treatment technology, and boron (B) is injected into a stainless steel-based current collector with the plating thickness of 20-100 nm to form Ti_xB inducing layer (B)x is 0.5 to 5). Using Borane (BH)₃) Is a boron source, the temperature of the workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99% -99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, with Borane (BH)₃) Is a boron source, the temperature of the workpiece is 900 ℃, and the pressure of the back is 5 multiplied by 10³Pa, working pressure 0.4Pa, gas source purity 99%, and injection dosage 10¹⁶ions/cm²Forming an inducing layer TiB with a thickness of 40nm₂。

Example 6

The preparation method comprises the following steps: the surface of the stainless steel base current collector is plated with titanium by using a low-temperature plasma surface treatment technology, and fluorine (F) is injected into the stainless steel base current collector with the plating thickness of 20nm to form TiF_xAnd an inducing layer (x is 0.1-5). LiF is used as a fluorine source, the temperature of a workpiece is 300-1000 ℃, and the pressure of the back bottom is 10 DEG³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99% -99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, LiF is used as the fluorine source, the workpiece temperature is 800 ℃, and the background air pressure is 5X 10³Pa, working pressure 0.1Pa, gas source purity 99%, and injection dosage 10¹⁶ions/cm²Forming an inducing layer TiF with a thickness of 30nm₃。

Example 7

The preparation method comprises the following steps: high-purity WC is used as a target material, and a WC induction layer with the thickness of 20-200 nm is deposited and grown on the surface of a stainless steel-based current collector by pulse laser deposition. The laser wavelength is 248nm, the workpiece temperature is 300-1000 ℃, and the background air pressure is 10^-5～10^-10mbar, the distance between the target liner and the target substrate is 30-70 mm.

In a preferred embodiment, the annealing temperature is 800 ℃ and the background gas pressure is 10 DEG^-8mbar, target liner distance of 55mm, purity of target WC of 99%, and deposition thickness of 50nm WC.

Example 8

The preparation method comprises the following steps: with high purity Fe_xC, depositing a layer of Fe with the thickness of 80-200 nm on the surface of a stainless steel base current collector by using a magnetron sputtering technology for the target material₃And C, inducing a layer. The working pressure is 0.1-2 Pa, the target purity is 99.00-99.99%, the workpiece temperature is 300-1000 ℃, the power is 200-500W, and the target-substrate distance is 4-10 cm.

In a preferred embodiment, the working pressure is 2Pa, the target material purity is 99%, the target-substrate distance is 6cm, the power is 300W, the deposition time is 20 minutes, the pause time is 5 minutes, and Fe₃The thickness of the C coating is 100nm, and the annealing temperature is 750 ℃.

Example 9

The preparation method comprises the following steps: fe with the grain diameter of 50nm_xMixing C (x is 0.1-5) and PVDF (polyvinylidene fluoride) as a binder at a mass ratio of 95:5, dispersing the mixture in NMP (PVDF: NMP is 1: 5) as a solvent/diluent, and spraying the slurry onto a copper foil (rate of 0.5mL/min, spray area of 5 cm)²) Drying at 120 deg.C, and covering a layer of Fe with thickness of 300nm on the surface of copper foil₃C inducing layer, namely coating the surface of the alloy with Fe₃C, a copper-based negative electrode current collector.

Example 10

The preparation method comprises the following steps: mixing WC with the grain size of 80nm and PVDF (polyvinylidene fluoride) serving as an adhesive in a mass ratio of 95:5, dispersing the mixture in NMP (1: 2 of the mass ratio of PVDF: NMP), coating the slurry on a stainless steel foil in a scraping mode, drying the stainless steel foil at 120 ℃, and covering a layer of WC with the thickness of 300nm on the surface of the stainless steel foil to obtain the stainless steel-based negative electrode current collector with the WC induction layer coated on the surface.

Example 11

The preparation method comprises the following steps: the surface of the negative current collector prepared in example 2 was coated with a layer of PEO/LiPF having a thickness of 50nm₆A polymer electrolyte membrane forming a negative current collector with a protective layer. PEO/LiPF₆The polymer electrolyte slurry is prepared by mixing dry materials (PEO, LiPF)₆And the molar ratio of O to Li is 12) and a solvent dimethyl sulfoxide (DMSO) are uniformly mixed according to the mass ratio of 1 to 5, and then the mixture is uniformly coated. The solvent evaporation temperature after coating was 120 ℃.

Example 12

The preparation method comprises the following steps: the surface of the negative current collector prepared in example 7 was coated with a layer of PPC/NaPF with a thickness of 50nm₆A polymer electrolyte membrane forming a negative current collector with a protective layer. PPC/NaPF₆The polymer electrolyte slurry is prepared by mixing dry materials (PPC, NaPF)₆And the molar ratio of O to Li is 12) and a solvent dimethyl sulfoxide (DMSO) are uniformly mixed according to the mass ratio of 1 to 5, and then the mixture is uniformly coated. The solvent evaporation temperature after coating was 120 ℃.

Example 13

The preparation method comprises the following steps: the surface of the negative current collector prepared in example 9 was coated with a layer of PPC/LiPF having a thickness of 50nm₆A polymer electrolyte membrane forming a negative current collector with a protective layer. PPC/LiPF₆The polymer electrolyte slurry is prepared by mixing dry materials (PPC, LiPF)₆Li 12) and dimethyl sulfoxide (DMSO) in a mass ratio of 1:5, and mixing uniformlyAnd (4) coating. The solvent evaporation temperature after coating was 120 ℃.

The measuring method comprises the following steps: the current collector of the invention is used as a working electrode, the metal lithium is used as a counter electrode, and PPC/LiPF is used₆And (3) a polymer electrolyte, and assembling the CR2032 button cell. The cell was charged and discharged at 60 ℃ using a LAND CT2001A charging and discharging instrument, and the current density was 1mA cm^-2The discharge capacity (the deposition amount of metal lithium on the current collector) is 2.0mAh cm^-2The charge (delithiation) cut-off potential was 0.1V.

Example 14

This example is intended to illustrate a method for producing a metal negative electrode of the inducing layer of the present invention.

The preparation method comprises the following steps: rolled on the surface of the negative current collector prepared in example 3 (linear charge 500 Nmm)^-1) And forming a layer of metal sodium with the thickness of 50 mu m to form the metal sodium negative electrode containing the inducing layer.

Example 15

The preparation method comprises the following steps: surface rolling (linear charge 500 Nmm) of negative current collector prepared in example 4^-1) A layer of metallic lithium with a thickness of 40 μm forms a metallic lithium negative electrode comprising the inducing layer according to the invention.

Example 16

The preparation method comprises the following steps: surface-rolled negative current collector prepared in example 5 (linear charge 500 Nmm)^-1) A layer of lithium metal with a thickness of 50 μm, the surface of which was covered with a layer of polymer with a thickness of 20nm by the method described in example 11And a material electrolyte forming a lithium metal negative electrode comprising the inducing layer and the protective layer of the present invention.

Example 17

The preparation method comprises the following steps: surface-rolled negative current collector prepared in example 9 (linear charge 650 Nmm)^-1) A layer of metal sodium with the thickness of 50 μm, and then a polymer electrolyte with the thickness of 20nm is covered on the surface of the metal sodium by the method described in the embodiment 12, so as to form the metal sodium cathode containing the inducing layer and the protective layer.

Example 18

This example is intended to illustrate a method of preparing a negative electrode current collector comprising the present invention.

The preparation method comprises the following steps: a lithium metal negative electrode prepared as described in example 14 was immersed in 0.1M SnCl₄Is formed on the surface of the lithium metal covered with Li-Li in a mixed solution of Tetrahydrofuran (THF) and propylene oxide (1 vol%) and kept for 5 hours_xA metallic lithium negative electrode with a Sn-polytetramethylene ether glycol composite protective layer (thickness of about 50 nm).

Example 19

This example illustrates one method of making a lithium metal anode comprising an inducing layer of the present invention.

The preparation method comprises the following steps: a lithium metal anode prepared as described in example 15 was immersed in a conventional electrolyte (e.g., 1M LiFSI/DOL-DME) containing MgX2 (10-100 mM). After the battery is assembled and is cycled for the first time, an organic lithium salt, a protective layer (with the thickness of about 50nm) rich in LiX (X ═ F, Cl, Br, I and the like), Li-Mg alloy and oligomers are generated on the surface of the metallic lithium, and the metallic lithium negative electrode containing the inducing layer and the protective layer simultaneously is obtained.

In a preferred embodiment, a lithium metal negative electrode prepared as described in example 15 is impregnated with a solution containing MgF₂(concentration 60mM) in a conventional electrolyte (1M LiFSI/DOL-DME). After the battery is assembled and is circulated for the first time, organic lithium salt, rich LiF and Li-Mg alloy are generated on the surface of the metal lithiumAnd a protective layer of gold and oligomer to obtain the lithium metal negative electrode simultaneously containing the inducing layer and the protective layer.

Example 20

The preparation method comprises the following steps: injecting carbon into the foam copper-based current collector by using a low-temperature plasma surface treatment technology to form Cu_xAnd a C inducing layer (x is 0.1-5.0). With CH₄As a carbon source, the temperature of the workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99% -99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, with CH₄The carbon source is a carbon source, the temperature of a workpiece is 600 ℃, the pressure of the back bottom is 2000Pa, the working pressure is 0.2Pa, the purity of a gas source is 99 percent, and the injection dosage is 10 percent¹⁶ions/cm²Forming an inducing layer Cu with a thickness of 50nm₂C。

Example 21

The preparation method comprises the following steps: injecting carbon into the surface of the stainless steel mesh collector by using a low-temperature plasma surface treatment technology to form Fe_xAnd a C inducing layer (x is 0.1-5). Using CH₄As carbon source, the workpiece temperature is 300-1000 deg.C, and the backing pressure is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99-99.99%, and injection dosage of 10%¹⁵～10¹⁸ions/cm². In a preferred embodiment, with CH₄As carbon source, the workpiece temperature is 700 ℃, and the background pressure is 10⁴Pa, working pressure 0.2Pa, gas source purity 99.5%, and injection dosage 5X 10¹⁶ions/cm²Forming an induction layer with a thickness of 20nmLayer Fe₂C. (Note: stainless steel is the Fe source)

Example 22

The preparation method comprises the following steps: injecting carbon into the surface of the nickel net current collector with the surface plated with tungsten of 200nm by using a low-temperature plasma surface treatment technology to form a WC induction layer. Using CH₄As a carbon source, the temperature of the workpiece is 300-1000 ℃, and the pressure of the back bottom is 10³～10⁵Pa, working pressure of 0.01-0.5 Pa, gas source purity of 99.00-99.99 percent and injection dosage of 10 percent¹⁵～10¹⁸ions/cm²。

In a preferred embodiment, with CH₄As carbon source, the temperature of the workpiece is 1000 ℃, and the pressure of the back bottom is 10 DEG⁴Pa, working pressure 0.4Pa, gas source purity 99.5%, and injection dosage 10¹⁷ions/cm²An inducing layer WC was formed to a thickness of 250 nm.

Example 23

The preparation method comprises the following steps: high-purity WC is used as a target material, and a WC induction layer with the thickness of 20-200 nm is deposited and grown on the surface of a nickel mesh current collector by pulse laser deposition. The laser wavelength is 248nm, the workpiece temperature is 300-1000 ℃, and the background air pressure is 10^-5～10^- ¹⁰mbar, and the distance of the target liner is 30-70 mm.

Example 24

The preparation method comprises the following steps: mixing WC with the particle size of 80nm and PVDF (polyvinylidene fluoride) serving as an adhesive according to the mass ratio of 95:5, dispersing the mixture in NMP (the mass ratio of a dry material (WC/PVDF mass ratio of 95:5) to a diluent is 1:3) to obtain slurry, coating the slurry on a stainless steel mesh in a scraping manner, drying the stainless steel mesh at 120 ℃, and covering a WC/PVDF composite inducing layer with the thickness of 300nm on the surface of the stainless steel mesh to obtain the stainless steel mesh negative electrode current collector with the WC inducing layer coated on the surface.

Example 25

The preparation method comprises the following steps: the surface of the negative current collector prepared in example 21 was coated with a layer of PEO/LiPF having a thickness of 50nm₆A polymer electrolyte membrane forming a negative current collector with a protective layer. PEO/LiPF₆The polymer electrolyte slurry is prepared by mixing dry materials (PEO, LiPF)₆And the molar ratio of O to Li is 12) and a solvent dimethyl sulfoxide (DMSO) are uniformly mixed according to the mass ratio of 1 to 5, and then the mixture is uniformly coated. The solvent evaporation temperature after coating was 120 ℃.

Example 26

The preparation method comprises the following steps: surface rolling (line load 500N mm) of the negative electrode current collector prepared in example 22^-1) A layer of metallic lithium with a thickness of 50 μm forms a metallic lithium negative electrode comprising the inducing layer according to the invention.

Example 27

The preparation method comprises the following steps: surface-rolled negative current collector prepared in example 23 (linear charge 550N mm)^-1) And forming a layer of metal sodium with the thickness of 40 mu m to form the metal sodium negative electrode containing the inducing layer.

Example 28

The preparation method comprises the following steps: will be as described in example 26The metal lithium cathode prepared by the method is immersed in a solution containing MgX₂(concentration 10-100mM) conventional electrolyte (such as 1M LiPF)₆EC/DMC/EMC). After the battery is assembled and is cycled for the first time, an organic lithium salt, a protective layer (with the thickness of about 50nm) rich in LiX (X ═ F, Cl, Br, I and the like), Li-Mg alloy and oligomers are generated on the surface of the metallic lithium, and the metallic lithium negative electrode containing the inducing layer and the protective layer simultaneously is obtained.

In a preferred embodiment, a lithium metal anode prepared as described in example 26 is immersed in a conventional electrolyte (1M LiPF) containing MgCl (concentration 50mM)₆EC/DMC/EMC 1:1:1 v/v/v). After the battery is assembled and is cycled for the first time, an organic lithium salt and a protective layer rich in LiCl, Li-Mg alloy and oligomer are generated on the surface of the metal lithium, and the metal lithium cathode containing the inducing layer and the protective layer is obtained.

Example 29

This example illustrates one method of making a sodium metal anode comprising an inducing layer of the present invention.

The preparation method comprises the following steps: a negative electrode of sodium metal prepared as described in example 27 was immersed in a solution containing MgX₂(concentration 10-100mM) conventional electrolyte (e.g., 1M NaPF)₆EC/DMC/EMC). After the battery assembly is completed and the first cycle is carried out, an organic sodium salt, a protective layer (with the thickness of about 50nm) rich in NaX (X ═ F, Cl, Br, I and the like) and Na-Mg alloy and oligomer are generated on the surface of the metal sodium, and the metal sodium negative electrode containing the inducing layer and the protective layer simultaneously is obtained.

In a preferred embodiment, a sodium metal negative electrode prepared as described in example 27 is immersed in a solution containing MgF₂(concentration 50mM) conventional electrolyte (1M NaPF)₆EC/DMC/EMC 1:1:1 v/v/v). After the battery assembly is completed and the first circulation is carried out, a protective layer which is rich in organic sodium salt, NaF and Na-Mg alloy and oligomer is generated on the surface of the metal sodium, and the metal sodium cathode which simultaneously contains the inducing layer and the protective layer is obtained.

Examples30

This example is intended to illustrate a method of assembling a secondary metal battery using a liquid electrolyte and the negative electrode current collector of the present invention.

The preparation method comprises the following steps: the required members such as the battery can and the separator are sufficiently dried. With dried LiFePO₄The positive plate was used as the positive electrode and the negative electrode current collector described in example 16 was used as the negative electrode, and a battery was assembled using a conventional (commercial) liquid electrolyte in air (or other inert atmosphere) with both water and oxygen contents below 5 ppm.

The measuring method comprises the following steps: the cell was cycled using a LAND CT2001A charge-discharge instrument with a current density of 2mA cm-2 and a charge-discharge voltage range of 2.5-4.0V.

Fig. 12 shows example 30 using a conventional liquid electrolyte to LiFePO with the negative electrode covered with a protective layer current collector (with or without metal lithium sandwiched between the inducing layer and the protective layer) and the protective layer₄Cycling performance curve for the positive cell.

Example 31

This example serves to illustrate a method of assembling a solid state metal battery using a polymer electrolyte and the negative electrode current collector of the present invention.

The preparation method comprises the following steps: the required members such as the battery can are sufficiently dried. With dried LiNi_1/3Co_1/3Mn_1/3O₂The positive plate was used as a positive electrode (coating surface capacity 4.0mAh cm)^-2) The negative electrode current collector described in example 2 was used as a negative electrode, and Li having a garnet structure was used_6.4La₃Zr_1.4Ta_0.6O₁₂(LLZTO) as a solid electrolyte, assembled into a battery in air (or other inert atmosphere) with water and oxygen content below 5 ppm.

The current density is 2.0mA cm when the test is carried out on a blue battery tester^-2The voltage range is 2.5-4.3V. Cycling at 50 ℃. The circulating coulombic efficiency is more than 99%. After 300 cycles, the capacity retention rate is more than 99%.

Example 32

The preparation method comprises the following steps: the required members such as the battery can and the separator are sufficiently dried. With dried LiFePO₄The positive plate was used as a positive electrode (coating surface capacity 4.0mAh cm)^-2) With the current collector described in example 4 as a negative electrode, PEO-LiTFSI (EO: Li ═ 12; noted as PEO-LiTFSI) polymer electrolyte, assembled into a battery in an air atmosphere having a water content of less than 1 ppm.

The current density is 2.0mA cm when the test is carried out on a blue battery tester^-2The voltage range is 2.5-4.0V. Cycling at 60 ℃. The circulating coulombic efficiency is more than 99%. After 300 cycles, the capacity retention rate is more than 99%.

Example 33

This example is intended to illustrate a method of assembling a secondary metal battery using a polymer-ceramic composite solid electrolyte and a metal negative electrode according to the present invention.

The preparation method comprises the following steps: the required members such as the battery can are sufficiently dried. With dried LiFePO₄The positive plate was used as a positive electrode (coating surface capacity 4.0mAh cm)^-2) With the metal negative electrode prepared in example 26 of the present invention as a negative electrode, a LLZTO/(PEO-LiTFSI) composite solid electrolyte (ceramic electrolyte: a polymer electrolyte mass ratio of 9:1) is added, and a battery is assembled in an air atmosphere with the water content of less than 1 ppm.

The current density is 2.0mA cm when the test is carried out on a blue battery tester^-2The voltage range is 2.5-4.0V, and the cycle is carried out at 60 ℃. The circulating coulombic efficiency is more than 99%. After 300 cycles, the capacity retention rate is more than 99%.

Example 34

This example is for explaining a method of assembling a secondary metal battery using a semi-solid electrolyte and the negative electrode current collector of the present invention.

The preparation method comprises the following steps: the required members such as the battery can are sufficiently dried. The dried LiNi_0.85Co_0.05Mn_0.1O₂The positive plate was used as a positive electrode (coating surface capacity 4.0mAh cm)^-2) The negative electrode current collector prepared in example 28 was used as a negative electrodeAdsorbed/adhered with a small amount (less than 5 wt%) of 1M DMF/LiPF₆Li of solution_1.3Al_0.3Ti_1.7(PO₄)₃(LATP) ceramic electrolytes (containing PVDF5 wt%) were assembled into cells in air (or other inert atmosphere) with water and oxygen content below 5ppm (DMF is dimethylformamide).

The current density is 2.0mA cm when the test is carried out on a blue battery tester^-2The voltage range is 2.5-4.3V. Cycling at 60 ℃. The circulating coulombic efficiency is more than 99%. After 300 cycles, the capacity retention rate is more than 99%.

Example 35

This example is intended to illustrate a method of assembling a secondary metal battery using a semi-solid electrolyte and a metal negative electrode of the present invention.

The preparation method comprises the following steps: the required members such as the battery can are sufficiently dried. The dried LiNi_0.5Mn_1.5O₄The positive plate was used as a positive electrode (coating surface capacity 4mAh cm)^-2) A battery was assembled using the metal negative electrode described in example 28 as a negative electrode, and PVDF/DMF/LiTFSI semi-solid (gel) electrolyte in an argon atmosphere with water and an oxygen content of less than 1 ppm.

The current density is 2.0mA cm when the test is carried out on a blue battery tester^-2The voltage range is 3.5-4.9V. Cycling at 60 ℃. The circulating coulombic efficiency is more than 99%. After 300 cycles, the capacity retention rate is more than 99%.

Example 36

This example is intended to illustrate a method of assembling a secondary metal battery using a commercial liquid electrolyte and a metal negative electrode of the present invention.

The preparation method comprises the following steps: the required members such as the battery can are sufficiently dried. With dried FeF₃The electrode slice is used as the anode (the coating surface density is 4.0mAh cm)^-2) A battery was assembled in an argon atmosphere containing less than 1ppm of water and oxygen, using the metal negative electrode described in example 14 as a negative electrode (the capacity of the metal lithium negative electrode was 20% more than that of the positive electrode plate), and using a 1M LiFSI/DOL-DME solution as an electrolyte.

In the blueThe current density is 2.0mA cm when the test is carried out on a pool tester^-2The voltage range is 1.5-4.0V, and the coulombic efficiency is more than 99%. After 300 cycles, the capacity retention rate is more than 99%.

Although the present invention has been described to a certain extent, it is apparent that appropriate changes in the respective conditions may be made without departing from the spirit and scope of the present invention. It is to be understood that the invention is not limited to the described embodiments, but is to be accorded the scope consistent with the claims, including equivalents of each element described.

Claims

1. The negative current collector is characterized by comprising a current collector base material and an inducing layer covering the surface of the current collector base material, wherein the inducing layer is used for inducing metal deposition;

wherein the material of the induction layer is A_xD_y(x: y ═ 0.1 to 10.0), and the element a is selected from one or more of: boron, carbon, nitrogen, magnesium, aluminum, silicon, phosphorus, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, yttrium, zirconium, niobium, molybdenum, silver, cadmium, indium, tin, antimony, barium, tungsten, iridium, platinum, gold, lead, bismuth, lanthanum, cerium, said element D being selected from one or more of carbon, boron, nitrogen, phosphorus, silicon, fluorine, hydrogen;

2. The negative electrode current collector of claim 1, wherein the inducing layer has a thickness of 10 to 2000nm, preferably 50 to 1500 nm.

3. The negative electrode current collector according to claim 1 or 2, wherein the surface of the inducing layer of the negative electrode current collector is further covered with a protective layer;

The protective layer material is selected from one or more of the following: PEO/LiTFSI polymer electrolyte membrane, PEO/LiPF₆Polymer electrolyte membrane, PPC/LiTFSI polymer electrolyte membrane, PPC/LiPF₆Polymer electrolyte membrane, PAN/LiClO₄Polymer electrolyte membrane, PAN/LiClO₄Polymer electrolyte membrane, PPC/NaTFSI polymer electrolyte membrane, PEO/NaPF₆Polymer electrolyte membrane, MgX₂-Li_yMg (X ═ F, Cl, Br, I; y ═ 0.001-1000) complex, LiF/Mg_xLi (x ═ 0.001 to 1000) complex, Li-Li_xAnd a Sn-PTMEG (x is 0.001-1000) composite protective layer.

4. The negative electrode current collector of claim 3, wherein an active metal layer is further included between the inducing layer and the protective layer;

preferably, the material of the active metal layer is lithium or sodium; and/or

Preferably, the thickness of the active metal layer is 0.1 to 200 μm, more preferably 0.5 to 100 μm.

5. The method for preparing the negative electrode current collector according to any one of claims 1 to 4, wherein the method comprises preparing an inducing layer on the surface of the current collector base material;

6. The method according to claim 5, wherein the method of preparing the inducing layer is a plasma-based ion implantation, the method comprising the steps of: placing a current collector base material containing an element A in a precursor atmosphere containing an element D, and combining the element D and the element A in the current collector base material on the surface of the current collector base material by a low-temperature plasma surface treatment technology to form an inducing layer;

The partial pressure of the precursor gas is 80-100%, preferably 95.0-99.9%.

7. The method according to claim 6, wherein the temperature of the current collector base material is 300-1200 ℃, preferably 500-1200 ℃, and more preferably 600-1000 ℃; and/or

The implantation dose is 10¹⁵～10¹⁸ions/cm²。

8. The method according to claim 6 or 7, wherein when the current collector base material does not contain element A, a plating layer of element A is plated on the surface of the current collector base material;

preferably, the thickness of the plating layer is 5nm to 500 nm.

9. The method according to claim 5, characterized in that the method of preparing the inducing layer is a coating, comprising the steps of: mixing and dispersing the inducing layer material and the bonding material in a diluent, coating slurry on the surface of the current collector substrate material, and drying to obtain the inducing layer;

preferably, the bonding material is selected from one or more of the following: PVDF, PAN, PAA, SBR, CMC; the diluent is selected from one or more of the following: NMP, DMSO, DMF, DMC, DEC, AN.

10. A battery comprising the negative electrode current collector of any one of claims 1 to 4 or the negative electrode current collector prepared according to the method of any one of claims 5 to 9;