CN111755668B - Nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, anode, lithium metal battery and preparation and application thereof - Google Patents

Nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, anode, lithium metal battery and preparation and application thereof Download PDF

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CN111755668B
CN111755668B CN201910233628.9A CN201910233628A CN111755668B CN 111755668 B CN111755668 B CN 111755668B CN 201910233628 A CN201910233628 A CN 201910233628A CN 111755668 B CN111755668 B CN 111755668B
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lithium
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lithium metal
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赖延清
洪波
高春晖
向前
范海林
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Central South University
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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

Abstract

The invention belongs to the field of lithium metal batteries, and particularly discloses a nitrogen-oxygen co-doped carbon-coated metal lithium anode active material which is characterized by comprising a carbon hollow ball and a metal lithium simple substance filled in an inner cavity of the carbon hollow ball; the spherical wall material of the carbon hollow sphere is nitrogen-oxygen co-doped graphitized carbon, and the spherical wall has a mesoporous structure. The invention also discloses a lithium metal anode containing the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material and a lithium metal battery. The nitrogen-oxygen co-doped carbon hollow sphere can effectively reduce overpotential in the nucleation and deposition processes of metal lithium, provide uniform nucleation and deposition sites, enable the metal lithium to stably and uniformly grow in a current collector, and realize uniform deposition and dissolution of a lithium metal anode in a long-cycle process. In addition, the stable and ordered carbon skeleton can greatly reduce the volume expansion in the circulation process, and greatly improve the cycle life and the safety performance of the lithium metal battery.

Description

Nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, anode, lithium metal battery and preparation and application thereof
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly discloses an active material of a lithium metal battery.
Background
At present, lithium ion batteries are widely applied to advanced portable electronic products, electric automobiles and energy storage power stations, and with the increasing demand for energy density of batteries, the development of high specific energy secondary batteries has become a research hotspot in recent years. The lithium metal anode has a high capacity3860mA/cm2The theoretical specific capacity and the electrode potential of-3.045V (relative to a standard hydrogen electrode) are known as 'holy cup' grade lithium anode materials, but the problems of dendritic crystals, high volume effect and the like in the repeated circulation process of the lithium anode cause low coulombic efficiency and poor circulation performance; also the growth of lithium dendrites may puncture the separator causing short circuits, causing serious safety problems.
In view of the problems of lithium metal anode's rechargeable performance, especially the problem of dendrite growth, researchers have recently proposed various methods to improve lithium anode performance, which can be roughly classified into: (1) by constructing an artificial SEI film on the surface of a lithium anode or using an electrolyte additive; (2) inorganic or organic all-solid-state electrolyte is adopted; (3) adopting high-concentration electrolyte; (4) a 3D current collector was used as a deposition substrate for lithium metal. From the electrochemical perspective, the 3D current collector can reduce the actual local current density in the battery, effectively inhibit the generation of lithium dendrites, and in addition, the structure of the 3D current collector can effectively relieve the volume expansion caused in the lithium anode dissolution and deposition process. However, the high specific surface area of the 3D current collector also causes a large number of side reactions to occur, so that the coulombic efficiency of the lithium anode is still difficult to improve. Therefore, the solution of the lithium dendrite problem and the improvement of the coulombic efficiency and volume effect of the lithium anode are the necessary ways to move the lithium anode or the lithium metal battery to the industrialization.
Disclosure of Invention
Aiming at the problems of dendritic crystals, low coulombic efficiency, poor cyclicity and the like of the conventional metal lithium anode, the first purpose of the invention is to provide a nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, aiming at improving the stability of the lithium anode and improving the electrical performance of the lithium anode.
The second objective of the invention is to provide a preparation method of the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material.
The third objective of the present invention is to provide a lithium metal anode added with the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material.
It is a fourth object of the present invention to provide a lithium metal battery equipped with the lithium metal anode.
Lithium metal batteries differ from lithium ion batteries in the nature of their mechanism of action, for example, the mechanism of action of a lithium metal battery anode in a battery is the deposition and dissolution of lithium metal, the basic reaction formula of which is: charging of Li++ e ═ Li; discharge Li-e ═ Li+(ii) a Whereas the anode of the conventional lithium ion battery is subject to intercalation and deintercalation of lithium ions in the graphite anode. The difference between the lithium metal battery and the lithium ion battery in the mechanism of action is essentially different in the requirements for the material.
Although the lithium metal battery theoretically has better specific discharge capacity, the lithium metal battery also has a plurality of problems, and the high activity of the lithium metal anode leads the lithium metal anode to be easy to react with nitrogen, oxygen, carbon dioxide, water vapor and the like in the air; these irreversible reactions pose a significant safety risk to the production of lithium batteries. Meanwhile, it cannot avoid continuous reaction with the solvent and additives in the electrolyte, resulting in continuous destruction and reformation of the SEI film on the surface of lithium metal during the deposition/dissolution of lithium, ultimately resulting in low coulombic efficiency and uncontrollable growth of lithium dendrites. For this reason, the present inventors have made extensive studies and have provided the following technical solutions:
a nitrogen-oxygen co-doped carbon-coated metal lithium anode active material comprises a carbon hollow ball and a metal lithium simple substance filled in an inner cavity of the carbon hollow ball; the spherical wall material of the carbon hollow sphere is nitrogen-oxygen co-doped graphitized carbon, and the spherical wall has a mesoporous structure.
The invention finds that N, O diatom doping has a synergistic effect. The nitrogen-oxygen co-doped carbon hollow sphere can effectively reduce overpotential in the nucleation and deposition processes of metal lithium, provide uniform nucleation and deposition sites, enable the metal lithium to stably and uniformly grow in a current collector, and realize uniform deposition and dissolution of a lithium metal anode in a long-cycle process. In addition, the stable and ordered carbon skeleton can greatly reduce the volume expansion in the circulation process, and greatly improve the cycle life and the safety performance of the lithium metal battery. The material can effectively solve the problems of dendritic crystals, low coulombic efficiency, poor cyclicity and the like of the existing lithium metal anode; the specific capacity of the first circle of the material and the cycling stability under high current density are obviously improved.
The research of the inventor also finds that the electrical property of the active material can be further improved by controlling the specific surface area and the thickness of the lithium metal anode active material and the volume ratio of the internal cavity.
Preferably, the specific surface area of the carbon hollow sphere is 50-1000m2A/g, preferably from 50 to 500m2Per g, more preferably 80 to 250m2(ii)/g; most preferably 100-2(ii) in terms of/g. The effects are more excellent in the preferred ranges, for example, the stability and electrical properties of the lithium metal anode active material are more excellent.
Preferably, the thickness of the spherical wall of the carbon hollow sphere is 0.5-100nm, preferably 5-95nm, and more preferably 5-30 nm; further preferably 15 to 25 nm; most preferably 15 to 20 nm. The electrical properties are more excellent in the preferred range.
Preferably, the volume of the inner cavity of the carbon hollow sphere accounts for 40-99%; preferably 60 to 97%; further preferably 80 to 95%. The electrical properties are more excellent in the preferred range.
During the technical development process, the inventor unexpectedly finds that N, O double doping has a synergistic effect; the synergistic effect can be further improved by further regulating and controlling the double doping content of N, O.
Preferably, the oxygen content in the hollow carbon sphere is 0.01 to 10 at.%, preferably 1 to 9at.%, and more preferably 1 to 7 at.%; more preferably 2.5 to 5.5 at.%.
Preferably, the nitrogen content in the hollow carbon sphere is 0.01 to 10 at.%, preferably 0.05 to 5 at.%, and more preferably 1 to 4 at.%.
Researches show that the synergistic effect of the doping of the N, O double doping can be further improved and the electrical performance can be further improved by controlling the doping content of the N, O double doping.
Preferably, in the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, the amount of the filled metal lithium is 0.4-200 mAh/cm2(ii) a Further preferably 5 to 160mAh/cm2(ii) a Further preferably 30 to 100mAh/cm2。
The invention also provides a preparation method of the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, wherein the carbon hollow spheres are subjected to oxidation treatment to obtain carbon oxide hollow spheres; roasting the carbon oxide hollow sphere in a nitrogen-containing atmosphere; obtaining the N, O codoped carbon hollow sphere;
and filling a metal lithium simple substance into the N, O codoped carbon hollow sphere to prepare the nitrogen-oxygen codoped carbon-coated metal lithium anode active material.
Preferably, the oxidation treatment is carried out in a strongly oxidizing acid.
Preferably, the strong oxidizing acid is one or more of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid.
In the present invention, the amount of O incorporated can be controlled by controlling the treatment time in the solution of the strongly oxidizing acid.
Preferably, the oxidation treatment time is 10-1200min, preferably 100-.
Preferably, the nitrogen-containing atmosphere contains at least one gas of nitrogen and ammonia.
Preferably, the roasting temperature is 500-1500 ℃, preferably 500-1200 ℃; further preferably 500-. Under the preferred roasting temperature, on one hand, the N content can be regulated and controlled to realize the atomic layer doping of N, and on the other hand, the graphitization degree of the carbon wall can be improved; and further, the multi-way cooperation improves the electrical properties such as the cyclicity of the prepared material.
Preferably, the calcination time is 10-1200min, preferably 60-1000min, and more preferably 300-800 min.
According to the invention, the N, O co-doped carbon hollow sphere can be filled with a lithium metal simple substance by adopting the existing method. Such as electroplating or melting.
The invention also provides a metal lithium battery anode which comprises the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material.
Preferably, the current collector comprises a planar metal current collector and an active layer compounded on the surface of the planar metal current collector; the active layer comprises the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material and a binder.
Preferably, the thickness of the active layer is 1 to 1000 μm, preferably 20 to 500 μm, and more preferably 50 to 300 μm; wherein the binder accounts for 1-50%, preferably 2-20%.
Preferably, the material of the planar metal current collector is at least one of copper, titanium, nickel, iron and cobalt; the thickness thereof is preferably 2 to 200. mu.m.
Preferably, the binder is at least one of polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyethylene, polypropylene, polyvinylidene chloride, SBR rubber, fluorinated rubber and polyurethane.
The anode can be prepared by adopting the existing method; for example, the anode is prepared by slurrying a binder and the active anode material of the present invention with a dispersant, coating the slurry on the surface of the planar metal current collector, and drying the slurry.
In the anode, the amount of metal lithium is 0.4-200 mAh/cm2(ii) a Further preferably 5 to 160mAh/cm2(ii) a Further preferably 30 to 100mAh/cm2。
The invention also provides a lithium metal battery which is provided with the anode.
Preferably, the metal lithium battery is a lithium sulfur battery, a lithium oxygen battery, a lithium iodine battery, a lithium selenium battery, a lithium tellurium battery, a lithium oxygen battery or a lithium carbon dioxide battery.
Advantageous effects
The invention provides a high-stability metal lithium anode active material, wherein an internal cavity of a carbon hollow sphere provides a storage site for a metal lithium simple substance, and nitrogen-oxygen double-synergistic doping of the spherical wall of the carbon hollow sphere can induce metal lithium deposition.
The lithium metal anode active material can effectively reduce the apparent current density, relieve the volume effect and inhibit the interface reaction, and solves the problems of dendritic crystals, low coulombic efficiency, poor cyclicity and the like of the conventional lithium metal anode; the specific capacity of the first circle of the material and the cycling stability are obviously improved.
Tests show that the inventionThe lithium metal anode active material has better stability, higher first discharge capacity and better cycle stability. Researches show that the material is 8-10 mA/cm2Can show good stability under high current density.
Drawings
FIG. 1 is an SEM image of hollow carbon spheres prepared in example 1;
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.
Example 1
Hollow carbon spheres (specific surface area 100 m)2The carbon wall thickness is 5nm, the internal cavity volume accounts for 90% of the total volume, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) performing ultrasonic treatment for 30min, stirring for 400min, centrifuging, and drying; and then the mixture is subjected to heat treatment in ammonia gas and argon gas (gas volume ratio: 2: 8) at 500 ℃ for 60min to obtain the doped carbon hollow sphere material (the oxygen content is 5.5 at.%, and the oxygen content is 3.2 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 20 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 1.
Comparative example 1
Pure copper foil is used as a working electrode, a metal lithium sheet is used as a counter electrode, and 1M LiTFSI/DOL/DME (volume ratio is 1: 1) contains 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2The charge-discharge cycle test was carried out at the current density of (1). The relevant results of the tests are shown in table 1.
Comparative example 2
Pure copper foil is used as a working electrode, and metal lithium is usedThe sheet is a counter electrode and contains 1 wt.% LiNO in a volume ratio of 1M LiTFSI/DOL to DME (1: 1)3Assembling the soft package battery for the electrolyte at 3mA/cm2The charge-discharge cycle test was carried out at the current density of (1). The relevant results of the tests are shown in table 1.
Comparative example 3
Mixing acetylene black and polyvinylidene fluoride according to a mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 20 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 1.
Comparative example 4
Hollow carbon spheres (specific surface area 100 m)2(g, carbon wall thickness 5nm, internal cavity volume 90% of the total volume), ammonia and argon placed at 500 ℃ (gas volume ratio: 2: 8) and performing heat treatment for 60min to obtain the doped hollow spherical carbon material (the nitrogen content is 3.5 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 20 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 1.
Comparative example 5
Hollow carbon spheres (specific surface area 100 m)2The carbon wall thickness is 5nm, the internal cavity volume accounts for 90% of the total volume, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 400min, and then centrifuged and dried to obtain the doped hollow sphere carbon material (with the oxygen content of 2.3 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 20 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 3mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 1.
Example 2
Full cell case:
hollow carbon spheres (specific surface area 100 m)2The carbon wall thickness is 5nm, the internal cavity volume accounts for 90% of the total volume, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 400min, and then centrifuged and dried to obtain the doped hollow sphere carbon material (with the oxygen content of 2.3 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 20 μm. Then depositing 50mAh/cm into the hollow carbon sphere cavity through electrochemical deposition2The lithium metal (2) was used as a negative electrode, a sulfur positive electrode (sulfur loading 52%) was used as a positive electrode, and 1M LiTFSI/DOL DME (volume ratio 1: 1) contained 1 wt.% LiNO3The whole cell was assembled for the electrolyte (E/S20) at 3mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 1.
Example 3
Hollow carbon spheres (specific surface area 146 m)2The carbon wall thickness is 12nm, the internal cavity volume accounts for 92% of the total volume), and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 300min, and then centrifuged and dried to obtain the doped hollow sphere carbon material (with the oxygen content of 1.98 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 50 μm. Then depositing 50mAh/cm into the hollow carbon sphere cavity through electrochemical deposition2The metal lithium of (2) was used as a negative electrode, the ternary material (811) was used as a positive electrode, and 1.0M LiPF was used6in EC: DMC: DEC: 1:1:1 Vol% with 1.0% VC as electrolyte (E/S: 5) to carry out the whole cell assembly, and the charge-discharge cycle test is carried out under the current of 1C. The results of the tests are shown in table 1.
Example 4
Hollow carbon spheres (specific surface area 153 m)2A carbon wall of 12nm thickness, an internal cavityVolume of 91% of the total volume), dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 350min, and then centrifuged and dried to obtain the doped hollow sphere carbon material (with the oxygen content of 2.1 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 40 μm. Then depositing 50mAh/cm into the hollow carbon sphere cavity through electrochemical deposition2The lithium metal of (2) was used as a negative electrode, air was used as a positive electrode, and 1.0M LiClO was used as a negative electrode4The whole cell was assembled using 100 Vol% in DMSO as an electrolyte (E/S10), and a charge-discharge cycle test was performed at a current of 1C. The results of the tests are shown in table 1.
TABLE 1
Figure BDA0002007473370000081
Compared with the comparative examples 1-4 and 1-5, the nitrogen-oxygen co-doped composite planar metal lithium anode has the best cycle performance.
Example 5
The carbon hollow sphere (the specific surface area is shown in table 2, the carbon wall thickness is 28nm, and the internal cavity volume accounts for 87% of the total volume) is dispersed in a mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid (the volume ratio is 3: 1), ultrasonic treatment is carried out for 30min, stirring is carried out for 600min, then centrifugation and drying are carried out, and the mixture is placed in ammonia gas at 500 ℃ for heat treatment for 240min, so that the doped hollow sphere carbon material (the oxygen content is 5 at.%, and the nitrogen content is 3 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 40 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 2mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 3.
TABLE 2
Figure BDA0002007473370000082
Figure BDA0002007473370000091
Compared with composite planar lithium metal anodes with different specific surface areas, the thickness of the lithium metal anode is more preferably 100-200m2The specific surface area per gram gives the best cycle performance.
Example 6
Hollow carbon spheres (specific surface area 150 m)2The carbon wall thickness is 5, 15, 25, 35, 55, 75 and 95nm respectively, the internal cavity volume accounts for 90 percent of the total volume, and the carbon wall thickness is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 2: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 600min, and then centrifuged and dried; and then the mixture is subjected to heat treatment in ammonia gas and argon gas (gas volume ratio: 1: 9) at 700 ℃ for 180min to obtain the doped hollow spherical carbon material (oxygen content is 6.7 at.%, nitrogen content is 5.4 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 30 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 5mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 3.
TABLE 3
Figure BDA0002007473370000092
The best cycling performance was obtained at the most preferred packing chamber volume of 15-20nm compared to composite planar metallic lithium anodes of different carbon wall thickness.
Example 7
Hollow carbon spheres (specific surface area 250 m)2The carbon wall has the thickness of 85nm, the internal cavity volume respectively accounts for 40%, 50%, 60%, 70%, 80%, 90% and 95% of the total volume, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 2) in the mixing ofPerforming ultrasonic treatment for 30min, stirring for 500min, centrifuging, and drying; and then the mixture is subjected to heat treatment for 400min in ammonia gas and argon gas (gas volume ratio: 3: 7) at 600 ℃ to obtain the doped hollow spherical carbon material (oxygen content is 3.4 at.%, nitrogen content is 2.8 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 30 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 2mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 4.
TABLE 4
Figure BDA0002007473370000101
The best cycling performance is achieved at the preferred 80% -95% packed chamber volume compared to composite planar metallic lithium anodes of different chamber volumes.
Example 8
Hollow carbon spheres (specific surface area 180 m)2The carbon wall thickness is 16nm, the internal cavity volume accounts for 90 percent, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 50min, 250 min, 450 min, 650min, 850 min and 1050min respectively, and then centrifuged and dried; and then the mixture is subjected to heat treatment in ammonia gas and argon gas (gas volume ratio: 3: 7) at 700 ℃ for 300min to obtain the doped hollow spherical carbon material (the oxygen content is 1.24 at.%, 2.75 at.%, 3.39 at.%, 4.47 at.%, 7.1 at.%, 8.9 at.%, and the nitrogen content is 3.28 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 40 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 4mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the test are shown in table 5.
TABLE 5
Figure BDA0002007473370000111
The results show that the best cycle performance is obtained at the preferred oxygen content of 2.5-5.5 at.%.
Example 9
Hollow carbon spheres (specific surface area 180 m)2The carbon wall thickness is 16nm, the internal cavity volume accounts for 90 percent, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 650min respectively, and then centrifuged, dried and ground; then, the mixture was subjected to heat treatment in ammonia gas and argon gas (gas volume ratio: 1: 1) at 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ for 600min, respectively, to obtain doped hollow sphere carbon materials (oxygen content: 4.47 at.%, nitrogen content: 0.09 at.%, 1.25 at.%, 3.28 at.%, 4.59 at.%, 6.47 at.%, 8.94 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 40 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 5mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the test are shown in table 5.
TABLE 6
Figure BDA0002007473370000112
Figure BDA0002007473370000121
The results show that the best cycle performance is obtained at a nitrogen content of preferably 1 to 4 at.%.
Example 10
Hollow carbon spheres (specific surface area 180 m)2(g) carbon wall thickness of 16nm and internal cavity volume of 90%), dispersing in concentrated sulfuric acid andperforming ultrasonic treatment for 30min in mixed solution of concentrated nitric acid (volume ratio of 3: 1), respectively stirring for 650min, centrifuging, drying, and grinding; and then the mixture is subjected to heat treatment in ammonia gas and argon gas (gas volume ratio: 1: 1) at 800 ℃ for 50, 250, 450, 650, 850 and 1050min to obtain the doped hollow sphere carbon material (the oxygen content is 4.47 at.%, and the nitrogen content is 0.4 at.%, 0.85 at.%, 1.82 at.%, 2.57 at.%, 3.28 at.%, and 5.24 at.%, respectively). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 40 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 10mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the test are shown in table 5.
TABLE 6
Figure BDA0002007473370000122
The results show that the best cycle performance is achieved at the preferred calcination time of 300-800 min.
Example 11
Hollow carbon spheres (specific surface area 180 m)2The carbon wall thickness is 16nm, the internal cavity volume accounts for 90 percent, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 650min respectively, and then centrifuged and dried; then the mixture is respectively placed in ammonia gas and argon gas (gas volume ratio: 1: 1) at 800 ℃ for heat treatment for 600min, and doped hollow sphere carbon material (oxygen content is 4.47 at.%, nitrogen content is 3.28 at.%) is obtained. And then respectively mixing the mixture with polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyvinylidene fluoride, polyethylene, polypropylene, SBR rubber, chlorinated rubber and polyurethane according to a mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) to a thickness of 40 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3The assembly of the button cell is carried out for the electrolyte,at 8mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the tests are shown in table 8.
TABLE 8
Figure BDA0002007473370000131
The results show that polyvinylidene fluoride has the best cycle performance.
Example 12
Hollow carbon spheres (specific surface area 180 m)2The carbon wall thickness is 16nm, the internal cavity volume accounts for 90 percent, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 650min respectively, and then centrifuged and dried; and then the mixture is subjected to heat treatment in ammonia gas and argon gas (gas volume ratio: 1: 1) at 800 ℃ for 600min to obtain the doped hollow spherical carbon material (the oxygen content is 4.47 at.%, and the nitrogen content is 3.28 at.%, respectively). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on copper foil, titanium foil, nickel foil, iron foil, cobalt foil (thickness of 10 μm), respectively, to a thickness of 40 μm. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 6mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the test are shown in table 5.
TABLE 9
Figure BDA0002007473370000141
The results show that the copper foil has the best cycle performance.
Example 13
Hollow carbon spheres (specific surface area 180 m)2The carbon wall thickness is 16nm, the internal cavity volume accounts for 90 percent, and the carbon wall is dispersed in concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) the mixed solution is subjected to ultrasonic treatment for 30min, stirred for 650min respectively, and then centrifuged and dried; then placing the mixture in ammonia gas and argon gas (gas volume ratio: 1: 1) at 800 DEG CAnd performing heat treatment for 600min to obtain the doped hollow sphere carbon material (the oxygen content is 4.47 at.%, and the nitrogen content is 3.28 at.%). Then mixing the mixture with polyvinylidene fluoride according to the mass ratio of 9: 1, and then coated on a copper foil (thickness of 10 μm) at a thickness of 50, 150, 250, 350, 550, 750, 950 μm, respectively. The electrode was used as a working electrode, a lithium metal sheet was used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio 1: 1) contained 1 wt.% LiNO3Assembling the button cell for the electrolyte at 2mA/cm2At the current density of (3), a charge-discharge cycle test was performed. The results of the test are shown in table 10.
Watch 10
Figure BDA0002007473370000142
The results show that the best cycle performance is achieved at the preferred coating thickness of 50-300 μm.

Claims (23)

1. A nitrogen-oxygen co-doped carbon-coated metal lithium anode active material is characterized by comprising a carbon hollow ball and a metal lithium simple substance filled in an inner cavity of the carbon hollow ball; the spherical wall material of the carbon hollow sphere is nitrogen-oxygen co-doped graphitized carbon, and the spherical wall has a mesoporous structure;
the specific surface area of the carbon hollow sphere is 50-1000m2/g；
The thickness of the spherical wall of the carbon hollow sphere is 5-95 nm;
the volume of the inner cavity of the carbon hollow sphere accounts for 40-99%;
the oxygen content in the carbon hollow sphere is 1-9 at%; the nitrogen content is 0.01-10 at.%,
in the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material, the amount of the filled metal lithium is 0.4-200 mAh/cm2 。
2. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the specific surface area of the carbon hollow sphere is 80-250m2/g。
3. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material as claimed in claim 1, wherein the specific surface area of the carbon hollow sphere is 100-200m2/g。
4. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the spherical wall thickness of the carbon hollow sphere is 5-30 nm.
5. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the spherical wall thickness of the carbon hollow sphere is 15-20 nm.
6. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the volume of the inner cavity of the carbon hollow sphere is 80-95%.
7. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the oxygen content in the carbon hollow sphere is 1-7 at.%.
8. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the oxygen content in the carbon hollow sphere is 2.5-5.5 at.%.
9. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the nitrogen content in the carbon hollow sphere is 1-4 at.%.
10. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the amount of the filled lithium metal in the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material is 5-160 mAh/cm2。
11. The nitrogen-oxygen co-doped carbon-coated lithium metal anode active material of claim 1, wherein the amount of the filled lithium metal in the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material is 30-100 mAh/cm2。
12. The preparation method of the nitrogen-oxygen co-doped carbon-coated metal lithium anode active material as claimed in any one of claims 1 to 11, wherein the carbon hollow spheres are subjected to oxidation treatment to obtain oxidized carbon hollow spheres; roasting the carbon oxide hollow sphere in a nitrogen-containing atmosphere; obtaining the N, O codoped carbon hollow sphere;
filling a metal lithium simple substance into the N, O codoped carbon hollow sphere to prepare the nitrogen-oxygen codoped carbon-coated metal lithium anode active material;
the oxidation treatment is carried out in strong oxidizing acid; the strong oxidizing acid is one or more of concentrated sulfuric acid, concentrated hydrochloric acid and concentrated nitric acid; the oxidation treatment time is 10-1200 min;
the nitrogen-containing atmosphere at least comprises at least one gas of ammonia gas;
the roasting temperature is 500-1500 ℃;
the oxidation treatment time is 10-1200 min.
13. The method for preparing the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material as claimed in claim 12, wherein the calcination temperature is 500-1200 ℃.
14. The method for preparing a nitrogen-oxygen co-doped carbon-coated lithium metal anode active material as claimed in claim 12, wherein the calcination time is 60-1000 min.
15. The method for preparing a nitrogen-oxygen co-doped carbon-coated lithium metal anode active material as claimed in claim 12, wherein the calcination time is 300-800 min.
16. The metal lithium battery anode is characterized by comprising a planar metal current collector and an active layer compounded on the surface of the planar metal current collector; the active layer comprises a binder and the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material prepared by the preparation method of any one of claims 1 to 11, or comprises the nitrogen-oxygen co-doped carbon-coated lithium metal anode active material prepared by the preparation method of any one of claims 12 to 15;
the thickness of the active layer is 1-1000 μm;
the material of the planar metal current collector is at least one of copper, titanium, nickel, iron and cobalt;
the binder is at least one of polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyethylene, polypropylene, polyvinylidene chloride, SBR rubber, fluorinated rubber and polyurethane; in the active layer, the adhesive accounts for 2-20%;
in the anode, the amount of metal lithium is 0.4-200 mAh/cm2。
17. The lithium metal battery positive electrode of claim 16, wherein the active layer has a thickness of 20 to 500 μm.
18. The lithium metal battery positive electrode of claim 16, wherein the active layer has a thickness of 50 to 300 μm.
19. The lithium metal battery positive electrode of claim 16, wherein the amount of lithium metal in the positive electrode is 5 to 160mAh/cm2。
20. The lithium metal battery positive electrode of claim 16, wherein the amount of lithium metal in the positive electrode is 30 to 100mAh/cm2。
21. The lithium metal battery anode of claim 16, wherein the planar metal current collector has a thickness of 2 to 200 μm.
22. A lithium metal battery equipped with the anode for a lithium metal battery as claimed in any one of claims 16 to 21.
23. The lithium metal battery of claim 22, wherein the lithium metal battery is a lithium sulfur battery, a lithium oxygen battery, a lithium iodine battery, a lithium selenium battery, a lithium tellurium battery, or a lithium carbon dioxide battery.
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