CN115377418A - Metal nitride composite lithium metal negative electrode material and preparation method thereof - Google Patents

Metal nitride composite lithium metal negative electrode material and preparation method thereof Download PDF

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Publication number
CN115377418A
CN115377418A CN202110560929.XA CN202110560929A CN115377418A CN 115377418 A CN115377418 A CN 115377418A CN 202110560929 A CN202110560929 A CN 202110560929A CN 115377418 A CN115377418 A CN 115377418A
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lithium
metal
nitride
negative electrode
alloy
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阮瑾
李晶泽
王志红
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a metal nitride composite metal lithium negative electrode material and a preparation method thereof, belonging to the field of lithium battery negative electrode materials. The invention leads the metal nitride and the metal lithium to generate the replacement reaction through the heat treatment, thereby forming the lithium metal surface protection layer which is stable and has good electronic conductivity and ionic conductivity. The modification method keeps the advantage of high lithium negative electrode capacity, can prevent the side reaction of the lithium metal and the electrolyte, and simultaneously provides sites for the deposition of the lithium metal by the alloy phase formed by the replacement reaction, thereby effectively inhibiting the generation of lithium dendrite and prolonging the service life of the battery. The composite lithium negative electrode provided by the invention not only maintains the advantages of metal lithium, but also has excellent dendritic crystal inhibition effect, and can prolong the cycle life of a lithium secondary battery when being used as a negative electrode material.

Description

Metal nitride composite lithium metal negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of battery cathode materials; in particular to a composite lithium metal negative electrode material and a preparation method thereof.
Background
With the rapid development of portable electronic products (notebook computers, mobile phones, cameras, electric bicycles, and the like) and the current situation that electric vehicles are replacing fuel vehicles with higher speed, lithium ion batteries have failed to meet the needs of people, and the development of novel chargeable and dischargeable energy storage devices with higher energy density, longer service life and more stability is urgently needed. Lithium metal is considered to be the best choice for the negative electrode material of the next generation lithium secondary battery due to its ultra-high theoretical specific capacity (3860 mAh/g) and extremely low electrochemical potential (-3.04V relative to the standard hydrogen electrode). However, practical application of metallic lithium negative electrodes is hampered by lithium dendrites. Lithium negative electrodes are subjected to repeated formation and breakage of lithium dendrites during charge and discharge cycles, the disconnected dendrites become "dead lithium" and do not contribute to capacity, and the dendrites penetrating the separator can cause short-circuiting of the battery and even explosion of the battery. In addition, lithium dendrites increase the surface area of the negative electrode, causing the continuous reaction of metallic lithium with the electrolyte, thereby reducing the coulombic efficiency of the battery. In addition, the solid electrolyte interface film generated by the reaction of lithium and the electrolyte has poor stability, is easy to crack, exposes fresh lithium inside the solid electrolyte, continuously consumes the electrolyte, shortens the cycle life of the battery and reduces the coulombic efficiency of the battery.
In order to solve these problems, researchers have made many attempts including the use of electrolyte additives, artificial SEI films, magnetron sputtering coating, etc., however, these modification methods are complicated to operate, are harsh in conditions, and cannot be mass-produced. Therefore, there is an urgent need for a method for modifying lithium metal, which is simple to prepare, has a good dendrite-inhibiting effect, and can be industrially produced.
Disclosure of Invention
In order to solve the problems, the invention uses metal nitride to perform a replacement reaction with metal lithium to form a composite lithium metal cathode, and can effectively inhibit dendritic crystal growth and other problems in the lithium ion deposition process by utilizing a surface protection layer provided by an alloy phase and the lithium nitride. The lithium nitride generated by the action of the metal nitride and the metal lithium has good ionic conductivity, the mobility of lithium ions on the surface of the metal negative electrode can be effectively improved, and meanwhile, the alloy layer formed on the surface can greatly improve the conductivity of the surface of the metal lithium, be beneficial to uniform distribution of an electric field and inhibit the growth of dendritic crystals. The composite lithium metal cathode provided by the invention is simple to prepare and stable in structure, and can prolong the service life of the lithium metal cathode.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Mixing metal nitride powder, adhesive and conductive agent, coating the mixture on copper foil, and performing vacuum drying to obtain a metal nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until metal luster appears;
(3) Bonding and tabletting the polished metal lithium and the metal nitride pole piece in the step (1), and simultaneously carrying out heating treatment;
(4) And separating the metal lithium and the metal nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using an anhydrous organic solvent to obtain the composite lithium metal cathode.
Further, in a preferred embodiment of the present invention, the metal nitride in step (1) is one or more of aluminum nitride, zinc nitride, copper nitride, cuprous nitride, tin nitride, magnesium nitride, calcium nitride, barium nitride, silver nitride, cobalt nitride, and chromium nitride.
Further, in a preferred embodiment of the present invention, the binder in step (1) is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile, and carboxymethyl cellulose.
Further, in a preferred embodiment of the present invention, the conductive agent in step (1) is one or more of conductive carbon black, conductive graphite, acetylene black, vapor grown carbon fiber, carbon nanotube and graphene.
Further, in a preferred embodiment of the present invention, the mass ratio of the metal nitride, the adhesive and the conductive agent in step (1) is 7:2:1.
further, in the preferred embodiment of the present invention, the tabletting pressure in step (3) is 100-500MPa.
Further, in the preferred embodiment of the present invention, the metal nitride in step (3) undergoes a substitution reaction with metal lithium, in this caseIn the preferred embodiment 1 of the invention, the substitution reaction is 4AlN + (21 + x) Li → Li 9 Al 4 +4Li 3 N+xLi。
Further, in a preferred embodiment of the present invention, the heating temperature in step (3) is 50-180 ℃.
Further, in a preferred embodiment of the present invention, the heating time in step (3) is 10-30 min.
Further, in a preferred embodiment of the present invention, the anhydrous organic solvent in step (4) is one or more combinations of ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethylene glycol dimethyl ether.
Further, in a preferred embodiment of the present invention, the metal nitride composite lithium metal negative electrode material obtained in step (4) contains a lithium alloy phase, which includes one or more of a lithium aluminum alloy, a lithium tin alloy, a lithium copper alloy, a lithium magnesium alloy, a lithium calcium alloy, a lithium barium alloy, a lithium silver alloy, a lithium cobalt alloy, and a lithium chromium alloy.
The method regulates and controls the thickness of the protective layer by controlling the temperature and time in the replacement reaction process, has controllability, is simple in preparation method, has low requirements on equipment, and can effectively improve the cycle performance of the lithium secondary battery by using large-scale industrial production.
Detailed Description
The following is an alternative embodiment of the embodiments of the present invention, and it will be apparent to those skilled in the art that several modifications may be made without departing from the principle of the embodiments of the present invention, and these modifications are also considered to be within the scope of the embodiments of the present invention.
Example 1
A preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Aluminum nitride powder, polyvinylidene fluoride and acetylene black are mixed according to a mass ratio of 7:2:1, mixing, coating on a copper foil, and performing vacuum drying to obtain an aluminum nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until metal luster appears;
(3) Attaching the polished lithium metal to the aluminum nitride pole piece in the step (1), tabletting, heating at the temperature of 100 ℃ for 10min under the pressure of 300 Mpa;
(4) And separating the metal lithium and the tin nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using ethylene carbonate to obtain the composite lithium metal cathode.
Example 2
A preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Mixing tin nitride powder, polyvinylidene fluoride and Super P in a mass ratio of 7:2:1, mixing, coating on a copper foil, and performing vacuum drying to obtain a tin nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until metal luster appears;
(3) Attaching the polished lithium metal to the aluminum nitride pole piece in the step (1), tabletting, heating at the temperature of 60 ℃ for 20min under the pressure of 200 Mpa;
(4) And separating the metal lithium and the tin nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using dimethyl carbonate to obtain the composite lithium metal cathode.
Example 3
A preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Calcium nitride powder, polytetrafluoroethylene and acetylene black are mixed according to a mass ratio of 7:2:1, mixing, coating on a copper foil, and drying in vacuum to obtain a calcium nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until metal luster appears;
(3) Attaching the polished lithium metal to the aluminum nitride pole piece in the step (1), tabletting, heating at the temperature of 100 ℃ for 20min under the pressure of 500 Mpa;
(4) And separating the metal lithium and the calcium nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using ethylene carbonate to obtain the composite lithium metal cathode.
Example 4
A preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Copper nitride powder, polytetrafluoroethylene and Super P are mixed according to a mass ratio of 7:2:1, mixing, then coating on a copper foil, and carrying out vacuum drying to obtain a copper nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until a metal luster appears;
(3) Bonding and tabletting the polished metal lithium and the copper nitride electrode plate in the step (1) under the pressure of 500Mpa, and simultaneously heating at the temperature of 120 ℃ for 20min;
(4) And separating the metal lithium and the copper nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using ethylene carbonate to obtain the composite lithium metal cathode.
Example 5
A preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Magnesium nitride powder, polytetrafluoroethylene and Super P are mixed according to a mass ratio of 7:2:1, mixing, coating on a copper foil, and performing vacuum drying to obtain a magnesium nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until a metal luster appears;
(3) Attaching the polished lithium metal to the magnesium nitride pole piece in the step (1), tabletting, heating at 80 ℃ for 20min under the pressure of 500 Mpa;
(4) And separating the metal lithium and the magnesium nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using diethyl carbonate to obtain the composite lithium metal cathode.
Example 6
A preparation method of a metal nitride composite lithium metal negative electrode material comprises the following steps:
(1) Mixing silver nitride powder, polytetrafluoroethylene and Super P according to a mass ratio of 7:2:1, mixing, coating on a copper foil, and drying in vacuum to obtain a silver nitride pole piece;
(2) Polishing the surface of the metal lithium in an argon atmosphere until metal luster appears;
(3) Bonding and tabletting the polished metal lithium and the silver nitride electrode plate in the step (1) under the pressure of 500Mpa, and simultaneously heating at the temperature of 100 ℃ for 20min;
(4) And separating the metal lithium and the silver nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using diethyl carbonate to obtain the composite lithium metal cathode.

Claims (10)

1. A metal nitride composite lithium metal negative electrode material is characterized in that a lithium metal negative electrode with a surface protection layer is formed by reacting a metal nitride with the surface of metal lithium through a hot pressing method.
2. The metal nitride composite lithium metal anode material of claim 1, wherein the metal nitride is one or more of aluminum nitride, zinc nitride, copper nitride, cuprous nitride, tin nitride, magnesium nitride, calcium nitride, barium nitride, silver nitride, cobalt nitride, and chromium nitride.
3. The method for preparing any one of the metal nitride composite lithium metal negative electrode materials according to claim 1 or 2, the preparation method comprising the steps of:
(1) Mixing metal nitride powder, an adhesive and a conductive agent, coating the mixture on a copper foil, and performing vacuum drying for 12 hours in an environment at 80 ℃ to obtain a metal nitride pole piece;
(2) Polishing the surface of the metal lithium in an inert atmosphere environment, and removing a surface passivation layer and impurities until the surface has metallic luster;
(3) Bonding and tabletting the polished metal lithium and the metal nitride pole piece in the step (1), and simultaneously carrying out heating treatment;
(4) And separating the metal lithium and the metal nitride pole piece, and simultaneously cleaning the surface of the lithium metal by using an anhydrous organic solvent to obtain the composite lithium metal cathode.
4. The preparation method of the metal nitride composite lithium metal negative electrode material according to claim 3, wherein the binder in the step (1) is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, polyacrylonitrile and carboxymethyl cellulose.
5. The method for preparing the metal nitride composite lithium metal anode material according to claim 3, wherein the conductive agent in the step (1) is one or more of conductive carbon black, conductive graphite, acetylene black, vapor-grown carbon fiber, carbon nanotube and graphene.
6. The method for preparing the metal nitride composite lithium metal negative electrode material according to claim 3, wherein the mass ratio of the metal nitride, the binder and the conductive agent in the step (1) is 7:2:1.
7. the method according to claim 3, wherein the heating temperature in the step (3) is 50 to 180 ℃ and the heating time is 10 to 30min.
8. The preparation method according to claim 3, wherein the anhydrous organic solvent in step (4) is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate and ethylene glycol dimethyl ether.
9. The preparation method according to claim 3, wherein the metal nitride composite lithium metal negative electrode material obtained in the step (4) contains a lithium alloy phase comprising one or more of a lithium aluminum alloy, a lithium tin alloy, a lithium copper alloy, a lithium magnesium alloy, a lithium calcium alloy, a lithium barium alloy, a lithium silver alloy, a lithium cobalt alloy and a lithium chromium alloy.
10. Use of the metal nitride composite lithium metal negative electrode material obtained by the method of any one of claims 1 to 9 in a lithium secondary battery.
CN202110560929.XA 2021-05-20 2021-05-20 Metal nitride composite lithium metal negative electrode material and preparation method thereof Pending CN115377418A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118039806A (en) * 2024-04-12 2024-05-14 蜂巢能源科技股份有限公司 Negative electrode plate, preparation method thereof and battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118039806A (en) * 2024-04-12 2024-05-14 蜂巢能源科技股份有限公司 Negative electrode plate, preparation method thereof and battery
CN118039806B (en) * 2024-04-12 2024-06-11 蜂巢能源科技股份有限公司 Negative electrode plate, preparation method thereof and battery

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