CN114744150A - Long-life metal lithium battery and preparation method thereof - Google Patents

Long-life metal lithium battery and preparation method thereof Download PDF

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Publication number
CN114744150A
CN114744150A CN202210374940.1A CN202210374940A CN114744150A CN 114744150 A CN114744150 A CN 114744150A CN 202210374940 A CN202210374940 A CN 202210374940A CN 114744150 A CN114744150 A CN 114744150A
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lithium
metal
metal lithium
battery
array
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Chinese (zh)
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赵红
张勇
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Dalian Jiaotong University
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Dalian Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention belongs to the field of electrochemical new energy and special functional materials, and particularly relates to a method for preparing a long-life metal lithium battery based on a continuous extrusion device. The method comprises the following steps: (1) preparing a lithium battery cathode: extruding a metal lithium array from the porous current collector by a continuous extrusion device, wherein the extrusion power is 5-10 kW, and the extrusion time is 40-240 min; (2) assembling the battery: and (2) assembling the lithium battery cathode, the diaphragm, the lithium battery anode and the electrolyte prepared in the step (1) to obtain the metal lithium battery. According to the metal lithium battery cathode, the metal lithium foil is extruded from the micron/nanometer pore channel through the continuous extrusion device to form the regularly-arranged micron/nanometer array, so that uniform charge distribution is formed on the surface of the metal lithium cathode, and lithium dendrites are avoided; the continuous extrusion device continuously generates a metal lithium array to participate in charge-discharge reaction, so that the problem of 'dead lithium' is avoided, and the cycle life of the metal lithium is obviously prolonged.

Description

Long-life metal lithium battery and preparation method thereof
Technical Field
The invention belongs to the field of electrochemical new energy and special function materials, and particularly relates to a method for preparing a long-life metal lithium battery based on a continuous extrusion device.
Background
The lithium metal is the metal with the minimum atomic weight (6.94) and the most negative standard potential (-3.045V), and the theoretical specific capacity of the lithium metal is as high as 3860mAh/g, so the lithium metal is a high-energy-density negative electrode material with the best application prospect. However, the metal lithium battery at present adopts metal lithium foil as a negative electrode, the stability of the high-activity metal lithium negative electrode is poor, the problem of lithium dendrite is easily caused by charge aggregation in the charge-discharge cycle process of the battery, the problem of 'lithium death' caused by the disconnection of the lithium dendrite and the metal lithium foil is solved, and the cycle life of the metal lithium is greatly reduced; lithium dendrites also tend to pierce the separator, causing cell shorting and causing safety problems such as cell explosion. In order to solve the problems of lithium dendrites and 'dead lithium', the method which is generally adopted internationally and domestically is as follows:
1) adjusting the electrolyte formula, and forming a stable solid electrolyte film (SEI film) on the surface of the lithium cathode;
2) and (3) controllably synthesizing an artificial SEI film on the surface of the lithium cathode by utilizing nano materials such as graphene.
However, these methods intelligently suppress the growth rate of lithium dendrites, and have not completely eliminated the "dead lithium" problem caused by the breakage of lithium dendrites and lithium dendrites, and secondary batteries using a metallic lithium foil as a negative electrode have not been put into commercial use.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a metal lithium battery based on a continuous extrusion device, which comprises the steps of extruding a metal lithium foil from a micron/nanometer pore channel to form a regularly-arranged micron/nanometer array, and forming uniform charge distribution on the surface of a metal lithium cathode to avoid the generation of lithium dendrites; the continuous extrusion device continuously generates metal lithium micron/nanometer arrays which are regularly arranged, and the metal lithium micron/nanometer arrays participate in charge-discharge reaction, so that the problem of 'dead lithium' is avoided, and the cycle life of the metal lithium is obviously prolonged. Therefore, the method provided by the invention can effectively eliminate the lithium dendrite and the safety problems of battery short circuit, battery explosion and the like caused by the lithium dendrite, and is a commercial lithium negative battery which can be safely used.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a metal lithium battery, which comprises the following steps:
(1) preparing a lithium battery cathode: extruding a metal lithium array from a porous current collector by a continuous extrusion device, wherein the extrusion power is 5-10 kW, and the extrusion time is 40-240 min;
(2) assembling the battery: and (2) assembling the lithium battery cathode, the diaphragm, the lithium battery anode and the electrolyte prepared in the step (1) to obtain the metal lithium battery.
In the above technical solution, further, the thickness of the lithium foil in the step (1) is 1-3 mm.
In the technical scheme, the diameter of the lithium metal array extruded in the step (1) is 0.5-10 μm, and the length of the lithium metal array is 1-10 μm.
In the above technical solution, further, the porous current collector in step (1) is a copper foil or a nickel foil with a porosity of 50-90%, and the pore diameter is 0.5-10 μm.
In the above technical solution, further, the continuous extrusion device in step (1) includes a screw guiding mechanism and a driving motor, and the driving motor is a dc motor, an ac motor or a pulse stepping motor.
In the above technical solution, further, the positive electrode of the lithium battery in the step (2) is any one of lithium nickelate, lithium manganate, lithium cobaltate, or lithium iron phosphate.
In the above technical solution, further, the separator in the step (2) is any one of polyethylene and polypropylene.
In the above technical solution, further, the electrolyte in the step (2) is a mixture of ethylene carbonate, propylene carbonate, and diethyl carbonate.
The invention also provides a lithium metal battery prepared by the preparation method.
The invention provides a using method of the metal lithium battery, which comprises the following steps:
1) after the metal lithium array is obtained through the continuous extrusion action of the screw guiding device driven by a pulse stepping motor, an alternating current motor or a direct current motor, the metal lithium array is discharged for use;
2) and after the discharge is completed, continuously extruding for 40-100 min by using a pulse stepping motor, an alternating current motor or a direct current motor to drive a screw rod guide device, and obtaining the metal lithium micron/nanometer array again for the next discharge.
The invention has the beneficial effects that:
according to the metal lithium battery cathode, the metal lithium foil is extruded from the micron/nanometer pore channel through the continuous extrusion device to form the regularly-arranged micron/nanometer array, so that uniform charge distribution is formed on the surface of the metal lithium cathode, and lithium dendrites are avoided; the continuous extrusion device continuously generates metal lithium micron/nanometer arrays which are regularly arranged, and the metal lithium micron/nanometer arrays participate in charge-discharge reaction, so that the problem of 'dead lithium' is avoided, and the cycle life of the metal lithium is obviously prolonged.
Compared with the conventional metal lithium battery, the preparation method can effectively eliminate the lithium dendrite and the safety problems of battery short circuit, battery explosion and the like caused by the lithium dendrite, and is a commercial lithium negative battery which can be safely used.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a lithium metal battery based on a continuous extrusion device according to the present invention;
fig. 2 is a graph showing cycle performance of lithium metal batteries manufactured in examples 1 to 3 of the present invention.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
(1) Pressing a metal lithium foil with the thickness of 1.5mm into a nickel foil with the porosity of 90 percent to be used as a metal lithium cathode;
(2) starting a pulse stepping motor, continuously extruding for 60min, and obtaining a metal lithium micron/nanometer array with the diameter of 1 micrometer and the length of 3 micrometers through the continuous extrusion action of a screw rod guide device;
(3) assembling the metal lithium cathode with the surface nano array, the lithium iron phosphate anode and the polypropylene diaphragm together to form a metal lithium battery, and dripping electrolyte into the metal lithium battery;
(4) the test is carried out at 0.1mA/cm by a blue battery tester2Testing the discharge performance of the metal lithium battery under the current density, wherein the test result is shown in figure 2;
(5) starting a pulse stepping motor, and enabling the discharged metal lithium electrode to be at 0.1mA/cm2And in the charging process under the current density, continuously extruding for 40 minutes, and obtaining a new lithium metal micrometer/nanometer array with the diameter of 1 micrometer and the length of 2 micrometers through the continuous extrusion action of a screw guide device to prepare for next discharging for use.
Example 2
(1) Pressing a metal lithium foil with the thickness of 2mm into a copper foil with the porosity of 80% to serve as a metal lithium negative electrode;
(2) starting a direct current motor, continuously extruding for 180min, and obtaining a lithium metal micro/nano array with the diameter of 1 mu m and the length of 8 mu m through the continuous extrusion action of a screw guide device;
(3) assembling the metal lithium cathode with the surface nano array, the lithium manganate anode and the polypropylene diaphragm into a metal lithium battery, and dripping electrolyte into the metal lithium battery;
(4) the battery tester by blue electricity is utilized to test the battery at 1.0mA/cm2Testing the discharge performance of the metal lithium battery under the current density, wherein the test result is shown in figure 2;
(5) starting a direct current motor, and enabling a discharged metal lithium electrode to be at 1.0mA/cm2And in the charging process under the current density, continuously extruding for 40 minutes, and obtaining a new lithium metal micrometer/nanometer array with the diameter of 1 micrometer and the length of 1 micrometer through the continuous extrusion action of a screw guide device to prepare for next discharging for use.
Example 3
(1) Pressing a metal lithium foil with the thickness of 2mm into a nickel foil with the porosity of 60% to serve as a metal lithium cathode;
(2) starting an alternating current motor, continuously extruding for 240min, and obtaining a metal lithium micron/nanometer array with the diameter of 2 microns and the length of 10 microns through the continuous extrusion action of a screw guide device;
(3) assembling the metal lithium cathode with the surface nano array, a lithium nickelate anode and a polypropylene diaphragm together to form a metal lithium battery, and dripping electrolyte into the metal lithium battery;
(4) using a blue battery tester at 0.5mA/cm2Testing the discharge performance of the metal lithium battery under the current density, wherein the test result is shown in figure 2;
(5) starting the AC motor, and making the discharged metal lithium electrode at 0.5mA/cm2And in the charging process under the current density, continuously extruding for 90 minutes, and obtaining a new metal lithium micron/nano array with the diameter of 2 microns and the length of 4 microns through the continuous extrusion action of a screw guide device to prepare for next discharging for use.
The above examples are merely preferred embodiments of the present invention, and are not intended to limit the embodiments. The protection scope of the present invention shall be subject to the scope defined by the claims. Other variations and modifications may be made on the basis of the above description. Obvious variations or modifications of this invention are within the scope of the invention.

Claims (10)

1. A method for preparing a lithium metal battery, the method comprising the steps of:
(1) preparing a lithium battery cathode: extruding a metal lithium array from a porous current collector by a continuous extrusion device, wherein the extrusion power is 5-10 kW, and the extrusion time is 40-240 min;
(2) assembling the battery: and (2) assembling the lithium battery cathode, the diaphragm, the lithium battery anode and the electrolyte prepared in the step (1) to obtain the metal lithium battery.
2. The method according to claim 1, wherein the lithium foil in the step (1) has a thickness of 1 to 3 mm.
3. The method according to claim 1, wherein the lithium metal array extruded in step (1) has a diameter of 0.5 to 10 μm and a length of 1 to 10 μm.
4. The preparation method according to claim 1, wherein the porous current collector in the step (1) is a copper foil or a nickel foil with a porosity of 50-90%, and the pore diameter is 0.5-10 μm.
5. The manufacturing method according to claim 1, wherein the continuous extrusion apparatus in the step (1) comprises a screw guide mechanism and a driving motor, and the driving motor is a direct current motor, an alternating current motor or a pulse stepping motor.
6. The method according to claim 1, wherein the positive electrode of the lithium battery in the step (2) is any one of lithium nickelate, lithium manganate, lithium cobaltate or lithium iron phosphate.
7. The method according to claim 1, wherein the separator in the step (2) is any one of polyethylene and polypropylene.
8. The method according to claim 1, wherein the electrolyte in step (2) is a mixture of ethylene carbonate, propylene carbonate, and diethyl carbonate.
9. A lithium metal battery obtained by the production method according to any one of claims 1 to 8.
10. A method of using a lithium metal battery as claimed in claim 9, characterized in that it comprises the following steps: 1) after the metal lithium array is obtained through the continuous extrusion action of the screw guiding device driven by a pulse stepping motor, an alternating current motor or a direct current motor, the metal lithium array is discharged for use;
2) and after the discharge is completed, continuously extruding for 40-100 min by using a screw guide device driven by a pulse stepping motor, an alternating current motor or a direct current motor, and obtaining the lithium metal micron/nanometer array again for the next discharge.
CN202210374940.1A 2022-04-11 2022-04-11 Long-life metal lithium battery and preparation method thereof Pending CN114744150A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109860521A (en) * 2019-03-19 2019-06-07 北京航空航天大学 A kind of lithium metal combination electrode of array structure and preparation method thereof
US20200091509A1 (en) * 2018-09-18 2020-03-19 Uchicago Argonne, Llc Production of lithium via electrodeposition
CN111668493A (en) * 2020-06-16 2020-09-15 南开大学 Three-dimensional current collector for inhibiting dendritic crystal of lithium metal negative electrode and application of three-dimensional current collector in metal lithium battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200091509A1 (en) * 2018-09-18 2020-03-19 Uchicago Argonne, Llc Production of lithium via electrodeposition
CN109860521A (en) * 2019-03-19 2019-06-07 北京航空航天大学 A kind of lithium metal combination electrode of array structure and preparation method thereof
CN111668493A (en) * 2020-06-16 2020-09-15 南开大学 Three-dimensional current collector for inhibiting dendritic crystal of lithium metal negative electrode and application of three-dimensional current collector in metal lithium battery

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