CN112151759A - Lithium metal cathode, preparation method and lithium ion battery - Google Patents
Lithium metal cathode, preparation method and lithium ion battery Download PDFInfo
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- CN112151759A CN112151759A CN202011020178.4A CN202011020178A CN112151759A CN 112151759 A CN112151759 A CN 112151759A CN 202011020178 A CN202011020178 A CN 202011020178A CN 112151759 A CN112151759 A CN 112151759A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 119
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 19
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 238000004544 sputter deposition Methods 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 3
- 229910005282 Li13Sn5 Inorganic materials 0.000 claims description 2
- 229910010655 Li22Sn5 Inorganic materials 0.000 claims description 2
- 229910010766 Li5Sn2 Inorganic materials 0.000 claims description 2
- 229910011205 Li7Sn2 Inorganic materials 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 7
- 229910006270 Li—Li Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- -1 argon ions Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a lithium metal negative electrode which comprises a substrate and a composite interface layer arranged on the substrate, wherein the substrate is made of lithium metal, and the composite interface layer is made of lithium tin alloy and lithium nitride. The lithium metal negative electrode is capable of inhibiting lithium dendrite growth. The invention also provides a preparation method of the lithium metal cathode and a lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium metal cathode, a preparation method of the lithium metal cathode and a lithium ion battery.
Background
The lithium metal has extremely high theoretical specific capacity (3860mAh/g) and lower oxidation-reduction potential (-3.040V vs+/H2) And a lower density (0.534 g/cm)3) The lithium ion battery anode material is the most ideal anode material of the lithium ion battery. However, the lithium metal negative electrode is liable to cause uncontrolled lithium dendrite growth due to uneven deposition of lithium during charge and discharge, and the lithium dendrite may pierce through the separator and contact with the positive electrode to cause short-circuiting, thereby causing a reduction in lithium ion safety; moreover, lithium dendrites can damage an SEI film on the surface of a lithium metal negative electrode, and the repeated fracture and repair processes of the SEI layer can cause continuous consumption of active lithium and electrolyte and continuous reduction of coulombic efficiency; in addition, in the process of dissolving the lithium dendrite, needle-shaped lithium close to the substrate part is preferentially dissolved due to higher current density, so that electrochemical inertia and chemically active 'dead lithium' are generated, the accumulation of the 'dead lithium' can block the migration of lithium ions, the polarization of the lithium ion battery is sharply increased, the capacity is rapidly attenuated, and the cycle stability of the lithium ion battery is reduced.
Disclosure of Invention
In view of the above, it is desirable to provide a lithium metal negative electrode capable of suppressing the growth of lithium dendrites.
In addition, a preparation method of the lithium metal negative electrode is also needed to be provided.
In addition, it is also necessary to provide a lithium ion battery including the lithium metal negative electrode.
The invention provides a lithium metal negative electrode which comprises a substrate and a composite interface layer arranged on the substrate, wherein the substrate is made of lithium metal, and the composite interface layer is made of lithium tin alloy and lithium nitride.
The invention also provides a preparation method of the lithium metal negative electrode, which comprises the following steps:
providing a substrate, wherein the substrate is made of lithium metal; and
and under the mixed atmosphere of nitrogen and argon, sputtering the substrate by taking tin metal as a target to form a composite interface layer on the substrate, thereby obtaining the lithium metal negative electrode, wherein the composite interface layer comprises lithium tin alloy and lithium nitride.
The invention also provides a lithium ion battery which comprises a positive electrode and the lithium metal negative electrode.
The lithium-tin alloy in the composite interface layer provided by the invention has strong lithium affinity and electronic conductivity, and is beneficial to nucleation of lithium ions at lithium-tin alloy sites preferentially in the electrodeposition process. The lithium nitride in the composite interface layer is used as a rapid lithium ion conductor, has high ionic conductivity, low electronic conductivity and a low migration energy barrier of Li + diffusion, can induce lithium ions to be rapidly transported to an alloy site along the substrate interface, and promotes the electrodeposition of the lithium ions along the surface of the substrate. According to the invention, by utilizing the synergistic effect of the lithium tin alloy and the lithium nitride, the transverse growth of lithium along the surface of the substrate can be realized, so that the problem that lithium vertically grows to form lithium dendrite in the charging and discharging processes of the lithium metal negative electrode is solved, the growth of the lithium dendrite is inhibited, and the cycle stability and the safety of the lithium metal battery are further improved.
Drawings
Fig. 1 is a flow chart of a method of manufacturing a lithium metal negative electrode in a preferred embodiment of the invention.
Fig. 2A and 2B are scanning microscope images of the surface and cross-section, respectively, of a lithium metal negative electrode prepared in example 1 of the present invention.
Fig. 3 is a voltage-time graph after constant current charge and discharge tests were performed on the batteries prepared in example 1 of the present invention and comparative example 1.
Fig. 4 is a scanning microscope photograph of the lithium metal negative electrode prepared in example 1 of the present invention after being charged and discharged for 50 cycles.
Fig. 5 is a scanning microscope picture of the lithium metal negative electrode prepared in comparative example 1 of the present invention after 50 cycles of charge and discharge.
Fig. 6 is a graph of cycle performance of the batteries prepared in example 2 of the present invention and comparative example 2 after the constant current charge and discharge test.
Fig. 7 is a graph of cycle performance of the batteries prepared in example 3 of the present invention and comparative example 3 after the constant current charge and discharge test.
Fig. 8 is a voltage-time diagram of a lithium metal battery prepared in example 4 of the present invention after a constant current charge and discharge test.
Fig. 9 is a voltage-time diagram of a lithium metal battery prepared in example 5 of the present invention after a constant current charge and discharge test.
Fig. 10 is a voltage-time diagram of a lithium metal battery prepared in example 6 of the present invention after a constant current charge and discharge test.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a lithium metal negative electrode, which comprises a substrate and a composite interface layer arranged on the substrate.
The substrate is made of lithium metal. Wherein the substrate may have a thickness of 100 to 500 μm. In this embodiment, the substrate is a lithium foil.
The composite interface layer is made of lithium tin alloy and lithium nitride. Wherein the lithium tin alloyAnd the lithium nitride is randomly distributed in the composite interface layer. Namely, the lithium tin alloy and the lithium nitride are randomly distributed on the surface of the substrate. The lithium tin alloy includes Li7Sn2、Li5Sn2、Li22Sn5And Li13Sn5At least one of (1). The lithium nitride may be in a glassy state. Wherein the thickness of the composite interface layer is 300nm-2.5 μm. Preferably, the thickness of the composite interfacial layer is 1.3 μm. Through multiple experiments, the inventor finds that when the thickness of the composite interface layer is too thin (the thickness is less than 300nm), the lithium metal negative electrode cannot well endure the circulation under the condition of high current density; when the thickness of the composite interfacial layer is too thick (greater than 2.5 μm), the lithium metal negative electrode is polarized too much and the cycling stability is reduced.
Referring to fig. 1, a method for preparing the lithium metal negative electrode according to a preferred embodiment of the present invention includes the following steps:
step S11, providing a substrate made of lithium metal.
And step S12, sputtering the substrate by taking tin metal as a target material under the mixed atmosphere of nitrogen and argon to form a composite interface layer on the substrate, thereby obtaining the lithium metal negative electrode.
Wherein the lithium metal negative electrode comprises a substrate and a composite interfacial layer deposited on the substrate. The substrate is a lithium foil, and the composite interface layer comprises a lithium tin alloy and lithium nitride.
During sputtering, nitrogen reacts with the substrate to form the lithium nitride. Meanwhile, in the sputtering process, argon gas and electrons collide and ionize to form argon ions, the argon ions bombard the tin metal to sputter tin atoms, and the sputtered tin atoms react with the substrate to generate the lithium-tin alloy. Wherein argon gas has the highest sputtering efficiency compared to the same type of gas (e.g., helium gas) and does not react with the tin metal.
Specifically, the lithium metal negative electrode can be obtained by a magnetron sputtering method. The volume ratio of the nitrogen gas in the mixed atmosphere may be 0.1 to 0.9. Wherein the nitrogen and the argon are used as working gases during sputtering.
The sputtering power is 40-100W, and the sputtering time is 10-140 min. The sputtering power and sputtering time together affect the thickness of the composite interfacial layer. Specifically, the longer the sputtering time and the higher the sputtering power, the greater the thickness of the composite interface layer. If the sputtering power is lower than 40W, the sputtering time is too long; if the sputtering power is higher than 100W, the sputtering time is too short, and the surface uniformity of the composite interface layer tends to be lowered.
Preferably, the sputtering power is 80W. Wherein the sputtering power is related to the type of the target. I.e. different targets require different powers of said sputtering. Preferably, the sputtering time is 20 min.
The sputtering pressure is 3-10 Pa. If the sputtering pressure is less than 3Pa, the sputtering pressure of the target cannot be reached, and the pressure is controlled by the gas flow (i.e., the gas flow of nitrogen and argon), and different gas flows correspond to different pressures. Wherein the maximum gas flow may be 100sccm for a sputtering pressure of 10 Pa.
The volume flow ratio of the nitrogen to the argon is (0-3) to (1-7). Preferably, the volume flow ratio of the nitrogen gas to the argon gas is 1: 1. The total introduction amount of the nitrogen and the argon is 40-100 sccm. Preferably, the total flow of the nitrogen and the argon is 40 sccm.
It is understood that when the volume flow rate of the nitrogen gas is 0, the composite interface layer only includes the lithium tin alloy, but not the lithium nitride, as shown in example 6.
It is understood that the thickness of the composite interfacial layer is related to the time of the sputtering. Preferably, when the sputtering power is 80W, the sputtering time is 20min, the volume ratio flow of the nitrogen gas to the argon gas is 1:1, and the total ventilation amount of the nitrogen gas and the argon gas is 80sccm, the thickness of the composite interface layer obtained by sputtering is 1.3 μm.
The invention also provides a lithium ion battery which comprises a positive electrode and the lithium metal negative electrode.
The present invention will be specifically described below by way of examples and comparative examples.
Example 1
In a first step, a lithium metal sheet is provided along with tin metal.
And secondly, carrying out magnetron sputtering on the lithium metal sheet by taking tin metal as a target material under the mixed atmosphere of nitrogen and argon to obtain the lithium metal cathode. Wherein the vacuum degree of the cavity before sputtering is set to 10-4Pa, the volume ratio flow of nitrogen to argon in the sputtering process is set to be 1:1, the total ventilation amount is set to be 80sccm, the magnetron sputtering power is set to be 80W, the air pressure is set to be 4Pa, and the magnetron sputtering time is set to be 20 min.
Assembling the battery:
the lithium metal negative electrode prepared in example 1 was assembled into a Li-Li symmetric battery in an argon-protected glove box. Wherein the diaphragm is PP, the electrolyte adopts a mixed solution of 1.0M lithium bistrifluoromethanesulfonylimide (LiTFSI) dissolved in 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) in a volume ratio of 1:1, and the additive is 2 wt% LiNO3。
Example 2
The method of manufacturing the lithium metal negative electrode of this example was the same as that of example 1.
Assembling the battery:
the lithium metal negative electrode prepared in example 2 and lithium iron phosphate (LiFePO) were used4) The positive electrode was assembled into a full cell, and the electrolyte and additives were the same as in example 1.
Example 3
The method of manufacturing the lithium metal negative electrode of this example was the same as that of example 1.
Assembling the battery:
lithium metal negative electrode prepared in example 3 and single crystal high nickel ternary positive electrode (LiNi) were used0.8Co0.1Mn0.1O2) The whole cell was assembled using 1.0M lithium hexafluorophosphate (LiPF) as electrolyte6) Dissolved in a mixed solution of Ethylene Carbonate (EC), dimethyl carbonate (EMC) and Ethyl Methyl Carbonate (EMC) at a volume ratio of 1:1: 1.
Example 4
The lithium metal negative electrode of this example was prepared by a method different from that of example 1 in that: the magnetron sputtering time in the second step was set to 10 min.
Assembling the battery:
a Li-Li symmetric battery was assembled using the lithium metal negative electrode prepared in example 4, in the same manner as in example 1.
Example 5
The lithium metal negative electrode of this example was prepared by a method different from that of example 1 in that: the magnetron sputtering time in the second step was set to 30 min.
Assembling the battery:
a Li-Li symmetric battery was assembled using the lithium metal negative electrode prepared in example 5, in the same manner as in example 1.
Example 6
The lithium metal negative electrode of this example was prepared by a method different from that of example 1 in that: in the second step, the volume ratio flow of nitrogen in the sputtering process is 0, the total gas amount of argon is 80sccm, and the magnetron sputtering time is set to be 15 min.
Assembling the battery:
a Li-Li symmetric battery was assembled using the lithium metal negative electrode prepared in example 6, in the same manner as in example 1.
Comparative example 1
The untreated lithium metal sheet was used as a lithium metal negative electrode.
Assembling the battery:
the lithium metal negative electrode prepared in comparative example 1 was assembled into a Li-Li symmetric battery in the same manner as in example 1.
Comparative example 2
The lithium metal negative electrode was the same as comparative example 1.
Assembling the battery:
the lithium metal negative electrode prepared in comparative example 2 and the lithium iron phosphate positive electrode were used to assemble a full cell, and the method was the same as in example 2.
Comparative example 3
The lithium metal negative electrode was the same as comparative example 1.
Assembling the battery:
a full cell was assembled using the lithium metal negative electrode prepared in comparative example 3 and the high nickel ternary positive electrode, in the same manner as in example 3.
The lithium metal cathodes prepared in examples 1 to 6 and the lithium metal cathodes prepared in comparative examples were subjected to a scanning electron microscope test, respectively. Referring to fig. 2A and 2B (electron micrographs of examples 4 to 6 and comparative example are not shown), the thicknesses of the composite interface layers in the lithium metal negative electrodes obtained in examples 1 to 3 were all 1.3 μm, and the thicknesses of the composite interface layers in the lithium metal negative electrodes prepared in examples 4 and 5 were 320nm and 2 μm, respectively.
SEM images of the surfaces of the lithium metal negative electrodes prepared in examples 4 to 6 were similar to example 1.
Please refer to fig. 3, at 5mA cm-2Current density of 1mAh cm-2As can be seen from the constant current charge and discharge test performed on the full cells prepared in example 1 and comparative example 1, the lithium metal battery prepared in example 1 exhibited excellent cycle stability and cycle life of more than 1600 hours. Whereas the lithium metal battery prepared in comparative example 1 began to exhibit voltage fluctuation in less than 200 hours, after which the polarization began to rapidly increase.
Referring to fig. 4, after 50 cycles of charge and discharge, the surface of the lithium metal negative electrode prepared in example 1 was very smooth and flat, and no lithium dendrite occurred. Referring to fig. 5, after 50 cycles of the cyclic charge and discharge, the surface of the lithium metal negative electrode prepared in comparative example 1 was completely covered with moss-like lithium dendrites, and the entire surface became rough and porous.
Referring to fig. 6, the half cells prepared in example 2 and comparative example 2 were tested for constant current charge and discharge at a test rate of 1C, and it can be seen that the lithium iron phosphate battery prepared in example 2 still maintains 133.7mAh g after 1000 cycles-1The discharge specific capacity and the capacity retention rate are as high as 83.7 percent. After the lithium iron phosphate battery prepared in the comparative example 2 is cycled for 1000 circles, the discharge specific capacity is rapidly attenuated, and the capacity retention rate is only 58.0%.
Referring to fig. 7, the half cells prepared in example 3 and comparative example 3 were subjected to constant current charge and discharge test at a test rate of 1C, and it can be seen that the half cells of the examples3 after the single crystal high nickel ternary battery is circulated for 200 circles, the single crystal high nickel ternary battery still keeps 136.5mAh g-1The specific discharge capacity and the capacity retention rate of (2) were 79.1%. After the single crystal high nickel ternary battery prepared in comparative example 3 is cycled for 200 circles, the discharge specific capacity is only left 39mAh g-1The capacity retention rate is only 30.0%.
At 5mA cm-2Current density of 1mAh cm-2The full cells prepared in examples 4 to 6 were respectively subjected to cycle performance tests. Referring to fig. 8, the polarization of the lithium metal battery prepared in example 4 slowly increases with time. Referring to fig. 9, the polarization of the lithium metal battery prepared in example 5 slowly increases with time, but the increase is more significant than that of the lithium metal battery prepared in example 4. Referring to fig. 10, the lithium metal battery prepared in example 6 has only a lithium tin alloy due to the synergistic effect of the lack of tin nitride having high ionic conductivity on the surface of the substrate (i.e., the lithium metal sheet), so that the polarization of the lithium metal battery starts to increase continuously after 300 hours.
The lithium-tin alloy in the composite interface layer provided by the invention has strong lithium affinity and electronic conductivity, and is beneficial to nucleation of lithium ions at lithium-tin alloy sites preferentially in the electrodeposition process. The lithium nitride in the composite interface layer is used as a rapid lithium ion conductor, has high ionic conductivity, low electronic conductivity and a low migration energy barrier of Li + diffusion, can induce lithium ions to be rapidly transported to an alloy site along the substrate interface, and promotes the electrodeposition of the lithium ions along the surface of the substrate. According to the invention, by utilizing the synergistic effect of the lithium tin alloy and the lithium nitride, the transverse growth of lithium along the surface of the substrate can be realized, so that the problem that lithium vertically grows to form lithium dendrite in the charging and discharging processes of the lithium metal negative electrode is solved, the growth of the lithium dendrite is inhibited, and the cycle stability and the safety of the lithium metal battery are further improved.
In addition, the compact and uniform composite interface layer is used as a barrier layer of the lithium metal negative electrode and the electrolyte, so that side reactions of the lithium metal negative electrode and the electrolyte can be inhibited, the consumption of active lithium and the electrolyte can be reduced, and the coulomb efficiency of the lithium metal battery can be improved.
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the embodiments of the present invention.
Claims (9)
1. The lithium metal negative electrode is characterized by comprising a substrate and a composite interface layer arranged on the substrate, wherein the substrate is made of lithium metal, and the composite interface layer is made of lithium tin alloy and lithium nitride.
2. The lithium metal negative electrode of claim 1, wherein the composite interfacial layer has a thickness of from 300nm to 2.5 μm.
3. The lithium metal negative electrode of claim 1, wherein the lithium tin alloy comprises Li7Sn2、Li5Sn2、Li22Sn5And Li13Sn5At least one of (1).
4. The lithium metal anode of claim 1, wherein the substrate is a lithium foil.
5. A method of making a lithium metal anode according to any of claims 1 to 4, comprising the steps of:
providing a substrate, wherein the substrate is made of lithium metal; and
and under the mixed atmosphere of nitrogen and argon, sputtering the substrate by taking tin metal as a target to form a composite interface layer on the substrate, thereby obtaining the lithium metal negative electrode, wherein the composite interface layer comprises lithium tin alloy and lithium nitride.
6. The method of preparing a lithium metal negative electrode according to claim 5, wherein the sputtering time is 10 to 140 min.
7. The method of claim 5, wherein the volume flow ratio of the nitrogen gas to the argon gas is (0-3): 1-7, and the total flow of the nitrogen gas and the argon gas is 40-100 sccm.
8. The method of preparing a lithium metal anode according to claim 5, wherein the sputtering power is 40 to 100W and the sputtering pressure is 3 to 10 Pa.
9. A lithium ion battery comprising a positive electrode, wherein the lithium ion battery further comprises the lithium metal negative electrode of any one of claims 1 to 4.
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