CN116504927A - Lithium metal interface protection method and application thereof - Google Patents
Lithium metal interface protection method and application thereof Download PDFInfo
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- CN116504927A CN116504927A CN202310040546.9A CN202310040546A CN116504927A CN 116504927 A CN116504927 A CN 116504927A CN 202310040546 A CN202310040546 A CN 202310040546A CN 116504927 A CN116504927 A CN 116504927A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 6
- 239000002033 PVDF binder Substances 0.000 claims abstract description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 3
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 2
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 claims description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 1
- 229910000733 Li alloy Inorganic materials 0.000 abstract description 16
- 239000001989 lithium alloy Substances 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 239000011241 protective layer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001245 Sb alloy Inorganic materials 0.000 description 4
- 239000002140 antimony alloy Substances 0.000 description 4
- BZHNHDOWFCBZNK-UHFFFAOYSA-N antimony lithium Chemical compound [Li].[Sb] BZHNHDOWFCBZNK-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 238000001548 drop coating Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—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
- H01M4/628—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
- 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
Abstract
The invention discloses a lithium metal interface protection method and application thereof, belonging to the technical field of lithium batteries, comprising the following steps: (1) Preparing a precursor treatment solution by taking metal fluoride, lithium salt, a high molecular polymer and an organic solvent as raw materials; the high molecular polymer is at least one of polyethylene oxide, polyvinylidene fluoride or poly (vinylidene fluoride-co-hexafluoropropylene); (2) And coating the precursor treatment liquid on the surface of the lithium metal pole piece, and performing heat treatment to obtain the metal lithium anode with the interface protection layer. The interface protection layer is a composite structure formed by a lithium alloy layer and a polymer layer; the lithium alloy layer is in direct contact with the metal lithium, and the lithium alloy layer can induce uniform deposition of the metal lithium in the charge and discharge processes; the polymer layer is arranged outside the lithium alloy layer and is provided with a hole structure, so that a channel can be provided for lithium ion diffusion and an extra space can be provided for lithium metal deposition; the lithium metal anode with the interface protection layer prepared by the method has excellent cycling stability in a liquid battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium metal interface protection method and application thereof.
Background
In recent years, the use of rechargeable secondary lithium ion batteries has been increasingly widespread, and has been expanded from small electronic devices such as hand-held mobile phones and communication devices to electric car devices, flexible smart devices, and the like. The growing market demand is beginning to drive the research of lithium batteries toward higher energy density and higher safety performance, while traditional lithium ion batteries have far from meeting the ever expanding market environment. In the case that the energy density of the existing ternary cathode material system is approaching the limit, researchers start turning their eyes to the lithium battery cathode material, and it is desirable to develop a material with a larger capacity than the conventional graphite cathode to increase the energy density of the lithium battery. Lithium metal is due to its extremely low density (0.534 g cm -3 ) Ultra-high theoretical capacity (3861 mAh g -1 ) And extremely low electrochemical potential (-3.04V vs. Standard Hydrogen Electrode (SHE)) are considered as the best choice for the negative electrode material of the next generation high specific energy secondary battery.
However, lithium metal batteries are still subject to problems such as low cycle efficiency and poor safety in commercial popularization and application. The special dissolution-deposition mechanism and the highly active chemical characteristics of lithium metal are used for determining the problems of lithium dendrite growth, SEI film rupture, infinite volume expansion and the like of a lithium metal cathode in the repeated charge and discharge process, and the series of problems can lead to the rapid decay of the performance of a lithium metal battery and even cause serious safety problems. Therefore, in order to realize commercial application of lithium metal batteries, the problem of deposition regulation of good lithium metal cathodes needs to be solved.
The Chinese patent document with publication number of CN112625592A discloses a preparation method of a lithium metal interface modification layer, which comprises the steps of mixing a siloxane polymer and a catalyst with a solvent containing lithium salt, and stirring to obtain a mixed solution; coating the mixed solution on a lithium foil, and performing heat treatment to obtain a lithium metal interface modification layer; the siloxane polymer can weaken the reaction of the solid electrolyte and lithium metal, and the polymer is crosslinked and polymerized under the action of a catalyst to form a network structure, so that the expansion of the lithium metal can be restrained.
The chinese patent document with publication number CN110212166a discloses a method for constructing a double-layer protection interface on the surface of a lithium metal anode, comprising: (a) Carrying out esterification reaction on polyphosphoric acid and polyalcohol to form polyphosphoric acid ester; (b) Adding the polyphosphate into an organic solvent to prepare an ester treatment solution; (c) And immersing the lithium metal sheet into the ester treatment liquid for etching reaction. The invention forms the organic/inorganic double-layer interface protective layer by in-situ etching on the metal surface, improves the air stability of the metal surface, and further can greatly improve the cycle performance and the safety performance of the metal surface when the metal surface is used for a lithium metal battery.
Disclosure of Invention
The invention provides a lithium metal interface protection method, which has simple steps and is easy to implement, and the obtained interface protection layer is an integrated composite structure formed by a lithium alloy layer and a polymer layer, wherein the lithium alloy layer is in direct contact with metal lithium, and the lithium alloy layer can induce uniform deposition of the metal lithium in the charge and discharge processes; the polymer layer maintains a pore structure to provide channels for lithium ion diffusion and additional space for lithium metal deposition; the lithium metal negative electrode with the interface protection layer prepared by the method provided by the invention has excellent cycling stability in a liquid battery.
The technical scheme adopted is as follows:
a lithium metal interface protection method, comprising the steps of:
(1) Preparing a precursor treatment solution by taking metal fluoride, lithium salt, a high molecular polymer and an organic solvent as raw materials; the high molecular polymer is at least one of polyethylene oxide, polyvinylidene fluoride or poly (vinylidene fluoride-co-hexafluoropropylene);
(2) And coating the precursor treatment liquid on the surface of the lithium metal pole piece, and performing heat treatment to obtain the metal lithium anode with the interface protection layer.
According to the invention, the precursor treatment liquid composed of metal fluoride, lithium salt, high molecular polymer and organic solvent is used for carrying out interface modification on the lithium metal pole piece, the metal fluoride can react with lithium metal to form a lithium alloy layer, an inorganic component LiF and the like, and further polymer crosslinking polymerization is carried out to obtain a polymer layer with a porous structure, so that a double-layer composite structure of the lithium alloy layer and the polymer layer is formed.
In the step (1), the metal fluoride is at least one of antimony fluoride, copper fluoride, aluminum fluoride, tin fluoride, tantalum fluoride and niobium fluoride, the metal fluoride can react with lithium metal to form a lithium alloy layer, an inorganic component LiF and the like, the lithium alloy layer can greatly improve the diffusivity of lithium ions and induce uniform deposition of metal lithium in the charge and discharge process, and the inorganic component LiF and the like can improve the ion conductivity and inhibit the growth of lithium dendrites.
Preferably, the metal fluoride is antimony fluoride, which is capable of reacting with lithium metal to form a lithium-antimony alloy layer and an inorganic component LiF.
In the step (1), the lithium salt is at least one of lithium nitrate, lithium bis (trifluoromethanesulfonyl) imide and lithium tetrafluoroborate, and the addition of the lithium salt can improve the lithium ion transmission efficiency of the polymer layer and the ion conductivity of the polymer layer.
Preferably, in the step (1), the organic solvent is at least one of ethylene glycol dimethyl ether, tetrahydrofuran and 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, and the organic solvent can realize uniform dispersion of each component in the solution.
Preferably, the concentration of the metal fluoride in the precursor treatment liquid is 0.05-0.2 mol/L, the mass fraction of the lithium salt is 1-6wt% based on the mass of the organic solvent, and the mass fraction of the high polymer is 0.2-5wt%.
Further preferably, the concentration of the metal fluoride in the precursor treatment liquid is 0.075 to 0.15mol/L, the mass fraction of the lithium salt is 2 to 5wt% based on the mass of the organic solvent, and the mass fraction of the high polymer is 0.4 to 3wt%.
Preferably, after mixing the metal fluoride, the lithium salt, the high molecular polymer and the organic solvent, stirring for 6-15 hours at 40-60 ℃ to promote the dissolution of the polymer, and preparing the uniform precursor treatment liquid.
Further preferably, the conditions of stirring are: 60℃for 12 hours.
Preferably, the precursor treatment liquid is dripped on the surface of the lithium metal anode, and the dripping amount is 20-40 mu L/cm 2 . The operation of the film preparation method by the dripping method is simpler.
Further preferably, the drop-coating amount is 25. Mu.L/cm 2 。
In the step (2), the solvent is volatilized by heat treatment, and the polymer film formation is accelerated, preferably, the heat treatment condition is 40-60 ℃ for 60-180 min.
The invention also provides a lithium metal battery, which comprises the metal lithium negative electrode with the interface protection layer, and specifically comprises a positive electrode, the metal lithium negative electrode with the interface protection layer, a diaphragm and electrolyte.
Preferably, the anode material is LiFePO 4 、LiCoO 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 Any one of the following.
Preferably, the membrane is selected from the Celgard series of membranes.
Preferably, the electrolyte is an ether electrolyte or a carbonate electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
(1) The interface protection layer prepared by the method is an integrated composite structure formed by a lithium alloy layer and a polymer layer; the lithium alloy layer is in direct contact with the metal lithium, so that the lithium alloy layer has high lithium ion diffusivity; the polymer layer is outside the lithium alloy layer; the lithium alloy layer can induce uniform deposition of metal lithium in the charge and discharge process; the polymer layer maintains a pore structure to provide a channel for lithium ion diffusion and additional space for lithium metal deposition, while reducing excessive consumption of electrolyte; in addition, the formation of inorganic components such as LiF also improves the density and ionic conductivity of the interface protective layer.
(2) The lithium metal electrode modified by the interface protection layer can realize rapid material exchange on the surface of the electrode, so that the polarization of the battery is obviously reduced, and the interface protection layer can adapt to the change of the volume of the electrode and induce the uniform deposition of metal lithium; the lithium metal anode with the interface protection layer, which is prepared by the invention, can be applied to a liquid battery to effectively prolong the cycle life of the battery.
Drawings
Fig. 1 is a cycle efficiency chart of the lithium metal battery assembled in comparative example 1.
Fig. 2 is a cycle efficiency chart of the lithium metal battery assembled in example 1.
Fig. 3 is an SEM image of a metallic lithium anode with an interface protection layer of example 2.
Fig. 4 is a cycle efficiency chart of the lithium metal battery assembled in example 2.
Fig. 5 is an SEM image of a metallic lithium anode with an interface protection layer of example 3.
Fig. 6 is a cross-sectional SEM image of a lithium metal negative electrode with an interface protection layer of example 3.
Fig. 7 is a cycle efficiency chart of the lithium metal battery assembled in example 3.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Comparative example 1
Combining untreated metallic lithium flakes with LiFePO 4 And assembling the positive plate, the Celgard 2320 type diaphragm and the ether electrolyte into a lithium metal battery. Firstly, circulating for 5 circles at a rate of 0.1C, then, performing long circulation at 0.5C, and circulating the battery for 70 weeks, wherein the capacity retention rate is 77.92%; the cycle efficiency chart is shown in fig. 1.
Example 1
Antimony fluoride (SbF) 3 ) Dissolving in ethylene glycol dimethyl ether to prepare a solution with the concentration of 0.05mol/L, adding 1wt% of lithium nitrate, 2wt% of lithium bis (trifluoromethanesulfonyl) imide, 0.8wt% of polyethylene oxide and 1.2wt% of poly (vinylidene fluoride-co-hexafluoropropylene) in the solvent according to the mass fraction, and stirring at 60 ℃ for 12 hours to obtain a precursor treatment solution;
uniformly dispersing the precursor treatment liquid on the lithium metal pole piece in a dripping way, wherein the dripping amount is 20 mu L/cm 2 And (3) after the solvent volatilizes, drying the mixture in a vacuum oven at 60 ℃ for 120min to obtain the metallic lithium anode with the interface protection layer.
Combining a lithium metal anode with an interface protection layer with LiFePO 4 The positive plate, celgard 2320 type diaphragm and ether electrolyte are assembled into a lithium metal battery, the lithium metal battery circulates for 5 circles at a multiplying power of 0.1C, then the lithium metal battery circulates for 160 weeks at a long cycle of 0.5C, and the capacity retention rate is 84.14%; the cycle efficiency chart is shown in fig. 2.
Example 2
The lithium metal interface protection method in this example differs from the method in example 1 only in that antimony fluoride (SbF 3 ) The concentration of (2) is 0.1mol/L, and the mass fraction of lithium nitrate is 2wt%; and obtaining the metallic lithium anode with the interface protection layer.
As shown in the SEM image of the metal lithium cathode with the interface protection layer in figure 3, the polymer on the surface layer of the modified lithium metal pole piece is connected with each other to form a honeycomb-like structure, the surface is relatively flat, the shape of the holes is nearly circular, the size distribution is uniform, and the bottom lithium antimony alloy is covered by the polymer layer.
Assembling a metal lithium negative electrode with an interface protection layer, a lithium iron phosphate positive plate, a Celgard 2320 type diaphragm and an ether electrolyte into a lithium metal battery, firstly circulating for 5 circles at a rate of 0.1C, and then circulating for 400 weeks at a rate of 0.5C, wherein the capacity retention rate is 88.88%; the cycle efficiency chart is shown in fig. 4.
Example 3
The lithium metal interface protection method in this example is different from the method in example 2 only in that the mass fraction of polyethylene oxide is 0.2wt%, and the mass fraction of poly (vinylidene fluoride-co-hexafluoropropylene) is 0.3wt%; and obtaining the metallic lithium anode with the interface protection layer.
As shown in the SEM image of the metal lithium cathode with the interface protection layer in figure 5, each lithium antimony alloy particle at the bottom of the modified lithium metal pole piece is crosslinked together by a polymer to form a multi-layer mesh-shaped structure morphology, and the diameters of holes are kept approximately the same and distributed uniformly; the cross-sectional SEM is shown in fig. 6, where the structure of the interfacial layer is clearly observed on the lithium metal substrate, the bottom is the lithium antimony alloy layer, and the upper is the polymer layer.
Assembling a metal lithium negative electrode with an interface protection layer, a lithium iron phosphate positive plate, a Celgard 2320 type diaphragm and an ether electrolyte into a lithium metal battery, firstly circulating for 5 circles at a rate of 0.1C, and then circulating for long circles at a rate of 0.5C, wherein the capacity retention rate is 94.6% after the battery circulates for 560 weeks; the cycle efficiency chart is shown in fig. 7.
Example 4
The lithium metal interface protection method in this embodiment differs from the method in embodiment 3 only in that aluminum fluoride is selected as the metal fluoride; and obtaining the lithium metal anode with the protective layer.
Example 5
The lithium metal interface protection method in this embodiment differs from the method in embodiment 3 only in that copper fluoride is selected as the metal fluoride; and obtaining the lithium metal anode with the protective layer.
Example 6
The lithium metal interface protection method in this example differs from the method in example 3 only in that the polymer content ratio is 0.8wt% polyethylene oxide, 1.2wt% polyvinylidene fluoride; and obtaining the lithium metal anode with the protective layer.
Example 7
The lithium metal interface protection method in this example differs from the method in example 3 only in that the polymer content ratio is 2wt% polyvinylidene fluoride; and obtaining the lithium metal anode with the protective layer.
Example 8
The lithium metal interface protection method in this example differs from the method in example 3 only in that the solvent is tetrahydrofuran; and obtaining the metallic lithium anode with the interface protection layer.
Example 9
The lithium metal interface protection method in this example differs from the method in example 3 only in that the solvent is 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether; and obtaining the metallic lithium anode with the interface protection layer.
Example 10
The lithium metal interface protection method in this example differs from the method in example 3 only in that the content ratio of lithium salt is 2wt% of lithium bis (trifluoromethanesulfonyl) imide, 2wt% of lithium tetrafluoroborate; and obtaining the metallic lithium anode with the interface protection layer.
Example 11
The lithium metal interface protection method in this example is different from that in example 3 only in that the drop-coating amount of the precursor treatment liquid is 30. Mu.L/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And obtaining the metallic lithium anode with the interface protection layer.
Example 12
The lithium metal interface protection method in this example is different from that in example 3 only in that the drop-coating amount of the precursor treatment liquid is 40. Mu.L/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And obtaining the metallic lithium anode with the interface protection layer.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A lithium metal interface protection method, comprising the steps of:
(1) Preparing a precursor treatment solution by taking metal fluoride, lithium salt, a high molecular polymer and an organic solvent as raw materials; the high molecular polymer is at least one of polyethylene oxide, polyvinylidene fluoride or poly (vinylidene fluoride-co-hexafluoropropylene);
(2) And coating the precursor treatment liquid on the surface of the lithium metal pole piece, and performing heat treatment to obtain the metal lithium anode with the interface protection layer.
2. The method according to claim 1, wherein in the step (1), the metal fluoride is at least one of antimony fluoride, copper fluoride, aluminum fluoride, tin fluoride, tantalum fluoride, and niobium fluoride.
3. The method according to claim 1, wherein in the step (1), the lithium salt is at least one of lithium nitrate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium tetrafluoroborate.
4. The method according to claim 1, wherein in the step (1), the organic solvent is at least one of ethylene glycol dimethyl ether, tetrahydrofuran, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether.
5. The method according to claim 1, wherein in the step (1), the concentration of the metal fluoride in the precursor treatment solution is 0.05 to 0.2mol/L, the mass fraction of the lithium salt is 1 to 6wt% and the mass fraction of the high polymer is 0.2 to 5wt%, based on the mass of the organic solvent.
6. The method for protecting a lithium metal interface according to claim 1, wherein the precursor treatment liquid is prepared by mixing a metal fluoride, a lithium salt, a high molecular polymer and an organic solvent and stirring the mixture at 40-60 ℃ for 6-15 hours.
7. The method for protecting a lithium metal interface according to claim 1, wherein the precursor treatment is applied dropwise to the surface of the lithium metal anode in an amount of 20 to 40 μl/cm 2 。
8. The method according to claim 1, wherein the heat treatment is performed at 40 to 60 ℃ for 60 to 180 minutes.
9. A lithium metal battery comprising a lithium metal anode with an interfacial protection layer made by the method of any one of claims 1-8.
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