CN113299899A - Lithium solid-state battery cathode and preparation method and application thereof - Google Patents
Lithium solid-state battery cathode and preparation method and application thereof Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 110
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 229910003149 α-MoO3 Inorganic materials 0.000 claims description 19
- 239000002127 nanobelt Substances 0.000 claims description 18
- 239000002074 nanoribbon Substances 0.000 claims description 18
- 239000007773 negative electrode material Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000002715 modification method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 41
- 239000007784 solid electrolyte Substances 0.000 description 37
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- H01M4/36—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 relates to the technical field of batteries, in particular to a negative electrode of a lithium solid-state battery, a preparation method of the negative electrode and the lithium solid-state battery comprising the negative electrode. The invention provides an all-solid-state battery electrolyte interface modification method and application thereof aiming at the problems of poor interface compatibility, large interface resistance and blocked lithium ion conduction of a solid-state electrolyte and metal lithium.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative electrode of a lithium solid-state battery, a preparation method of the negative electrode and the lithium solid-state battery comprising the negative electrode.
Background
At present, commercial lithium ion batteries (a carbon material is used as a negative electrode, and a transition metal compound is used as a positive electrode) which are widely used are gradually difficult to meet the application requirements of daily life and industrial technology due to the fact that the actual capacity is gradually close to the theoretical value, and the problems of flammability, easy corrosion, poor thermal stability, safety and the like of organic electrolyte exist. The lithium metal has the most negative electrode potential (-3.045Vvs. standard hydrogen electrode) and the highest specific capacity (3860mAh/g), can meet the requirement of high energy density of an electrode material, and is a promising negative electrode material. However, in the charge-discharge cycle process of the battery, because the lithium metal electrode is active, dendritic crystals are easily grown on the surface of the negative electrode, so that the diaphragm is pierced to cause short circuit and thermal runaway is caused, and serious safety accidents are brought. And the 'dead lithium' formed after the dendrite is broken can reduce the utilization rate of lithium and increase the internal resistance, thereby shortening the service life of the battery. The problem of lithium dendrites greatly limits the practical application of metallic lithium. The all-solid-state battery can solve the potential safety hazard problem, and the solid-state electrolyte has extremely high shear modulus, so that infinite volume change during lithium circulation can be prevented, and formation of lithium dendrites is inhibited, so that the all-solid-state battery taking lithium as a negative electrode has great application prospect.
However, the solid electrolyte generally has poor interfacial contact with metallic lithium, resulting in increased interfacial resistance, hindered conduction of lithium ions, degraded battery performance, and dendrite growth.
Disclosure of Invention
The invention provides an all-solid-state battery electrolyte interface modification method and application thereof aiming at the problems of poor interface compatibility, large interface resistance and blocked lithium ion conduction of a solid-state electrolyte and metal lithium. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a lithium solid-state battery negative electrode material comprises metallic lithium and an oxide or lithium titanate; the oxide is an oxide of a metal or a nonmetal.
In some embodiments, the negative electrode material is obtained by heating and melting metallic lithium and an oxide or lithium titanate.
In some embodiments, the metal oxide is selected from zinc oxide, aluminum oxide, magnesium oxide, silicon oxide, molybdenum oxide, or the like.
In some embodiments, the molybdenum oxide is α -MoO3A nanoribbon.
In some embodiments, the oxide particles have a particle size of less than 10 μm.
In some embodiments, the oxide is present in the negative electrode material in an amount of 5-70 wt.%.
A preparation method of a lithium solid-state battery negative electrode material comprises the following steps:
heating the metallic lithium to a molten state, adding metallic or nonmetallic oxides, and continuously heating and stirring to be uniform to obtain the cathode material.
In some embodiments, the oxide is α -MoO3A nanoribbon.
In some embodiments, the α -MoO is3The preparation method of the nanobelt comprises the following steps of:
In some embodiments, the dropwise addition of the hydrogen peroxide solution to the molybdenum powder is performed under ice bath conditions.
In some embodiments, the concentration of the hydrogen peroxide solution is 10-35 wt%.
In some embodiments, the hydrothermal synthesis is carried out at a temperature of 140 ℃ to 160 ℃ for 12-24 h.
The negative electrode material is applied to a solid-state lithium ion battery.
In some embodiments, the application is a solid-state lithium ion battery comprising a positive electrode material, a negative electrode material, and a solid-state electrolyte, wherein the solid-state electrolyte is between the positive and negative electrode materials.
Advantageous effects
The lithium ion battery cathode material has strong wettability and small surface tension in a high-temperature molten state, is in a sticky state and has strong plasticity. After cooling and solidification, it exhibits a metallic luster and an excellent texture. The lithium ion battery cathode material can be well wetted and attached to the solid electrolyte in a high-temperature molten state and under a certain pressure, is filled into the surface gap of the solid electrolyte, and keeps close contact with the solid electrolyte.
Drawings
FIG. 1 is a-MoO3Nanoribbons, X-ray powder diffraction patterns and scanning electron microscopy patterns of solid state electrolytes.
Fig. 2 is a comparative X-ray powder diffraction pattern for a lithium mixture negative electrode.
Fig. 3 is a scanning electron micrograph of a cross section of a lithium mixture negative electrode and a solid electrolyte, and metallic lithium and a solid electrolyte.
Fig. 4 is a graph comparing the wettability of lithium mixture negative electrodes with lithium metal.
FIG. 5 is an electrochemical impedance spectrum of a solid-state symmetric lithium ion battery
Fig. 6 is a plot of limiting current density for a solid state symmetric lithium ion battery.
Fig. 7 is a time-voltage curve of a constant current charge and discharge test of a solid-state symmetric lithium symmetric battery.
FIG. 8 is lithium/Li metal6.4La3Zr1.5Ta0.6O12Solid electrolyte/metallic lithium, and lithium mixture negative electrode/Li6.4La3Zr1.5Ta0.6O12Time-voltage curve of constant current charge and discharge test of solid electrolyte/lithium mixture negative electrode symmetrical battery.
Detailed Description
The content percentages of the components described in the present specification refer to mass percentages unless otherwise specified.
The invention provides a lithium mixture cathode, which is prepared from metallic lithium and alpha-phase nano molybdenum oxide (hereinafter, the metallic lithium and the alpha-MoO are all described as alpha-MoO)3Nanobelts). After the materials are subjected to high-temperature blending and melting, the cathode material applied to the solid lithium ion battery can be prepared. The negative electrode material of the solid lithium battery can endow negative metal lithium with stronger viscosity and wettability, reduce surface tension, increase the affinity of solid electrolyte and lithium, reduce interface impedance, improve the conduction of lithium ions, and is beneficial to the deposition of the lithium ions, thereby improving the utilization rate and the cycle life of the battery.
Example 1 lithium mixture negative electrode
(a)α-MoO3Preparing a nanobelt: 9.6g of molybdenum powder was slowly added dropwise to 80mL of 30 wt.% hydrogen peroxide until the molybdenum powder was completely dissolved and the solution was yellow, and the experiment was performed using a water-ice bath. Deionized water was added to the resulting yellow solution to 1L and after stirring for 8h, the solution appeared pale yellow. Performing a hydrothermal experiment on the light yellow solution, wherein the hydrothermal condition is 180 ℃, and keeping the temperature for 24 hours. After hydrothermal treatment, centrifuging the obtained milky white solution, taking the lower-layer precipitate and drying to obtain alpha-MoO3A nanoribbon.
(b) And (3) placing the clean lithium metal in a stainless steel crucible and heating until the lithium metal is in a liquid spherical shape. Slowly adding the prepared alpha-MoO into liquid spherical metal lithium3The nanobelt was stirred until alpha-MoO3The nanobelt is reacted completely to obtain a lithium mixture cathode, metallic lithium and alpha-MoO3The mass ratio of the nanobelts is 10: 3.
EXAMPLE 2 lithium mixture negative electrode
(a)α-MoO3Preparing a nanobelt: 9.6g of molybdenum powder was slowly added dropwise to 80mL of 30 wt.% hydrogen peroxide until the molybdenum powder was completely dissolved and the solution was yellow, and the experiment was performed using a water-ice bath. Deionized water was added to the resulting yellow solution to 1L and after stirring for 8h, the solution appeared pale yellow. Performing a hydrothermal experiment on the light yellow solution, wherein the hydrothermal condition is 160 ℃, and keeping the temperature for 24 hours. After hydrothermal treatment, centrifuging the obtained milky white solution, taking the lower-layer precipitate and drying to obtain alpha-MoO3A nanoribbon.
(b) And (3) placing the clean lithium metal in a stainless steel crucible and heating until the lithium metal is in a liquid spherical shape. Slowly adding the prepared alpha-MoO into liquid spherical metal lithium3The nanobelt was stirred until alpha-MoO3The nanobelt is reacted completely to obtain a lithium mixture cathode, metallic lithium and alpha-MoO3The mass ratio of the nanobelts is 10: 3.
Assembly of ion-symmetric cells with lithium-mixture negative electrodes
(a) Garnet-type solid electrolyte Li6.4La3Zr1.5Ta0.6O12The preparation of (1): weighing LiOH & H according to stoichiometric ratio2O,La2O3, ZrO2And Ta2O5Wherein LiOH. H2The O excess is 10% to compensate for Li loss during subsequent sintering. Weighing LiOH & H2O, La2O3,ZrO2And Ta2O5Mixing, high-energy ball milling, and calcining at 900 deg.C for 12 hr to obtain cubic phase Li6.4La3Zr1.5Ta0.6O12And (3) powder. Prepared Li6.4La3Zr1.5Ta0.6O12The powder was again ball milled for 2 hours and then compressed into tablets and sintered a second time at 1100 c for 12 hours. Grinding the prepared ceramic wafer by using a grinding disc, and removing mother powder and impurities on the surface of the membrane to obtain solid electrolyte Li6.4La3Zr1.5Ta0.6O12。
(b) The prepared solid electrolyte Li6.4La3Zr1.5Ta0.6O12And placing the lithium mixture cathode in a molten state until two sides of the solid electrolyte are completely attached by the lithium mixture cathode, wherein the edges of the solid electrolyte are kept clean around and cannot be adhered by the lithium mixture cathode. Then packaging the lithium ion button battery case in a CR2032 lithium ion button battery case, adding foam nickel on two sides of a positive electrode and a negative electrode, and packaging by using a packaging machine; this operation was carried out in a glove box (oxygen < 0.1ppm, water < 0.1 ppm).
α-MoO3Nanoribbons and solid electrolyte Li6.4La3Zr1.5Ta0.6O12Is characterized by
According to X-ray powder diffraction analysis shown in (a) of FIG. 1, it was revealed that α -MoO was produced3Nanobelt all diffraction peaks and alpha-MoO3(JCPDS card number: 05-0508; a: 0.3962nm, b: 1.385nm, c: 0.3697nm) corresponding to characteristic diffraction peaks, indicating alpha-MoO3The nanoribbons are orthorhombic phase alpha-MoO 3; (b) the X-ray powder diffraction analysis showed that the solid electrolyte Li was prepared6.4La3Zr1.5Ta0.6O12Corresponds to the space group standard card (JCPDS number 0039-. It can be seen that in LiOH. H2In the case of 10% excess of O, Li6.4La3Zr1.5Ta0.6O12A cubic garnet phase; after high-temperature sintering, La with a heterogeneous phase generated by Li volatilization does not exist2Zr2O7。
α -MoO shown in (a) of FIG. 23Scanning electron microscopy of nanoribbons Electron diffraction patterns of a selected region of the α -MoO3 nanoribbons3The crystallographic axes in the nanoribbons extend in a certain direction, also illustrating alpha-MoO3Nanoribbons and single crystals are composed of numerous ribbons. It can be observed that alpha-MoO3The dimensions of the individual nanoribbons are about 200nm in width and on the order of micrometers in length. (b) Shown is a solid electrolyte Li6.4La3Zr1.5Ta0.6O12According to a scanning electron microscope image, the particle size is 2-5 mu m after sintering, the combination between particles is very good, and the density is very high.
Characterization of lithium mixture negative electrodes
From the xrd comparison of the lithium mixture negative electrode shown in FIG. 3, we can observe pure Mo metal (PDF # 01-077-2144), pure Li metal (PDF #89-3940) and Li2The X-ray diffraction pattern of the O-phase (PDF #00-001-1208) Li-Mo composite material does not contain alpha-MoO3Phase, indicating that the α -MoO3 nanoribbons have reacted completely with Li metal. Of note are Li foils and Li-Mo compositesThe green shaded areas in the XRD pattern are from Kapton tape used for XRD measurements.
Metallic lithium and solid electrolyte and Li according to FIG. 4 (a)6.4La3Zr1.5Ta0.6O12Scanning electron microscope image of the interface morphology of (a), top lithium metal and bottom Li6.4La3Zr1.5Ta0.6O12There is a large gap between the electrolytes (in the dotted line in the figure). The negative electrode of lithium mixture shown in (b) of FIG. 4 and the solid electrolyte Li6.4La3Zr1.5Ta0.6O12The scanning electron microscope image of the interface morphology of (a) shows that the negative electrode of the lithium mixture can be well filled into the surface voids of the garnet particles and remain with Li6.4La3Zr1.5Ta0.6O12The close contact of the solid electrolyte shows that the lithium ion battery cathode material has stronger viscosity and adhesion and smaller surface tension compared with the metallic lithium.
FIG. 5 shows the measurement of lithium metal and α -MoO at different mass ratios3The appearance of the cathode of the lithium mixture of the nanobelt shows that pure molten lithium forms a sphere in the crucible, and has poor wettability and high surface tension. When 10 wt% of alpha-MoO is added3In nanobelts, the spherical molten lithium flattens but has some protrusions due to still having some surface tension, following the α -MoO3The proportion of nanoribbons increases gradually, the wettability of the molten lithium mixture negative electrode increases significantly, and the surface tension becomes smaller and smaller. alpha-MoO3The nanobelt content is greater than or equal to 30 wt%, the surface of the molten lithium mixture negative electrode is already level with the horizontal plane, and the surface tension becomes small. When added alpha-MoO3When the content of the nanobelt is 70 wt% or more, the molten lithium mixture negative electrode becomes viscous like clay and has strong plasticity. After the negative electrode of the lithium mixture is cooled and solidified, it shows metallic luster and excellent texture. The molten lithium mixture negative electrode can quickly and uniformly wet the solid electrolyte Li6.4La3Zr1.5Ta0.6O12And metallic lithium in a molten state is hardly adhered at allSolid electrolyte Li6.4La3Zr1.5Ta0.6O12。
Electrochemical performance testing of lithium mixture negative electrodes
According to FIG. 6, metallic lithium/Li6.4La3Zr1.5Ta0.6O12Solid electrolyte/metallic lithium, and lithium mixture negative electrode/Li6.4La3Zr1.5Ta0.6O12Electrochemical impedance spectroscopy evaluation of solid electrolyte/lithium mixture negative symmetric cells for interfacial resistance, lithium metal/Li6.4La3Zr1.5Ta0.6O12The arc impedance of a solid electrolyte/lithium metal symmetrical cell is about 520 Ω cm2The interface resistance was calculated to be 260. omega. cm2. Lithium mixture negative electrode/Li6.4La3Zr1.5Ta0.6O12The interfacial resistance of a solid electrolyte/lithium mixture negative electrode symmetric cell was calculated to be 1 Ω cm2Much lower than metallic lithium/Li6.4La3Zr1.5Ta0.6O12Solid electrolyte/lithium metal symmetric cells. The sharp drop in interface resistance is due to the lithium mixture negative electrode and Li6.4La3Zr1.5Ta0.6O12There are no interfacial voids between the solid electrolytes.
Shown in a of FIG. 7 is a lithium mixture negative electrode/Li6.4La3Zr1.5Ta0.6O12The limiting current density of the solid electrolyte/lithium mixture negative electrode symmetric cell was observed to increase almost linearly in charge/discharge polarization voltage at 1700. mu.A. cm with increasing current density-2The limiting current density at the short circuit position is 1700 muA cm-2. In a of FIG. 7, metallic lithium/Li6.4La3Zr1.5Ta0.6O12The limiting current density of the solid electrolyte/metal lithium symmetrical battery only reaches 40 mA-cm-2. In contrast, lithium mixture negative electrodes and Li6.4La3Zr1.5Ta0.6O12The solid electrolyte interface is more excellent in the transmission of a large current.
FIG. 8Metallic lithium/Li6.4La3Zr1.5Ta0.6O12Solid electrolyte/metallic lithium, and lithium mixture negative electrode/Li6.4La3Zr1.5Ta0.6O12Time-voltage curve of constant current charge and discharge test of solid electrolyte/lithium mixture negative electrode symmetrical battery. Metallic lithium/Li6.4La3Zr1.5Ta0.6O12The solid electrolyte/lithium metal symmetric cell was short-circuited within 40 hours, which indicated lithium metal/Li6.4La3Zr1.5Ta0.6O12The interfacial properties of solid electrolytes are poor. However, lithium mixture negative electrode/Li6.4La3Zr1.5Ta0.6O12The solid electrolyte/lithium mixture negative electrode symmetrical battery can be 400 muA-cm-2Current density of 1200 hours, which indicates a negative electrode of lithium mixture with Li6.4La3Zr1.5Ta0.6O12The interface of the solid electrolyte is stable, and current circulation can be maintained for a long time.
In summary, a suitable lithium mixture negative electrode was developed by adding α -MoO3 nanobelts or other metal oxides to molten metallic lithium. The method has potential expansibility, is simple to operate and does not need any complex equipment. Among them, a series of metal oxides such as α -MoO3 nanobelts are also easily produced in large quantities and are inexpensive. The lithium mixture negative electrode remarkably reduces the interface resistance to a solid electrolyte, has excellent cycle stability, and has higher limiting current than a common solid battery. These show that the lithium mixture negative electrode has a wide application prospect in solid-state batteries.
Claims (10)
1. The negative electrode material of the lithium solid-state battery is characterized by comprising metallic lithium and oxide or lithium titanate; the oxide is an oxide of a metal or a nonmetal.
2. The negative electrode material for a lithium solid state battery according to claim 1, wherein the negative electrode material is obtained by heating and melting metallic lithium and an oxide or lithium titanate.
3. The negative electrode material for a lithium solid state battery according to claim 1, wherein the metal oxide is selected from zinc oxide, aluminum oxide, magnesium oxide, silicon oxide, molybdenum oxide, or the like; the molybdenum oxide is alpha-MoO3A nanoribbon;
the particle diameter of the oxide particles is less than 10 μm; the content of the oxide in the negative electrode material is 5-70 wt.%.
4. The method for preparing the negative electrode material for the lithium solid-state battery according to claim 1, comprising the steps of: heating the metallic lithium to a molten state, adding metallic or nonmetallic oxides, and continuously heating and stirring to be uniform to obtain the cathode material.
5. The method according to claim 4, wherein the oxide is α -MoO3A nanoribbon.
6. The method of claim 5, wherein said α -MoO is in the form of a3The preparation method of the nanobelt comprises the following steps of: step 1, dropwise adding a hydrogen peroxide solution into molybdenum powder to dissolve the molybdenum powder, and adding the dissolved solution into deionized water for dilution; step 2, carrying out hydro-thermal synthesis on the solution obtained in the step 1, centrifugally separating a product, drying and grinding to obtain alpha-MoO3A nanoribbon.
7. The method according to claim 4, wherein the hydrogen peroxide solution is added dropwise to the molybdenum powder under ice bath conditions; the concentration of the hydrogen peroxide solution is 10-35 wt%.
8. The preparation method as claimed in claim 4, wherein the hydrothermal synthesis is carried out at a temperature of 140 ℃ and a temperature of 160 ℃ for 12-24 h.
9. Use of the negative electrode material of claim 1 in a solid state lithium ion battery.
10. The use of claim 9, wherein the solid state lithium ion battery comprises a positive electrode material, a negative electrode material, a solid state electrolyte, wherein the solid state electrolyte is between the positive and negative electrode materials.
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| CN113871597B (en) * | 2021-09-27 | 2023-11-10 | 电子科技大学长三角研究院(湖州) | Lithium composite anode material with three-dimensional framework structure and reserved space on surface and preparation method thereof |
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