CN112786881A - Solid-state lithium battery and preparation method thereof - Google Patents

Solid-state lithium battery and preparation method thereof Download PDF

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CN112786881A
CN112786881A CN201911080974.4A CN201911080974A CN112786881A CN 112786881 A CN112786881 A CN 112786881A CN 201911080974 A CN201911080974 A CN 201911080974A CN 112786881 A CN112786881 A CN 112786881A
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positive electrode
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mofs
metal oxide
lithium
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张鹏
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Beijing Electric Vehicle Co Ltd
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Beijing Electric Vehicle Co Ltd
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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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/028—Positive 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the technical field of lithium batteries, in particular to a solid-state lithium battery and a preparation method thereof. The solid lithium battery comprises a positive electrode, a negative electrode and a solid electrolyte, wherein the solid electrolyte is an MOFs-based composite solid electrolyte; the positive electrode is made of a modified positive electrode material, and the modified positive electrode material comprises a positive electrode material and a carbon-metal oxide composite material coated on the surface of the positive electrode material; the carbon-metal oxide composite material is derived from MOFs. According to the invention, the carbon with an amorphous structure and the metal oxide are uniformly and cooperatively coated on the surface of the anode, and the anode and the MOFs-based composite solid electrolyte form the solid lithium battery, so that the interfacial resistance is effectively reduced, the transmission of lithium ions is promoted, and the cycling stability and the rate capability are improved.

Description

Solid-state lithium battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a solid-state lithium battery and a preparation method thereof.
Background
The power battery is used as the only energy source of the pure electric vehicle, and the performance of the power battery directly influences the performance of the whole vehicle. The lithium ion battery has the advantages of high specific energy, long cycle life, no memory effect, safety, reliability, rapid charge and discharge, and the like, and becomes a hotspot of the research on novel power supply technology.
The traditional liquid lithium battery has the safety problems of poor thermal stability, flammability, easy liquid leakage and the like. The use of a solid electrolyte instead of a liquid electrolyte is an effective solution to the above problems.
Compared with a liquid lithium battery which is influenced by an integral structure, an electrochemical window and the like, the solid lithium battery is easier to have high energy density, but the traditional organic solid electrolyte cannot meet the practical application due to the defects of limited electrochemical window, low room-temperature conductivity and the like. Meanwhile, the traditional inorganic ceramic electrolyte has the defects of large interface resistance, poor matching with electrode materials and the like. And the interface of the solid electrolyte and the solid electrode has poor lithium ion transport kinetics, so that the solid lithium battery needs further improvement to improve electrical properties.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the solid lithium battery and the preparation method thereof are provided, and the interface stability, the cycling stability and the rate capability of the solid lithium battery are improved by improving the anode material and matching with the solid electrolyte.
The invention provides a solid-state lithium battery, which comprises a positive electrode, a negative electrode and a solid-state electrolyte,
the solid electrolyte is MOFs-based composite solid electrolyte;
the positive electrode is made of a modified positive electrode material, and the modified positive electrode material comprises a positive electrode material and a carbon-metal oxide composite material coated on the surface of the positive electrode material;
the carbon-metal oxide composite material is derived from MOFs.
Preferably, the material of the positive electrode is a lithium-rich manganese-based material, as shown in formula (I);
xLi2MnO3·(1-x)LiMO2，
wherein M is at least one of Mn, Ni and Co, and x is more than 0 and less than 1.
Preferably, the MOFs-based composite solid electrolyte is lithium isopropoxide@Mg2(dobdc), Li-IL @ MOF, MIT-20-LiCl, MIT-20-LiBr, UIO/Li-IL, P @ CMOF composite solid electrolyte, Li-IL @ MOF-LZZO, or MOF-LZZO.
Preferably, the mass ratio of the metal oxide to the positive electrode material in the carbon-metal oxide composite material is 1: 20-2000.
Preferably, the metal in the metal oxide is a metal having a reduction potential of less than-0.27V.
Preferably, the negative electrode is a lithium electrode.
The invention discloses a preparation method of a solid-state lithium battery, which comprises the following steps:
uniformly mixing the anode material and MOFs to obtain a mixture;
sintering the mixture under the protection of nitrogen or inert gas to obtain a modified positive electrode material; the modified anode material comprises an anode material and a carbon-metal oxide composite material coated on the surface of the anode material;
and assembling the positive electrode formed by the modified positive electrode material, the negative electrode and the MOFs-based composite solid electrolyte to obtain the solid lithium battery.
Preferably, the sintering temperature is 300-800 ℃, and the sintering time is 4-10 hours.
Preferably, the mixture is placed for 0.5 to 3 hours under the protection of nitrogen or inert gas and then sintered.
Preferably, the cathode material is uniformly mixed with the MOFs, and specifically includes:
carrying out ball milling on the anode material and MOFs to obtain a mixture; or
And uniformly stirring the anode material and MOFs in a solvent, and drying to obtain a mixture.
Compared with the prior art, the invention uniformly and synergistically coats the amorphous carbon and the metal oxide on the surface of the anode to form the solid lithium battery together with the MOFs-based composite solid electrolyte. Has the following advantages:
(1) the nano-crystals in the MOFs-based composite solid electrolyte are tightly stacked, and at the interface between an electrode and the electrolyte, the three-dimensional open structure of the MOFs material enables the composite material to be in direct contact with an electrode active material, so that a rich nano-wetting interface is formed, the interface resistance is effectively reduced, the transmission of lithium ions is promoted, and the cycle stability and the rate capability are improved.
(2) The carbon coating and the metal oxide coating are organically combined, the respective advantages of the carbon coating and the metal oxide are integrated, the electronic conductivity of the material is improved by the carbon coating, the side reaction of the electrode material and the electrolyte is reduced by the amorphous metal oxide coating, the ionic conductivity is improved, and the comprehensive performance of the cathode material is improved to the maximum extent.
Drawings
Fig. 1 is a schematic structural view of a solid lithium battery according to an embodiment of the present invention;
fig. 2 is a graph showing discharge capacities at different rates when samples of the lithium-rich manganese-based positive electrode materials coated in example 1 of the present invention and comparative example 1 were used as positive electrodes;
FIG. 3 is a graph showing the capacity cycling at 0.1C for a positive electrode made of a sample of the lithium-rich manganese-based positive electrode material coated with the composite carbon material according to example 1 and comparative example 1 of the present invention;
legends note:
1 is a positive electrode, and the surface of the positive electrode is coated with a carbon-metal oxide composite material; 2 is a solid electrolyte which is a MOFs-based composite solid electrolyte; and 3 is a negative electrode.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The embodiment of the invention discloses a solid-state lithium battery, which has a specific structure as shown in figure 1 and comprises a positive electrode 1, a negative electrode 3 and a solid-state electrolyte 2,
the solid electrolyte is MOFs-based composite solid electrolyte;
the positive electrode is made of a modified positive electrode material, and the modified positive electrode material comprises a positive electrode material and a carbon-metal oxide composite material coated on the surface of the positive electrode material;
the carbon-metal oxide composite material is derived from MOFs.
The MOFs-based composite solid electrolyte is a solid electrolyte formed by compounding MOFs with ionic liquid, oxide and other materials, has a pore channel structure, can limit the movement of large-size particles without influencing the movement of small-size lithium ions, and has a higher lithium ion transfer number.
Preferably, the MOFs-based composite solid electrolyte is lithium isopropoxide @ Mg2(dobdc), an ionic liquid Li-IL infiltrated MOF material, MIT-20-LiCl, MIT-20-LiBr, UIO/Li-IL, P @ CMOF composite solid state electrolyte, Li-IL @ MOF-LZZO, or MOF-LZZO.
MOFs (Metal-Organic Frameworks) are hybrid Organic-inorganic materials with intramolecular pores formed by self-assembly of Organic ligands and Metal ions or clusters through coordination bonds. Has the advantages of high specific surface area, controllable structure, rich organic substances and the like. Can load high-density charged substances in a smaller volume, so that the cation jumping position is more compact, the activation energy of ion transmission can be reduced, and the ion conductivity is increased.
The derivation referred to in the present invention means that MOFs are decomposed at high temperature.
In the present invention, the surface of the positive electrode is coated with a carbon-metal oxide composite material.
Preferably, the material of the positive electrode is a lithium-rich manganese-based material, as shown in formula (I);
xLi2MnO3·(1-x)LiMO2，
wherein M is at least one of Mn, Ni and Co, and x is more than 0 and less than 1.
The carbon-metal oxide composite material derived from the MOFs has a hybrid micro-nano structure. The invention uses the carbon-metal oxide composite material for coating the lithium-rich manganese-based anode material, namely: the carbon coating and the metal oxide coating are creatively and organically combined, the respective advantages of the carbon coating and the metal oxide are combined, the electronic conductivity of the material is improved by the carbon coating, the side reaction of the electrode material and the electrolyte is reduced by the amorphous metal oxide coating, the ionic conductivity is improved, and the comprehensive performance of the lithium-rich manganese-based cathode material is improved to the maximum extent, such as the cycle stability and the rate capability. Moreover, the cost increase caused by multiple coating is avoided.
The MOFs may be Ti-MIL-125, ZIF-67, UiO-66, Al-MIL-101-NH2ZIF-7, and the like.
According to a preferred embodiment of the present invention, the mass ratio of the metal oxide to the positive electrode material in the carbon-metal oxide composite material is 1:20 to 2000.
The metal in the metal oxide is a metal with a reduction potential of less than-0.27V. Such as: any one or more of magnesium, aluminium, zirconium, titanium, zinc, barium, strontium, vanadium, neodymium, cadmium and yttrium.
In the solid-state lithium battery of the present invention, the negative electrode is preferably a lithium electrode.
The embodiment of the invention also discloses a preparation method of the solid-state lithium battery, which comprises the following steps:
uniformly mixing the anode material and MOFs to obtain a mixture;
sintering the mixture under the protection of nitrogen or inert gas to obtain a modified positive electrode material; the modified anode material comprises an anode material and a carbon-metal oxide composite material coated on the surface of the anode material;
and assembling the positive electrode formed by the modified positive electrode material, the negative electrode and the MOFs-based composite solid electrolyte to obtain the solid lithium battery.
The modified cathode materials or MOFs involved in the present invention can be prepared by any of the existing preparation methods or according to the method of the present invention, or can be directly obtained from commercial sources.
The positive electrode material is preferably a lithium-rich manganese-based material, and is shown as a formula (I);
xLi2MnO3·(1-x)LiMO2，
wherein M is at least one of Mn, Ni and Co, and x is more than 0 and less than 1.
The lithium-rich manganese-based material can be obtained by solid-phase sintering of a precursor formed by carbonate coprecipitation. MOFs can be prepared by solvothermal methods.
In order to avoid introducing other metals during the heat treatment process, the metals in the MOFs are metals with a reduction potential of less than-0.27V, such as: any one or more of magnesium, aluminium, zirconium, titanium, zinc, barium, strontium, vanadium, neodymium, cadmium and yttrium.
According to the preparation method, firstly, the anode material and the MOFs are uniformly mixed to obtain a mixture.
The MOFs and the positive electrode material are mixed according to the mass ratio of the metal oxide to the positive electrode material of 0.05-5%, preferably 1.0-2.0%. In addition, the choice of ligand in the MOFs determines the carbon content of the carbon-metal oxide composite.
The method for mixing the cathode material and the MOFs includes two major types of dry mixing and wet mixing, in an embodiment of the present invention, the step of forming the mixture includes ball-milling the cathode material and the MOFs by using a ball mill, that is, mixing is achieved by using a dry mixing method, and preferably, the step of forming the mixture includes: placing the anode material, the MOFs and the grinding balls into a ball milling tank to form an object to be milled, wherein the mass ratio of the anode material to the grinding balls is preferably 1: 1-5: 1, and the weight ratio of small balls to medium balls in the grinding balls is further preferably 0.5: 1-2: 1; and performing ball milling on the object to be milled for 2-6 hours at the rotating speed of 400-700 rpm to obtain a mixture. Ball milling is carried out by a ball mill, namely mixing is carried out by a simple physical method; in order to achieve rapid and efficient ball milling, the conditions for ball milling may be selected within the above ranges. The grinding balls are those commonly used in ball mills in the prior art, wherein the medium balls and the small balls are commonly used in the art, and therefore the specific size is not limited herein, for example, the medium balls with the diameter of 20mm and the small balls with the diameter of 15mm are selected.
In another embodiment of the present invention, the mixture is formed by wet mixing, that is, the process of forming the mixture includes: and uniformly stirring the anode material and MOFs in a solvent, and drying to obtain a mixture. Specifically, the method comprises the following steps: placing the anode material and MOFs in a solvent to form a mixed solution; stirring and heating the mixed solution until the solvent is completely volatilized to obtain a primary mixture; and drying the primary mixture to obtain a mixture. In order to further optimize the coating effect, it is preferable that the process of forming the mixed solution includes: dispersing MOFs in a solvent to form a first dispersion; and dispersing the anode material in the first dispersion liquid to obtain a mixed liquid, mixing the raw materials in steps, improving the dispersibility of the MOFs in the solvent, and further optimizing the coating performance of the MOFs on the anode material.
The solvent can be a substance having dispersibility and chemical inertness to MOFs and the positive electrode material, preferably the solvent is one or more of deionized water, alcohol or tetrahydrofuran, and more preferably the mass ratio of the solvent to the positive electrode material is 1-3: 1. The specific drying time and drying temperature are determined by the volatilization performance of the selected solvent, and the drying temperature is preferably 70-120 ℃, and the drying time is preferably 1-12 hours.
According to the preparation method, after the mixture is obtained, the mixture is sintered under the protection of nitrogen or inert gas, and the modified cathode material is obtained. The modified anode material comprises an anode material and a carbon-metal oxide composite material coated on the surface of the anode material.
Preferably, the mixture is placed for 0.5 to 3 hours under the protection of nitrogen or inert gas and then sintered. The sintering temperature is preferably 300-800 ℃, and the sintering time is preferably 4-10 hours. And 6h, on one hand, the stability and uniformity of coating are improved, and on the other hand, the stability of the crystal structure of the anode material substrate formed after sintering is ensured.
According to the preparation method, after the modified anode material is obtained, the anode, the cathode and the MOFs-based composite solid electrolyte formed by the modified anode material are assembled to obtain the solid lithium battery.
The method for assembling the solid-state lithium battery is not particularly limited, and the solid-state lithium battery can be assembled in a manner known by a person skilled in the art.
For further understanding of the present invention, the following examples are given to illustrate the solid-state lithium battery provided by the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
Preparation of precursor Mn by carbonate coprecipitation method0.54Ni0.13Co0.13(CO3)0.8Then weighing lithium carbonate and the precursor according to the molar sum ratio of lithium to metal ions of 1.25:0.8, and uniformly mixing by dry ball milling. Placing the mixture in a sagger, placing in a muffle furnace, introducing dry air, heating to 450 ℃ at a heating rate of 3.5 ℃/min, sintering for 4h, continuing heating to 900 ℃, sintering for 15h, naturally cooling, crushing, dissociating, and sieving with a 400-mesh sieve to obtain the lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2. Lithium carbonate was added in an excess of 0.05 wt% (i.e., the amount weighed multiplied by 1.05 wt%) to compensate for the loss of lithium during high temperature sintering.
Dissolving organic ligand phthalic acid in a mixed solvent of DMF and methanol, performing ultrasonic mixing uniformly to obtain a transparent mixed solution, adding tetrabutyl titanate containing Ti, continuing performing ultrasonic mixing uniformly, adding the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining for reaction at 150 ℃ for 48 hours, performing solid-liquid separation, washing, and drying in a vacuum drying oven at 50 ℃ for 24 hours to obtain a precursor Ti-MIL-125 of carbon and metal Ti oxide.
According to the metal oxide and Li1.2Mn0.54Ni0.13Co0.13O2The mass ratio of the Ti-MIL-125 to the Li is 2.0 percent to 11.2Mn0.54Ni0.13Co0.13O2Adding into ethanol, ethanol and Li1.2Mn0.54Ni0.13Co0.13O2The weight ratio of the components is 2:1, stirring is carried out at a certain temperature until the components are dried by distillation, and the components are put into a vacuum drying oven and dried for 8 hours at the temperature of 80 ℃ to obtain uniformly mixed powder.
Placing the powder in a sagger, placing the sagger in a muffle furnace, introducing argon, starting to heat after 2h, sintering at 600 ℃ for 6h, and sieving to obtain the carbon and titanium oxide coated lithium-rich manganese-based anode material C/TiO2@Li1.2Mn0.54Ni0.13Co0.13O2。
And (2) mixing the carbon and titanium oxide coated lithium-rich manganese-based positive electrode material, a conductive agent SP and a binder PVDF according to a mass ratio of 80: 10: mixing uniformly according to the proportion of 10, adding NMP to prepare slurry, uniformly coating the slurry on an aluminum foil current collector, drying at 120 ℃, tabletting, and then assembling the CR2025 button cell in a glove box by taking metal lithium as a negative electrode and UIO/Li-IL as a solid electrolyte.
The assembled button CR2025 battery was subjected to constant current charge and discharge testing using a battery charge and discharge tester (model number LAND2001A) from wuhan blue electric company. The testing temperature of the battery is 25 ℃, and the voltage range is 2.0-4.8V.
Comparative example 1:
preparation of precursor Mn by carbonate coprecipitation method0.54Ni0.13Co0.13(CO3)0.8Then weighing lithium carbonate and the precursor according to the molar sum ratio of lithium to metal ions of 1.25:0.8, and uniformly mixing by dry ball milling. Placing the mixture in a sagger, placing in a muffle furnace, introducing dry air, heating to 450 ℃ at a heating rate of 3.5 ℃/min, sintering for 4h, continuing heating to 900 ℃, sintering for 15h, naturally cooling, crushing, dissociating, and sieving with a 400-mesh sieve to obtain the lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2. Lithium carbonate was added in an excess of 0.05 wt% (i.e. adding a nominal amount of 1.05 wt%) to compensate for the loss of lithium during high temperature sintering.
The mass ratio of the metal oxide to the TiO is 2.0 percent to 1 percent in sequence2And Li1.2Mn0.54Ni0.13Co0.13O2Adding into ethanol, ethanol and Li1.2Mn0.54Ni0.13Co0.13O2The weight ratio of the components is 2:1, stirring is carried out at a certain temperature until the components are dried by distillation, and the components are put into a vacuum drying oven and dried for 8 hours at the temperature of 80 ℃ to obtain uniformly mixed powder.
Placing the powder into a sagger, placing the sagger into a muffle furnace, sintering the sagger at 600 ℃ for 6 hours in air atmosphere, and sieving the sagger to obtain the titanium oxide coated lithium-rich manganese-based anode material TiO2@LiNi0.5Co0.2Mn0.3O2。
And (3) mixing the lithium-rich manganese-based positive electrode material obtained in the comparative example 1, a conductive agent SP and a binder PVDF according to a mass ratio of 80: 10: mixing them uniformly according to a ratio of 10, adding NMP to prepare slurry, uniformly coating it on the aluminium foil current collector, drying at 120 deg.C, tabletting, then using metal lithium as negative electrode and ceramic as solid electrolyte, and assembling them into the CR2025 button cell in the glove box. The assembled button CR2025 battery was subjected to constant current charge and discharge testing using a battery charge and discharge tester (model number LAND2001A) from wuhan blue electric company. The testing temperature of the battery is 25 ℃, and the voltage range is 2.0-4.8V.
Fig. 2 is a graph showing discharge capacities at different rates when samples of the lithium-rich manganese-based positive electrode materials coated in example 1 of the present invention and comparative example 1 were used as positive electrodes. The Ti-MIL-125 coated lithium-rich manganese-based positive electrode material is 4.8V-2.0V, the 0.1C discharge average gram capacity is 259.8mAh/g, the 1C multiplying power average discharge gram capacity is 212.4mAh/g, and TiO2The coated lithium-rich manganese-based positive electrode material is 4.8V-2.0V, the 0.1C discharge average gram capacity is 237.6mAh/g, and the 1C multiplying power average discharge gram capacity is only 147.5 mAh/g. This is because the electron conductivity of the MOFs-derived composite material is better, and thus the rate performance advantage is obvious.
Fig. 3 is a graph showing capacity cycling at 0.1C for a sample of the lithium-rich manganese-based positive electrode material coated with the composite carbon material in example 1 of the present invention and comparative example 1. The discharge capacity of example 1 decayed slowly as the number of cycles increased, and the capacity retention rate was 97.6% after 100 cycles. The discharge capacity of comparative example 1 increased with the number of cycles, the capacity fading was significant after 100 cycles, and the capacity retention rate was 91.3% after 100 cycles. Therefore, the lithium-rich manganese-based positive electrode material coated by the MOFs-derived composite material is beneficial to inhibiting capacity fading in the circulation process, and the circulation stability is better.
Example 2
According to the metal oxide and Li1.2Mn0.54Ni0.13Co0.13O2The mass ratio of (A) to (B) is 5.0 to 1, and UiO-66 and Li are mixed1.2Mn0.54Ni0.13Co0.13O2Adding into ethanol, ethanol and Li1.2Mn0.54Ni0.13Co0.13O2The weight ratio of the components is 2:1, stirring the mixture at a certain temperature until the mixture is dried by distillation, putting the mixture into a vacuum drying oven, and drying the mixture for 8 hours at the temperature of 80 ℃ to obtain uniformly mixed powderAnd (3) grinding.
Placing the powder in a sagger, placing the sagger in a muffle furnace, introducing argon, starting to heat after 3h, sintering at 580 ℃ for 10h, and sieving to obtain the carbon and zirconium oxide coated lithium-rich manganese-based cathode material C/ZrO2@Li1.2Mn0.54Ni0.13Co0.13O2。
And (2) mixing the carbon and titanium oxide coated lithium-rich manganese-based positive electrode material, a conductive agent SP and a binder PVDF according to a mass ratio of 80: 10: mixing the raw materials uniformly according to a proportion of 10, adding NMP to prepare slurry, uniformly coating the slurry on an aluminum foil current collector, drying at 120 ℃, tabletting, and then assembling the CR2025 button cell in a glove box by taking metal lithium as a negative electrode and Li-IL @ MOF-LZZO as a solid electrolyte.
The assembled button CR2025 battery was subjected to constant current charge and discharge testing using a battery charge and discharge tester (model number LAND2001A) from wuhan blue electric company. The testing temperature of the battery is 25 ℃, and the voltage range is 2.0-4.8V.
The UiO-66 coated lithium-rich manganese-based positive electrode material is 4.8V-2.0V, the 0.1C discharge average gram capacity is 265.8mAh/g, and the 1C multiplying power average discharge gram capacity is 213.4 mAh/g.
The discharge capacity of the battery prepared in the embodiment is slowly attenuated along with the increase of the cycle number, and the capacity retention rate is 98% after 100 cycles.
Example 3
According to the metal oxide and Li1.2Mn0.54Ni0.13Co0.13O2The mass ratio of the Al to the metal is 5.0 percent to 1, and Al-MIL-101-NH is added2Li1.2Mn0.54Ni0.13Co0.13O2Adding into ethanol, ethanol and Li1.2Mn0.54Ni0.13Co0.13O2The weight ratio of the components is 2:1, stirring is carried out at a certain temperature until the components are dried by distillation, and the components are put into a vacuum drying oven and dried for 8 hours at the temperature of 80 ℃ to obtain uniformly mixed powder.
Placing the powder in a sagger, placing the sagger in a muffle furnace, introducing argon, starting to heat after 2h, sintering at 800 ℃ for 3h, and sieving to obtain a carbon and titanium oxide coated lithium-rich manganese-based positive electrode material C/Al2O3@Li1.2Mn0.54Ni0.13Co0.13O2。
And (2) mixing the carbon and titanium oxide coated lithium-rich manganese-based positive electrode material, a conductive agent SP and a binder PVDF according to a mass ratio of 80: 10: mixing uniformly according to the proportion of 10, adding NMP to prepare slurry, uniformly coating the slurry on an aluminum foil current collector, drying at 120 ℃, tabletting, and then assembling into a CR2025 button cell in a glove box by taking metal lithium as a negative electrode and Li-IL @ MOF as a solid electrolyte.
The assembled button CR2025 battery was subjected to constant current charge and discharge testing using a battery charge and discharge tester (model number LAND2001A) from wuhan blue electric company. The testing temperature of the battery is 25 ℃, and the voltage range is 2.0-4.8V.
Al-MIL-101-NH2The coated lithium-rich manganese-based positive electrode material is 4.8V-2.0V, the 0.1C discharge average gram capacity is 260mAh/g, and the 1C multiplying power average discharge gram capacity is 214.4 mAh/g.
The discharge capacity of the battery prepared in the embodiment is slowly attenuated along with the increase of the cycle number, and after 100 cycles, the capacity retention rate is 98.2%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A solid-state lithium battery comprising a positive electrode, a negative electrode and a solid-state electrolyte,
the solid electrolyte is MOFs-based composite solid electrolyte;
the positive electrode is made of a modified positive electrode material, and the modified positive electrode material comprises a positive electrode material and a carbon-metal oxide composite material coated on the surface of the positive electrode material;
the carbon-metal oxide composite material is derived from MOFs.
2. The solid-state lithium battery according to claim 1, wherein a material of the positive electrode is a lithium-rich manganese-based material, as shown in formula (I);
xLi2MnO3·(1-x)LiMO2，
wherein M is at least one of Mn, Ni and Co, and x is more than 0 and less than 1.
3. The lithium solid-state battery according to claim 1, characterized in that the MOFs-based composite solid-state electrolyte is lithium isopropoxide @ Mg2(dobdc), Li-IL @ MOF, MIT-20-LiCl, MIT-20-LiBr, UIO/Li-IL, P @ CMOF composite solid electrolyte, Li-IL @ MOF-LZZO, or MOF-LZZO.
4. The solid lithium battery according to claim 1, wherein a mass ratio of the metal oxide to the positive electrode material in the carbon-metal oxide composite material is 1:20 to 2000.
5. The solid state lithium battery according to claim 4, wherein the metal in the metal oxide is a metal having a reduction potential of less than-0.27V.
6. The solid state lithium battery of claim 1, wherein the negative electrode is a lithium electrode.
7. A preparation method of a solid-state lithium battery is characterized by comprising the following steps:
uniformly mixing the anode material and MOFs to obtain a mixture;
sintering the mixture under the protection of nitrogen or inert gas to obtain a modified positive electrode material; the modified anode material comprises an anode material and a carbon-metal oxide composite material coated on the surface of the anode material;
and assembling the positive electrode formed by the modified positive electrode material, the negative electrode and the MOFs-based composite solid electrolyte to obtain the solid lithium battery.
8. The method according to claim 7, wherein the sintering temperature is 300 to 800 ℃ and the sintering time is 4 to 10 hours.
9. The preparation method according to claim 7, wherein the mixture is sintered after being placed for 0.5 to 3 hours under the protection of nitrogen or inert gas.
10. The preparation method according to claim 7, wherein the anode material is uniformly mixed with the MOFs, and specifically comprises:
carrying out ball milling on the anode material and MOFs to obtain a mixture; or
And uniformly stirring the anode material and MOFs in a solvent, and drying to obtain a mixture.
CN201911080974.4A 2019-11-07 2019-11-07 Solid-state lithium battery and preparation method thereof Pending CN112786881A (en)

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