CN115149206A - Fluorine modified quasi-solid mixed matrix lithium battery diaphragm and lithium battery preparation method - Google Patents

Fluorine modified quasi-solid mixed matrix lithium battery diaphragm and lithium battery preparation method Download PDF

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CN115149206A
CN115149206A CN202210823437.XA CN202210823437A CN115149206A CN 115149206 A CN115149206 A CN 115149206A CN 202210823437 A CN202210823437 A CN 202210823437A CN 115149206 A CN115149206 A CN 115149206A
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lithium
solid
lithium battery
battery
mixed matrix
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黄文欢
王顺
杨秀芳
张亚男
康祎璠
殷政
杨冬
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Shaanxi University of Science and Technology
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity

Abstract

The invention disclosesA fluorine modified quasi-solid mixed matrix lithium battery diaphragm and a lithium battery preparation method are provided, firstly, F-containing lithium battery diaphragm is synthesized by a high-temperature oil bath method + And then blending it with a lithium salt, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) to obtain F + Conducting solid polymer viscous liquid, F + Pouring the conductive solid polymer viscous liquid into a polytetrafluoroethylene template, and preparing the F by a film scraping method + Finally, the conductive solid polymer film, a lithium iron phosphate anode and a lithium cathode are assembled into a CR2032 type battery to obtain the F with good thermal stability and rapid ion transmission + The conducting quasi-solid mixed matrix lithium battery has a material of 150mAh g at a rated capacitance of 0.1C ‑1 And the rated capacitance of 1C is 125mAh g ‑1 The coulombic efficiency is close to 100%.

Description

Fluorine modified quasi-solid mixed matrix lithium battery diaphragm and lithium battery preparation method
Technical Field
The invention belongs to the field of solid-state batteries, and particularly relates to a preparation method of a fluorine modified quasi-solid mixed matrix lithium battery diaphragm, and an assembly and test method of the quasi-solid lithium battery.
Background
In recent years, with the gradual depletion of energy and various pollution problems of fossil fuels to the environment, it is becoming very important to develop clean, efficient, and green renewable energy. The battery has been receiving attention from researchers as a high-efficiency green energy storage device, and among them, a lithium ion secondary battery having a high energy density is widely used due to its high energy density. They enter various aspects of our lives, including portable electronic products, computers, game machines, mobile communication products, electric cars, and the like. As battery requirements and applications continue to increase, battery technology that achieves higher energy and power densities, better safety, and lower costs has become a focus of attention. Based on this, there are great opportunities and unprecedented challenges facing the production of high-energy, high-safety, low-cost advanced energy storage devices.
At present, because of the continuous improvement of lithium ion battery technology, lithium ion batteries have the advantages of high capacity, high energy density, strong cycle stability and the like, and have gradually replaced lead storage batteries to become a new generation of energy storage devices. However, the conventional liquid lithium ion battery has serious potential safety hazards, such as growth of lithium dendrites on the surfaces of lithium metal and a diaphragm, leakage risk of electrolyte, easy short circuit of the battery and further explosion of the battery. The appearance of the solid-state battery not only has the advantages of the traditional liquid-state lithium ion battery, but also perfectly reduces the potential safety hazard of the traditional liquid-state lithium ion battery, and the solid-state battery is an energy storage device which does not have liquid inside and all devices are solid. However, the solid-state battery has the disadvantages of excessive interface impedance, relatively high cost, low conductivity, poor mechanical stability, high interface impedance with an electrode and the like due to the fact that the inside of the solid-state battery is solid, and practical application of the all-solid-state metal lithium battery is limited. The appearance of quasi-solid electrolyte not only has the advantages of the traditional liquid battery, but also has the advantages of the solid battery. The solid electrolyte can improve the mechanical strength of the solid electrolyte, reduce the interface impedance and improve the conductivity. Therefore, the development of applicable quasi-solid electrolytes has great application potential in the manufacture of large energy storage devices.
The separator serves as a reservoir for the electrolyte of the lithium metal battery, prevents direct contact between positive and negative electrodes, and protects the lithium metal negative electrode during charge/discharge cycles. In addition, it plays an important role in the transport of lithium ions from the electrolyte between the positive and negative electrodes. Polyolefin (polypropylene (PP) or polyethylene) films are recognized as commercial separators due to their good electrochemical stability. However, it has the characteristics of poor thermal stability, uncontrollable electrolyte wettability and ion transport, and the like. Therefore, there is an urgent need to prepare a functional separator that replaces the commercial separator.
As a typical porous material, metal Organic Frameworks (MOFs) show great potential for applications in ion exchange, catalysis, gas storage, adsorption and separation. The inorganic MOFs material has the characteristics of good stability, higher specific surface area, excellent pores and the like, and can provide a rapid channel for the transmission of lithium ions. The introduction of fluorine functional ligands into the MOF structure not only can adjust the properties of the MOF surface, but also can create a specific pore environment, realize a special pore effect and a unique and controllable pore effect of a plurality of functional MOF-based materials, and promote the development of functional membranes.
The polymer electrolytes such as polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and the like have wide application prospects in solid-state lithium-sulfur batteries due to the advantages of low cost, good mechanical stability, good compatibility with electrodes, strong film forming capability, strong thermoplasticity and the like. The inorganic polymer diaphragm is formed by polymerizing a polymer and an inorganic MOFs material and adding a lithium ion conductive filler. The method not only combines the characteristics of inorganic MOFs materials, but also combines the characteristics of polymer electrolytes, and makes certain progress in the aspect of preparing the functionalized diaphragm to replace the traditional commercial diaphragm. For example, a professor team in songsheng, chongqing university prepares a lithium metal battery mixed quasi-solid electrolyte by a composite mixing design of three materials, wherein polyethylene oxide is used as a polymer main body, the interface compatibility of the polymer and lithium metal is improved, the crystallinity of the polyethylene oxide is inhibited, the conductivity of the polyethylene oxide is improved, and the mechanical and electrochemical stability of the electrolyte is enhanced through a garnet conductor. The mixed quasi-solid electrolyte showed 7.4X 10 4 S cm -1 High ionic conductivity and a high electrochemical stability window of 5.5V. Secondly, professor ZhouhaoBuxu of Japan Industrial and technical Integrated research institute (AIST), etc. prepared a quasi-solid electrolyte by using CuBTC metal organic framework (MOF, cuBTC-PSS) as a main material and modifying PSS polymer (poly 4-styrene sodium sulfonate) in the channel thereof, based on which a pouch battery having NCM-811 as a positive electrode and a lithium sheet as a negative electrode was assembled, and the pouch battery maintained a capacity of 171mAh g even after 300 cycles at a high temperature of 90 deg.C -1 The capacity retention rate was 89%.
Disclosure of Invention
The invention aims to provide a preparation method of a fluorine modified quasi-solid mixed matrix lithium battery diaphragm, which solves the problems of poor thermal stability, and uncontrollable electrolyte wettability and ion transmission of the existing lithium battery diaphragm.
The invention also aims to provide a preparation method of the fluorine modified quasi-solid mixed matrix lithium battery.
The first technical scheme adopted by the invention is that the preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm specifically comprises the following steps:
step 1, weighing zirconium tetrachloride solid and tetrafluoroterephthalic acid in sequence, adding the zirconium tetrachloride solid and the tetrafluoroterephthalic acid into a mixed solution of water and glacial acetic acid, stirring at room temperature, carrying out oil bath at 100 ℃ for 24 hours, then washing with methanol at least three times, and carrying out centrifugal drying to obtain white precursor powder A;
step 2, weighing precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and lithium bistrifluoromethanesulfonylimide LiTFSI, placing the precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and lithium bistrifluoromethanesulfonylimide LiTFSI in a flat-bottomed flask, adding N-methylpyrrolidone NMP, and stirring at room temperature to obtain white viscous liquid B;
step 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template, uniformly coating the white viscous liquid B on the polytetrafluoroethylene template by adopting a film scraping method, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a white polymer solid film C with the thickness of 80-100 microns;
and 4, cutting the prepared white polymer solid film C into round pieces, drying the round pieces overnight in vacuum at 60 ℃, and placing the round pieces in a glove box with the water oxygen value of less than 0.01ppm to obtain a solid polymer diaphragm D.
The present invention is also characterized in that,
in the step 1, the molar ratio of the zirconium tetrachloride solid to the tetrafluoroterephthalic acid is 1:1; the volume ratio of the water to the glacial acetic acid is 3.
In the step 2, the mass ratio of the precursor powder A to the polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP to the lithium bis (trifluoromethanesulfonyl) imide LiTFSI is 1:8:1, stirring for not less than 48 hours at room temperature; the polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP can be replaced by any one of polyethylene oxide PEO and polyvinylidene fluoride.
The size of the teflon template of step 3 is 15 × 15cm.
The vacuum drying time of the step 4 is 12 hours, and the diameter of the round piece of the step 4 is 19mm.
The second technical scheme adopted by the invention is that the preparation method of the fluorine modified quasi-solid mixed matrix lithium battery adopts a fluorine modified quasi-solid mixed matrix lithium battery diaphragm, and the specific operation steps are as follows:
step 1, weighing lithium iron phosphate powder, carbon black and polyvinylidene fluoride (PVDF) in an agate mortar, wherein the mass ratio of the PVDF to the lithium iron phosphate powder is 7:2:1, grinding, and adding N, N-2-methyl pyrrolidone (NMP) to form uniform and viscous black slurry; coating the prepared black slurry on an aluminum foil, carrying out vacuum drying at 60 ℃ for 12h, and cutting into sheets with the diameter of 14mm to obtain a lithium iron phosphate pole piece E;
step 2, assembling the prepared lithium iron phosphate pole piece E, the solid polymer diaphragm D and the lithium piece cathode into a CR2032 battery, wherein electrolytes are bis (trifluoromethane) sulfimide lithium LiTFSI and LiNO 3 (ii) a The solvent is 1, 3-dioxolane DOL and glycol dimethyl ether DME, and the volume ratio of the electrolyte to the solvent is 1:1; the method specifically comprises the following steps: placing a lithium iron phosphate pole piece E in a positive electrode shell, placing a solid polymer diaphragm D dipped with electrolyte on the lithium iron phosphate pole piece E by adopting insulating nickel, sequentially placing a lithium piece, a gasket, an elastic piece and a negative electrode shell, and assembling on a packaging machine with the pressure of 2.5N, wherein the whole process is carried out in a glove box with the water oxygen value less than 0.01 ppm;
step 3, standing the assembled battery for 12 hours, and placing the assembled battery on blue electricity to perform a circulation test;
step 4, testing the relation between the current and the potential of the assembled battery at different scanning speeds on an electrochemical workstation;
and 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz.
The present invention is also characterized in that,
and 3, the circulating voltage range of the battery is 2.5-4V, and the initial voltage of the battery is not lower than 2V.
Step 4, the scanning voltage range is 2.5-4.2V, and the scanning speed is 0.001V/s; the number of scanning cycles is 6, wherein the frequency is 0.01-1000000Hz when EIS is measured.
Step 2 the lithium iron phosphate electrodeThe sheet E may be made of lithium cobaltate, lithium manganate, liNi 0.33 Mn 0.33 Co 0.33 O 2 Any of these alternatives.
Step 2 lithium bis (trifluoromethanesulfonylimide) LiTFSI and LiNO 3 In a molar ratio of 1:5; in the step 1, the grinding time is 30min.
The synthesis principle of the key steps in the invention is as follows:
firstly, synthesis of a precursor: the precursor is characterized in that the synthesized 4-fluoroterephthalic acid as the raw material has strong electronegativity, small polarization and lower LUMO and HOMO energy, so that the oxidation resistance of the F-containing MOF material is remarkably enhanced, but the reduction resistance of the F-containing MOF material is remarkably weakened, so that F ions in the F-containing MOF material are reduced and decomposed with metal lithium on the surface of a negative electrode to form a layer of stable LiF-rich interface film, the resistance of an SEI film can be reduced, the characteristics are favorable for improving the cycle stability of the lithium ion battery, and meanwhile, the fluorine ions have the characteristic of high flash point, so that the flame retardant characteristic of the electrolyte can be improved, and the thermal stability of the lithium ion battery is further improved.
Preparing a fluorine modified quasi-solid mixed matrix lithium battery diaphragm material precursor: UIO-66- (F) synthesized from tetrafluoroterephthalic acid and zirconium tetrachloride 4 The lithium ion battery has extremely high thermal stability, a large number of mesopores and micropores, and an ultra-high specific surface area, is beneficial to the rapid transmission of lithium ions, and improves the cycle characteristics of the lithium ion battery.
Preparing a fluorine modified quasi-solid mixed matrix lithium battery diaphragm material: because the traditional commercial diaphragm is expensive, the lithium dendrites are easy to pierce the diaphragm in the lithium ion battery, and the phenomena of battery short circuit, even fire explosion and the like are caused. By doping lithium salt with the polymer and adopting the inorganic MOF material, the problems of formation of lithium dendrite and leakage of electrolyte can be effectively prevented.
(IV) preparation of quasi-solid lithium metal CR2032 type battery: the lithium iron phosphate is selected as the anode of the quasi-solid polymer lithium ion battery, because the lithium iron phosphate anode is the safest anode material at present, the conductivity of the lithium iron phosphate anode can be well improved by doping the lithium iron phosphate anode with a conductive polymer, the lattice stability of the lithium iron phosphate is good, and the influence of the insertion and the extraction of lithium ions on the lattice is small, so that the lithium iron phosphate anode has good reversibility. Besides the adoption of the cathode material except lithium iron phosphate, the method can also be used for preparing solid/quasi-solid polymer lithium ion batteries.
The invention has the advantages that
(1) The precursor is synthesized by a high-temperature oil bath method, and the zirconium-based MOF material is synthesized, so that lithium ions are rapidly transmitted in the pore canal due to the thermal stability and the porous structure of the material, and the cycle performance of the lithium battery is improved.
(2) The fluorine substituent-modified zirconium-based metal organic framework/polyethylene oxide mixed matrix lithium battery diaphragm material is prepared by a blade coating method, and because fluorine ions in raw material organic ligands have high electronegativity, the lithium battery diaphragm material can obtain circulation stability in the circulation process;
(3) The use of solid polymer films to replace traditional commercial membranes is an inexpensive and recyclable manufacturing process by uniformly mixing MOF, lithium salts and polymers to form solid polymer films.
(4) The method is simple and has strong operability; the lithium/sodium battery can be applied to any solid/quasi-solid polymer lithium/sodium battery, and has wide application range.
(5) The invention provides a preparation method of a fluorine modified quasi-solid mixed matrix lithium battery diaphragm, and further provides a preparation method of a quasi-solid lithium battery using the diaphragm material. The method can be used for any quasi-solid polymer lithium/sodium battery, and the applicable range of the material is greatly improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a fluorine modified quasi-solid hybrid matrix lithium battery separator according to the present invention;
FIG. 2 is a flow chart of a method for preparing a fluorine modified quasi-solid hybrid matrix lithium battery according to the present invention;
fig. 3 is a graph showing the relationship between efficiency and specific capacity after the fluorine modified quasi-solid mixed matrix lithium battery of the present invention is cycled for 100 cycles at a rated capacitance of 0.1C.
Fig. 4 is a graph showing the relationship between efficiency and specific capacity after 300 cycles of the fluorine modified quasi-solid mixed matrix lithium battery of the present invention at a rated capacitance of 1C.
FIG. 5 is a graph showing the relationship between current and potential at different scanning rates for a fluorine modified quasi-solid state mixed matrix lithium battery of the present invention.
FIG. 6 is the electrochemical impedance of the fluorine modified quasi-solid hybrid matrix lithium battery of the present invention at different frequencies.
Detailed Description
The invention provides a preparation method of a fluorine modified quasi-solid mixed matrix lithium battery diaphragm, which comprises UIO-66- (F) 4 Synthesizing a metal organic framework material, blending the metal organic framework material with PVDF-HFP polymer and lithium salt to prepare a fluorine substituent group modified zirconium-based metal organic framework/polyethylene oxide mixed matrix lithium battery diaphragm, and assembling the diaphragm with a lithium iron phosphate positive electrode and a lithium negative electrode to form a quasi-solid polymer lithium ion battery.
The present invention is further illustrated by the following specific examples.
Example 1
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm is shown in figure 1 and comprises the following specific operation steps:
step 1, weighing (5 mmol, 1.1652g) zirconium tetrachloride solid and (5 mmol, 1.19045g) tetrafluoroterephthalic acid in sequence, adding a mixed solution of water and glacial acetic acid (V: vs = 3) into the mixed solution, stirring the mixed solution at room temperature for 1 hour, carrying out oil bath at 100 ℃ for 24 hours, washing the solid powder with methanol at least three times, and carrying out centrifugal drying to obtain white precursor powder a;
step 2, weighing precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and lithium bistrifluoromethanesulfonylimide (LiTFSI) in a mass ratio of 1:8:1, placing the mixture in a 50mL flat-bottom flask, adding 20mL of N-methylpyrrolidone (NMP), and stirring the mixture at room temperature for 76 hours to obtain white viscous liquid B;
step 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template with the thickness of 15 x 15cm, uniformly coating the white viscous liquid B on a polytetrafluoroethylene substrate by adopting a film scraping method, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a white polymer solid film C with the thickness of about 80 micrometers;
and 4, cutting the prepared white polymer solid film C into a wafer with the diameter of 19mm, drying the wafer in vacuum overnight at the temperature of 60 ℃, and placing the wafer in a glove box with the water oxygen value of less than 0.01ppm to obtain a solid polymer diaphragm D.
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery comprises the following specific operation steps:
step 1, weighing 0.35g of lithium iron phosphate powder, 0.1g of Super P and 0.05g of polyvinylidene fluoride (PVDF) in an agate mortar, wherein the mass ratio of the Super P to the PVDF is 7:2:1, fully grinding for 30min, and then adding a proper amount of N, N-2-methylpyrrolidone (NMP) to form uniform and viscous black slurry. Coating the prepared slurry on an aluminum foil, drying the aluminum foil in vacuum at 60 ℃ for 12 hours, and cutting the aluminum foil into sheets with the diameter of 14mm to obtain the lithium iron phosphate pole piece E.
Step 2, assembling the prepared lithium iron phosphate anode E, the solid polymer diaphragm D and the lithium sheet cathode into a CR2032 battery, wherein the electrolyte is LiTFSI with the concentration of 1M and LiNO with the concentration of 0.2M 3 The solvent is 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and the volume is 1:1, specifically: the LFP pole piece is placed in the positive electrode shell, the solid polymer diaphragm D dipped with the electrolyte is placed on the LFP pole piece by adopting insulating nickel, the lithium piece, the gasket, the elastic piece and the negative electrode shell are sequentially placed, the assembly is carried out on a packaging machine with the pressure of 2.5N, and the whole process is carried out in a glove box with the water oxygen value of less than 0.01 ppm.
Step 3, standing the assembled battery for 12 hours, and placing the assembled battery on blue electricity to perform a circulation test, wherein the initial voltage is not lower than 2V, and the voltage range is 2.5-4.0V;
step 4, testing the relation between the current and the potential of the assembled battery at different scanning speeds on an electrochemical workstation, wherein the voltage range is 2.2-4.2V;
and 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz.
Example 2
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm comprises the following specific operation steps:
step 1, weighing (5 mmol, 1.1652g) zirconium tetrachloride solid and (5 mmol, 1.19045g) tetrafluoroterephthalic acid in sequence, adding the weighed materials into a mixed solution of water and glacial acetic acid, stirring at room temperature for 1 hour, performing oil bath at 100 ℃ for 24 hours, washing solid powder with methanol, and performing centrifugal drying to obtain white precursor powder A;
the volume ratio of the mixed solution of water and glacial acetic acid is 3;
step 2, weighing precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and lithium bistrifluoromethanesulfonylimide (LiTFSI) in a mass ratio of 1:8:1, placing the mixture into a 50mL flat-bottom flask, adding 20mL of N-methylpyrrolidone (NMP), and stirring the mixture at room temperature for 48 hours to obtain white viscous liquid B;
step 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template with the thickness of 15 x 15cm, uniformly coating the white viscous liquid B on a polytetrafluoroethylene substrate by adopting a film scraping method, and performing vacuum drying at 60 ℃ for 48 hours to obtain a white polymer solid film C with the thickness of about 100 micrometers;
and 4, cutting the prepared white polymer solid film C into a wafer with the diameter of 19mm to obtain a solid polymer diaphragm D, drying the solid polymer diaphragm D in vacuum overnight at the temperature of 60 ℃, and placing the solid polymer diaphragm D in a glove box with the water oxygen value of less than 0.01 ppm.
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery comprises the following specific operation steps:
step 1, 0.4g of lithium cobaltate powder (LICoO) is weighed 2 ) 0.05g of carbon black, 0.05g of polyvinylidene fluoride (PVDF) in an agate mortar, in a mass ratio of 8:1:1, grinding for 30min, and adding a proper amount of N, N-2-methyl pyrrolidone (NMP) to form uniform and viscous black slurry. And coating the prepared slurry on an aluminum foil, carrying out vacuum drying at 60 ℃ for 12h, and cutting into sheets with the diameter of 14mm to obtain a lithium cobaltate pole piece E.
Step 2, assembling the prepared lithium cobaltate anode E, the solid polymer diaphragm D and the lithium sheet cathode into a CR2032 battery, wherein the electrolyte is LiTFSI with the concentration of 1M and LiNO with the concentration of 0.2M 3 The solvent is 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and the volume ratio is 1:1. the method specifically comprises the following steps: placing lithium cobaltate pole piece in the positive electrode shell, dippingA solid polymer diaphragm D of the electrolyte is formed by placing a lithium cobaltate electrode plate by adopting insulating nickel, sequentially placing a lithium plate, a gasket, an elastic sheet and a negative electrode shell, and assembling on a packaging machine with the pressure of 2.5N, wherein the whole process is carried out in a glove box with the water oxygen value of less than 0.01 ppm.
Step 3, standing the assembled battery for 12 hours, and placing the assembled battery on blue electricity to perform a circulation test, wherein the initial voltage is not lower than 2V, and the voltage range is 2.5-4.0V;
step 4, testing the relation between the current and the potential of the assembled battery on an electrochemical workstation at different scanning speeds, wherein the voltage range is 2.2-4.2V;
and 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz.
Example 3
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm comprises the following specific operation steps:
step 1, weighing (5 mmol, 1.1652g) zirconium tetrachloride solid and (5 mmol, 1.19045g) tetrafluoroterephthalic acid in sequence, adding the weighed materials into a mixed solution of water and glacial acetic acid, stirring at room temperature for 1 hour, carrying out oil bath at 100 ℃ for 24 hours, washing the solid powder with methanol for at least three times, and carrying out centrifugal drying to obtain white precursor powder A;
the volume ratio of the mixed solution of water and glacial acetic acid is 3;
step 2, weighing precursor powder A, polyethylene oxide (PEO) and lithium bistrifluoromethanesulfonimide (LiTFSI) in a mass ratio of 1:8:1, placing the mixture into a 50mL flat-bottom flask, adding 20mL of N, N-2-methylpyrrolidone (NMP), and stirring the mixture at room temperature for 24 hours to obtain white viscous liquid B;
and 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template with the thickness of 15 x 15cm, uniformly coating the white viscous liquid B on a polytetrafluoroethylene substrate by a film scraping method, and performing vacuum drying at 60 ℃ for 48 hours to obtain a white polymer solid film C with the thickness of about 80 micrometers.
And 4, cutting the prepared white polymer solid film C into a wafer with the diameter of 19mm to obtain a solid polymer diaphragm D, drying the solid polymer diaphragm D in vacuum overnight at the temperature of 60 ℃, and placing the solid polymer diaphragm D in a glove box with the water oxygen value of less than 0.01 ppm.
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery comprises the following specific operation steps:
step 1, weighing 0.35g of lithium manganate (LiMn) 2 O 4 ) Powder, 0.1g carbon black, 0.05g polyvinylidene fluoride (PVDF) in an agate mortar in a mass ratio of 7:2:1, grinding for 30min, and adding a proper amount of N, N-2-methyl pyrrolidone (NMP) to form uniform and viscous black slurry. And coating the prepared slurry on an aluminum foil, drying the aluminum foil in vacuum at 60 ℃ for 12 hours, and cutting the aluminum foil into sheets with the diameter of 14mm to obtain the lithium manganate pole piece E.
Step 2, assembling the prepared lithium manganate anode E, the solid polymer diaphragm D and the lithium sheet cathode into a CR2032 battery, wherein the electrolyte is LiTFSI with the concentration of 1M and LiNO with the concentration of 0.2M 3 The solvent is 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and specifically comprises the following components: place the lithium manganate pole piece in positive pole shell, will dip in the solid polymer diaphragm D who gets electrolyte, adopt insulating nickel to place lithium manganate pole piece on, place lithium piece, gasket, shell fragment and negative pole shell in proper order, assemble on the packaging machine that pressure is 2.5N, whole process all goes on in the water oxygen value is less than 0.01ppm glove box.
Step 3, standing the assembled battery for 12 hours, and placing the assembled battery on blue electricity to perform a circulation test, wherein the initial voltage is not lower than 2V, and the voltage range is 2.5-4.0V;
step 4, testing the relation between the current and the potential of the assembled battery on an electrochemical workstation at different scanning speeds, wherein the voltage range is 2.2-4.2V;
step 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz;
example 4
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm comprises the following specific operation steps:
step 1, weighing (5 mmol, 1.1652g) zirconium tetrachloride solid and (5 mmol, 1.19045g) tetrafluoroterephthalic acid in sequence, adding the weighed zirconium tetrachloride solid and the (5 mmol, 1.19045g) tetrafluoroterephthalic acid into a mixed solution of water and glacial acetic acid, stirring at room temperature for 1 hour, carrying out oil bath at 100 ℃ for 24 hours, washing the solid powder with methanol for at least three times, and carrying out centrifugal drying to obtain white precursor powder A;
the volume of the mixed solution of water and glacial acetic acid is 3:2, washing with methanol for not less than 3 times;
step 2, weighing precursor powder A, polyvinylidene fluoride (PVDF) and lithium bistrifluoromethanesulfonylimide (LiTFSI), wherein the mass ratio of the precursor powder A to the PVDF is 1:8:1, placing the mixture into a 50mL flat-bottom flask, adding 20mL of N, N-2-methylpyrrolidone (NMP), and stirring the mixture at room temperature for 48 hours to obtain white viscous liquid B;
step 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template with the thickness of 15 x 15cm, uniformly coating the white viscous liquid B on a polytetrafluoroethylene substrate by adopting a film scraping method, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a white polymer solid film C with the thickness of about 80 micrometers;
and 4, cutting the prepared white polymer solid film C into a wafer with the diameter of 19mm to obtain a solid polymer diaphragm D, drying the solid polymer diaphragm D in vacuum overnight at the temperature of 60 ℃, and placing the solid polymer diaphragm D in a glove box with the water oxygen value of less than 0.01 ppm.
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery comprises the following specific operation steps:
step 1, weighing 0.35g of lithium iron phosphate powder, 0.1g of carbon black and 0.05g of polyvinylidene fluoride (PVDF) in an agate mortar, wherein the mass ratio of the lithium iron phosphate powder to the PVDF is 7:2:1, grinding for 30min, and adding a proper amount of N, N-2-methyl pyrrolidone (NMP) to form uniform and viscous black slurry. Coating the prepared slurry on an aluminum foil, drying the aluminum foil in vacuum at 60 ℃ for 12 hours, and cutting the aluminum foil into sheets with the diameter of 14mm to obtain the lithium iron phosphate pole piece E.
Step 2, assembling the prepared lithium iron phosphate anode E, the solid polymer diaphragm D and the lithium sheet cathode into a CR2032 battery, wherein the electrolyte is LiTFSI with the concentration of 1M and LiNO with the concentration of 0.2M 3 The solvent is 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and the volume ratio is 1:1. the method specifically comprises the following steps: placing LFP pole piece in positive shell, dipping solid polymer diaphragm D of electrolyte, placing LFP pole piece with insulating nickel, placing lithium piece, gasket, elastic piece and negative shell in turn, assembling on 2.5N packaging machine, and the whole process is carried out under water oxygenValues less than 0.01ppm were carried out in a glove box.
Step 3, standing the assembled battery for 12 hours, and performing a circulation test on the battery by placing the battery on blue electricity, wherein the initial voltage is not lower than 2V, and the voltage range is 2.5-4.0V;
step 4, testing the relation between the current and the potential of the assembled battery at different scanning speeds on an electrochemical workstation, wherein the voltage range is 2.2-4.2V;
and 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz.
Example 5
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm comprises the following specific operation steps:
step 1, weighing (5 mmol, 1.1652g) zirconium tetrachloride solid and (5 mmol, 1.19045g) tetrafluoroterephthalic acid in sequence, adding the weighed zirconium tetrachloride solid and the (5 mmol, 1.19045g) tetrafluoroterephthalic acid into a mixed solution of water and glacial acetic acid, stirring at room temperature for 1 hour, carrying out oil bath at 100 ℃ for 24 hours, washing the solid powder with methanol for at least three times, and carrying out centrifugal drying to obtain white precursor powder A;
the volume ratio of the mixed solution of water and glacial acetic acid is 3:2, methanol washing is not less than 3 times.
Step 2, weighing the precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and lithium bistrifluoromethanesulfonylimide (LiTFSI), wherein the mass ratio of the precursor powder A to the PVDF-HFP is 1:8:1, placing the mixture into a 50mL flat-bottom flask, adding 20mL of N, N-2-methylpyrrolidone (NMP), and stirring the mixture at room temperature for 48 hours to obtain white viscous liquid B;
step 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template with the thickness of 15 x 15cm, uniformly coating the white viscous liquid B on a polytetrafluoroethylene substrate by adopting a film scraping method, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a white polymer solid film C with the thickness of about 80 micrometers;
and 4, cutting the prepared white polymer solid film C into a wafer with the diameter of 19mm to obtain a solid polymer diaphragm D, drying the solid polymer diaphragm D in vacuum overnight at the temperature of 60 ℃, and placing the solid polymer diaphragm D in a glove box with the water oxygen value of less than 0.01 ppm.
The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery comprises the following specific operation steps:
step 1, weighing 0.4g of LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NCM 111) powder, 0.05g carbon black, 0.05g polyvinylidene fluoride (PVDF) in an agate mortar in a mass ratio of 8:1:1, grinding for 30min, and adding a proper amount of N, N-2-methyl pyrrolidone (NMP) to form uniform and viscous black slurry. Coating the prepared slurry on an aluminum foil, vacuum-drying at 60 ℃ for 12h, and cutting into sheets with the diameter of 14mm to obtain LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NCM 111) Pole piece E.
Step 2, preparing LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NCM 111) E, solid Polymer separator D and lithium plate cathode Assembly site CR2032 cell with 1M LiTFSI and 0.2M LiNO as electrolyte 3 The solvent is 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and the volume ratio is 1:1. the method specifically comprises the following steps: placing LiNi in the positive electrode shell 0.33 Mn 0.33 Co 0.33 O 2 (NCM 111) pole piece, placing the solid polymer diaphragm D dipped with the electrolyte on LiNi by adopting insulating nickel 0.33 Mn 0.33 Co 0.33 O 2 And (NCM 111) pole pieces, a lithium piece, a gasket, a spring piece and a negative electrode shell are sequentially placed on the (NCM 111) pole pieces and assembled on a packaging machine with the pressure of 2.5N, and the whole process is carried out in a glove box with the water oxygen value of less than 0.01 ppm.
Step 3, standing the assembled battery for 12 hours, and performing a circulation test on the battery by placing the battery on blue electricity, wherein the initial voltage is not lower than 2V, and the voltage range is 2.5-4.0V;
step 4, testing the relation between the current and the potential of the assembled battery on an electrochemical workstation at different scanning speeds, wherein the voltage range is 2.2-4.2V;
and 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz.
As shown in FIGS. 1 and 2, is F + A conductive quasi-solid mixed matrix lithium battery diaphragm and a lithium battery preparation flow diagram.
As shown in FIG. 3, is F + And (3) a relation graph of efficiency and specific capacity after the conductive quasi-solid mixed matrix lithium battery diaphragm circulates for 100 circles under the current density of 0.1C. Clearly, UIO-66- (F) 4 The solid polymer film has a specific charge-discharge capacity of 150mA h g after circulating for 100 circles under the current density of 0.1C -1 Coulombic efficiency approaches 100%.
As shown in FIG. 4, is F + The relation graph of the efficiency and the specific capacity of the conductive quasi-solid mixed matrix lithium battery is obtained after 100 cycles under the current density of 1C. Clearly, UIO-66- (F) 4 Under the current density of 1C, after the solid polymer film is cycled for 100 circles, the charge-discharge specific capacity is reduced to some extent compared with 0.1C, and the charge-discharge specific capacity is 125mA h g -1 Coulombic efficiency also approaches 100%. The synthesized metal organic MOFs material containing the fluorine functional group has the characteristics of favorable specific surface area and pores, and can accelerate the transportation of lithium ions. In addition, a LiF-rich interfacial film is formed on the surfaces of the fluorine ions and the negative electrode, and the impedance of the SEI film on the interface between the diaphragm and the negative electrode can be reduced, so that the cyclic stability of the quasi-solid polymer lithium ion battery is improved, and meanwhile, the fluorine ions have the characteristic of high flash point, the flame retardant characteristic of the traditional electrolyte can be improved, and the thermal stability of the quasi-solid polymer lithium ion battery is further improved.
As shown in fig. 5, F prepared according to the present invention + Conducting quasi-solid mixed matrix lithium battery in electrochemical workstation, F + CV testing of conductive quasi-solid state mixed matrix lithium batteries showed identical shape of CV curves at different scan rates over a voltage range of 2.5-4.0V and overlapping in successive cycles, indicating F + Conductive quasi-solid state mixed matrix lithium battery separator materials have a high degree of reversibility and pseudocapacitance for lithium ion storage.
As shown in fig. 6, F prepared according to the present invention + The electrochemical impedance test of the conductive quasi-solid mixed matrix lithium battery is carried out under an electrochemical workstation, and the frequency range of the electrochemical impedance test of the F + conductive quasi-solid mixed matrix lithium battery is 0.01-100000Hz. It can be seen from the graph that the charge transfer resistance is 179.83. Omega. Indicating F + Conductive quasi-solid mixed baseThe lithium battery diaphragm material has lower impedance and high lithium ion transmission characteristics.

Claims (10)

1. The preparation method of the fluorine modified quasi-solid mixed matrix lithium battery diaphragm is characterized by comprising the following specific operation steps:
step 1, sequentially weighing zirconium tetrachloride solid and tetrafluoroterephthalic acid, adding the zirconium tetrachloride solid and the tetrafluoroterephthalic acid into a mixed solution of water and glacial acetic acid, stirring at room temperature, carrying out oil bath at 100 ℃ for 24 hours, washing with methanol at least three times, and carrying out centrifugal drying to obtain white precursor powder A;
step 2, weighing precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and lithium bistrifluoromethanesulfonylimide LiTFSI, placing the precursor powder A, polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and lithium bistrifluoromethanesulfonylimide LiTFSI in a flat-bottomed flask, adding N-methylpyrrolidone NMP, and stirring at room temperature to obtain white viscous liquid B;
step 3, pouring the white viscous liquid B onto a polytetrafluoroethylene template, uniformly coating the white viscous liquid B on the polytetrafluoroethylene template by adopting a film scraping method, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a white polymer solid film C with the thickness of 80-100 microns;
and 4, cutting the prepared white polymer solid film C into round pieces, drying the round pieces overnight in vacuum at 60 ℃, and placing the round pieces in a glove box with the water oxygen value of less than 0.01ppm to obtain a solid polymer diaphragm D.
2. The method for preparing a fluorine-modified quasi-solid mixed matrix lithium battery separator according to claim 1, wherein the molar ratio of the zirconium tetrachloride solid to the tetrafluoroterephthalic acid in step 1 is 1:1; the volume ratio of the water to the glacial acetic acid is 3.
3. The method for preparing the fluorine-modified quasi-solid mixed matrix lithium battery diaphragm according to claim 1, wherein the mass ratio of the precursor powder A, the polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP and the lithium bis (trifluoromethanesulfonyl) imide LiTFSI in the step 2 is 1:8:1, stirring at room temperature for not less than 48 hours; the polyvinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP can be replaced by any one of polyethylene oxide PEO and polyvinylidene fluoride.
4. The method for preparing a fluorine-modified quasi-solid mixed matrix lithium battery separator according to claim 1, wherein the polytetrafluoroethylene template in step 3 is 15 x 15cm in size.
5. The method for preparing a fluorine modified quasi-solid mixed matrix lithium battery separator as claimed in claim 1, wherein the vacuum drying time of step 4 is 12 hours, and the diameter of the disk of step 4 is 19mm.
6. A method for manufacturing a fluorine-modified quasi-solid mixed matrix lithium battery, characterized in that F according to any one of claims 1 to 5 is used + The conductive quasi-solid mixed matrix lithium battery diaphragm specifically comprises the following operation steps:
step 1, weighing lithium iron phosphate powder, carbon black and polyvinylidene fluoride (PVDF) in an agate mortar, wherein the mass ratio of the PVDF to the lithium iron phosphate powder is 7:2:1, grinding, and adding N, N-2-methyl pyrrolidone (NMP) to form uniform and viscous black slurry; coating the prepared black slurry on an aluminum foil, drying the aluminum foil in vacuum at 60 ℃ for 12 hours, and cutting the aluminum foil into sheets with the diameter of 14mm to obtain a lithium iron phosphate pole piece E;
step 2, assembling the prepared lithium iron phosphate pole piece E, the solid polymer diaphragm D and the lithium piece cathode into a CR2032 battery, wherein electrolytes are bis (trifluoromethane) sulfimide lithium LiTFSI and LiNO 3 (ii) a The solvent is 1, 3-dioxolane DOL and ethylene glycol dimethyl ether DME, and the volume ratio of the electrolyte to the solvent is 1:1; the method specifically comprises the following steps: placing a lithium iron phosphate pole piece E in a positive shell, placing a solid polymer diaphragm D dipped with electrolyte on the lithium iron phosphate pole piece E by adopting insulating nickel, sequentially placing a lithium piece, a gasket, an elastic piece and a negative shell, and assembling on a packaging machine with the pressure of 2.5N, wherein the whole process is carried out in a glove box with the water oxygen value of less than 0.01 ppm;
step 3, standing the assembled battery for 12 hours, and placing the assembled battery on blue electricity to perform a circulation test;
step 4, testing the relation between the current and the potential of the assembled battery at different scanning speeds on an electrochemical workstation;
and 5, testing the electrochemical impedance of the assembled battery on an electrochemical workstation, wherein the frequency is 0.001-100000Hz.
7. The method of claim 6, wherein the cycling voltage of the cell of step 3 is in the range of 2.5-4V, and the starting voltage of the cell is not less than 2V.
8. The method of claim 6, wherein the range of the scanning voltage in step 4 is 2.5-4.2V, and the scanning speed is 0.001V/s; the number of scanning cycles is 6, wherein the frequency is 0.01-1000000Hz when EIS is measured.
9. The method for preparing a fluorine-modified quasi-solid mixed matrix lithium battery according to claim 6, wherein the lithium iron phosphate pole piece E in the step 2 is selected from lithium cobaltate, lithium manganate and LiNi 0.33 Mn 0.33 Co 0.33 O 2 Any of these alternatives.
10. The method of claim 6, wherein the step 2 comprises LiTFSI and LiNO as lithium 1 bistrifluoromethanesulfonylimide 3 In a molar ratio of 1:5; in the step 1, the grinding time is 30min.
CN202210823437.XA 2022-07-13 2022-07-13 Fluorine modified quasi-solid mixed matrix lithium battery diaphragm and lithium battery preparation method Pending CN115149206A (en)

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