CN115020641A - Lithium metal negative plate and preparation method and application thereof - Google Patents

Lithium metal negative plate and preparation method and application thereof Download PDF

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CN115020641A
CN115020641A CN202210508081.0A CN202210508081A CN115020641A CN 115020641 A CN115020641 A CN 115020641A CN 202210508081 A CN202210508081 A CN 202210508081A CN 115020641 A CN115020641 A CN 115020641A
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lithium metal
ceramic micro
nanofiber membrane
electronic conductor
negative electrode
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CN115020641B (en
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闫建华
焦科锦
马岩岩
管梦昕
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Wuyi University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention provides a lithium metal negative plate and a preparation method and application thereof. According to the invention, the flexible oxide electronic conductor ceramic micro-nano fiber membrane is completely or partially wrapped by lithium metal, so that the flexible oxide electronic conductor ceramic micro-nano fiber membrane is used as a three-dimensional main body structure of the lithium metal cathode, lithium ion deposition sites can be directionally regulated, the appearance of lithium deposition is improved, the growth of lithium dendrites is inhibited, the flexible oxide electronic conductor ceramic micro-nano fiber membrane can bear high temperature of over 600 ℃, even when the lithium metal in the composite cathode is melted into liquid state by high temperature, the composite cathode can still maintain the three-dimensional structure of the flexible oxide electronic conductor ceramic micro-nano fiber membrane fabric, the non-collapse of the cathode structure is ensured, and the cycle stability and the safety of the lithium metal battery are improved.

Description

Lithium metal negative plate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a lithium metal negative plate and a preparation method and application thereof.
Background
Lithium ion batteries are one of the most widely used secondary batteries in the current battery market, however, the current commercial lithium ion batteries are close to the theoretical energy density and cannot meet the requirements of future high-energy-density energy storage devices. Compared with the common lithium ion battery, the lithium metal has extremely high theoretical specific capacity (3860mAh/g) and the lowest electrochemical potential (-3.04V relative to a standard hydrogen electrode), and can obviously improve the energy density of the battery when being used as the negative electrode of the lithium battery. However, the lithium metal negative electrode is affected by irregular growth of lithium dendrites and corrosion of the electrolyte, and is difficult to be industrially applied.
Thus, two key issues must be addressed in order for a lithium metal anode to be commercially viable. The first problem is to construct a mechanically stable three-dimensional host framework for a hostless lithium metal negative electrode that needs to be able to accommodate the large volume expansion of lithium deposition and to suppress the irregular growth of lithium dendrites during the required sufficient repeated cycling. A second problem is to control the continued corrosion of the lithium metal by the liquid electrolyte, as this corrosion continues to consume active lithium and liquid electrolyte.
Therefore, it is necessary to provide a new lithium metal negative electrode sheet.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. To this end, the present invention provides a lithium metal negative electrode sheet.
The invention also provides a preparation method of the lithium metal negative plate.
The invention also provides an application of the lithium metal negative plate.
The invention provides a lithium metal negative plate, which comprises a flexible oxide electronic conductor ceramic micro-nanofiber membrane and lithium metal distributed in the flexible oxide electronic conductor ceramic micro-nanofiber membrane.
The invention relates to a technical scheme of a lithium metal negative plate, which at least has the following beneficial effects:
according to the invention, the flexible oxide electronic conductor ceramic micro-nano fiber membrane is completely or partially wrapped by lithium metal, so that the flexible oxide electronic conductor ceramic micro-nano fiber membrane is used as a three-dimensional main body structure of the lithium metal cathode, lithium ion deposition sites can be directionally regulated, the appearance of lithium deposition is improved, and the growth of lithium dendrites is inhibited.
According to some embodiments of the invention, the flexible oxide electronic conductor ceramic micro-nanofiber membrane comprises at least one of a flexible titanium dioxide electronic conductor ceramic micro-nanofiber membrane and a flexible niobium oxide electronic conductor ceramic micro-nanofiber membrane.
According to some embodiments of the invention, the thickness of the flexible oxide electronic conductor ceramic micro-nanofiber membrane is 20 μm to 50 μm.
According to some embodiments of the invention, the mass of the flexible oxide electronic conductor ceramic micro-nanofiber membrane accounts for 10% -90% of the total mass of the lithium metal negative plate.
The second aspect of the present invention provides a method for preparing a lithium metal negative electrode sheet, comprising the steps of:
s1, sequentially arranging a first flexible oxide semiconductor ceramic micro-nanofiber membrane, a lithium metal sheet and a second flexible oxide semiconductor ceramic micro-nanofiber membrane for hot-pressing reduction reaction to obtain a flexible oxide electronic conductor ceramic micro-nanofiber membrane distributed with lithium metal;
s2, rolling the flexible oxide electronic conductor ceramic micro-nanofiber membrane distributed with the lithium metal to obtain the lithium metal negative plate.
According to the invention, a hot-pressing reduction reaction is carried out on a first flexible oxide semiconductor ceramic micro-nanofiber membrane and a second flexible oxide semiconductor ceramic micro-nanofiber membrane through lithium metal, so that the lithium metal reduces the flexible oxide semiconductor ceramic micro-nanofiber membrane to obtain a flexible oxide electronic conductor ceramic micro-nanofiber membrane, and part or all of the lithium metal is wrapped on the surface of each micro-nanofiber.
According to some embodiments of the invention, the hot-press reduction reaction satisfies at least the following conditions:
the temperature of the hot pressing is 100-170 ℃; the pressure of the hot pressing is 0.1MPa to 1.0 MPa; the hot pressing time is 3 min-60 min.
According to some embodiments of the invention, the rolled height is 10 μm to 200 μm.
According to some embodiments of the present invention, the first flexible oxide semiconductor ceramic micro-nanofiber membrane and the second flexible oxide semiconductor ceramic micro-nanofiber membrane are prepared by an electrostatic spinning technology.
The third aspect of the invention provides an application of the lithium metal negative plate in the preparation of a liquid battery, a quasi-solid battery, a semi-solid battery or a solid battery.
A fourth aspect of the present invention provides a quasi-solid state battery comprising a positive plate, a negative plate, and a gel electrolyte disposed between the positive plate and the negative plate;
the negative electrode sheet is selected from the lithium metal negative electrode sheet.
According to some embodiments of the invention, the gel electrolyte comprises a separator and a polymer gel electrolyte attached to the separator.
According to some embodiments of the invention, the membrane comprises at least one of a polymer micro-nanofiber membrane and an oxide ion conductor ceramic micro-nanofiber membrane.
According to some embodiments of the present invention, the polymeric micro-nanofiber membrane comprises at least one of a polypropylene microporous membrane, a polyethylene microporous membrane, and a polyimide micro-nanofiber membrane.
According to some embodiments of the invention, the oxide ion conductor ceramic micro-nanofiber membrane comprises at least one of a lithium lanthanum zirconium oxide micro-nanofiber membrane, a lithium lanthanum titanium oxide micro-nanofiber membrane, and an aluminum-doped lithium lanthanum zirconium oxide micro-nanofiber membrane.
According to some embodiments of the invention, the composition of the lithium lanthanum zirconium oxygen micro-nanofiber membrane is Li 7 La 3 Zr 2 O 12 (LLZO); the component of the lithium lanthanum titanium oxide micro-nano fiber membrane is Li 3X La 2/3-X TiO 3 (X ═ 0.11, LLTO); the component of the aluminum-doped lithium lanthanum zirconium oxide micro-nano fiber membrane is Li 6.4 La 3 Zr 2 Al 0.2 O 12 (LLZO doped Al).
According to some embodiments of the invention, the oxide ion conductor ceramic micro-nanofiber membrane has a thickness of 20 μm to 50 μm.
According to some embodiments of the invention, the oxide ion conductor ceramic micro-nanofiber membrane has a porosity of 40% to 60%.
According to some embodiments of the invention, the mass of the separator accounts for 10% to 90% of the total mass of the gel electrolyte.
According to some embodiments of the invention, the material of the positive electrode sheet comprises at least one of lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel cobalt manganese aluminate, lithium cobalt oxide, or a lithium rich manganese based material.
According to some embodiments of the invention, the method of manufacturing a quasi-solid state battery comprises the steps of:
s11, mixing a polymer monomer, a cosolvent and lithium salt to obtain a polymer gel electrolyte;
s21, sequentially placing a positive plate and a diaphragm from bottom to top, dropwise adding the gel electrolyte precursor solution on the diaphragm, placing a composite lithium metal negative plate on the upper surface of the diaphragm, packaging, and carrying out in-situ polymerization reaction to obtain the quasi-solid battery.
The invention adopts the gel electrolyte containing the diaphragm, can control the corrosion of the electrolyte to lithium metal, and reduces the consumption of the electrolyte and active lithium. The gel electrolyte precursor solution is subjected to in-situ polymerization reaction in the packaged battery to obtain the integrated composite lithium metal quasi-solid battery, and the problems of poor interface contact and high impedance of an electrode and an electrolyte during packaging are solved.
According to some embodiments of the invention, the mass ratio of the polymer monomer, the cosolvent and the lithium salt is 1-1.4: 0.8-1.4: 0.6 to 1.2.
According to some embodiments of the invention, the polymeric monomer comprises at least one of 1, 3-dioxolane, ethylene oxide, methyl methacrylate, polyacrylonitrile, polyvinylidene fluoride, or polyvinylidene fluoride-hexafluoropropylene.
According to some embodiments of the invention, the co-solvent comprises at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate, or ethylene glycol dimethyl ether.
According to some embodiments of the invention, the lithium salt comprises at least one of lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate, or lithium hexafluorophosphate.
According to some embodiments of the invention, the in situ polymerization reaction satisfies at least the following conditions:
the temperature of the in-situ polymerization reaction is 10-60 ℃; the time of the in-situ polymerization reaction is 0.5 to 24 hours.
According to some embodiments of the invention, in step S11, the step of mixing is: premixing the polymer monomer and the cosolvent, and then adding the lithium salt.
Drawings
FIG. 1 is a schematic structural view of a lithium metal quasi-solid state battery prepared in example 1 of the present invention;
fig. 2 is an SEM image of the composite lithium metal negative electrode sheet prepared in example 1;
fig. 3 is an impedance spectrum of the composite lithium metal negative electrode sheet prepared in example 1 and the negative electrode sheet prepared in comparative example 1 after one cycle of each cycle;
fig. 4 is a physical diagram of the gel electrolyte precursor solution prepared in example 1 before and after gelation;
fig. 5 is an SEM image of the surface of a negative electrode sheet after 300 cycles of the composite lithium metal quasi-solid state battery prepared in example 1;
fig. 6 is a 0.2C charge and discharge performance graph of the composite lithium metal quasi-solid state battery prepared in example 1 and comparative example 1 and the battery prepared in comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
Example 1
Preparing a flexible titanium dioxide semiconductor ceramic micro-nanofiber membrane: 0.15g of polyethylene oxide (Mw 600000) was added to a mixed solvent of 6.6g of ethanol and 4.5g of glacial acetic acid at room temperature, and stirred for 6 hours to be sufficiently dissolved, thereby preparing a mixed solution; then adding 3g of isopropyl titanate into the mixed solution, and stirring to form a precursor solution which is uniformly mixed; and (3) carrying out electrostatic spinning on the precursor solution to obtain a precursor fiber film, wherein the spinning parameters are as follows: the environment temperature is 25 ℃, the relative humidity is 50%, the perfusion speed is 1.5mL/h, the voltage is 15kV, the distance between the receiving device and the spinning nozzle is 15cm, and the rotating speed of the receiving device is 50 r/min; and (3) calcining the precursor fiber film in an air atmosphere, heating to 600 ℃ at the heating rate of 2 ℃/min, and preserving heat for 1h to obtain the flexible titanium dioxide semiconductor ceramic micro-nano fiber film.
This embodiment 1 provides a lithium metal negative plate, and lithium metal negative plate includes flexible oxide electronic conductor ceramic micro-nanofiber membrane and the lithium metal of distribution on flexible oxide electronic conductor ceramic micro-nanofiber membrane. The preparation method comprises the following steps:
s1, placing a first flexible titanium dioxide semiconductor ceramic micro-nano fiber membrane, a lithium metal sheet and a second flexible titanium dioxide semiconductor ceramic micro-nano fiber membrane in a glove box in an argon atmosphere from bottom to top in sequence, and then carrying out hot pressing, wherein the hot pressing temperature is 160 ℃, the hot pressing pressure is 0.2MPa, and the hot pressing time is 10min, so as to obtain the flexible titanium dioxide electronic conductor ceramic micro-nano fiber membrane compounded with lithium metal;
s2, standing for 10min at 25 ℃; then rolling the flexible titanium dioxide electronic conductor ceramic micro-nanofiber membrane compounded with the lithium metal, wherein the rolling height is 100 mu m; obtaining a composite lithium metal fabric negative plate, wherein the thickness of the composite lithium metal fabric negative plate is 100 mu m; the mass of the flexible titanium dioxide electronic conductor ceramic micro-nanofiber membrane accounts for 40% of the total mass of the lithium metal negative plate.
Example 2
Embodiment 2 also provides a lithium metal negative electrode plate, which has the same composition and preparation method as those of embodiment 1, and the difference is that the flexible oxide electronic conductor ceramic micro-nanofiber membrane in embodiment 2 is a flexible niobium oxide electronic conductor ceramic micro-nanofiber membrane.
Comparative example 1
The comparative example 1 provides a lithium metal negative plate, and the first flexible titanium dioxide semiconductor ceramic micro-nanofiber membrane, the lithium metal plate and the second flexible titanium dioxide semiconductor ceramic micro-nanofiber membrane are sequentially placed to obtain the lithium metal negative plate.
Performance testing
The lithium metal negative electrode sheet prepared in example 1 was subjected to a scanning electron microscope test, and the result is shown in fig. 2, in which lithium metal was attached to the flexible titanium dioxide electron conductor ceramic micro-nanofibers, thereby forming a composite lithium metal negative electrode sheet having a three-dimensional main body frame.
Impedance tests are carried out on the lithium metal negative electrode sheet prepared in the example 1 and the negative electrode sheet prepared in the comparative example 1, and the result is shown in fig. 3, wherein the impedance of the lithium metal negative electrode sheet is very small, which indicates that the flexible titanium dioxide electronic conductor ceramic micro-nano fiber membrane fabric attached with lithium metal has very high electronic conductivity. The lithium metal negative electrode sheet of comparative example 1 has poor conductivity and high resistance due to only physical stacking.
The lithium metal negative electrode sheet of example 1 was prepared as a quasi-solid battery by the following steps:
preparing a precursor solution of the gel electrolyte: in a glove box under argon atmosphere, 1.33g of 1, 3-dioxolane and 1.08g of ethylene glycol dimethyl ether were mixed, and then 0.72g of lithium bistrifluoromethanesulfonylimide and 0.38g of lithium hexafluorophosphate were added, and stirring was continued for 2 hours to obtain a gel electrolyte precursor solution.
Preparing a lithium metal quasi-solid battery: fig. 1 is a schematic structural view of a lithium metal quasi-solid state battery according to example 1 of the invention; placing a positive electrode shell, a lithium iron phosphate positive plate and the polypropylene microporous membrane in a glove box in an argon atmosphere in sequence, dripping 25 mu L of gel electrolyte precursor solution onto the polypropylene microporous membrane by using a liquid transfer gun, then placing the lithium metal negative plate, the steel sheet, the elastic sheet and the negative electrode shell of the embodiment 1 and the comparative example 1 in sequence, packaging, and carrying out in-situ polymerization for 2h at 25 ℃ to obtain the lithium metal quasi-solid battery.
Fig. 4 is a photograph of a gel electrolyte precursor solution prepared in example 1 before and after gelation. As can be seen from fig. 4, the gel electrolyte precursor solution can be completely gelled after being allowed to stand at normal temperature.
The surface of the negative electrode plate was subjected to SEM test after the composite lithium metal quasi-solid state battery prepared in example 1 was cycled for 300 cycles. As can be seen from fig. 5, the surface of the negative electrode sheet is flat, lithium ions are deposited in the three-dimensional pore structure of the lithium metal composite negative electrode sheet, irregular lithium dendrites are not formed, and the lithium metal in the negative electrode sheet is not corroded by the electrolyte to form dead lithium because the gel electrolyte is used.
Fig. 6 is a 0.2C charge and discharge performance graph of the lithium metal quasi-solid battery prepared in example 1 and the battery prepared in comparative example 1. As can be seen from FIG. 6, the lithium metal quasi-solid battery provided by the invention has the advantages that the charging specific capacity is still 154.8 mA.h/g, the discharging specific capacity is still 154.4 mA.h/g, the coulombic efficiency is 99.8% and the specific capacity and the coulombic efficiency are well kept stable after being cycled for 80 circles under the high multiplying power of 0.2C. The specific capacity of the battery prepared in the comparative example 1 is gradually reduced when the battery is circulated for 45 circles at 0.2 ℃, the specific capacity of the battery for 45 circles is only 97.0 mA.h/g, the specific capacity of the battery for discharge is only 86.6 mA.h/g, and the coulombic efficiency is only 89.3%.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The lithium metal negative plate is characterized by comprising a flexible oxide electronic conductor ceramic micro-nanofiber membrane and lithium metal distributed in the flexible oxide electronic conductor ceramic micro-nanofiber membrane.
2. The lithium metal negative electrode sheet according to claim 1, wherein the flexible oxide electronic conductor ceramic micro-nanofiber membrane comprises at least one of a flexible titanium dioxide electronic conductor ceramic micro-nanofiber membrane and a flexible niobium oxide electronic conductor ceramic micro-nanofiber membrane.
3. The lithium metal negative electrode sheet according to claim 1 or 2, wherein the thickness of the flexible oxide electronic conductor ceramic micro-nanofiber membrane is 20-50 μm.
4. The lithium metal negative electrode sheet according to claim 1, wherein the mass of the flexible oxide electronic conductor ceramic micro-nanofiber membrane accounts for 10-90% of the total mass of the lithium metal negative electrode sheet.
5. The method for preparing the lithium metal negative electrode sheet according to any one of claims 1 to 4, comprising the steps of:
s1, sequentially arranging a first flexible oxide semiconductor ceramic micro-nanofiber membrane, a lithium metal sheet and a second flexible oxide semiconductor ceramic micro-nanofiber membrane for hot-pressing reduction reaction to obtain a flexible oxide electronic conductor ceramic micro-nanofiber membrane distributed with lithium metal;
s2, rolling the flexible oxide electronic conductor ceramic micro-nanofiber membrane distributed with the lithium metal to obtain the lithium metal negative plate.
6. The method for preparing the lithium metal negative electrode sheet according to claim 5, wherein the hot-press reduction reaction at least satisfies the following conditions:
the hot pressing temperature is 100-170 ℃; the pressure of the hot pressing is 0.1MPa to 1.0 MPa; the hot pressing time is 3 min-60 min.
7. The method of manufacturing a lithium metal negative electrode sheet according to claim 5, wherein the rolled height is 10 to 200 μm.
8. The use of the lithium metal negative electrode sheet according to any one of claims 1 to 4 in the preparation of a liquid battery, a quasi-solid battery, a semi-solid battery or a solid battery.
9. A quasi-solid battery is characterized by comprising a positive plate, a negative plate and a gel electrolyte arranged between the positive plate and the negative plate;
the negative electrode sheet is selected from the lithium metal negative electrode sheet according to any one of claims 1 to 4.
10. The quasi-solid state battery of claim 9, wherein the gel electrolyte comprises a separator and a polymer gel electrolyte attached to the separator.
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CN117602950B (en) * 2023-11-23 2024-05-14 东华大学 Preparation method of flexible metallized ceramic nanofiber interdigital electrode

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