CN112768749A - Preparation method and application of dual-functional solid electrolyte for solid battery - Google Patents

Preparation method and application of dual-functional solid electrolyte for solid battery Download PDF

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CN112768749A
CN112768749A CN202011622041.6A CN202011622041A CN112768749A CN 112768749 A CN112768749 A CN 112768749A CN 202011622041 A CN202011622041 A CN 202011622041A CN 112768749 A CN112768749 A CN 112768749A
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solid
solid electrolyte
battery
ion conductor
mass
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苑克国
葛志浩
李立飞
王华宇
何华俊
王丽平
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Tianmu Lake Institute of Advanced Energy Storage Technologies 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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

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Abstract

The invention relates to a preparation method and application of a bifunctional solid electrolyte for a solid battery, and belongs to the technical field of chemical power sources. The method utilizes the characteristic that dopamine is oxidized and polymerized in an alkalescent solution environment to generate a nano poly-dopamine high-molecular polymer and generates a high-conductivity molecular nano-coating layer containing nitrogen elements when being heated at high temperature in an inert atmosphere, and improves the interface stability, power performance and air stability of the fast ion conductor by coating the poly-dopamine high-molecular nano-carbon layer on the surface of the fast ion conductor, so that the fast ion conductor can conduct ions and electrons, and has wide application prospect.

Description

Preparation method and application of dual-functional solid electrolyte for solid battery
Technical Field
The invention relates to a preparation method and application of a bifunctional solid electrolyte for a solid battery, and belongs to the technical field of chemical power sources.
Background
At present, lithium ion batteries are increasingly widely applied in real social life, however, although organic electrolytes used in traditional lithium ion batteries have the advantages of high ionic conductivity, easy control of electrode/electrolyte interfaces, convenient process treatment and the like, the flammability of the organic electrolytes causes great potential safety hazards to the batteries, especially when the batteries are large in capacity, and in addition, the limited electrochemical window causes great difficulty to the high-voltage battery system. While a solid-state battery assembled using a solid electrolyte with high ionic conductivity is expected to improve battery safety and achieve high energy density, in the process of developing a solid-state battery that can be put to practical use, it has been found that the solid-state battery has low energy density/power density and poor long-term cycle stability, unstable solid electrode/electrolyte interface, and low chemical stability of the solid electrolyte in air, which are not negligible and may also be the most difficult problems to be solved for commercial application of the current batteries.
In view of the above-mentioned drawbacks, the present inventors have made active research and innovation to create a method for preparing a dual-functional solid electrolyte for a solid battery and its application, so that the dual-functional solid electrolyte has industrial application value.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method and application of a bifunctional solid electrolyte for a solid-state battery. The method utilizes the characteristic that dopamine is oxidized and polymerized in an alkalescent solution environment to generate a nano poly-dopamine high-molecular polymer and generates a high-conductivity molecular nano-coating layer containing nitrogen elements when being heated at high temperature in an inert atmosphere, and improves the interface stability, power performance and air stability of the fast ion conductor by coating the poly-dopamine high-molecular nano-carbon layer on the surface of the fast ion conductor, so that the fast ion conductor can conduct ions and electrons, and has wide application prospect.
The invention relates to a preparation method of a bifunctional solid electrolyte for a solid battery, which comprises the following specific preparation steps:
dispersing 100 parts by mass of a fast ion conductor, 1-50 parts by mass of one or more of ammonium carbonate, ammonium bicarbonate, hexamethylenetetramine and urea and 1-50 parts by mass of dopamine in a solvent in sequence, performing high-energy ball milling for 1-24 hours, heating to 700-900 ℃ at a heating rate of 3-10 ℃/min in a nitrogen or argon inert gas atmosphere, performing heat preservation and calcination for 1-24 hours, and discharging to obtain the dual-functional solid electrolyte composite material for the solid battery.
Further, the fast ion conductor is LixLa3M2O12,M＝Nb、Ta、Ti、Zr，x＝5、7；Li1+xAlxN2-x(PO4)3,N＝Ti、Ge、Zr；Li10MP2S12,M＝Ge、Si、Sn；Li10±1MP2X12(M ═ Ge, Si, Sn, Al or P; X ═ O, S or Se); li6PS5Cl、Li9.54Si1.74P1.44S11.7Cl0.3、Li3.25Ge0.25P0.75S4、Li3PS4、Li4GeS4。
Further, the solvent is one or more of water, dimethyl sulfoxide, N-dimethylformamide, sulfolane, N-dimethylacetamide, acetone, isopropanol, pyridine, acetone, dioxane, ethanol, N-methylpyrrolidone, ethyl acetate and tetrahydrofuran.
The application of the difunctional solid electrolyte for the solid-state battery is characterized in that the difunctional solid electrolyte for the solid-state battery is used as a raw material to prepare the soft package lithium battery.
By the scheme, the invention at least has the following advantages:
according to the bifunctional solid electrolyte for the solid battery, which is prepared by the method, a common low-cost and easy large-scale production method is adopted, ammonia gas is generated through decomposition of an inorganic compound containing a nitrogen element, so that the surface of a fast ion conductor is kept in a weak alkaline environment with a pH value of 7-9, then a layer of nano high polymer is uniformly generated on the surface of the fast ion conductor by dopamine under the action of high-energy ball milling, and a surface-treated bifunctional solid electrolyte material for the solid battery is obtained after high-temperature calcination.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Taking 10g of Li1.3Al0.3Ti1.7(PO4)3(LATP), 1.0g of hexamethylenetetramine, 5g of dopamine and 50g of deionized water are subjected to high-speed ball milling for 60min at a rotating speed of 500r/min, the LATP slurry is dried for 3h at 110 ℃, heated to 350 ℃ at 5 ℃/min in a high-purity argon atmosphere and kept at normal pressure for 3h, then continuously heated to 850 ℃ at 5 ℃/min and kept at the temperature for 3h, and naturally cooled to room temperature to obtain the LATP-C solid electrolyte material.
The method comprises the steps of mechanically stirring 80 parts by mass of lithium nickel cobalt manganese oxide 622 positive electrode active material, 15 parts by mass of LATP-C solid electrolyte and 2 parts by mass of conductive agent acetylene black at the speed of 50rpm for 45min, then adding 20 parts by mass of 15% LA132 adhesive, mechanically stirring at 1500rpm for 2h, and sieving with a 200-mesh sieve to obtain positive electrode slurry. Coating the slurry on an aluminum foil by using an aluminum foil current collector with the thickness of 12 mu m, and drying by gradient heating and baking, wherein the rolling thickness of the pole piece is 85 mu m, and the compaction density of the pole piece is 3.5g/cm3And die-cutting and punching the pole piece to obtain the positive electrode piece with the thickness of 4.5 multiplied by 6.5 mm. The negative electrode plate is made of 120 μm thick lithium metal strip, and is die-cut to obtain 4.7 × 6.7m sheetsm is the negative electrode slice. And (3) obtaining the soft package lithium battery by using a fast ion conductor diaphragm with the width of 70mm through a Z-shaped lamination method. The dosage of the electrolyte added into the soft package battery is 0.2g/Ah, and the interface between the diaphragm and the electrode is wetted.
The electrochemical performance test conditions of the soft package battery are as follows, the constant current charge-discharge cutoff voltage of the battery is 2.5-4.2V, and the charge-discharge multiplying power is 0.1C. The first discharge capacity of the pouch cell was 9.37Ah, the second discharge capacity was 9.49Ah, the coulombic efficiency was 99.56%, the 100 th discharge capacity was 8.65Ah, and the capacity retention rate was 92.3%.
Example 2
Take 10gLi10SiP2S12(LGPS), 5.0g of ammonium bicarbonate, 5g of dopamine and 50g of absolute ethyl alcohol are subjected to high-speed ball milling for 60min at a rotating speed of 500r/min, LGPS slurry is dried for 3h at 80 ℃, heated to 350 ℃ at 5 ℃/min in a high-purity argon atmosphere and kept at normal pressure for 3h, then continuously heated to 700 ℃ at 5 ℃/min and kept at the temperature for 3h, and the LGPS-C solid electrolyte material is obtained after natural cooling to room temperature.
80 parts by mass of NCM622 positive electrode active material, 15 parts by mass of LATP-C solid electrolyte, 1.5 parts by mass of conductive agent acetylene black Super C65 and 2.5 parts by mass of PVDF5130 are mechanically stirred for 45min at the speed of 500rpm, then 19 parts by mass of multi-wall carbon nanotube slurry with the solid content of 5.3 percent and 45 parts by mass of N-methylpyrrolidone (NMP) are added and mechanically stirred for 2h at the speed of 1500rpm, and the positive electrode slurry is obtained after passing through a 200-mesh sieve. Then coating the slurry on an aluminum foil by using an aluminum foil current collector with the thickness of 16 mu m, and drying by gradient heating and baking, wherein the rolling thickness of the pole piece is 85 mu m, and the compaction density of the pole piece is 3.5g/cm3The die-cut punching sheet of the pole piece is a positive electrode piece with the thickness of 4.5 multiplied by 6.5 mm. The negative electrode plate is manufactured by cutting a metal lithium belt with the thickness of 170 mu m into 4.7 multiplied by 6.7 mm. The LGPS-C fast ion conductor ceramic diaphragm with the width of 70mm is utilized to obtain the soft package lithium battery of the solid electrolyte composite cathode material by a zigzag lamination method.
The electrochemical performance test conditions of the soft package battery are as follows, the constant current charge-discharge cutoff voltage of the battery is 2.5-4.2V, and the charge-discharge multiplying power is 0.1C. The first discharge capacity of the soft package battery was 9.48Ah, the second discharge capacity was 9.20Ah, the coulombic efficiency was 95.53%, the 100 th discharge capacity was 8.23Ah, and the capacity retention rate was 86.8%.
Example 3
Taking 10g of Li7La3Zr2O12(LLZO), 5.0g of ammonium bicarbonate, 5g of dopamine and 50g of acetonitrile solvent are subjected to high-speed ball milling for 60min at a rotating speed of 500r/min, the LLZO slurry is dried for 3h at 80 ℃, heated to 350 ℃ at 5 ℃/min in a high-purity argon atmosphere and kept at normal pressure for 3h, then continuously heated to 850 ℃ at 5 ℃/min and kept at the temperature for 3h, and the temperature is naturally reduced to room temperature, so that the LLZO-C solid electrolyte material is obtained.
80 parts by mass of NCM811 positive electrode active material, 15 parts by mass of LATP-C solid electrolyte, 1.5 parts by mass of conductive agent acetylene black Super C65 and 2.5 parts by mass of PVDF5130 are mechanically stirred for 45min at the speed of 500rpm, then 19 parts by mass of multi-wall carbon nanotube slurry with the solid content of 5.3 percent and 45 parts by mass of N-methylpyrrolidone (NMP) are added and mechanically stirred for 2h at the speed of 1500rpm, and the positive electrode slurry is obtained after passing through a 200-mesh sieve. Then coating the slurry on an aluminum foil by using an aluminum foil current collector with the thickness of 16 mu m, and drying by gradient heating and baking, wherein the rolling thickness of the pole piece is 85 mu m, and the compaction density of the pole piece is 3.5g/cm3The die-cut punching sheet of the pole piece is a positive electrode piece with the thickness of 4.5 multiplied by 6.5 mm. The negative electrode plate is manufactured by cutting a metal lithium belt with the thickness of 170 mu m into 4.7 multiplied by 6.7 mm. The soft-packaged lithium battery of the solid electrolyte composite cathode material is obtained by a zigzag lamination method by utilizing a LLZO _ C fast ion conductor ceramic diaphragm with the width of 70 mm.
The electrochemical performance test conditions of the soft package battery are as follows, the constant current charge-discharge cutoff voltage of the battery is 2.0-4.3V, and the charge-discharge multiplying power is 0.1C. The first discharge capacity of the soft package battery was 4.45Ah, the second discharge capacity was 4.8Ah, the coulombic efficiency was 98.44%, the 100 th discharge capacity was 3.52Ah, and the capacity retention rate was 79.1%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A preparation method of a bifunctional solid electrolyte for a solid battery is characterized by comprising the following specific preparation steps:
dispersing 100 parts by mass of a fast ion conductor, 1-50 parts by mass of one or more of ammonium carbonate, ammonium bicarbonate, hexamethylenetetramine and urea and 1-50 parts by mass of dopamine in a solvent in sequence, performing high-energy ball milling for 1-24 hours, heating to 700-900 ℃ at a heating rate of 3-10 ℃/min in a nitrogen or argon inert gas atmosphere, performing heat preservation and calcination for 1-24 hours, and discharging to obtain the dual-functional solid electrolyte composite material for the solid battery.
2. The method of claim 1 for preparing a bifunctional solid electrolyte for a solid-state battery, wherein: the fast ion conductor is LixLa3M2O12,M＝Nb、Ta、Ti、Zr，x＝5、7；Li1+xAlxN2-x(PO4)3,N＝Ti、Ge、Zr；Li10MP2S12,M＝Ge、Si、Sn；Li10±1MP2X12(M ═ Ge, Si, Sn, Al or P; X ═ O, S or Se); li6PS5Cl、Li9.54Si1.74P1.44S11.7Cl0.3、Li3.25Ge0.25P0.75S4、Li3PS4、Li4GeS4。
3. The method of claim 1 for preparing a bifunctional solid electrolyte for a solid-state battery, wherein: the solvent is one or more of water, dimethyl sulfoxide, N-dimethylformamide, sulfolane, N-dimethylacetamide, acetone, isopropanol, pyridine, acetone, dioxane, ethanol, N-methylpyrrolidone, ethyl acetate and tetrahydrofuran.
4. Use of a bifunctional solid electrolyte for a solid-state battery, characterized in that: and preparing the soft package lithium battery by using the bifunctional solid electrolyte for the solid battery as a raw material.
CN202011622041.6A 2020-12-30 2020-12-30 Preparation method and application of dual-functional solid electrolyte for solid battery Withdrawn CN112768749A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113488694A (en) * 2021-06-01 2021-10-08 北京科技大学 Method for improving interface between super-ionic conductor and polymer in composite electrolyte

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113488694A (en) * 2021-06-01 2021-10-08 北京科技大学 Method for improving interface between super-ionic conductor and polymer in composite electrolyte

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Application publication date: 20210507