CN111934020B - High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof - Google Patents

High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof Download PDF

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CN111934020B
CN111934020B CN202010676638.2A CN202010676638A CN111934020B CN 111934020 B CN111934020 B CN 111934020B CN 202010676638 A CN202010676638 A CN 202010676638A CN 111934020 B CN111934020 B CN 111934020B
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lithium
precursor
charging
electrolyte
battery
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CN111934020A (en
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方淳
李琪
韩建涛
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Huazhong 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to the technical field of lithium ion batteries, and discloses a high-voltage-resistant electrolyte interface layer, and an in-situ preparation method and application thereof. The preparation method comprises the following steps: (1) uniformly mixing a fluorine-containing acrylate monomer and a lithium salt to prepare a precursor; (2) assembling a precursor, a positive electrode, a negative electrode and an electrolyte matrix into a battery, wherein the precursor is arranged between the electrolyte matrix and a positive electrode material; (3) and charging the battery to polymerize the acrylate monomer, and curing the precursor into a polymer electrolyte layer to obtain the high-voltage-resistant electrolyte interface layer. The invention uses electrochemical polymerization method to complete polymerization in the charging process without secondary assembly, thereby solving the technical problems of poor contact, formation of space charge layer and increase of contact resistance.

Description

High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-voltage-resistant electrolyte interface layer and an in-situ preparation method and application thereof.
Background
The problems of contact and stability of the anode-electrolyte interface in the all-solid-state battery include that a space charge layer formed by poor solid-solid interface contact increases internal resistance, interface side reaction, structural collapse of the anode material under high voltage, particle breakage and the like, and all-round industrialization of the lithium ion battery is always limited. At present, it is widely believed that the addition of fluorine-containing alkali metal salt, solvent/cosolvent, functional additive, etc. to an organic carbonate-based electrolyte system can improve the high-voltage resistance of the battery, and researchers have tried to prepare a high-voltage-resistant solid electrolyte by introducing a fluorine-containing polymer, however, the fluorine-containing solid electrolyte still has a great challenge in optimizing the performance of the high-voltage lithium ion battery due to the contact resistance formed by a secondary assembly process. The in-situ artificial interface layer construction technology becomes one of the most widely researched interface engineering technologies at present by virtue of the advantages of low technical difficulty, good process compatibility and the like.
CN 103682354B discloses an all-solid-state lithium ion battery composite electrode material, a preparation method thereof and an all-solid-state lithium ion battery, and specifically discloses an all-solid-state lithium ion battery composite electrode material which is prepared by preparing 0.1-20 parts of polymer monomer, 0.1-50 parts of ethylene glycol derivative, 0.1-10 parts of lithium salt, 0.1-10 parts of polymerization initiator and 50-99.9 parts of plasticizer to obtain a mixed solution, arranging the mixed solution on the surface of an electrode active material by an electrostatic spinning method, an electro-blowing spinning method, a liquid phase spraying method or a printing method, and polymerizing the surface of the electrode active material by a thermal polymerization method, an electron beam polymerization method or an ultraviolet polymerization method to generate a coating layer. Although the technical method uses polymer monomers to construct the interface between the interface layer bonding electrode and the electrolyte, the preparation method mainly uses light, heat and electron beam to initiate polymerization, a secondary assembly process is also needed in the preparation of the battery, the process easily causes poor contact, further forms a space charge layer and increases contact resistance, and an improved space exists.
Therefore, the prior art still lacks a preparation method of a high-voltage resistant electrolyte interface layer, which can overcome the problems that poor contact is easily caused by secondary assembly.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides an in-situ preparation method of a high voltage resistant electrolyte interface layer, which aims at an electrochemical polymerization method, wherein polymerization is initiated and completed during charging without secondary assembly, thereby solving the technical problems of poor contact, formation of a space charge layer and increase of contact resistance. The detailed technical scheme of the invention is as follows.
An in-situ preparation method of a high-voltage resistant electrolyte interface layer comprises the following steps:
(1) uniformly mixing a fluorine-containing acrylate monomer and a lithium salt to prepare a precursor;
(2) assembling a precursor, a positive electrode, a negative electrode and an electrolyte matrix into a battery, wherein the precursor is arranged between the electrolyte matrix and the positive electrode;
(3) and charging the battery to polymerize the acrylate monomer, and curing the precursor into a polymer electrolyte layer to obtain the high-voltage-resistant electrolyte interface layer.
The electrochemical initiation polymerization method is characterized in that an initiation voltage and a current are applied to a working electrode, an electrode material provides electrons for an initiator substance, the monomer polymerization is initiated, and a covalent bond is formed between an initiator product and the surface of the electrode.
Preferably, the charging is constant current charging, and the charging rate is 0.1-0.5C.
Preferably, the cathode material is a high-nickel ternary cathode material, and the voltage window of charging is 2.8-4.7V.
Preferably, the precursor in the step (1) comprises the following components in parts by mass: 10-90 parts of fluorine-containing acrylate monomer, 9-50 parts of lithium salt and 0-5 parts of initiator, wherein the mass ratio of the acrylate monomer to the lithium salt is preferably (1-2): 1.
The addition of lithium salt is the key to improving the ionic conductivity. In the system, lithium salt can be solvated by electropolymerized solid polymer electrolyte, and an ether oxygen structure in acrylate can be complexed with lithium ions. Under the condition of adding lithium salt, lithium ions with positive charges can be weakly bound to negative dipole moment related to negative electric atoms contained in a repeating unit, but the lithium salt is excessive to exceed the dissolving capacity of a system, crystallization can be separated out to influence the stability of an interface layer, the mass ratio of the acrylate monomer to the lithium salt is (1-2):1, and the optimal solution of the ion conduction effect is selected.
Preferably, the temperature of the charging process in the step (3) is controlled to be 40-70 ℃.
Preferably, the fluorine-containing acrylate monomer comprises one or more of trifluoroethyl acrylate, trifluoroethyl methacrylate, polyfluoroalkyl acrylate, polyfluoroalkyl ethyl acrylate and polyfluoroalkyl ethyl methacrylate, and the lithium salt is one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium chloride, lithium iodide, lithium tris (pentafluoroethyl) trifluorophosphate, lithium dioxalate borate, lithium difluorooxalate borate, lithium difluorodioxalate phosphate, lithium tetrafluorooxalate phosphate, lithium carbonate and lithium fluoride.
Preferably, the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, dibenzoyl oxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2, 2-dimethoxy-2-phenyl acetophenone;
the invention also protects a high-voltage resistant electrolyte interface layer prepared according to the preparation method.
The invention also protects the application of the interface layer in the all-solid-state lithium battery.
The invention has the following beneficial effects:
(1) according to the electrochemical polymerization method, polymerization is completed in the charging process, and secondary assembly is not needed, so that the technical problems of forming a space charge layer and increasing contact resistance due to poor contact are solved, and the interface resistance is reduced;
(2) the interface layer has good physical isolation capability, the solid electrolyte matrix is isolated from the high-voltage anode material to form a high-voltage all-solid-state electrolyte battery with compatible and stable interface, and the electrolyte coating precursor solution can be used as an ion-conducting binder in the anode material to participate in preparation, so that the specific energy of the all-solid battery is further improved;
(3) the polymerized polymer layer can realize seamless integration between the electrolyte-electrode interface with a complex shape, can be charged at a high voltage of more than 4V, has short preparation time and simple method, has good mechanical flexibility and is adaptive to the design of the current battery production and preparation production line;
(4) the interface layer of the invention greatly improves the oxidative decomposition potential of polyethylene oxide (PEO), solves the problem of the electrochemical stability of the interface, improves the high-capacity characteristic of the high-nickel ternary cathode material, widens the electrochemical window, obviously improves the cycle performance, and establishes the Li-favorable interface between the cathode and the electrolyte+The transmission anti-oxidation interface layer has wide market application prospect.
Drawings
FIG. 1 is a comparison of charge and discharge curves for two cycles before the present invention is applied to a PEO-based electrolyte to prepare a battery;
FIG. 2 is a comparative graph of cycling efficiency of cells prepared by applying the present invention to a PEO-based electrolyte;
figure 3 comparative plot of electrochemical window of cell prepared by applying the present invention to PEO-based electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Preparation examples
And preparing the positive electrode. The positive electrode active material is LiNi0.8Co0.1Mn0.1O2(NCM811), the conductive agent is conductive carbon black (Super P, Timcal Ltd.), the binder is polyvinylidene fluoride (PVDF, HSV 900, Arkema), the dispersant is N-methyl-2-pyrrolidone (NMP), and the conductive agent is LiNi0.8Co0.1Mn0.1O2: super P: PVDF (polyvinylidene fluoride) is mixed and ground according to the mass ratio of 7:2:1, is coated on an aluminum foil, is dried, rolled and stamped to prepare an electrode plate, and the active substance NCM811 on the surface of the electrode is controlled to be 2mg/cm2。
And preparing an ether-based electrolyte matrix. Dissolving polyethylene oxide (PEO) and LiTFSI in a solvent acetonitrile according to a mass ratio of 20:1 in a glove box protected by inert gas, stirring for 10h at 60 ℃ until the materials are fully dissolved, pouring the materials into a mold, standing for 24h at room temperature, and then sending the materials into an oven at 80 ℃ for drying for 24h to further remove the solvent, thereby obtaining the PEO-based electrolyte matrix.
And preparing a negative electrode. The negative electrode is a lithium plate.
Example 1
(1) Preparing a precursor: mixing 100g of trifluoroethyl methacrylate monomer and 100g of lithium trifluoromethanesulfonylimide LiTFSI in a glove box protected by inert gas, adding 3g of initiator Azobisisobutyronitrile (AIBN), stirring for 4 hours until lithium salt is fully dissolved, wherein the water content in the glove box is less than 0.1ppm, and the oxygen content is less than 0.1 ppm;
(2) assembling a battery, coating the precursor on the opposite side surfaces between the anode and the ether-based electrolyte matrix, and assembling the prepared anode, cathode and ether-based electrolyte matrix into the battery in a glove box;
(3) and (3) electrochemically initiating polymerization, transferring the assembled battery into an oven, setting the temperature of the oven to be 60 ℃, keeping the temperature for 2 hours, charging the battery, setting the current multiplying power to be 0.1 ℃, starting constant-current charging from the initial voltage of 2.8V, and stopping charging until the voltage reaches 4.3V.
Comparative example 1
This example differs from example 1 in that no precursor was used and no electrochemically initiated polymerization was carried out.
And assembling the prepared anode, cathode and ether-based electrolyte matrix into a battery in a glove box, transferring the assembled battery into an oven, setting the temperature of the oven to be 60 ℃, and preserving heat for 2 hours to obtain the lithium battery without the high-voltage-resistant electrolyte interface layer.
Test examples
The battery samples of example 1 and comparative example were subjected to electrochemical performance tests using a novice electrochemical tester.
The constant current charging and discharging is a method for circularly testing the battery by constant current, and the testing system is LiNi0.8Co0.1Mn0.1O2(NCM811)/Li, constant rate cycle mode, voltage window set to 2.8-4.3V, charge and discharge rate 0.1C, all charge and discharge cycle tests were performed at 60 deg.C in the experiment.
The measurement results are shown in FIG. 1, and the first-turn discharge capacity of example 1 is 180mA h g-1(Curve 1), the discharge capacity of the second turn was 176mA h g-1(Curve 2), whereas the first two cycles of the comparative example 1(PEO) had a discharge capacity of 148mA h g-1(curve 3), 146mA h g-1(Curve 4).
The cycle efficiency test shows that the capacity retention rate of example 1(NCM811/TFEMA-PEO/Li) is 77% after 40 cycles, while the capacity retention rate of comparative example 1(NCM811/PEO/Li) is reduced to below 50% after 30 cycles, and the measurement results are shown in FIG. 2.
Electrochemical window test, the results of the measurement are shown in fig. 3, and the comparative example (PEO) starts oxidation reaction at 4.3V (see the position indicated by the arrow in fig. 3 in detail), while example 1(PEO-PTFEMA) maintains electrochemical stability until 5.2V (see the position indicated by the arrow in fig. 3 in detail).
By comparison, the coating was constructed to increase the oxidative decomposition potential of the PEO-based electrolyte from 4.3V to 5.2V (fig. 3), solving the problem of electrochemical stability of the interface. Under the condition, the battery in the embodiment 1 can better exert the high-capacity characteristic of the high-nickel ternary cathode material, and the discharge capacity is up to 180mA h g in the first-circle charging-1Much higher than the 148mA hr g of comparative example-1(FIG. 1), and the capacity retention rate was 77% after 40 cycles (FIG. 2). The electrochemical window is widened, the cycle performance is obviously improved, and the coating is proved to be favorable for Li to be established in the positive electrode-electrolyte interface+A transmitting, oxidation resistant interface layer, demonstrates the operability of the invention.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. An in-situ preparation method of an electrolyte interface layer is characterized by comprising the following steps:
(1) uniformly mixing a fluorine-containing acrylate monomer and a lithium salt to prepare a precursor;
(2) assembling a precursor, a positive electrode, a negative electrode and an electrolyte matrix into a battery, wherein the precursor is arranged between the electrolyte matrix and the positive electrode;
(3) charging the battery to polymerize the acrylate monomer, and curing the precursor into a polymer electrolyte layer to obtain an electrolyte interface layer; the charging is constant current charging, and the charging multiplying power is 0.1-0.5C.
2. The preparation method according to claim 1, wherein the positive electrode is a high-nickel ternary positive electrode material, and the voltage window of charging is 2.8-4.7V.
3. The method of claim 1, wherein the precursor further comprises an initiator.
4. The preparation method according to claim 1 or 3, wherein the precursor in step (1) comprises the following components in parts by mass: 10-90 parts of fluorine-containing acrylate monomer, 9-50 parts of lithium salt and 0-5 parts of initiator.
5. The preparation method according to claim 4, wherein the mass ratio of the acrylate monomer to the lithium salt is (1-2): 1.
6. The method according to claim 1, wherein the charging process temperature in the step (3) is controlled to 40 to 70 ℃.
7. The method of claim 1, wherein the fluorine-containing acrylate monomer comprises one or more selected from the group consisting of trifluoroethyl acrylate, trifluoroethyl methacrylate, polyfluoroalkyl acrylate, polyfluoroalkyl ethyl acrylate, and polyfluoroalkyl ethyl methacrylate, and the lithium salt is one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium chloride, lithium iodide, lithium tris (pentafluoroethyl) trifluorophosphate, lithium dioxalate, lithium difluorooxalate, lithium difluorodioxalate, lithium tetrafluorooxalate, lithium carbonate, and lithium fluoride.
8. The method of claim 4, wherein the initiator comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, dibenzoyl oxide, benzoyl t-butyl peroxide, methyl ethyl ketone peroxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2, 2-dimethoxy-2-phenylacetophenone.
9. An electrolyte interface layer produced by the production method according to any one of claims 1 to 8.
10. Use of an interfacial layer according to claim 9 in an all solid-state lithium battery.
CN202010676638.2A 2020-07-14 2020-07-14 High-pressure-resistant all-solid-state lithium battery interface layer and in-situ preparation method and application thereof Expired - Fee Related CN111934020B (en)

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