CN116190767A - Sulfide solid electrolyte film based on self-healing binder, preparation method thereof and all-solid-state lithium battery - Google Patents

Sulfide solid electrolyte film based on self-healing binder, preparation method thereof and all-solid-state lithium battery Download PDF

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CN116190767A
CN116190767A CN202211604948.9A CN202211604948A CN116190767A CN 116190767 A CN116190767 A CN 116190767A CN 202211604948 A CN202211604948 A CN 202211604948A CN 116190767 A CN116190767 A CN 116190767A
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self
solid electrolyte
healing
sulfide solid
equal
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姚霞银
赵潇蕾
刘高瞻
刘自强
薛晓琳
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
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    • H01M10/052—Li-accumulators
    • 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
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Abstract

The invention belongs to the technical field of solid electrolyte, and relates to a sulfide solid electrolyte film based on a self-healing binder, a preparation method thereof and an all-solid-state lithium battery. The sulfide solid electrolyte film based on the self-healing adhesive comprises a self-healing adhesive and sulfide solid electrolyte, wherein the self-healing adhesive is formed by polymerizing methyl methacrylate and an ester monomer, and the ester monomer is one or more of n-butyl acrylate, n-amyl acrylate and n-hexyl acrylate. The self-healing adhesive has self-healing capability in the electrolyte film, and the self-healing function of the self-healing adhesive after mechanical damage can relieve the volume change of the battery in the charging and discharging process, so that the stable and efficient long-term cycle performance is ensured.

Description

Sulfide solid electrolyte film based on self-healing binder, preparation method thereof and all-solid-state lithium battery
Technical Field
The invention belongs to the technical field of solid electrolyte, and relates to a sulfide solid electrolyte film based on a self-healing binder, a preparation method thereof and an all-solid-state lithium battery.
Background
All-solid-state lithium batteries have the advantages of high safety and high energy density compared to conventional lithium ion batteries. Among reported solid electrolytes, sulfide solid electrolytes, which have high ionic conductivity and can be densified by cold pressing at room temperature to produce a good interface, are among the most promising solid electrolytes for commercialization. However, since the inorganic solid electrolyte is hard and brittle, the assembled all-solid battery is prone to crack and develop during cycling, resulting in failure of the battery. In addition, the electrode tabs are susceptible to volume expansion during battery cycling. Therefore, an excellent binder for obtaining an ultra-thin electrolyte membrane is an important direction for improving the energy density of all-solid-state batteries.
The film forming method of mixing the binder with the sulfide electrolyte to form a slurry and then performing wet coating is widely used for mass production due to simple operation. However, most of the conventional binders are used, and the stability of the battery is poor due to the volume expansion occurring during the battery cycle and the separation of the inside of the material.
Disclosure of Invention
Aiming at the defects of the all-solid-state battery in the prior art, the invention provides a sulfide solid electrolyte film based on a self-healing binder, a preparation method thereof and an all-solid-state lithium battery.
An object of the present invention is to provide a self-healing binder-based sulfide solid electrolyte film including a self-healing binder and a sulfide solid electrolyte, the self-healing binder being polymerized from Methyl Methacrylate (MMA) and an ester monomer.
Preferably, the ester monomer is one or more of n-butyl acrylate (nBA), n-amyl acrylate (nPA) and n-Hexyl Acrylate (HA).
Preferably, the preparation method of the self-healing adhesive comprises the following steps: methyl methacrylate and ester monomer are dissolved in organic solvent, initiator is added to carry out copolymerization reaction, and self-healing adhesive is obtained after precipitation.
The polymer obtained by the copolymerization reaction of methyl methacrylate and one or more of n-butyl acrylate, n-amyl acrylate and n-hexyl acrylate is used as a sulfide solid electrolyte binder, and the binder has self-healing capability in an electrolyte film, and the self-healing function of the self-healing binder after mechanical damage enables the self-healing binder to relieve the volume change in the battery charging and discharging process and ensures stable and efficient long-term circulation performance. This behavior is due to the favorable van der Waals forces forming the snap-lock connection between the polymer chains. In addition, the self-healing adhesive does not contain other polar functional groups except ester groups, so that the self-healing adhesive has higher stability with sulfide solid electrolyte, and the prepared electrolyte film has lower impedance value and higher ionic conductivity.
Preferably, the mass ratio of the methyl methacrylate to the ester monomer is 1:10-10:1.
Preferably, in the preparation method of the self-healing adhesive, the organic solvent is one or a mixture of more of toluene, chlorobenzene, xylene, paraxylene, tetrahydrofuran, dimethyl carbonate, dimethylformamide, glyme, dibutyl ether, triethyl phosphate, dimethyl sulfoxide, butyl butyrate, ethyl acetate, benzyl acetate and butyl isobutyrate.
Preferably, in the preparation method of the self-healing adhesive, the initiator comprises one or a mixture of more than one of a free radical initiator, a redox initiator, an azo initiator and a difunctional initiator.
Preferably, the ratio of the addition amount of the initiator to the total weight of the methyl methacrylate and the ester monomer is 1: 100-1: 500.
preferably, in the preparation method of the self-healing adhesive, the time of the copolymerization is 1-48 hours, and the temperature is 10-200 ℃.
Preferably, in the preparation method of the self-healing adhesive, the solvent is adopted for precipitation, and the solvent is one or a mixture of more of n-hexane, n-heptane, methanol, ethanol, 1, 2-ethylenediamine, dichloroethane, chloroform, dibromomethane, dichloromethane, 1, 2-ethanedithiol, tetrahydrofuran and hexene.
Preferably, in the sulfide solid electrolyte film based on the self-healing adhesive, the mass percent of the self-healing adhesive is more than 0 percent and less than or equal to 20 percent.
Preferably, the sulfide solid electrolyte is one or more of chemical formulas shown in formula I, formula II, and formula III:
(100-x-y)Li 2 S·xP 2 S 5 ·yM m N n the compound of the formula I,
wherein x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, x+y is more than or equal to 0 and less than or equal to 100, m is more than or equal to 0 and less than or equal to 4, N is more than or equal to 0 and less than 6, M is one or more of Ge, si, sn, sb, and N is one or more of Se, O, cl, br, I;
Li 10±l Ge 1-g G g P 2-q Q q S 12-w W w the compound of the formula II is shown in the specification,
wherein l is more than or equal to 0 and less than 1, g is more than or equal to 0 and less than 1, Q is more than or equal to 0 and less than or equal to 2, W is more than or equal to 0 and less than 1, G is Si and/or Sn, Q is one or more of Sb, as and Ti, and W is one or more of O, se, F, cl, br, I;
Li 6±l P 1-e E e S 5-r±t R r X 1±t the compound of the formula III,
wherein l is more than or equal to 0 and less than 1, e is more than or equal to 0 and less than 1, R is more than or equal to 0 and less than 1, t is more than or equal to 0 and less than 1, E is one or more of Ge, si, sn, sb, R is O and/or Se, and X is one or more of F, cl, br, I.
The sulfide solid electrolyte in the sulfide solid electrolyte film has one or more of the chemical formulas shown in the formulas I, II and III, and the self-healing adhesive has higher stability in the sulfide solid electrolyte, thereby being beneficial to improving the ion conductivity of the electrolyte film and being more beneficial to improving the cycle performance of a battery.
Preferably, the thickness of the sulfide solid electrolyte film based on the self-healing binder is 5 to 100 μm, more preferably 20 to 70 μm.
Preferably, the ionic conductivity of the sulfide solid electrolyte film based on the self-healing binder is 0.01 to 10mS/cm, more preferably 0.1 to 10mS/cm, still more preferably 0.8 to 8mS/cm, still more preferably 1 to 5mS/cm.
Another object of the present invention is to provide a method for preparing a sulfide solid electrolyte film based on a self-healing binder, the method comprising the steps of:
adding the self-healing binder and the sulfide solid electrolyte into an inert solvent, mixing in a closed container, and uniformly dispersing to obtain sulfide solid electrolyte slurry; and (3) coating the sulfide solid electrolyte slurry on a substrate, drying and pressing to obtain the sulfide solid electrolyte film based on the self-healing adhesive.
Preferably, the addition amount of the self-healing adhesive is more than 0 percent and less than or equal to 20 percent of the total mass of the self-healing adhesive and the sulfide solid electrolyte.
Preferably, the inert solvent is one or more of toluene, chlorobenzene, xylene, dimethyl carbonate, dimethylformamide, n-hexane, glyme, dibutyl ether, ethanol, 1, 2-ethylenediamine, dichloroethane, chloroform, dibromomethane, anisole, triethyl phosphate, dimethyl sulfoxide, dichloromethane, 1, 2-ethanedithiol, acetonitrile, tetrahydrofuran, isopentyl ether, butyl butyrate, isopropyl ether, n-heptane, hexene, ethyl acetate and benzyl acetate.
Preferably, the mixing method is one or more of mechanical stirring, mechanical oscillation, ultrasonic dispersion, ball milling, roller milling and agate mortar milling, and the mixing time is 0.1-12 hours.
Preferably, the substrate is one or more of copper foil, aluminum foil, glass plate, steel plate, PET substrate and PE substrate, or the substrate is an extension product plated on the copper foil, aluminum foil, glass plate, steel plate, PET substrate or PE substrate.
Preferably, the drying temperature is 10 to 200 ℃ and the drying time is 0.1 to 48 hours.
Preferably, the pressing is performed in an isostatic press, wherein the pressing temperature is 20-100 ℃ and the pressing pressure is 0.1-500 MPa.
Another object of the present invention is to provide an all-solid lithium battery comprising a positive electrode, a negative electrode, and an electrolyte layer comprising a sulfide solid electrolyte film based on a self-healing binder as described above.
Preferably, the electrolyte layer is a superposition of one or more sulfide solid electrolyte films based on self-healing binders.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes the polymer obtained by polymerizing methyl methacrylate and one or more of n-butyl acrylate, n-amyl acrylate and n-hexyl acrylate as a sulfide solid electrolyte binder, and the binder has self-healing capability in an electrolyte film; the self-healing adhesive has the advantages that the lock catch connection formed by favorable Van der Waals force among high molecular chains can self-heal after mechanical damage, so that the volume change in the battery charging and discharging process can be relieved, and the stable and efficient long-term cycle performance is ensured;
2. the self-healing adhesive does not contain other polar functional groups except ester groups, has higher stability with sulfide solid electrolyte, and the prepared electrolyte film has lower impedance value and higher ionic conductivity;
3. the sulfide solid electrolyte in the sulfide solid electrolyte film has one or more of chemical formulas shown in the formulas I, II and III, and the self-healing adhesive has higher stability in the sulfide solid electrolyte, thereby being beneficial to improving the ion conductivity of the electrolyte film and being more beneficial to improving the cycle performance of a battery;
4. the all-solid-state lithium battery assembled by the sulfide solid electrolyte film has excellent cycling stability;
5. the sulfide solid electrolyte film has simple preparation process, is suitable for large-scale production, and can realize an all-solid-state battery with high energy density by matching with a high-capacity positive electrode material.
Drawings
FIG. 1 is a cross-sectional scanning electron microscope image of a self-healing binder-based sulfide solid electrolyte film of example 1;
FIG. 2 is an AC impedance spectrum of the sulfide solid electrolyte film based on the self-healing adhesive of example 1;
fig. 3 is a battery cycle performance diagram of the all-solid battery of example 1;
FIG. 4 is an AC impedance spectrum of the sulfide solid electrolyte film of comparative example 1;
fig. 5 is a battery cycle performance diagram of the all-solid battery of comparative example 1;
FIG. 6 is an AC impedance spectrum of the sulfide solid electrolyte film of comparative example 2;
fig. 7 is a battery cycle performance diagram of the all-solid battery of comparative example 2.
Detailed Description
The technical solution of the present invention will be further described by means of specific examples and drawings, it being understood that the specific examples described herein are only for aiding in understanding the present invention and are not intended to be limiting. And the drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure. Unless otherwise indicated, all materials used in the examples of the present invention are those commonly used in the art, and all methods used in the examples are those commonly used in the art.
Example 1
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 97 parts by weight of Li 6 PS 5 Dispersing the Cl electrolyte and 3 parts by weight of self-healing binder into toluene, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 30 parts of methyl methacrylate and 70 parts of n-butyl acrylate are dissolved in a toluene organic solvent, then 0.4 part of 2-bromoisobutyryl bromide initiator is added to carry out free radical copolymerization reaction for 5 hours at 75 ℃, and the self-healing adhesive is obtained after n-hexane precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 80 ℃ for 12 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after hot isostatic pressing at 60 ℃ for 200 MPa.
The cross-sectional scanning electron microscope image of the sulfide solid electrolyte film based on the self-healing adhesive is shown in figure 1, and the film thickness is about 20 mu m. The AC impedance spectrum of the sulfide solid electrolyte film based on the self-healing adhesive of example 1 is shown in FIG. 2, and the film room temperature impedance value is 0.9Ω·mm -1 The ionic conductivity was calculated to be 2.83mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The battery can stably circulate for 1000 circles at 0.5C, the capacity retention rate is 74%, and the battery circulation performance chart is shown in figure 3.
Example 2
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 6.05 PS 4.9 O 0.1 Cl 1.05 Dispersing the electrolyte and 1 part by weight of self-healing binder into dimethylbenzene, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 30 parts of methyl methacrylate and 70 parts of n-butyl acrylate were dissolved in xyleneAnd (3) adding 0.4 part of 2-bromo-isobutyryl bromide initiator into the organic solvent, carrying out free radical copolymerization at 75 ℃ for 5 hours, and precipitating by n-heptane to obtain the self-healing adhesive.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 90 ℃ for 12 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after cold isostatic pressing at 20 ℃ for 200 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 15 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 2 was 1.2. Omega. Mm -1 The ionic conductivity was calculated to be 1.59mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, the lithium magnesium alloy is a negative electrode, and the all-solid-state battery is assembled. The battery can stably circulate for 1000 circles at 0.2C, and the capacity retention rate is 80.4%.
Example 3
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 95 parts by weight of Li 10 GeP 1.98 Sb 0.02 S 11.97 O 0.03 Dispersing the electrolyte and 5 parts by weight of self-healing binder into toluene, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 40 parts of methyl methacrylate and 60 parts of n-amyl acrylate are dissolved in a xylene organic solvent, then 0.3 part of alpha-bromoisobutyric acid ethyl ester initiator is added to carry out free radical copolymerization reaction for 4 hours at 70 ℃, and the self-healing adhesive is obtained after n-hexane precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying for 14 hours at 90 ℃, and is subjected to cold isostatic pressing for 200MPa at 20 ℃ to obtain the sulfide solid electrolyte film based on the self-healing adhesive.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 20 mu m. The room temperature resistance value of the sulfide solid electrolyte membrane based on self-healing adhesive of example 3 was 1.5Ω·mm -1 The ionic conductivity was calculated to be 1.7mS/cm.
By LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi in the composite positive electrode material is positive electrode active substance 0.6 Co 0.2 Mn 0.2 O 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The battery can stably circulate for 1500 circles at 0.2C, and the capacity retention rate is 80.41%.
Example 4
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 9.88 GeP 1.96 Sb 0.04 S 11.88 Cl 0.12 Dispersing the electrolyte and 1 part by weight of self-healing binder into tetrahydrofuran, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 30 parts of methyl methacrylate and 70 parts of n-butyl acrylate are dissolved in tetrahydrofuran organic solvent, then 0.3 part of alpha-bromoisobutyric acid ethyl ester initiator is added to carry out free radical copolymerization reaction for 4 hours at 70 ℃, and the self-healing adhesive is obtained after n-hexane precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 80 ℃ for 15 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after cold isostatic pressing at 20 ℃ for 250 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 38 mu m. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 4 was 1.1. Omega. Mm -1 The ionic conductivity was calculated to be 4.4mS/cm.
By LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi in the composite positive electrode material is positive electrode active substance 0.6 Co 0.2 Mn 0.2 O 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The battery can stably circulate for 1000 circles at 0.1C, and the capacity retention rate is 89.3%.
Example 5
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 9.88 GeP 1.96 Sb 0.04 S 11.88 Cl 0.12 Dispersing the electrolyte and 1 part by weight of self-healing binder into tetrahydrofuran, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 30 parts of methyl methacrylate and 70 parts of n-hexyl acrylate are dissolved in tetrahydrofuran organic solvent, then 0.4 part of potassium persulfate initiator is added to carry out free radical copolymerization reaction for 5 hours at 78 ℃, and the self-healing adhesive is obtained after n-heptane precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 85 ℃ for 15 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after hot isostatic pressing at 60 ℃ for 300 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 25 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 5 was 1.42. Omega. Mm -1 The ionic conductivity was calculated to be 2.24mS/cm.
By LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi in the composite positive electrode material is positive electrode active substance 0.6 Co 0.2 Mn 0.2 O 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The battery can be at 1CThe capacity retention rate was 86.98% after 3000 cycles of stabilization.
Example 6
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 6 PS 5 Cl 0.5 Br 0.5 Dispersing the electrolyte and 1 part by weight of self-healing binder into tetrahydrofuran, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 40 parts of methyl methacrylate and 60 parts of n-butyl acrylate are dissolved in tetrahydrofuran organic solvent, then 0.4 part of potassium persulfate initiator is added to carry out free radical copolymerization reaction for 5 hours at 78 ℃, and the self-healing adhesive is obtained after n-heptane precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 85 ℃ for 12 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after cold isostatic pressing at 20 ℃ for 200 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 20 mu m. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 6 was 1.5Ω·mm -1 The ionic conductivity was calculated to be 1.7mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, the lithium boron alloy is a negative electrode, and the all-solid-state battery is assembled. The battery can stably circulate for 1500 circles at 0.1C, and the capacity retention rate is 86.17%.
Example 7
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 10 GeP 1.98 Sb 0.02 S 11.97 O 0.03 The electrolyte and 1 part by weight of self-healing binder are dispersed into tetrahydrofuranMechanically stirring and mixing the raw materials in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 50 parts of methyl methacrylate and 50 parts of n-butyl acrylate are dissolved in tetrahydrofuran organic solvent, then 0.3 part of azodiisobutyronitrile initiator is added to carry out free radical copolymerization reaction for 8 hours at 75 ℃, and the self-healing adhesive is obtained after n-heptane precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 90 ℃ for 10 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after cold isostatic pressing at 30 ℃ for 250 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 15 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 7 was 0.7Ω·mm -1 The ionic conductivity was calculated to be 2.73mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The cell was stable for 4000 cycles at 0.2C with a capacity retention of 89.2%.
Example 8
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 98 parts by weight of Li 5.4 PS 4.4 Cl 1.6 Dispersing the electrolyte and 2 parts by weight of self-healing binder into toluene, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 40 parts of methyl methacrylate, 55 parts of n-butyl acrylate and 5 parts of n-amyl acrylate are dissolved in toluene organic solvent, then 0.4 part of potassium persulfate initiator is added to carry out free radical copolymerization reaction for 5 hours at 78 ℃, and the self-healing adhesive is obtained after methanol precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 90 ℃ for 12 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after hot isostatic pressing at 60 ℃ for 200 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 50 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 8 was 4.1. Omega. Mm -1 The ionic conductivity was calculated to be 1.55mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The cell was stable for 5000 cycles at 1C with a capacity retention of 76.11%.
Example 9
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 95 parts by weight of Li 7 P 2 S 8 The electrolyte I and 5 parts by weight of self-healing binder are dissolved in dimethylbenzene, and are ground and mixed in an agate mortar in a closed container for 1 hour to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 50 parts of methyl methacrylate and 50 parts of n-amyl acrylate are dissolved in a xylene organic solvent, then 0.4 part of potassium persulfate initiator is added to carry out free radical copolymerization reaction for 5 hours at 78 ℃, and the self-healing adhesive is obtained after methanol precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred into a vacuum oven to be dried for 1 hour under the temperature of 90 ℃, and is subjected to hot isostatic pressing for 200MPa at the temperature of 60 ℃ to obtain the sulfide solid electrolyte film based on the self-healing adhesive.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 15 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 9 was 2.1. Omega. Mm -1 The ionic conductivity was calculated to be 0.91mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The battery can stably circulate for 1500 circles at 1C, and the capacity retention rate is 80.3%.
Example 10
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 5.5 PS 4.5 Cl 1.5 Dispersing the electrolyte and 1 part by weight of self-healing binder into toluene, and grinding and mixing the mixture in an agate mortar in a closed container for 1 hour to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 30 parts of methyl methacrylate and 70 parts of n-butyl acrylate are dissolved in a toluene organic solvent, then 0.3 part of azodiisobutyronitrile initiator is added to carry out free radical copolymerization reaction for 8 hours at 85 ℃, and the self-healing adhesive is obtained after methanol precipitation.
(2) The slurry is coated on copper foil by an adjustable coating machine, and is transferred into a vacuum oven to be dried for 10 hours at 90 ℃ and is subjected to hot isostatic pressing for 200MPa at 60 ℃ to obtain the sulfide solid electrolyte film based on the self-healing adhesive.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 23 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 10 was 2.23. Omega. Mm -1 The ionic conductivity was calculated to be 1.31mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The cell was stable for 800 cycles at 0.1C with a capacity retention of 92.3%.
Example 11
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 5.4 PS 4.4 Cl 1.2 Br 0.4 Dispersing the electrolyte and 1 part by weight of self-healing binder into dimethylbenzene, and mechanically stirring and mixing in a closed container for 25 minutes to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 30 parts of methyl methacrylate and 70 parts of n-butyl acrylate are dissolved in a dimethylformamide organic solvent, then 0.3 part of azodiisobutyronitrile initiator is added to carry out free radical copolymerization reaction for 8 hours at 75 ℃, and the self-healing adhesive is obtained after methanol precipitation.
(2) The slurry is coated on copper foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying for 12 hours at the temperature of 85 ℃, and is subjected to hot isostatic pressing for 200MPa at the temperature of 60 ℃ to obtain the sulfide solid electrolyte film based on the self-healing adhesive.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 27 μm. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 11 was 2.3. Omega. Mm -1 The ionic conductivity was calculated to be 1.5mS/cm.
By LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi in the composite positive electrode material is positive electrode active substance 0.6 Co 0.2 Mn 0.2 O 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The cell was stable for 2000 cycles at 0.5C with a capacity retention of 73.4%.
Example 12
The sulfide solid electrolyte film based on the self-healing adhesive of the present embodiment is prepared by the following method:
(1) In a glove box, 99 parts by weight of Li 5.4 PS 4.4 Cl 1.6 Dispersing the electrolyte and 1 part by weight of self-healing binder into toluene, and mechanically stirring and mixing in a closed container for 25 minutes to obtain uniform slurry; the self-healing adhesive is prepared by the following method: 40 parts of methylMethyl acrylate and 60 parts of n-butyl acrylate are dissolved in dimethylformamide organic solvent, then 0.3 part of azodiisobutyronitrile initiator is added to carry out free radical copolymerization reaction for 8 hours at 75 ℃, and the self-healing adhesive is obtained after methanol precipitation.
(2) The slurry is coated on an aluminum foil by an adjustable coating machine, and is transferred to a vacuum oven for vacuum drying at 80 ℃ for 12 hours, and the sulfide solid electrolyte film based on the self-healing adhesive is obtained after cold isostatic pressing at 30 ℃ for 200 MPa.
The thickness of the prepared sulfide solid electrolyte film based on the self-healing adhesive is about 12 mu m. The room temperature resistance value of the self-healing adhesive-based sulfide solid electrolyte film of example 12 was 0.8Ω·mm -1 The ionic conductivity was calculated to be 1.91mS/cm.
By LiNi 0.6 Co 0.2 Mn 0.2 O 2 LiNi in the composite positive electrode material is positive electrode active substance 0.6 Co 0.2 Mn 0.2 O 2 And the mass ratio is 70 percent, the sulfide solid electrolyte film based on the self-healing binder is an electrolyte layer, and the metal lithium is a negative electrode, so that the all-solid-state battery is assembled. The battery can stably circulate for 1000 circles at 0.3C, and the capacity retention rate is 82.3%.
Comparative example 1
Comparative example 1 differs from example 1 in that the binder of comparative example 1 was prepared by the following method: 30 parts of styrene and 70 parts of n-butyl acrylate are dissolved in toluene organic solvent, then 0.4 part of 2-bromo-isobutyryl bromide initiator is added to carry out free radical copolymerization reaction for 5 hours at 75 ℃, and the adhesive is obtained after methanol precipitation; the other steps are the same as in example 1.
The sulfide solid electrolyte film obtained in comparative example 1 had a thickness of about 20 μm. The alternating current impedance spectrum of the sulfide solid electrolyte film of comparative example 1 is shown in FIG. 4, and the film room temperature impedance value is 2.8Ω·mm -1 The ionic conductivity was calculated to be 0.91mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 70% by mass of the sulfide solid electrolyte film is electricAnd the electrolyte layer, the metal lithium is used as a negative electrode, and the all-solid-state battery is assembled. The capacity retention rate of the battery after 1000 cycles at 0.5C was 0.7%, and the battery cycle performance chart is shown in fig. 5.
Comparative example 2
Comparative example 2 differs from example 1 in that step (1) of comparative example 2 is: in a glove box, 97 parts by weight of 75Li 2 S·25P 2 S 5 Dispersing the electrolyte and 3 parts by weight of self-healing binder into toluene, and mechanically stirring and mixing in a closed container for 2 hours to obtain uniform slurry; the preparation method of the self-healing adhesive is the same as that of the example 1.
The sulfide solid electrolyte thin film obtained in comparative example 2 had a thickness of about 20 μm. The alternating current impedance spectrum of the sulfide solid electrolyte film of comparative example 2 is shown in FIG. 6, and the film room temperature impedance value is 10.8Ω·mm -1 The ionic conductivity was calculated to be 0.24mS/cm.
By LiCoO 2 LiCoO in the composite positive electrode material is positive electrode active substance 2 The mass ratio is 70%, the sulfide solid electrolyte film is an electrolyte layer, the metal lithium is a negative electrode, and the all-solid-state battery is assembled. The capacity of the battery drops to 0 after 800 cycles at 0.5C, and the battery cycle performance chart is shown in fig. 7.
From the experimental results of examples 1 to 12 and comparative examples 1 to 2, it is apparent that the use of one or more of the chemical formulas shown in formulas I, II and III as the sulfide solid electrolyte and the use of the polymer obtained by polymerizing methyl methacrylate with one or more of n-butyl acrylate, n-pentyl acrylate and n-hexyl acrylate as the sulfide solid electrolyte binder, and the preparation of the electrolyte thin film from the self-healing binder and the sulfide solid electrolyte as described above are advantageous in improving the ionic conductivity of the electrolyte thin film and more in improving the cycle performance of the battery.
The various aspects, embodiments, features of the invention are to be considered as illustrative in all respects and not restrictive, the scope of the invention being indicated only by the appended claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In the preparation method of the invention, the sequence of each step is not limited to the listed sequence, and the sequential change of each step is also within the protection scope of the invention without the inventive labor for the person skilled in the art. Furthermore, two or more steps or actions may be performed simultaneously.
Finally, it should be noted that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention's embodiments. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions in a similar manner, and need not and cannot fully practice all of the embodiments. While these obvious variations and modifications, which come within the spirit of the invention, are within the scope of the invention, they are to be construed as being without departing from the spirit of the invention.

Claims (10)

1. The sulfide solid electrolyte film based on the self-healing adhesive is characterized by comprising the self-healing adhesive and sulfide solid electrolyte, wherein the self-healing adhesive is formed by polymerizing methyl methacrylate and an ester monomer.
2. The self-healing binder-based sulfide solid electrolyte film according to claim 1, wherein the ester monomer is one or more of n-butyl acrylate, n-pentyl acrylate and n-hexyl acrylate.
3. The sulfide solid electrolyte film based on the self-healing adhesive according to claim 1 or 2, wherein the preparation method of the self-healing adhesive comprises the following steps: methyl methacrylate and ester monomer are dissolved in organic solvent, initiator is added to carry out copolymerization reaction, and self-healing adhesive is obtained after precipitation.
4. The sulfide solid electrolyte film based on the self-healing adhesive according to claim 1, wherein the mass percent of the self-healing adhesive in the sulfide solid electrolyte film based on the self-healing adhesive is more than 0% and less than or equal to 20%.
5. The self-healing binder based sulfide solid electrolyte thin film of claim 1, wherein the sulfide solid electrolyte is one or more of the chemical formulas of formula I, formula II, and formula III:
(100-x-y)Li 2 S·xP 2 S 5 ·yM m N n the compound of the formula I,
wherein x is more than or equal to 0 and less than 100, y is more than or equal to 0 and less than 100, x+y is more than or equal to 0 and less than or equal to 100, m is more than or equal to 0 and less than or equal to 4, N is more than or equal to 0 and less than 6, M is one or more of Ge, si, sn, sb, and N is one or more of Se, O, cl, br, I;
Li 10±l Ge 1-g G g P 2-q Q q S 12-w W w the compound of the formula II is shown in the specification,
wherein l is more than or equal to 0 and less than 1, g is more than or equal to 0 and less than 1, Q is more than or equal to 0 and less than or equal to 2, W is more than or equal to 0 and less than 1, G is Si and/or Sn, Q is one or more of Sb, as and Ti, and W is one or more of O, se, F, cl, br, I;
Li 6±l P 1-e E e S 5-r±t R r X 1±t the compound of the formula III,
wherein l is more than or equal to 0 and less than 1, e is more than or equal to 0 and less than 1, R is more than or equal to 0 and less than 1, t is more than or equal to 0 and less than 1, E is one or more of Ge, si, sn, sb, R is O and/or Se, and X is one or more of F, cl, br, I.
6. The self-healing binder based sulfide solid electrolyte thin film according to claim 1, wherein the thickness of the self-healing binder based sulfide solid electrolyte thin film is 5 to 100 μm.
7. The self-healing binder based sulfide solid electrolyte thin film according to claim 1, wherein the ion conductivity of the self-healing binder based sulfide solid electrolyte thin film is 0.01 to 10mS/cm.
8. The method for preparing a self-healing binder-based sulfide solid electrolyte thin film according to claim 1, wherein the method comprises the steps of:
adding the self-healing binder and the sulfide solid electrolyte into an inert solvent, mixing in a closed container, and uniformly dispersing to obtain sulfide solid electrolyte slurry; and (3) coating the sulfide solid electrolyte slurry on a substrate, drying and pressing to obtain the sulfide solid electrolyte film based on the self-healing adhesive.
9. The method according to claim 8, wherein the inert solvent is one or more of toluene, chlorobenzene, xylene, dimethyl carbonate, dimethylformamide, n-hexane, glyme, dibutyl ether, ethanol, 1, 2-ethylenediamine, dichloroethane, chloroform, dibromomethane, anisole, triethyl phosphate, dimethyl sulfoxide, dichloromethane, 1, 2-ethanedithiol, acetonitrile, tetrahydrofuran, isopentyl ether, butyl butyrate, isopropyl ether, n-heptane, hexene, ethyl acetate, and benzyl acetate;
and/or the mixing method is one or more of mechanical stirring, mechanical oscillation, ultrasonic dispersion, ball milling, roller milling and agate mortar milling, and the mixing time is 0.1-12 hours.
10. An all-solid-state lithium battery comprising a positive electrode, a negative electrode, and an electrolyte layer, characterized in that the electrolyte layer comprises the self-healing binder-based sulfide solid electrolyte film according to claim 1.
CN202211604948.9A 2022-12-14 2022-12-14 Sulfide solid electrolyte film based on self-healing binder, preparation method thereof and all-solid-state lithium battery Pending CN116190767A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117497888A (en) * 2023-12-26 2024-02-02 中科深蓝汇泽新能源(常州)有限责任公司 Recoverable sulfide composite solid electrolyte and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117497888A (en) * 2023-12-26 2024-02-02 中科深蓝汇泽新能源(常州)有限责任公司 Recoverable sulfide composite solid electrolyte and preparation method thereof
CN117497888B (en) * 2023-12-26 2024-04-26 中科深蓝汇泽新能源(常州)有限责任公司 Recoverable sulfide composite solid electrolyte and preparation method thereof

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