CN114204115A - Single-ion conductor polymer electrolyte and preparation method and application thereof - Google Patents

Single-ion conductor polymer electrolyte and preparation method and application thereof Download PDF

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CN114204115A
CN114204115A CN202111491263.3A CN202111491263A CN114204115A CN 114204115 A CN114204115 A CN 114204115A CN 202111491263 A CN202111491263 A CN 202111491263A CN 114204115 A CN114204115 A CN 114204115A
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ion conductor
lithium
inorganic filler
electrolyte
polymer electrolyte
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董洁
陈规伟
冀亚娟
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Eve Energy 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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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

Abstract

The invention provides a single-ion conductor polymer electrolyte, a preparation method and application thereof, wherein the single-ion conductor polymer electrolyte comprises a combination of a single-ion conductor, an oxide solid electrolyte and a polymer matrix; the single-ion conductor comprises inorganic filler and bis (trifluoromethane) sulfonyl imide lithium grafted on the surface of the inorganic filler through sulfonyl chloride groups; the bis (trifluoromethane) sulfonyl imide is grafted on the inorganic filler framework to limit the migration of anions in the inorganic filler framework, so that the problem of concentration polarization of the anions can be effectively solved, the migration number of lithium ions in an electrolyte can be further improved, and finally, the electrical property of the lithium ion solid-state battery containing the single-ion conductor polymer electrolyte is effectively improved.

Description

Single-ion conductor polymer electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrolytes, and particularly relates to a single-ion conductor polymer electrolyte and a preparation method and application thereof.
Background
Lithium ion batteries are widely used due to their advantages of environmental friendliness, excellent cycle performance, etc., wherein electrolytes are used as key components of lithium ion batteries and are closely linked with the cycle life, safety, capacity, etc. of the batteries. The most widely applied organic liquid electrolyte in the market at present, but the organic liquid electrolyte is easy to leak organic solvent, burn and explode, and has a great potential safety hazard, so the solid electrolyte has become a hot spot of the current research.
The solid electrolyte mainly comprises three categories of inorganic solid electrolyte, polymer solid electrolyte and organic/inorganic composite solid electrolyte. The research make internal disorder or usurp on all solid-state lithium secondary batteries mainly includes two major categories by electrolyte distinction: one type of lithium secondary battery is composed of an organic polymer electrolyte, also called a polymer all-solid-state lithium battery; the other type is a lithium secondary battery composed of an inorganic solid electrolyte, which is also called an inorganic all-solid-state lithium battery. CN112062991A discloses a method for preparing an organic-inorganic solid electrolyte, which uses a high-temperature solid-phase synthesis method to synthesize lithium fluoride and lithium hydroxide as raw materials in vacuum, and then mix them with organic polyethylene oxide to prepare a solid electrolyte film, and at the end of the reaction, the molten product in the quartz tube is rapidly cooled to room temperature, thereby resulting in different textures and grain boundary morphologies. Continuous heating and removal of water under high vacuum drive chemical equilibrium. The method has the advantages of simple preparation, short time consumption and strong controllability, can be used for producing high-quality lithium oxyfluoride materials, is suitable for large-scale quantitative preparation, and has short time consumption and high purity. However, most polymer matrixes are similar to liquid electrolytes and are double-ion conductors, and the transference number of lithium ions is low (t)Li +<0.5), during charging and discharging, anions are gathered on the surface of the anode to cause concentration polarization problem, and the cycle life of the lithium ion battery is influenced.
Therefore, in order to increase the lithium ion transport number of the polymer matrix, solve the problem of concentration polarization generated by anions, and improve the coulombic efficiency and the cycle life of the lithium ion battery, aiming at the problem of low transport number of polymer-based lithium ions, the single-ion conductor polymer electrolyte with high lithium ion transport number is developed, which is a problem to be solved urgently in the field.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a single ion conductor polymer electrolyte comprising a combination of a single ion conductor, an oxide solid electrolyte and a polymer matrix; the single-ion conductor comprises an inorganic filler and lithium bistrifluoromethane sulfimide grafted on the surface of the inorganic filler through sulfonyl chloride groups; the bis (trifluoromethane) sulfonyl imide is grafted on the inorganic filler framework to limit the migration of anions in the inorganic filler framework, so that the migration number of lithium ions in electrolyte can be effectively improved, and the coulombic efficiency and the cycle life of the lithium ion battery are further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a single ion conductor polymer electrolyte comprising a combination of a single ion conductor, an oxide solid state electrolyte, and a polymer matrix;
the single-ion conductor comprises an inorganic filler and lithium bistrifluoromethane sulfimide grafted on the surface of the inorganic filler through sulfonyl chloride groups.
The single ion conductor polymer electrolyte provided by the invention comprises a combination of a single ion conductor, an oxide solid electrolyte and a polymer matrix; the ion conductor comprises an inorganic filler and lithium bistrifluoromethanesulfonylimide grafted on the surface of the inorganic filler through sulfonyl chloride groups; the lithium bis (trifluoromethanesulfonyl) imide is fixed on the inorganic filler framework, so that the migration of anions in the lithium bis (trifluoromethanesulfonyl) imide is limited, the problem of concentration polarization of the anions is effectively solved, the migration number of lithium ions in the polymer electrolyte is further improved, and the coulombic efficiency and the cycle performance of the lithium ion solid-state battery containing the single-ion conductor polymer electrolyte are effectively improved.
Preferably, the single-ion conductor is prepared by a method comprising the following steps:
(A1) reacting inorganic filler with methanesulfonyl chloride in a solvent to obtain modified inorganic filler;
(A2) and (D) reacting the modified inorganic filler obtained in the step (A1) with lithium bis (trifluoromethanesulfonyl) imide in a solvent to obtain the single-ion conductor.
In the invention, the preparation of the single-ion conductor is carried out in two steps, firstly, inorganic filler is reacted with methanesulfonyl chloride to obtain sulfonyl chloride-based modified inorganic filler shown in a schematic diagram in figure 1; and then directly mixing the obtained sulfonyl chloride-modified inorganic filler with lithium bis (trifluoromethanesulfonyl) imide to obtain the single-ion conductor of the lithium trifluoromethanesulfonyl imide-modified inorganic filler, wherein the schematic diagram of the single-ion conductor is shown in figure 2.
Preferably, the inorganic filler of step (A1) comprises SiO2Any one or combination of at least two of halloysite, mullite, serpentine, kaolinite, aluminum silicate, magnesium silicate, strontium magnesium silicate or nickel silicate.
Preferably, the mass ratio of the inorganic filler and the methanesulfonyl chloride in the step (A1) is 1 (2-10), such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1: 9.
Preferably, the solvent of step (a1) comprises toluene.
Preferably, the reaction time in the step (A1) is 8-12 h, such as 8.4h, 8.8h, 9.2h, 9.6h, 10h, 10.4h, 10.8h, 11.2h or 11.6 h.
Preferably, the temperature of the reaction in the step (A1) is 60 to 80 ℃, such as 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃ or 78 ℃.
Preferably, the mass ratio of the modified inorganic filler in the step (A2) to the lithium bis (trifluoromethanesulfonylimide) is 1 (2-10), such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1: 9.
Preferably, the solvent of step (a2) comprises acetonitrile.
Preferably, the reaction time in the step (A2) is 12-24 h, such as 14h, 16h, 18h, 20h, 21h, 22h or 23 h.
As a preferred technical scheme of the invention, the preparation method of the single-ion conductor comprises the following steps:
(A1) reacting an inorganic filler and methanesulfonyl chloride in a mass ratio of 1 (2-10) in a solvent for 8-12 h at 60-80 ℃ to obtain a modified inorganic filler;
(A2) and (D) reacting the modified inorganic filler obtained in the step (A1), lithium bis (trifluoromethanesulfonimide) and bipyridine in a solvent for 12-24 h to obtain the single-ion conductor.
Preferably, the mass ratio of the single-ion conductor to the oxide solid electrolyte is (1-3): 1, such as 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1 or 2.8: 1.
As a preferable technical scheme, the mass ratio of the single ion conductor to the oxide solid electrolyte in the single ion conductor polymer solid electrolyte provided by the invention is (1-3): 1, and if the dosage ratio of the single ion conductor is too much, the tensile strength of an electrolyte membrane formed by the obtained single ion conductor polymer electrolyte is reduced; if the amount of the oxide solid electrolyte used therein is too large, the resulting single-ion conductor polymer electrolyte may result in a decrease in the ion transport number of the electrolyte membrane formed therefrom.
Preferably, the oxide solid electrolyte includes any one of a garnet-type oxide solid electrolyte, a NaSICON-type oxide solid electrolyte, or a perovskite-type oxide solid electrolyte or a combination of at least two thereof.
Preferably, the mass ratio of the single ion conductor to the polymer matrix is (0.1-0.5): 1, such as 0.15:1, 0.2:1, 0.25:1, 0.3:1, 0.35:1, 0.4:1 or 0.45: 1.
Preferably, the polymer matrix comprises any one of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, or polyacrylonitrile, or a combination of at least two thereof.
In a second aspect, the present invention provides a method for preparing a single-ion conductor polymer electrolyte according to the first aspect, the method comprising the steps of:
(1) mixing a single-ion conductor and an oxide solid electrolyte in an organic solvent to obtain a suspension;
(2) and (3) mixing a polymer matrix with the suspension obtained in the step (1) to obtain the single-ion conductor polymer electrolyte.
Preferably, the organic solvent in step (1) comprises any one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, or acetonitrile.
Preferably, the mixing of step (1) is carried out under ultrasonic conditions.
Preferably, the mixing time in step (1) is 5-30 min, such as 7min, 9min, 11min, 13min, 15min, 17min, 19min, 21min, 23min, 25min, 27min or 29 min.
Preferably, the mixing of step (2) is carried out in a planetary mixer.
Preferably, the mixing time in the step (2) is 1-3 h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h or 2.8 h.
In a third aspect, the present invention provides a lithium ion solid-state battery comprising the single-ion conductor polymer solid-state electrolyte according to the first aspect, a positive electrode sheet, a negative electrode sheet, and an aluminum plastic film.
Preferably, the positive electrode material in the positive electrode plate comprises any one of lithium cobaltate, a ternary material, lithium iron phosphate, a lithium-rich manganese-based material or spinel-type lithium manganate or a combination of at least two of the materials.
Preferably, the negative electrode material in the negative electrode plate comprises any one or a combination of at least two of graphite, amorphous carbon, lithium titanate, SiOx/C composite material or Sn-based composite material.
In a fourth aspect, the present invention provides a method for manufacturing a lithium-ion solid-state battery according to the third aspect, the method comprising the steps of:
(B1) coating the single-ion conductor polymer electrolyte on the surface of the positive plate to obtain a composite positive electrode; coating the single-ion conductor polymer electrolyte on the surface of the negative plate to obtain a composite negative electrode;
(B2) and (D) superposing the composite positive electrode and the composite negative electrode obtained in the step (B1), and packaging by adopting an aluminum-plastic film to obtain the lithium ion solid-state battery.
Preferably, the step (B1) further includes a step of drying after the coating on the surface of the positive electrode sheet and the coating on the surface of the negative electrode sheet.
Preferably, the drying time is 8-12 h, such as 8.5h, 9h, 9.5h, 10h, 10.5h, 11h or 11.5 h.
Preferably, the drying temperature is 50 to 70 ℃, such as 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃ or 68 ℃.
Preferably, the thickness of the surface coating of the positive electrode sheet and the thickness of the surface coating of the negative electrode sheet after the drying are respectively 20-40 μm, such as 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, 34 μm, 36 μm or 38 μm.
Preferably, the step (B2) further includes the steps of vacuum pumping, heat sealing, hot pressing and cold pressing after the packaging is finished.
Preferably, the heat-sealing temperature is 180-200 ℃, such as 182 ℃, 184 ℃, 186 ℃, 188 ℃, 190 ℃, 192 ℃, 194 ℃, 196 ℃ or 198 ℃.
Preferably, the pressure for heat sealing is 0.1 to 1Mpa, such as 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa or 0.9 Mpa.
Preferably, the heat sealing time is 5-10 s, such as 5.5s, 6s, 6.5s, 7s, 7.5s, 8s, 8.5s, 9s or 9.5 s.
Preferably, the hot pressing temperature is 80 to 100 ℃, such as 82 ℃, 84 ℃, 86 ℃, 88 ℃, 100 ℃, 102 ℃, 104 ℃, 106 ℃ or 108 ℃.
Preferably, the pressure of the hot pressing and the pressure of the cold pressing are respectively and independently 0.1 to 0.5Mpa, such as 0.15Mpa, 0.2Mpa, 0.25Mpa, 0.3Mpa, 0.35Mpa, 0.4Mpa or 0.45 Mpa.
Preferably, the time of the hot pressing and the cold pressing is 20-300 s, such as 50s, 80s, 110s, 140s, 170s, 200s, 230s, 260s or 290s, and the like.
Preferably, the cold pressing temperature is 20 to 30 ℃, such as 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃ or 29 ℃ and the like.
Compared with the prior art, the invention has the following beneficial effects:
the single ion conductor polymer electrolyte provided by the invention comprises a combination of a single ion conductor, an oxide solid electrolyte and a polymer matrix; the single ion conductor comprises inorganic filler and a conductive materialBis (trifluoromethanesulfonyl) imide grafted on the surface of the inorganic filler through sulfonyl chloride; the bis (trifluoromethanesulfonyl) imide is fixed on an inorganic filler framework to limit the migration of anions in the inorganic filler framework, so that the problem of concentration polarization generated by the anions can be effectively solved, and further the migration number of lithium ions can be effectively improved, and particularly, the migration number of ions of the single-ion conductor polymer electrolyte is 0.4-0.72, and the ionic conductivity is 7.46 multiplied by 10-5～2.42×10-4S/cm, the coulombic efficiency and the cycle performance of the lithium ion solid-state battery containing the single-ion conductor polymer electrolyte are effectively improved, and specifically, the cycle times at 25 ℃ of the lithium ion solid-state battery containing the single-ion conductor polymer electrolyte provided by the invention are 68-78 times, and the cycle times at 45 ℃ are 76-86 times.
Drawings
FIG. 1 is a schematic view of the structure of a sulfonyl chloride-based modified inorganic filler in preparation example 1;
FIG. 2 is a schematic structural diagram of a single-ion conductor of the lithium trifluoromethanesulfonimide-modified inorganic filler obtained in preparation example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A single ion conductor is prepared by the following steps:
(1) SiO with the mass ratio of 1:5 at 70 DEG C2And methanesulfonyl chloride in toluene for 10h to obtain a sulfonyl chloride-based modified inorganic filler shown in the schematic diagram of FIG. 1;
(2) the modified SiO obtained in the step (A1) with the mass ratio of 1:52Reacting the compound with lithium bis (trifluoromethanesulfonyl) imide in acetonitrile for 20h to obtain the single-ion conductor of the lithium trifluoromethanesulfonyl imide modified inorganic filler shown in a schematic diagram in figure 2.
Preparation example 2
A single ion conductor is prepared by the following steps:
(1) reacting halloysite and methanesulfonyl chloride in a mass ratio of 1:2 in toluene at 60 ℃ for 12 hours to obtain modified halloysite;
(2) and (3) reacting the modified halloysite obtained in the step (A1) with lithium bis (trifluoromethanesulfonyl) imide in a mass ratio of 1:2 in acetonitrile for 24h to obtain the single-ion conductor.
Preparation example 3
A single ion conductor is prepared by the following steps:
(1) reacting kaolinite and methanesulfonyl chloride in a mass ratio of 1:10 in toluene for 8 hours at 80 ℃ to obtain modified kaolinite;
(2) and (3) reacting the modified kaolinite obtained in the step (A1) with lithium bis (trifluoromethanesulfonyl) imide in a mass ratio of 1:10 in acetonitrile for 12h to obtain the single-ion conductor.
Example 1
A single ion conductor polymer electrolyte comprising a single ion conductor (preparation example 1), a garnet-type oxide solid electrolyte (LLZO) and polyethylene oxide (Aladdin, 68441-17-8) in a mass ratio of 2:1: 10;
the preparation method comprises the following steps:
(1) placing a single-ion conductor and garnet type oxide solid electrolyte in N-methyl pyrrolidone, and dispersing for 15min by ultrasonic to obtain a suspension;
(2) mixing polyethylene oxide with the suspension obtained in the step (1), and stirring for 2h by a planetary mixer to obtain the single-ion conductor polymer electrolyte.
Example 2
A single-ion conductor polymer electrolyte comprises a single-ion conductor (preparation example 2) with a mass ratio of 1:1:10, a NaSICON type oxide solid electrolyte (LATP) and polyvinylidene fluoride (Achima, HSV 761);
the preparation method comprises the following steps:
(1) placing a single-ion conductor and a NaSICON type oxide solid electrolyte in N, N-dimethylformamide, and dispersing for 5min by ultrasonic to obtain a suspension;
(2) and (2) mixing polyvinylidene fluoride and the suspension obtained in the step (1), and stirring for 1h by using a planetary stirrer to obtain the single-ion conductor polymer electrolyte.
Example 3
A single ion conductor polymer electrolyte comprising a single ion conductor (preparation example 3), a perovskite type oxide solid electrolyte (LLTO), and polyvinylidene fluoride-hexafluoropropylene (suwei, 21510) in a mass ratio of 3:1: 20;
the preparation method comprises the following steps:
(1) placing a single-ion conductor and a perovskite type oxide solid electrolyte in acetonitrile, and performing ultrasonic dispersion for 30min to obtain a suspension;
(2) and (2) mixing polyvinylidene fluoride-hexafluoropropylene with the suspension obtained in the step (1), and stirring for 3 hours by using a planetary stirrer to obtain the single-ion conductor polymer electrolyte.
Example 4
A single-ion conductor polymer electrolyte, which is different from example 1 only in that the mass ratio of the single-ion conductor to the garnet-type oxide solid electrolyte is 0.5:1, and the other components, the amounts and the preparation method are the same as those of example 1.
Example 5
A single-ion conductor polymer electrolyte, which is different from example 1 only in that the mass ratio of the single-ion conductor to the garnet-type oxide solid electrolyte is 4:1, and the other components, the amounts and the preparation method are the same as those of example 1.
Comparative example 1
A polymer electrolyte, which comprises SiO with the mass ratio of 2:2:1:102Lithium bistrifluoromethanesulfonylimide, garnet-type oxide solid electrolytes, and polyethylene oxide (alatin, 68441-17-8);
the preparation method comprises the following steps: mixing SiO2Dispersing in N-methyl pyrrolidone for 15min, adding polyoxyethylene and garnet type oxide solid electrolyte, mixing in planetary stirrer for 30min, adding lithium bis (trifluoromethanesulfonyl) imide, mixing in planetary stirrer for 1h to obtain the final productThe polymer electrolyte is described.
And (3) performance testing:
(1) and (3) ion conductivity test: manufacturing a symmetrical battery of stainless steel sheets, arranging an elastic sheet and a stainless steel gasket in the middle of a negative electrode shell respectively with an upward opening of the negative electrode shell, clamping a solid electrolyte membrane to cover the stainless steel gasket, clamping a stainless steel sheet to cover the solid electrolyte membrane in addition, strictly aligning, clamping a positive electrode shell to cover, then arranging a negative electrode of the button battery on a sealing die of the button battery upwards by using tweezers, adjusting the pressure to 10MPa, and maintaining the pressure for 5s to assemble the button battery. EIS testing using an electrochemical workstation, frequency range 106-1And Hz, the amplitude is 5mV, the ionic conductivity of the electrolyte membrane is calculated by utilizing the formula of ionic conductivity sigma L/(R multiplied by A), wherein L is the thickness of the electrolyte membrane, A is the effective area of the electrolyte membrane, R is the bulk resistance of the electrolyte membrane, and the resistance value at the intersection point of the EIS graph and the solid axis is taken as the ionic conductivity.
(2) Ion transport number test: manufacturing a lithium-lithium symmetric battery, wherein the opening of a negative shell faces upwards, placing an elastic sheet and a gasket in the middle of the negative shell in sequence, clamping a lithium sheet on a steel gasket, strictly aligning, clamping a solid electrolyte membrane to cover the lithium sheet, clamping a lithium sheet to cover the solid electrolyte membrane, strictly aligning, clamping a gasket to cover the lithium sheet, strictly aligning, clamping a positive shell to cover, placing a button battery with the negative electrode facing upwards on a button battery sealing mould by using tweezers, adjusting the pressure to 10MPa, maintaining the pressure for 5s, and finishing the assembly of the lithium-lithium symmetric battery; adopting an electrochemical workstation to carry out direct current polarization, testing EIS before and after cell polarization, and utilizing a formula ion migration number t+＝[I×(ΔV-I0R0)]/[I0×(ΔV-IR)]Calculating the ion transference number, I, of the electrolyte membrane0Is the intercept point of the y-axis during polarization, I is the value of the steady state during electric polarization, R0Is the pre-polarization resistance value, R is the post-polarization resistance value, and Δ V is the bias voltage.
(3) And (3) testing the cycle performance: manufacturing a lithium ion solid-state battery, coating a single-ion conductor polymer electrolyte on the surface of a positive plate (the positive plate comprises 97 wt% of NCM ternary material, 1 wt% of carbon black, 1 wt% of PVDF and an aluminum foil with the thickness of 12 mu m), and drying at 60 ℃ for 10 hours to obtain a composite positive electrode with the coating thickness of 30 mu m; coating a single-ion conductor polymer electrolyte on the surface of a negative plate (the negative plate comprises 80 wt% of graphite, 15 wt% of silica active substance, 2 wt% of carbon nano tube and carbon black, 3 wt% of PAA and copper foil with the thickness of 8 mu m), and drying at 60 ℃ for 10h to obtain a composite negative electrode with the coating thickness of 30 mu m; superposing the obtained composite anode and the composite cathode to enable the capacity of the obtained soft package solid-state battery to be 1200mA/h, packaging by adopting an aluminum-plastic film, vacuumizing, carrying out heat sealing at 190 ℃ and 0.5MPa for 7s, carrying out hot pressing at 90 ℃ and 0.25MPa for 150s, and carrying out cold pressing at 25 ℃ and 0.25MPa for 150s to obtain the lithium ion solid-state battery; and (3) testing the cycle times of the solid-state battery with a blue tester under the condition of 0.2C when the capacity of the solid-state battery reaches 80% at the temperature of 45 ℃ and 25 ℃ respectively to obtain the cycle performance.
The single ion conductor polymer electrolytes obtained in examples 1 to 5 and comparative example 1 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
Figure BDA0003399459320000111
Figure BDA0003399459320000121
As can be seen from the data in table 1: the single-ion conductor polymer electrolyte provided by the invention has higher ion migration number and higher ion conductivity, and the lithium ion battery prepared by adopting the electrolyte has more excellent cycle performance; specifically, the single ion conductive polymer electrolytes obtained in examples 1 to 5 had an ion transport number of 0.4 to 0.72 and an ion conductivity of 7.46X 10-5～2.42×10-4S/cm, 68-78 times of circulation at 25 ℃ and 76-86 times of circulation at 45 ℃.
Comparing example 1 with comparative example 1, it can be found that the ion transport number and ion conductivity of the general polymer solid electrolyte provided in the prior art are lower, and further the cycle number of the prepared lithium ion battery is lower, which proves that the cycle performance is poorer.
Further comparing examples 1 and 4-5, it can be found that the low addition amount of the single ion conductor in the single ion conductor polymer electrolyte (example 4) and the low addition amount of the garnet-type oxide solid electrolyte (example 5) both affect the cycle performance of the prepared lithium ion battery.
The applicant states that the present invention is illustrated by the above examples to a single ion conductor polymer electrolyte and its preparation method and application, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A single ion conductor polymer electrolyte, comprising a combination of a single ion conductor, an oxide solid state electrolyte, and a polymer matrix;
the single-ion conductor comprises an inorganic filler and lithium bistrifluoromethane sulfimide grafted on the surface of the inorganic filler through sulfonyl chloride groups.
2. The single ion conductor polymer electrolyte of claim 1 wherein the single ion conductor is prepared by a process comprising the steps of:
(A1) reacting inorganic filler with methanesulfonyl chloride in a solvent to obtain modified inorganic filler;
(A2) reacting the modified inorganic filler obtained in the step (A1) with lithium bistrifluoromethanesulfonimide in a solvent to obtain the single-ion conductor;
preferably, the inorganic filler of step (A1) comprises SiO2Halloysite, mullite, serpentine, kaolinite, aluminum silicate, magnesium silicate, silicic acidAny one or a combination of at least two of magnesium strontium or nickel silicate;
preferably, the mass ratio of the inorganic filler to the methanesulfonyl chloride in the step (A1) is 1 (2-10);
preferably, the solvent of step (a1) comprises toluene;
preferably, the reaction time of the step (A1) is 8-12 h;
preferably, the temperature of the reaction in the step (A1) is 60-80 ℃;
preferably, the mass ratio of the modified inorganic filler in the step (A2) to the lithium bis (trifluoromethanesulfonyl) imide is 1 (2-10);
preferably, the solvent of step (a2) comprises acetonitrile;
preferably, the reaction time of the step (A2) is 12-24 h.
3. The single ion conductor polymer electrolyte according to claim 1 or 2, wherein the mass ratio of the single ion conductor to the oxide solid electrolyte is (1-3): 1;
preferably, the oxide solid electrolyte includes any one of a garnet-type oxide solid electrolyte, a NaSICON-type oxide solid electrolyte, or a perovskite-type oxide solid electrolyte or a combination of at least two thereof.
4. The single ion conductor polymer electrolyte of any of claims 1 to 3, wherein the mass ratio of the single ion conductor to the polymer matrix is (0.1-0.5): 1;
preferably, the polymer matrix comprises any one of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, or polyacrylonitrile, or a combination of at least two thereof.
5. A method for preparing the single ion conductor polymer electrolyte as defined in any one of claims 1 to 4, wherein the method comprises the steps of:
(1) mixing a single-ion conductor and an oxide solid electrolyte in an organic solvent to obtain a suspension;
(2) and (3) mixing a polymer matrix with the suspension obtained in the step (1) to obtain the single-ion conductor polymer electrolyte.
6. The method according to claim 5, wherein the organic solvent of step (1) comprises any one of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, or acetonitrile;
preferably, the mixing of step (1) is carried out under ultrasonic conditions;
preferably, the mixing time in the step (1) is 5-30 min;
preferably, the mixing of step (2) is performed in a planetary mixer;
preferably, the mixing time in the step (2) is 1-3 h.
7. A lithium ion solid-state battery comprising the single-ion conductor polymer solid-state electrolyte according to any one of claims 1 to 4, a positive electrode sheet, a negative electrode sheet and an aluminum plastic film.
8. The lithium ion solid-state battery according to claim 7, wherein the positive electrode material in the positive electrode sheet comprises any one of lithium cobaltate, a ternary material, lithium iron phosphate, a lithium-rich manganese-based material or spinel-type lithium manganate or a combination of at least two of the above materials;
preferably, the negative electrode material in the negative electrode plate comprises any one or a combination of at least two of graphite, amorphous carbon, lithium titanate, SiOx/C composite material or Sn-based composite material.
9. A method for producing the lithium-ion solid-state battery according to claim 7 or 8, comprising the steps of:
(B1) coating the single-ion conductor polymer electrolyte on the surface of the positive plate to obtain a composite positive electrode; coating the single-ion conductor polymer electrolyte on the surface of the negative plate to obtain a composite negative electrode;
(B2) and (D) superposing the composite positive electrode and the composite negative electrode obtained in the step (B1), and packaging by adopting an aluminum-plastic film to obtain the lithium ion solid-state battery.
10. The manufacturing method according to claim 9, wherein the step (B1) further comprises a step of drying after coating on the surface of the positive electrode sheet and after coating on the surface of the negative electrode sheet;
preferably, the drying time is 8-12 h;
preferably, the drying temperature is 50-70 ℃;
preferably, the thicknesses of the surface coating of the positive plate and the surface coating of the negative plate after drying are respectively and independently 20-40 μm;
preferably, the step (B2) further comprises the steps of vacuum pumping, heat sealing, hot pressing and cold pressing after the packaging is finished;
preferably, the heat sealing temperature is 180-200 ℃;
preferably, the pressure of the heat sealing is 0.1-1 MPa;
preferably, the heat sealing time is 5-10 s;
preferably, the hot pressing temperature is 80-100 ℃;
preferably, the pressure of the hot pressing and the pressure of the cold pressing are respectively and independently 0.1-0.5 MPa;
preferably, the time of the hot pressing and the time of the cold pressing are respectively and independently 20-300 s;
preferably, the cold pressing temperature is 20-30 ℃.
CN202111491263.3A 2021-12-08 2021-12-08 Single-ion conductor polymer electrolyte and preparation method and application thereof Pending CN114204115A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117497842A (en) * 2023-12-27 2024-02-02 江苏蓝固新能源科技有限公司 Polymer electrolyte, preparation method and application thereof in secondary battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117497842A (en) * 2023-12-27 2024-02-02 江苏蓝固新能源科技有限公司 Polymer electrolyte, preparation method and application thereof in secondary battery
CN117497842B (en) * 2023-12-27 2024-03-12 江苏蓝固新能源科技有限公司 Polymer electrolyte, preparation method and application thereof in secondary battery

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