CN110336072B - Double-polymer composite solid electrolyte, electrolyte membrane and in-situ preparation method thereof - Google Patents

Double-polymer composite solid electrolyte, electrolyte membrane and in-situ preparation method thereof Download PDF

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CN110336072B
CN110336072B CN201910480021.0A CN201910480021A CN110336072B CN 110336072 B CN110336072 B CN 110336072B CN 201910480021 A CN201910480021 A CN 201910480021A CN 110336072 B CN110336072 B CN 110336072B
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solid electrolyte
polymer monomer
solution
polymer
drying
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CN110336072A (en
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孟繁慧
刘婧
郑涛
高凡
周江
伍绍中
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Tianjin Juyuan New Energy Technology Co ltd
Tianjin Lishen Battery JSCL
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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
    • H01M10/052—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
    • H01M10/0561—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
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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
    • H01M2300/00—Electrolytes
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    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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    • H01M2300/0091—Composites in the form of mixtures
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Abstract

The invention discloses an in-situ preparation method of a double-polymer composite solid electrolyte, which comprises the following steps: firstly, dissolving 2-cyano-ethyl acrylate in a micromolecular solvent to prepare a first polymer monomer solution; secondly, dissolving 1, 3-dioxolane in a small molecular solvent to prepare a second polymer monomer solution; dissolving a polymerization initiator and lithium salt in a small molecular solvent to prepare a polymerization initiation solution; fourthly, mixing the two polymer monomer solutions to obtain a first mixed solution; fifthly, mixing the polymerization reaction initiating solution with the first mixed solution to obtain a solid electrolyte solution; and sixthly, drying the solid electrolyte solution to obtain the composite solid electrolyte. The invention also discloses a double-polymer composite solid electrolyte, a solid electrolyte membrane and a preparation method. The invention can improve the room-temperature conductivity of the solid electrolyte, widen the electrochemical window, improve the mechanical strength and solve the problem of poor interface contact of the solid electrolyte.

Description

Double-polymer composite solid electrolyte, electrolyte membrane and in-situ preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a double-polymer composite solid electrolyte, an electrolyte membrane and an in-situ preparation method thereof.
Background
At present, the lithium ion battery has the advantages of high voltage, high specific energy, more recycling times, long storage time and the like, is widely applied to the fields of consumer electronics, new energy automobiles, energy storage and the like, and has important research on electrical performance, service life and safety performance.
Solid-state lithium ion batteries have received much attention due to their high energy density and high safety. The solid-state battery utilizes the chemical inertia and high-strength mechanical characteristics of the solid electrolyte, can inhibit the occurrence of side reactions in the battery and inhibit the formation of lithium dendrites, further optimizes and promotes the safety of the lithium battery, and provides a solution for the application of lithium metal in the lithium ion battery. Currently, solid electrolytes of solid lithium ion batteries, including oxide electrolytes, sulfide electrolytes, and polymer electrolytes, are widely studied. Wherein, the polymer solid electrolyte has good elasticity, easy film formation and good mechanical processing performance, and is easy for industrialized production.
However, the problems of the polymer solid electrolyte, such as the variation in the ionic conductivity, electrochemical window, mechanical strength, and other properties, and the poor contact between the heterogeneous interfaces, are also one of the key problems that always restrict the large-scale application of the polymer electrolyte.
Therefore, in view of the above problems of the polymer solid electrolyte, a polymer solid electrolyte technology is needed to improve the room temperature conductivity of the solid electrolyte, widen the electrochemical window, and improve the mechanical strength, and at the same time, to achieve soft contact between the solid electrolyte and the electrode active material and between the solid electrolyte and the electrode, and to effectively solve the solid-solid interface problem between the solid electrolyte and the electrode active material, and between the solid electrolyte and the electrode.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a dual polymer composite solid electrolyte, an electrolyte membrane and an in-situ preparation method thereof, which can improve the room-temperature conductivity of the solid electrolyte, widen the electrochemical window, improve the mechanical strength, and simultaneously realize soft contact between the solid electrolyte and the electrode active material and between the solid electrolyte and the electrode, effectively solve the solid-solid interface problem between the solid electrolyte and the electrode active material, and between the solid electrolyte and the electrode, and have great practical significance.
To this end, the present invention provides a biopolymer composite solid electrolyte comprising: comprises 2 to 72 percent of first polymer component, 2 to 72 percent of second polymer component and 0.5 to 30 percent of lithium salt by mass percentage.
Wherein the first polymer component is 1, 3-dioxolane;
the second polymer component is poly-2-cyano-ethyl acrylate;
the lithium salt includes LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 At least one of (1).
In addition, the present invention also provides an in-situ preparation method of the biopolymer composite solid electrolyte according to claim 1, comprising the steps of:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile small molecular solvent to prepare a polymerization initiation liquid;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
and sixthly, placing the solid electrolyte solution in a dry atmosphere for primary drying, and then placing the solid electrolyte solution in a vacuum box for secondary drying to finally obtain the composite solid electrolyte.
In the first step, in the first polymer monomer solution, the mass content of 2-cyano-ethyl acrylate is 20-100%, and the mass content of a small molecular solvent is 0-80%;
in the second step, in the second polymer monomer solution, the mass content of 1, 3-dioxolane is 20-100%, and the mass content of a small molecular solvent is 0-80%;
in the first, second and third steps, the small molecule solvent comprises at least one of N-methylpyrrolidone, NMP, dimethyl carbonate, DMC, dimethylacetamide, DMAC, and acetonitrile AN.
Wherein, in the third step, the lithium salt comprises LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 And at least one of lithium salts;
in the third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum tris (trifluoromethyl-sulfonate);
in the third step, the molar concentration of the initiator in the polymerization initiating solution is 0-0.01M;
in the third step, the mass percentage of the lithium salt in the initiation liquid of the polymerization reaction is 5-60%.
Wherein, in the fourth step, the mass ratio of the first polymer monomer solution obtained in the first step to the first polymer monomer solution obtained in the second step is 20-80;
in the fifth step, in the solid electrolyte solution obtained by mixing the polymerization reaction initiating solution obtained in the third step and the first mixed solution obtained in the fourth step, the mass content of the polymerization reaction initiating solution is 10 to 50%, and the mass content of the first mixed solution is 50 to 90%.
Wherein, in the sixth step, when the solid electrolyte solution is placed in a drying atmosphere for primary drying, the drying temperature is 30-120 ℃, and the drying time is 1-20 hours;
and then, carrying out secondary drying in a vacuum box at the drying temperature of 30-120 ℃ for 1-60 hours to finally obtain the composite solid electrolyte.
In addition, the invention also provides a double polymer composite solid electrolyte membrane which comprises the double polymer composite solid electrolyte.
In addition, the invention also provides an in-situ preparation method of the double-polymer composite solid electrolyte membrane, which comprises the following steps:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile small molecular solvent to prepare a polymerization initiation liquid;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
and sixthly, coating the solid electrolyte solution in a mold of the electrolyte membrane, then placing the mold in a dry atmosphere for primary drying, and then placing the mold in a vacuum box for secondary drying to finally obtain the composite solid electrolyte membrane.
In the first step, in the first polymer monomer solution, the mass content of 2-cyano-ethyl acrylate is 20-100%, and the mass content of a small molecular solvent is 0-80%;
in the second step, in the second polymer monomer solution, the mass content of 1, 3-dioxolane is 20-100%, and the mass content of a small molecular solvent is 0-80%;
in the first step and the second step, the small molecule solvent comprises at least one of N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC), dimethylacetamide (DMAC) and acetonitrile AN;
in the third step, the lithium salt includes LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 And at least one of lithium salts;
in the third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum tris (trifluoromethyl-sulfonate);
in the third step, the molar concentration of the initiator in the polymerization reaction initiating solution is 0-0.01M;
in the third step, the mass percentage of the lithium salt in the initiation liquid of the polymerization reaction is 5-60%.
Wherein, in the fourth step, the mass ratio of the first polymer monomer solution obtained in the first step to the first polymer monomer solution obtained in the second step is 20-80;
in the fifth step, in the solid electrolyte solution obtained by mixing the polymerization initiation liquid obtained in the third step and the first mixed solution obtained in the fourth step, the mass content of the polymerization initiation liquid is 10 to 50%, and the mass content of the first mixed solution is 50 to 90%;
in the sixth step, when the solid electrolyte solution is placed in a drying atmosphere for primary drying, the drying temperature is 30-120 ℃, and the drying time is 1-20 hours;
and then, coating the solid electrolyte solution in a mold of the electrolyte membrane, and then placing the mold in a vacuum box for secondary drying at the drying temperature of 30-120 ℃ for 1-60 hours to finally obtain the composite solid electrolyte membrane.
Compared with the prior art, the technical scheme provided by the invention has the advantages that the double-polymer composite solid electrolyte, the electrolyte membrane and the in-situ preparation method thereof can improve the room-temperature conductivity of the solid electrolyte, widen the electrochemical window and improve the mechanical strength, can realize the soft contact between the solid electrolyte and the electrode active material and between the solid electrolyte and the electrode, effectively solve the solid-solid interface problem between the solid electrolyte and the electrode active material and between the solid electrolyte and the electrode, and have great practical significance.
Drawings
FIG. 1 is a flow chart of an in situ preparation method of a biopolymer composite solid electrolyte provided by the invention;
FIG. 2 is a flow chart of a method for the in situ preparation of a biopolymer composite solid electrolyte membrane according to the present invention;
FIG. 3 is a schematic view showing a conductivity test curve of a solid electrolyte membrane prepared in example 1 using an in-situ preparation method of a biopolymer composite solid electrolyte membrane according to the present invention;
FIG. 4 is a schematic view of a conductivity test curve of the solid electrolyte membrane prepared in example 2 using the in situ preparation method of a biopolymer composite solid electrolyte membrane according to the present invention;
fig. 5 is a schematic view showing a conductivity test curve of the solid electrolyte membrane prepared in example 3 using the in-situ preparation method of a biopolymer composite solid electrolyte membrane according to the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the accompanying drawings and embodiments.
The invention provides a double-polymer composite solid electrolyte, which comprises 2-72% of a first polymer component, 2-72% of a second polymer component and 0.5-30% of lithium salt by mass percent.
Wherein the first polymer component is 1, 3-dioxolane;
the second polymer component is poly-2-cyano-ethyl acrylate;
the lithium salt includes LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 And the like.
Referring to fig. 1, in order to prepare the above-mentioned dual polymer composite solid electrolyte, the present invention provides an in-situ preparation method of a dual polymer composite solid electrolyte, which adopts a synergistic effect of dual in-situ polymerization to prepare the dual polymer composite solid electrolyte, and specifically comprises the following steps:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile small molecular solvent to prepare a polymerization initiation liquid;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
and sixthly, placing the solid electrolyte solution in a dry atmosphere (such as a drying oven filled with nitrogen) for primary drying, and then placing the solid electrolyte solution in a vacuum oven for secondary drying to finally obtain the composite solid electrolyte.
For the present invention, in the fourth step, in particular, the first polymer monomer solution obtained in the first step and the second polymer monomer solution obtained in the second step may be mixed by mass according to the formula of the desired composite solid electrolyte.
In the first step, the mass content of the 2-cyano-ethyl acrylate in the first polymer monomer solution is 20-100%, and the mass content of the small molecular solvent is 0-80%.
In the second step, the mass content of the 1, 3-dioxolane in the second polymer monomer solution is 20-100%, and the mass content of the small molecular solvent is 0-80%.
In the first step, the second step and the third step, the small molecule solvent comprises at least one of N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC), dimethylacetamide (DMAC) and Acetonitrile (AN).
In a third step, the lithium salt comprises LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 And the like.
In a third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum tris (trifluoromethyl-sulfonate).
In the third step, the molar concentration of the initiator in the polymerization initiating solution is 0-0.01M.
In the third step, the mass percentage of the lithium salt in the initiation liquid of the polymerization reaction is 5-60%.
Specifically, in the fourth step, the mass ratio of the first polymer monomer solution obtained in the first step to the first polymer monomer solution obtained in the second step is 20 to 80.
Specifically, in the fifth step, in the solid electrolyte solution obtained by mixing the polymerization initiation liquid obtained in the third step and the first mixed solution obtained in the fourth step, the mass content of the polymerization initiation liquid is 10 to 50%, and the mass content of the first mixed solution is 50 to 90%.
In the sixth step, when the solid electrolyte solution is placed in a dry atmosphere for first drying, the drying temperature is 30-120 ℃, and the drying time is 1-20 hours;
and then, carrying out secondary drying in a vacuum box at the drying temperature of 30-120 ℃ for 1-60 hours to finally obtain the composite solid electrolyte.
Further, with respect to the present invention, the present invention also provides a two-polymer composite solid electrolyte membrane comprising the aforementioned two-polymer composite solid electrolyte.
Referring to fig. 2, in order to prepare the above-mentioned biopolymer composite solid electrolyte membrane, the present invention provides an in-situ preparation method of a biopolymer composite solid electrolyte membrane, which adopts a synergistic effect of dual in-situ polymerization reactions to prepare the biopolymer composite solid electrolyte membrane, and specifically comprises the following steps:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile small molecular solvent to prepare a polymerization initiation liquid;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiating solution obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
and sixthly, coating the solid electrolyte solution in a mold of the electrolyte membrane, then placing the mold in a dry atmosphere (such as a drying box filled with nitrogen) for primary drying, and then placing the mold in a vacuum box for secondary drying to finally obtain the composite solid electrolyte membrane.
For the present invention, in the fourth step, specifically, the mass ratio of the first polymer monomer solution obtained in the first step and the second polymer monomer solution obtained in the second step may be determined according to the formula of the desired composite solid electrolyte.
Specifically, in the first step, the mass content of the 2-cyano-ethyl acrylate in the first polymer monomer solution is 20-100%, and the mass content of the small molecular solvent is 0-80%.
In the second step, the mass content of the 1, 3-dioxolane in the second polymer monomer solution is 20-100%, and the mass content of the small molecular solvent is 0-80%.
In the first step, the second step and the third step, the small molecule solvent comprises at least one of N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC), dimethylacetamide (DMAC) and Acetonitrile (AN).
In a third step, the lithium salt comprises LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 And the like.
In a third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum tris (trifluoromethyl-sulfonate).
In the third step, the molar concentration of the initiator in the polymerization initiating solution is 0-0.01M.
In the third step, the molar concentration of the lithium salt in the polymerization initiation liquid is 0.1-6M.
Specifically, in the fourth step, the mass ratio of the first polymer monomer solution obtained in the first step to the first polymer monomer solution obtained in the second step is 20 to 80.
Specifically, in the fifth step, in the solid electrolyte solution obtained by mixing the polymerization initiation liquid obtained in the third step and the first mixed solution obtained in the fourth step, the mass content of the polymerization initiation liquid is 10 to 50%, and the mass content of the first mixed solution is 50 to 90%.
In the sixth step, the solid electrolyte solution is coated in a die of the electrolyte membrane, and then the die is placed in a drying atmosphere for first drying, wherein the drying temperature is 30-120 ℃, and the drying time is 1-20 hours;
and then, carrying out secondary drying in a vacuum box at the drying temperature of 30-120 ℃ for 1-60 hours to finally obtain the composite solid electrolyte membrane.
In order to more clearly understand the technical solution of the present invention, the technical solution of the present invention is explained below by specific examples.
Example 1.
In example 1, the in-situ preparation method of a biopolymer composite solid electrolyte membrane provided by the present invention specifically includes the following steps:
the method comprises the following steps of firstly, preparing 100g of polymer monomer 2-ethyl cyanoacrylate solution (namely first polymer monomer solution), wherein 80g of polymer monomer 2-ethyl cyanoacrylate and 20g of small molecule solvent DMC are contained for standby.
In the second step, 100g of a polymer monomer 1, 3-dioxolane solution (i.e., a second polymer monomer solution) containing 80g of the polymer monomer 1, 3-dioxolane and 20g of a small molecule solvent DMC was prepared for use.
In the third step, the polymerization initiator aluminum trifluoromethanesulfonate Al (OTf) 3 、LiPF 6 Dissolving in DMC to obtain the trigger solution of aluminium triflate Al (OTf) 3 In a concentration of 0.02M and LiPF 6 The mass percentage of the active ingredients is 20 percent for standby.
And step four, mixing the polymer monomer 2-ethyl cyanoacrylate solution obtained in the step one with the polymer monomer 1, 3-dioxolane solution obtained in the step two according to the mass ratio of 1.
And step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution (namely the polymer monomer mixed solution) obtained in the step four according to a mass ratio of 1.
And sixthly, coating the solid electrolyte solution in a die of an electrolyte membrane, then placing the die in a drying atmosphere for drying at the drying temperature of 60 ℃ for 20 hours, and then performing secondary drying in a vacuum box at the drying temperature of 80 ℃ for 60 hours to obtain the composite solid electrolyte membrane.
For the present invention, in example 1, the resulting composite solid electrolyte membrane was subjected to an ionic conductivity test to give a conductivity of 2.8 x 10 -4 S/cm. See fig. 3 for an illustration. Fig. 3 is an electrochemical impedance spectrum of the composite solid electrolyte membrane, in which the abscissa Z "and Z' are the imaginary part and the real part of the impedance, respectively, and the curve in the diagram can simulate the ionic resistance R of the solid electrolyte membrane, and the electrical conductivity σ can be calculated by the formula σ = L/RS, where L and S are the thickness and the area of the solid electrolyte membrane, respectively. Conductivity sigma of 2.8 x 10 at room temperature -4 S/cm, which shows that the solid electrolyte has high ionic conductivity at normal temperature, and the solid battery is expected to work normally at normal temperature.
Example 2.
In embodiment 2, the in-situ preparation method of the biopolymer composite solid electrolyte membrane provided by the invention specifically comprises the following steps:
in the first step, 100g of a polymer monomer ethyl 2-cyanoacrylate solution (i.e., a first polymer monomer solution) is taken for standby.
In the second step, 100g of a polymer monomer 1, 3-dioxolane solution (i.e., a second polymer monomer solution) containing 20g of the polymer monomer 1, 3-dioxolane and 80g of a small molecule solvent DMC was prepared for use.
Thirdly, carrying out polymerization reaction on initiators of azobisisobutyronitrile and LiPF 6 Dissolving in DMC to obtain trigger solution of azodiisobutyronitrile (0.01M) and LiPF 6 5 percent for standby.
And step four, mixing the polymer monomer 2-ethyl cyanoacrylate solution obtained in the step one with the polymer monomer 1, 3-dioxolane solution obtained in the step two according to a required composite solid electrolyte formula, and stirring to obtain a first mixed solution (namely a polymer monomer mixed solution) according to a mass ratio of 1.
And step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution (namely the polymer monomer mixed solution) obtained in the step four according to a mass ratio of 1.
And sixthly, coating the solid electrolyte solution in a mold of the electrolyte membrane, then putting the mold into a drying atmosphere for drying at the drying temperature of 60 ℃ for 20 hours, and then carrying out secondary drying in a vacuum box at the drying temperature of 120 ℃ for 1 hour to obtain the composite solid electrolyte membrane.
For the present invention, in example 2, the resulting composite solid electrolyte membrane was subjected to an ion conductivity test to give a conductivity of 3.1 x 10 -4 S/cm. As shown in fig. 4. FIG. 4 is an electrochemical impedance spectrum of the composite solid electrolyte membrane, wherein the horizontal and vertical coordinates Z 'and Z' are the imaginary part and the real part of the impedance, respectively, and the curve in the diagram can simulate the ionic resistance R of the solid electrolyte membrane, and the conductivity sigma can be expressed by the formulaσ = L/RS, where L, S are the solid electrolyte membrane thickness and area, respectively. Electrical conductivity sigma of 3.1 x 10 at room temperature -4 S/cm, which shows that the solid electrolyte has high ionic conductivity at normal temperature, and the solid battery is expected to work normally at normal temperature.
Example 3.
In embodiment 3, the in-situ preparation method of the biopolymer composite solid electrolyte membrane provided by the invention specifically comprises the following steps:
in the first step, 100g of a polymer monomer ethyl 2-cyanoacrylate solution (i.e., a first polymer monomer solution) is prepared, wherein the solution contains 20g of the polymer monomer ethyl 2-cyanoacrylate and 80g of a small molecule solvent DMC for standby.
In the second step, 100g of a solution of the polymer monomer 1, 3-dioxolane (i.e., a second polymer monomer solution) is taken for use.
And thirdly, dissolving a polymerization initiator benzoyl peroxide and LiFSI in DMC to prepare a polymerization initiation liquid, wherein the concentration of the benzoyl peroxide is 0.01M, and the mass percentage of the LiFSI is 60% for later use.
And step four, mixing the polymer monomer 2-ethyl cyanoacrylate solution obtained in the step one with the polymer monomer 1, 3-dioxolane solution obtained in the step two according to a mass ratio of 1.
And step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution (namely the polymer monomer mixed solution) obtained in the step four according to a mass ratio of 1.
And sixthly, coating the solid electrolyte solution in a die of an electrolyte membrane, then placing the die in a drying atmosphere for drying at the drying temperature of 30 ℃ for 20 hours, and then performing secondary drying in a vacuum box at the drying temperature of 120 ℃ for 1 hour to obtain the composite solid electrolyte membrane.
For the present invention, in example 3, the ion conductivity of the resulting composite solid electrolyte membrane was carried outThe test gave a conductivity of 3.5 x 10 -4 S/cm. See fig. 5 for an illustration. Fig. 5 is an electrochemical impedance spectrum of the composite solid electrolyte membrane, in which the abscissa Z "and Z' are the imaginary part and the real part of the impedance, respectively, and the curve in the diagram can simulate the ionic resistance R of the solid electrolyte membrane, and the electrical conductivity σ can be calculated by the formula σ = L/RS, where L and S are the thickness and the area of the solid electrolyte membrane, respectively. Conductivity sigma of 3.5 x 10 at room temperature -4 S/cm, which shows that the solid electrolyte has high ionic conductivity at normal temperature, and the solid battery is expected to work normally at normal temperature.
Based on the technical scheme, the double-polymer composite solid electrolyte is prepared through the synergistic effect of double in-situ polymerization reactions, wherein the double in-situ polymerization reactions comprise the in-situ polymerization reaction of 1, 3-dioxolane and the in-situ polymerization reaction of 2-cyano-ethyl acrylate. In the composite solid electrolyte, poly (2-cyano-ethyl acrylate) is used for providing higher mechanical strength and wider electrochemical window, and poly (1, 3-dioxolane) with poorer mechanical properties is used for constructing a soft structure, so that the heterogeneous interface soft contact of the solid electrolyte is realized. Meanwhile, the two have the function of lithium ion conduction.
In addition, the double in-situ polymerization reaction has a synergistic effect, so that the two polymer electrolytes realize complementation in the two performances of mechanical strength and an electrochemical window, the two polymer solid electrolytes are uniformly and interactively dispersed to form a main body structure of the composite solid electrolyte, and the ionic conductivity is improved and the interface impedance is reduced through the controllable preparation of the amorphous polymer.
In summary, compared with the prior art, the double-polymer composite solid electrolyte, the electrolyte membrane and the in-situ preparation method thereof provided by the invention can improve the room-temperature conductivity of the solid electrolyte, widen the electrochemical window and improve the mechanical strength, can realize soft contact between the solid electrolyte and the electrode active material and between the solid electrolyte and the electrode, effectively solve the solid-solid interface problem between the solid electrolyte and the electrode active material and between the solid electrolyte and the electrode, and have great practical significance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A dual polymer composite solid electrolyte, comprising: the lithium ion battery comprises, by mass, 2% -72% of a first polymer component, 2% -72% of a second polymer component and 0.5% -30% of lithium salt;
wherein the first polymer component is 1, 3-dioxolane;
the second polymer component is poly-2-cyano-ethyl acrylate;
the lithium salt comprises LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 At least one of (a);
the double-polymer composite solid electrolyte comprises the following preparation steps:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile small molecular solvent to prepare a polymerization initiation liquid;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
sixthly, placing the solid electrolyte solution in a dry atmosphere for primary drying, and then placing the solid electrolyte solution in a vacuum box for secondary drying to finally obtain a composite solid electrolyte;
in the first step, the second step and the third step, the small molecule solvent comprises at least one of N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC), dimethylacetamide (DMAC) and acetonitrile AN;
in the third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum trifluoromethanesulfonate.
2. A method for the in situ preparation of the bipolymer composite solid electrolyte according to claim 1, comprising the steps of:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile small molecular solvent to prepare a polymerization initiation liquid;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiating solution obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
sixthly, placing the solid electrolyte solution in a dry atmosphere for primary drying, and then placing the solid electrolyte solution in a vacuum box for secondary drying to finally obtain a composite solid electrolyte;
in the first step, the second step and the third step, the small molecule solvent comprises at least one of N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC), dimethylacetamide (DMAC) and acetonitrile AN;
in the third step, the lithium salt includes LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 At least one ofSeed growing;
in the third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum trifluoromethanesulfonate.
3. The in-situ preparation method of claim 2, wherein in the first step, the mass content of the 2-cyano-ethyl acrylate in the first polymer monomer solution is 20 to 100%, and the mass content of the small molecular solvent is 0 to 80% but not 0;
in the second step, the mass content of the 1, 3-dioxolane in the second polymer monomer solution is 20-100%, and the mass content of the small molecular solvent is 0-80% and is not 0.
4. The in-situ preparation method according to claim 2, wherein in the third step, the molar concentration of the initiator in the polymerization initiating solution is 0 to 0.01M and is not 0;
in the third step, the mass percentage of the lithium salt in the polymerization reaction initiation liquid is 5-60%.
5. The in-situ preparation method according to claim 2, wherein in the fourth step, the mass ratio of the first polymer monomer solution obtained in the first step to the first polymer monomer solution obtained in the second step is 20 to 80;
in the fifth step, the polymerization reaction initiation liquid obtained in the third step and the first mixed solution obtained in the fourth step are mixed to obtain a solid electrolyte solution, wherein the mass content of the polymerization reaction initiation liquid is 10 to 50 percent, and the mass content of the first mixed solution is 50 to 90 percent.
6. The in-situ preparation method of claim 2, wherein in the sixth step, when the solid electrolyte solution is placed in a dry atmosphere for first drying, the drying temperature is 30 to 120 ℃, and the drying time is 1 to 20 hours;
and then, carrying out secondary drying in a vacuum box at the drying temperature of 30-120 ℃ for 1-60 hours to finally obtain the composite solid electrolyte.
7. A bipolymer composite solid electrolyte membrane comprising the bipolymer composite solid electrolyte of claim 1.
8. A method for the in situ preparation of a bipolymer composite solid electrolyte membrane according to claim 7, comprising the steps of:
firstly, dissolving a polymer monomer 2-cyano-ethyl acrylate in a volatile micromolecular solvent to prepare a first polymer monomer solution;
secondly, dissolving a polymer monomer 1, 3-dioxolane in a volatile small molecular solvent to prepare a second polymer monomer solution;
dissolving a polymerization initiator and lithium salt in a volatile micromolecular solvent to prepare a polymerization reaction initiating solution;
step four, mixing the first polymer monomer solution obtained in the step one with the second polymer monomer solution obtained in the step two, and uniformly stirring to obtain a first mixed solution;
step five, mixing the polymerization reaction initiation liquid obtained in the step three with the first mixed solution obtained in the step four, and uniformly stirring to obtain a solid electrolyte solution;
sixthly, coating the solid electrolyte solution in a mold of the electrolyte membrane, then placing the mold in a dry atmosphere for primary drying, and then placing the mold in a vacuum box for secondary drying to finally obtain a composite solid electrolyte membrane;
in the first and second steps, the small molecule solvent comprises at least one of N-methyl pyrrolidone (NMP), dimethyl carbonate (DMC), dimethylacetamide (DMAC) and acetonitrile AN;
in the third step, the lithium salt includes LiTFSI, liFSI, liPF 6 、LiBO 3 And LiClO 4 At least one of;
in the third step, the polymerization initiator includes at least one of benzoyl peroxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and aluminum trifluoromethanesulfonate.
9. The in-situ preparation method of claim 8, wherein in the first step, the mass content of the 2-cyano-ethyl acrylate in the first polymer monomer solution is 20 to 100%, and the mass content of the small molecular solvent is 0 to 80% but not 0;
in the second step, in the second polymer monomer solution, the mass content of the 1, 3-dioxolane is 20-100%, and the mass content of the small molecular solvent is 0-80% and is not 0;
in the third step, the molar concentration of the initiator in the polymerization reaction initiating solution is 0 to 0.01M and is not 0;
in the third step, the mass percentage of the lithium salt in the polymerization reaction initiation liquid is 5-60%.
10. The in-situ preparation method according to claim 8, wherein in the fourth step, the mass ratio of the first polymer monomer solution obtained in the first step to the first polymer monomer solution obtained in the second step is 20 to 80;
in the fifth step, mixing the polymerization reaction initiating solution obtained in the third step with the first mixed solution obtained in the fourth step to obtain a solid electrolyte solution, wherein the mass content of the polymerization reaction initiating solution is 10-50%, and the mass content of the first mixed solution is 50-90%;
in the sixth step, the solid electrolyte solution is placed in a dry atmosphere for first drying, wherein the drying temperature is 30 to 120 ℃, and the drying time is 1 to 20 hours;
and then coating the solid electrolyte solution in a die of the electrolyte membrane, and then placing the die in a vacuum box for secondary drying at the drying temperature of 30-120 ℃ for 1-60 hours to finally obtain the composite solid electrolyte membrane.
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