CN112820937A - Solid electrolyte, preparation method thereof and high-nickel ternary all-solid-state battery - Google Patents

Solid electrolyte, preparation method thereof and high-nickel ternary all-solid-state battery Download PDF

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CN112820937A
CN112820937A CN201911122093.4A CN201911122093A CN112820937A CN 112820937 A CN112820937 A CN 112820937A CN 201911122093 A CN201911122093 A CN 201911122093A CN 112820937 A CN112820937 A CN 112820937A
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lithium
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廖华平
周时国
姬迎亮
温新鸽
张二勇
李帅鹏
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Zhengzhou Yutong Group Co ltd
Zhengzhou Yutong Bus Co Ltd
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Abstract

The invention relates to a solid electrolyte, a preparation method thereof and a high-nickel ternary all-solid-state battery, and belongs to the technical field of solid batteries. The invention provides a solid electrolyte, which consists of 60-75 wt% of polymer matrix, 10-25 wt% of alkali metal salt and 0-15 wt% of additive, wherein the alkali metal salt and the additive are dispersed in the polymer matrix. The structural unit shown in the formula I and the structural unit shown in the formula II in the molecular chain structure of the polymer matrix contain carbonate bonds, the structural unit shown in the formula III contains ester bonds and ether bonds, metal ions can be complexed and transferred, the solid electrolyte can resist high voltage of more than 4.5V, the solid electrolyte can be used for various batteries, is suitable for a high-nickel ternary system with high requirements on the electrolyte, and is favorable for improving the energy density of all-solid-state batteries.

Description

Solid electrolyte, preparation method thereof and high-nickel ternary all-solid-state battery
Technical Field
The invention relates to a solid electrolyte, a preparation method thereof and a high-nickel ternary all-solid-state battery, and belongs to the technical field of solid batteries.
Background
With the rapid development of electric automobiles in China, higher requirements are put forward on the safety and energy density of power batteries. At present, the commercialized lithium ion battery generally adopts flammable liquid electrolyte, and the safety risk is high. The solid electrolyte is an effective means for solving the safety performance of the lithium ion battery by replacing the original liquid electrolyte, and the solid lithium battery is considered to be the next generation of high-energy-density and high-safety battery which is most likely to be popularized and applied in the industry.
Until now, the research on all solid-state lithium batteries using PEO as a solid electrolyte has been the most mature. However, the PEO electrolyte has a low withstand voltage window (less than 4.0V) and can only be used in the lithium iron phosphate system. The energy density of all solid-state lithium iron phosphate batteries commercially operated in blue car in France is low and is lower than 220 Wh/kg. In order to further increase the energy density of the solid-state battery, it is preferable to use a higher capacity of the positive electrode material. Currently, among high capacity cathode materials, a high nickel ternary material is most widely used.
Compared with a lithium iron phosphate all-solid-state battery, the preparation of the high-nickel ternary all-solid-state battery has the following difficulties: (1) the charging voltage of the high-nickel ternary positive electrode material is higher, generally 4.2V or more, while the voltage resistance of the traditional PEO-based electrolyte is less than 4.0V, and an electrolyte with the voltage resistance higher than 4.2V needs to be developed; (2) the high nickel ternary positive electrode material in the charged state (full-charge state) has strong chemical oxidation, and an electrolyte in contact with the high nickel ternary positive electrode material has very good chemical oxidation resistance. (3) The conventional high-voltage-resistant electrolyte is relatively unstable in a low-potential interval and is easy to react with a lithium metal negative electrode.
In order to solve the above problems, it is necessary to provide a high voltage resistant electrolyte.
Disclosure of Invention
A first object of the present invention is to provide a solid electrolyte having a high withstand voltage capability.
The second purpose of the invention is to provide a preparation method of the solid electrolyte, which is simple to operate and easy to implement.
The third purpose of the invention is to provide a high-nickel ternary all-solid-state battery.
The technical scheme of the invention is as follows:
a solid electrolyte, the solid electrolyte is composed of 60 wt% -75 wt% of polymer matrix, 10 wt% -25 wt% of alkali metal salt and 0 wt% -15 wt% of additive which are dispersed in the polymer matrix;
the additive is inorganic nanoparticles, a plasticizer or an ionic liquid;
the molecular chain structure of the polymer matrix consists of a structural unit shown in a formula I and/or a structural unit shown in a formula II;
or the molecular chain structure of the polymer matrix consists of one or two of a structural unit shown in a formula I and a structural unit shown in a formula II and a structural unit shown in a formula III, wherein the structural unit shown in the formula III is W in percentage by mass in the polymer matrixⅢIs 0 wt%<WⅢ≤40wt％；
Figure BDA0002275726850000021
Wherein the content of the first and second substances,
the R is1、R2、R3、R4、R5、R6And R7Each independently selected from H or C1～C4Alkyl groups of (a);
the R is8Is selected from C1～C4Alkyl groups of (a);
n is1An integer selected from 5 to 11;
the number average molecular weight of the polymer matrix is 104～5×105。
The solid electrolyte comprises 60-75 wt% of a polymer matrix, 10-25 wt% of alkali metal salt and 0-15 wt% of additives, wherein the alkali metal salt and the additives are dispersed in the polymer matrix, a structural unit shown in a formula I and a structural unit shown in a formula II in a molecular chain structure of the polymer matrix contain carbonate bonds, a structural unit shown in a formula III contains ester bonds and ether bonds (short chain ether bonds) and can complex and transmit metal ions, and the solid electrolyte can resist high voltage of more than 4.5V, can be used for various batteries, is suitable for a high-nickel ternary system with high requirements on the electrolyte, and is favorable for improving the energy density of all-solid-state batteries.
Preferably, said R is1、R2、R3、R4、R5、R6And R7Each independently selected from H or C1～C2Alkyl groups of (a); the R is8Is selected from C1～C2Alkyl group of (1).
Preferably, said R is1、R2、R3、R4、R5、R6And R7Each independently selected from H; the R is8Selected from methyl.
Preferably, said n1Is selected from 9.
In order to further improve the film-forming properties of the solid electrolyte, the mass percentage W of the structural unit of formula iii in the polymer matrix is preferablyⅢ15 to 30 percent.
The alkali metal salt in the solid electrolyte corresponds to the battery to be manufactured, and preferably, the alkali metal salt is a lithium salt or a sodium salt.
Preferably, the lithium salt is one or more than two of lithium hexafluorophosphate, lithium perchlorate, lithium difluoro oxalate borate, lithium bis (trifluoromethyl) sulfonyl imide and lithium bis (fluoro) sulfonyl imide.
The addition of inorganic nano-particles is beneficial to improving the strength of the solid electrolyte, and the addition of a plasticizer or an ionic liquid is beneficial to improving the room-temperature ionic conductivity of the solid electrolyte, and preferably, the inorganic nano-particles are aluminum oxide, titanium dioxide and Li7La3Zr2O12、Li7La3Zr1.5Ta0.5O12One or more than two of lithium aluminum titanium phosphate and lithium aluminum germanium phosphate; the plasticizer is one or more than two of succinonitrile, ethylene carbonate and propylene carbonate; the ionic liquid is piperidine ionic liquid and/or quaternary ammonium salt ionic liquid.
A method of preparing a solid electrolyte comprising the steps of:
adding a photoinitiator into a mixed solution consisting of 60-75 wt% of polymerized monomers, 10-25 wt% of alkali metal salt and 0-15 wt% of additives, and initiating polymerization by using ultraviolet light to obtain the high-performance ultraviolet-curing polyurethane resin;
the additive is inorganic nanoparticles, a plasticizer or an ionic liquid;
the polymerized monomer is composed of a compound shown as a formula IV and/or a compound shown as a formula V;
or the polymerized monomer consists of one or two of the compound shown in the formula IV and the compound shown in the formula V and the compound shown in the formula VI, wherein the mass percentage of the compound shown in the formula VI in the polymerized monomer is WⅥIs 0 wt%<WⅥ≤40wt％；
Figure BDA0002275726850000031
Wherein the content of the first and second substances,
the R is1、R2、R3、R4、R5、R6And R7Each independently selected from H or C1～C4Alkyl groups of (a);
the R is8Is selected from C1～C4Alkyl groups of (a);
n is1An integer selected from 5 to 11;
the number average molecular weight of the polymer matrix is 104～5×105。
The solid electrolyte is in the shape of a solid electrolyte membrane, and can be prepared by coating a mixed solution of 60-75 wt% of polymerized monomer, 10-25 wt% of alkali metal salt and 0-15 wt% of additive on the surface of a base material, and then initiating polymerization by using ultraviolet light, wherein the base material can be a polytetrafluoroethylene plate or a release film, and the wavelength of the ultraviolet light is 365 nm.
The preparation method of the solid electrolyte only needs to carry out ultraviolet light initiated polymerization on 60-75 wt% of polymerized monomer, 10-25 wt% of alkali metal salt and 0-15 wt% of additive, and the preparation method is simple to operate, easy to implement and suitable for popularization and application.
In order to further improve the polymerization efficiency, preferably, the photoinitiator is azobisisobutyronitrile, benzoyl peroxide or 2-hydroxy-2-methyl-1-phenyl-1-propanone.
The photoinitiator can be used in the amount which is conventional in the art, and the addition amount of the photoinitiator is 0.4-0.6 wt% of the mixed solution.
The method comprises the following steps of (1) adopting ultraviolet light power capable of initiating polymerization, finishing the reaction when the polymerization is completed, wherein the power of the ultraviolet light is 150-200W, and the polymerization time is 1-20 min.
A high-nickel ternary all-solid-state battery includes a positive electrode, a negative electrode, and the above solid electrolyte between the positive electrode and the negative electrode.
The solid electrolyte in the high-nickel ternary all-solid-state battery can resist high voltage of more than 4.5V, can be used for the high-nickel ternary all-solid-state battery, and is favorable for improving the energy density of the all-solid-state battery.
In order to prevent the electrolyte isolation layer from being damaged by high chemical oxidizability of a high-nickel positive electrode material in a charging state and further prolong the service life of the battery, preferably, the positive electrode comprises a positive electrode current collector, and a positive electrode material and a polymer-based coating layer which are sequentially coated on the surface of the positive electrode current collector; the anode material consists of a ternary active substance and an inorganic compound coated on the surface of the ternary active substance; the polymer-based coating layer consists of 50 to 70 weight percent of polymer, 20 to 30 weight percent of alkali metal salt and 10 to 40 weight percent of ionic liquid; the polymer is polyacrylonitrile, polyvinylidene fluoride, polyvinyl chloride or polyimide.
In order to further prevent the electrolyte isolating layer from being damaged by high chemical oxidizability of the high-nickel cathode material in a charging state and further prolong the service life of the battery, the ternary active material is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.1Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.9Co0.05Al0.05O2(ii) a The inorganic compound is lithium niobate, lithium aluminate, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate or Li7La3Zr2O12(ii) a The alkali metal salt is lithium salt; the lithium salt is lithium hexafluorophosphate, lithium perchlorate, lithium difluoro oxalate borate, lithium bis (trifluoromethyl) sulfonyl imide or lithium bis (fluoro) sulfonyl imide; the ionic liquid is piperidine ionic liquid.
The thickness of the polymer-based coating layer is 100nm to 1 μm.
The positive electrode active material, the positive electrode electrolyte, the conductive agent and the binder form positive electrode slurry, and the positive electrode slurry is coated on the positive electrode current collector, wherein the mass percentage of the positive electrode active material in the positive electrode slurry is 70-80%, and the mass percentage of the positive electrode electrolyte in the positive electrode slurry is 10-25%. The positive electrode electrolyte is Li7La3Zr2O12(LLZO)、Li7La3Zr1.5Ta0.5O12(LLZTO), Lithium Aluminum Titanium Phosphate (LATP), and Lithium Aluminum Germanium Phosphate (LAGP).
In order to stabilize the surface of metallic lithium and prevent lithium dendrite formation, it is preferable that the negative electrode includes a metallic lithium sheet andpolyvinyl ether electrolyte coated on the surface of the metal lithium sheet; the polyvinyl ether electrolyte consists of a polyvinyl ether matrix and alkali metal salt dispersed in the polyvinyl ether matrix, wherein the number average molecular weight of the polyvinyl ether matrix is 5 multiplied by 103～105(ii) a The polyvinyl ether electrolyte is obtained by carrying out photoinitiated polymerization on a mixed solution of a compound shown in a formula VII and lithium salt;
Figure BDA0002275726850000051
n is2Is 2 to 15.
The alkali metal salt is lithium salt or sodium salt, and the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium difluorooxalato borate (LiDFOB), lithium bistrifluoromethylsulfonyl imide (LiTFSI), and lithium bistrifluorosulfonimide (LiFSI).
The thickness of the polyvinyl ether electrolyte is 500 nm-5 μm.
The photoinitiator for photo-initiated polymerization is Azobisisobutyronitrile (AIBN), Benzoyl Peroxide (BPO) or 2-hydroxy-2-methyl-1-phenyl-1-propanone.
Drawings
Fig. 1 is a schematic diagram of the basic structural unit of a high-nickel ternary all-solid-state battery of example 8;
FIG. 2 is a room temperature impedance spectrum of the solid electrolyte membrane obtained in example 1;
fig. 3 is an electrochemical window test pattern of the solid electrolyte membrane prepared in example 1.
In the figure, 1 is a 811 positive electrode sheet, 2 is a PAN electrolyte layer, 3 is a solid electrolyte membrane, 4 is a polyvinyl ether electrolyte layer, and 5 is a metallic lithium sheet.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The specific embodiment of the preparation method of the solid electrolyte of the invention is as follows:
example 1
The method for preparing the solid electrolyte of the embodiment includes the following steps:
(1) preparing a mixed solution of methoxy polyethylene glycol acrylate (mPEG-AC, molecular weight 480), Vinylene Carbonate (VC) and lithium bistrifluoromethylsulfonyl imide (LiTFSI), wherein the mass percentage of the mPEG-AC, the VC and the LiTFSI are 22.5 wt%, 52.5 wt% and 25 wt% in sequence.
(2) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into the mixed solution obtained in the step (1), wherein the mass percentage of the 2-hydroxy-2-methyl-1-phenyl-1-acetone in the mixed solution is 0.5 wt%, coating the mixed solution on the surface of a polytetrafluoroethylene plate, initiating polymerization by 365nm wavelength ultraviolet light, wherein the power of an ultraviolet light source is 180W, finishing the reaction after 3min of polymerization, stripping the mixed solution from the surface of the polytetrafluoroethylene plate to obtain a film-shaped solid electrolyte with the thickness of 380 mu m, and the number average molecular weight of the polymer matrix is 15 ten thousand.
Example 2
The method for preparing the solid electrolyte of the embodiment includes the following steps:
(1) preparing a mixed solution of methoxy polyethylene glycol acrylate (mPEG-AC, molecular weight 480), Vinylene Carbonate (VC), ionic liquid (1-butyl-1 methylpiperidine bis (trifluoromethanesulfonyl) imide salt) and lithium bistrifluoromethylsulfonyl imide (LiTFSI), wherein the mass percentages of the mPEG-AC, the VC, the ionic liquid and the LiTFSI are 10 wt%, 52.5 wt%, 12.5 wt% and 25 wt% in sequence.
(2) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into the mixed solution obtained in the step (1), wherein the mass percentage of the 2-hydroxy-2-methyl-1-phenyl-1-acetone in the mixed solution is 0.5 wt%, coating the mixed solution on the surface of a polytetrafluoroethylene plate, initiating polymerization by 365nm wavelength ultraviolet light, wherein the power of an ultraviolet light source is 180W, finishing the reaction after 3min of polymerization, stripping the mixed solution from the surface of the polytetrafluoroethylene plate to obtain a film-shaped solid electrolyte with the thickness of 380 mu m, and the number average molecular weight of the polymer matrix is 15 ten thousand.
Example 3
The method for preparing the solid electrolyte of the embodiment includes the following steps:
(1) preparing a mixed solution of ethylene carbonate (VEC), Vinylene Carbonate (VC) and lithium bistrifluoromethylsulfonyl imide (LiTFSI), wherein the mass percentage of the VEC, the VC and the LiTFSI is 22.5 wt%, 52.5 wt% and 25 wt% in sequence.
(2) Adding 2-hydroxy-2-methyl-1-phenyl-1-acetone into the mixed solution obtained in the step (1), wherein the mass percentage of the 2-hydroxy-2-methyl-1-phenyl-1-acetone in the mixed solution is 0.5 wt%, coating the mixed solution on the surface of a polytetrafluoroethylene plate, initiating polymerization by using 365nm wavelength ultraviolet light, wherein the power of an ultraviolet light source is 180W, finishing the reaction after 4min of polymerization, stripping the mixed solution from the surface of the polytetrafluoroethylene plate to obtain a film-shaped solid electrolyte with the thickness of 380 mu m, and the number average molecular weight of a polymer matrix is 12 ten thousand.
Secondly, the specific examples of the solid electrolyte of the present invention are as follows:
example 4
The solid electrolyte of this example, which was prepared by the method of preparing the solid electrolyte of example 1, consisted of 75 wt% of the polymer matrix, and 25 wt% of LiTFSI dispersed in the polymer matrix.
The molecular chain structure of the polymer matrix consists of a structural unit shown as a formula IIIa and a structural unit shown as a formula Ia, the mass percentage of the structural unit shown as the formula IIIa in the polymer matrix is 30 wt%, and the number average molecular weight of the polymer matrix is 15 ten thousand.
Figure BDA0002275726850000071
Example 5
The solid electrolyte of this example, prepared by the method of preparing the solid electrolyte of example 2, consisted of 62.5 wt% of a polymer matrix, and 25 wt% of LiTFSI and 12.5 wt% of 1-butyl-1 methylpiperidine bis (trifluoromethanesulfonyl) imide salt dispersed in the polymer matrix.
The molecular chain structure of the polymer matrix consists of a structural unit shown as a formula IIIb and a structural unit shown as a formula Ib, the mass percentage of the structural unit shown as the formula IIIb in the polymer matrix is 16 wt%, and the number average molecular weight of the polymer matrix is 15 ten thousand.
Figure BDA0002275726850000072
Example 6
The solid electrolyte of this example, prepared by the method of preparing the solid electrolyte of example 3, consisted of 75 wt% of the polymer matrix, and 25 wt% of LiTFSI dispersed in the polymer matrix.
The molecular chain structure of the polymer matrix consists of a structural unit shown as the formula ic and a structural unit shown as the formula IIc, the weight ratio of the structural unit shown as the formula ic to the structural unit shown as the formula IIc is 52.5:22.5, and the number average molecular weight of the polymer matrix is 13 ten thousand.
Figure BDA0002275726850000081
Thirdly, the specific embodiment of the high-nickel ternary all-solid-state battery of the invention is as follows:
example 7
In the high-nickel ternary all-solid-state battery of this embodiment, the positive electrode 811 is a positive electrode plate (811 material is coated with lithium niobate), the negative electrode is a metallic lithium negative electrode, and the solid electrolyte located between the positive electrode and the negative electrode is the solid electrolyte prepared in embodiment 1.
And assembling the positive electrode, the solid electrolyte and the negative electrode into an all-solid-state battery, wherein the battery core is assembled in a lamination mode.
Example 8
In the high-nickel ternary all-solid-state battery of the embodiment, the positive electrode is formed by coating a PAN electrolyte layer (the mass percentage of PAN, 1-butyl-1 methylpiperidine bis (trifluoromethanesulfonyl) imide salt and LiTFSI are 60 wt%, 15 wt% and 25 wt% in sequence) on a 811 positive electrode plate (811 material is coated with lithium niobate), and the coating thickness is 1 μm.
The negative electrode is a polyvinyl ether electrolyte layer polymerized in situ on a metal lithium sheet, and the preparation method comprises the following steps: mixing 75 wt% of methoxy (nonavinyloxy) ethyl vinyl ether and 25 wt% of LiTFSI to obtain a mixed solution, adding an initiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, wherein the amount of the initiator is 0.5 wt% of the mixed solution, then coating the mixed solution on the surface of a metal lithium sheet, initiating polymerization by using ultraviolet light with a wavelength of 365nm, wherein the power of an ultraviolet light source is 180W, finishing the reaction after polymerizing for 2min, and the thickness of a polyvinyl ether electrolyte layer is 5 mu m.
The solid electrolyte located between the positive electrode and the negative electrode was the solid electrolyte membrane prepared in example 1.
The positive electrode, the solid electrolyte and the negative electrode are assembled into an all-solid-state battery, a battery core is assembled in a lamination mode, and the basic structural units of the all-solid-state battery are shown in figure 1, wherein 1 is a 811 positive electrode plate, 2 is a PAN electrolyte layer, 3 is a solid electrolyte membrane, 4 is a polyvinyl ether electrolyte layer, and 5 is a metal lithium sheet.
Example 9
In the high-nickel ternary all-solid-state battery of the embodiment, the positive electrode is formed by coating a PVDF electrolyte layer (containing PVDF, 1-butyl-1 methylpiperidine bis (trifluoromethanesulfonyl) imide salt and LiTFSI in the mass percentage of 60 wt%, 15 wt% and 25 wt% in sequence) on a 811 positive electrode plate (coated with lithium niobate by 811 material), and the coating thickness is 1 μm.
The negative electrode is a polyvinyl ether electrolyte layer polymerized in situ on a metal lithium sheet, and the preparation method comprises the following steps: mixing 75 wt% of methoxy (nonavinyloxy) ethyl vinyl ether and 25 wt% of LiTFSI to obtain a mixed solution, adding an initiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, wherein the amount of the initiator is 0.5 wt% of the mixed solution, then coating the mixed solution on the surface of a metal lithium sheet, initiating polymerization by using ultraviolet light with a wavelength of 365nm, wherein the power of an ultraviolet light source is 180W, finishing the reaction after polymerizing for 2min, and the thickness of a polyvinyl ether electrolyte layer is 5 mu m.
The solid electrolyte located between the positive electrode and the negative electrode was the solid electrolyte membrane prepared in example 2.
And assembling the positive electrode, the solid electrolyte and the negative electrode into an all-solid-state battery, wherein the battery core is assembled in a lamination mode.
Example 10
In the high-nickel ternary all-solid-state battery of the embodiment, the positive electrode is formed by coating a PVDF electrolyte layer (containing PVDF, 1-butyl-1 methylpiperidine bis (trifluoromethanesulfonyl) imide salt and LiTFSI in the mass percentage of 60 wt%, 15 wt% and 25 wt% in sequence) on a 811 positive electrode plate (coated with lithium niobate by 811 material), and the coating thickness is 1 μm.
The negative electrode is a polyvinyl ether electrolyte layer polymerized in situ on a metal lithium sheet, and the preparation method comprises the following steps: mixing 75 wt% of methoxy (nonavinyloxy) ethyl vinyl ether and 25 wt% of LiTFSI to obtain a mixed solution, adding an initiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, wherein the amount of the initiator is 0.5 wt% of the mixed solution, then coating the mixed solution on the surface of a metal lithium sheet, initiating polymerization by using ultraviolet light with a wavelength of 365nm, wherein the power of an ultraviolet light source is 180W, finishing the reaction after polymerizing for 2min, and the thickness of a polyvinyl ether electrolyte layer is 5 mu m.
The solid electrolyte located between the positive electrode and the negative electrode was the solid electrolyte membrane prepared in example 3.
And assembling the positive electrode, the solid electrolyte and the negative electrode into an all-solid-state battery, wherein the battery core is assembled in a lamination mode.
Fourth, related test example
Test example 1
The electrolyte room temperature resistance and the electrochemical window of the solid electrolyte membrane obtained in example 1 were measured to obtain a room temperature resistance spectrum of the solid electrolyte membrane obtained in example 1 as shown in fig. 2, and an electrochemical window test spectrum of the solid electrolyte membrane obtained in example 1 as shown in fig. 3.
As can be seen from FIG. 2, the measured impedance value of the electrolyte membrane was 180. omega. in terms of the area (2.01 cm) of the electrolyte membrane2) Thickness (380 μm) and resistance, and the room-temperature ionic conductivity was calculated to be 1.05X 10-4s/cm. As can be seen from fig. 3, the electrochemical window of the electrolyte membrane reached 5.1V.
Test example 2
The room-temperature ionic conductivity and the electrochemical window of the solid electrolyte membranes prepared in examples 1 to 3 were characterized, and the obtained results are shown in table 1.
TABLE 1 Room temperature Ionic conductivities and electrochemical windows of solid electrolyte membranes prepared in examples 1 to 3
Ion conductivity at room temperature (S/cm) Electrochemical window (V)
Example 1 1.05×10-4 5.1
Example 2 8.05×10-4 5.1
Example 3 1.01×10-4 5.0
As can be seen from Table 1, the room temperature ionic conductivities of the electrolyte membranes with different formulations can reach 10-4s/cm, the room temperature conductivity of the electrolyte membrane of the composite ionic liquid in the embodiment 2 is obviously improved. In addition, the electrochemical window of the electrolyte membrane can reach more than 5V, which indicates that the electrolyte is suitable for being used in a high-voltage solid-state battery system.
Test example 3
The electrochemical properties of the high-nickel ternary all-solid-state batteries of examples 7 to 10 were characterized, and the obtained results are shown in table 2.
TABLE 2 Performance of the high-nickel ternary all-solid-state batteries of examples 7-10
First week reversible capacity (mAh/g) Capacity retention after 50 weeks
Example 7 183.4 78.5％
Example 8 184.0 92.3％
Example 9 183.8 93.6％
Example 10 183.9 91.8％
Experimental results show that the prepared electrolyte membrane can be used in a high-voltage material battery, and the all-solid-state high-nickel ternary battery with the surface modified positive and negative electrodes has good cycle performance.

Claims (10)

1. A solid electrolyte, characterized in that the solid electrolyte consists of 60-75 wt% of polymer matrix, 10-25 wt% of alkali metal salt and 0-15 wt% of additive dispersed in the polymer matrix;
the additive is inorganic nanoparticles, a plasticizer or an ionic liquid;
the molecular chain structure of the polymer matrix consists of a structural unit shown in a formula I and/or a structural unit shown in a formula II;
or the molecular chain structure of the polymer matrix consists of one or two of a structural unit shown in a formula I and a structural unit shown in a formula II and a structural unit shown in a formula III, wherein the structural unit shown in the formula III is W in percentage by mass in the polymer matrixⅢIs 0 wt%<WⅢ≤40wt％；
Figure FDA0002275726840000011
Wherein the content of the first and second substances,
the R is1、R2、R3、R4、R5、R6And R7Each independently selected from H or C1～C4Alkyl groups of (a);
the R is8Is selected from C1～C4Alkyl groups of (a);
n is1An integer selected from 5 to 11;
the number average molecular weight of the polymer matrix is 104～5×105。
2. The solid electrolyte according to claim 1, wherein R is1、R2、R3、R4、R5、R6And R7Each independently selected from H or C1～C2Alkyl groups of (a); the R is8Is selected from C1～C2Alkyl group of (1).
3. The solid electrolyte according to claim 2, wherein R is1、R2、R3、R4、R5、R6And R7Each independently selected from H; the above-mentionedR8Selected from methyl.
4. The solid electrolyte according to any one of claims 1 to 3, wherein the structural unit represented by the formula III is contained in the polymer matrix in a mass percentage WⅢ15 to 30 percent.
5. The solid electrolyte according to any one of claims 1 to 3, wherein the inorganic nanoparticles are alumina, titania, Li7La3Zr2O12、Li7La3Zr1.5Ta0.5O12One or more than two of lithium aluminum titanium phosphate and lithium aluminum germanium phosphate;
the plasticizer is one or more than two of succinonitrile, ethylene carbonate and propylene carbonate;
the ionic liquid is piperidine ionic liquid and/or quaternary ammonium salt ionic liquid.
6. A method for producing a solid electrolyte according to claim 1, comprising the steps of:
adding a photoinitiator into a mixed solution consisting of 60-75 wt% of polymerized monomers, 10-25 wt% of alkali metal salt and 0-15 wt% of additives, and initiating polymerization by using ultraviolet light to obtain the high-performance ultraviolet-curing polyurethane resin;
the additive is inorganic nanoparticles, a plasticizer or an ionic liquid;
the polymerized monomer is composed of a compound shown as a formula IV and/or a compound shown as a formula V;
or the polymerized monomer consists of one or two of the compound shown in the formula IV and the compound shown in the formula V and the compound shown in the formula VI, wherein the mass percentage of the compound shown in the formula VI in the polymerized monomer is WⅥIs 0 wt%<WⅥ≤40wt％；
Figure FDA0002275726840000021
Wherein the content of the first and second substances,
the R is1、R2、R3、R4、R5、R6And R7Each independently selected from H or C1～C4Alkyl groups of (a);
the R is8Is selected from C1～C4Alkyl groups of (a);
n is1An integer selected from 5 to 11;
the number average molecular weight of the polymer matrix is 104～5×105。
7. A high-nickel ternary all-solid-state battery comprising a positive electrode, a negative electrode, and the solid electrolyte of claim 1 between the positive electrode and the negative electrode.
8. The high-nickel ternary all-solid battery according to claim 7, wherein the positive electrode comprises a positive electrode current collector and a positive electrode material and a polymer-based coating layer sequentially coated on the surface of the positive electrode current collector;
the anode material consists of a ternary active substance and an inorganic compound coated on the surface of the ternary active substance;
the polymer-based coating layer consists of 50 to 70 weight percent of polymer, 20 to 30 weight percent of alkali metal salt and 10 to 40 weight percent of ionic liquid; the polymer is polyacrylonitrile, polyvinylidene fluoride, polyvinyl chloride or polyimide.
9. The high-nickel ternary all-solid-state battery according to claim 8, wherein the ternary active material is LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.1Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2Or LiNi0.9Co0.05Al0.05O2；
The inorganic compound is lithium niobate, lithium aluminate, lithium aluminum titanium phosphate, lithium aluminum germanium phosphate or Li7La3Zr2O12；
The alkali metal salt is lithium salt; the lithium salt is lithium hexafluorophosphate, lithium perchlorate, lithium difluoro oxalate borate, lithium bis (trifluoromethyl) sulfonyl imide or lithium bis (fluoro) sulfonyl imide;
the ionic liquid is piperidine ionic liquid.
10. The high-nickel ternary all-solid-state battery according to claim 7, wherein the negative electrode comprises a metallic lithium sheet and a polyvinyl ether electrolyte coated on the surface of the metallic lithium sheet;
the polyvinyl ether electrolyte consists of a polyvinyl ether matrix and alkali metal salt dispersed in the polyvinyl ether matrix, wherein the number average molecular weight of the polyvinyl ether matrix is 5 multiplied by 103～105；
The polyvinyl ether electrolyte is obtained by carrying out photoinitiated polymerization on a mixed solution of a compound shown in a formula VII and lithium salt;
Figure FDA0002275726840000031
n is2Is 2 to 15.
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