CN111403805A - Composite solid electrolyte, preparation method thereof and lithium ion battery - Google Patents

Composite solid electrolyte, preparation method thereof and lithium ion battery Download PDF

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CN111403805A
CN111403805A CN202010349672.9A CN202010349672A CN111403805A CN 111403805 A CN111403805 A CN 111403805A CN 202010349672 A CN202010349672 A CN 202010349672A CN 111403805 A CN111403805 A CN 111403805A
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lithium
solid electrolyte
composite solid
composite
salt
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李�诚
陆子恒
陈佳华
杨铮
羿井司
刘国华
杨春雷
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • 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

Abstract

The invention discloses a composite solid electrolyte, a preparation method thereof and a lithium ion battery. The preparation method of the composite solid electrolyte provided by the invention comprises the following steps: mixing inorganic ceramic powder, lithium salt and an organic solvent to form a composite electrolyte; and carrying out molding operation on the composite electrolyte to obtain the composite solid electrolyte. The composite solid electrolyte provided by the invention has excellent electrochemical stability at high temperature, and the assembled lithium ion battery can meet the operation requirement in a high-temperature environment.

Description

Composite solid electrolyte, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the technical field of lithium battery electrolyte preparation, in particular to a composite solid electrolyte, a preparation method thereof and a lithium ion battery.
Background
In recent years, in the field of new energy automobiles, the demand for lithium ion batteries has increased year by year. At present, a lithium ion battery generally adopts liquid electrolyte for ion conduction, but accidents such as liquid leakage, electrode corrosion, combustion and explosion and the like easily occur in organic electrolyte, and great potential safety hazards exist.
The solid electrolyte is a hotspot of research in the electrolyte field due to the advantages of high safety, high energy density and the like, but the existing solid polymer electrolyte has not ideal comprehensive performance at higher temperature, and the preparation process is complex and is not beneficial to industrial application. In view of safety, stability and special working environment, solid electrolyte materials capable of operating at high temperature are sought to meet the operating requirements of lithium ion batteries assembled by solid polymer electrolytes under high temperature conditions.
Disclosure of Invention
In order to solve the problem that the existing solid polymer electrolyte has not ideal comprehensive performance at a higher temperature, the invention provides a novel composite solid electrolyte and a preparation method thereof. The invention further provides a lithium ion battery comprising the composite solid electrolyte.
In order to achieve the above object, the present invention provides a composite solid electrolyte, comprising inorganic ceramic powder, lithium salt and an organic solvent, wherein the inorganic ceramic powder and the lithium salt are doped to form a skeleton, and the organic solvent is adsorbed on the skeleton.
Further, in the composite solid electrolyte, the content of the inorganic ceramic powder is 70-90 wt%, the content of the lithium salt is 1-20 wt%, and the content of the organic solvent is 1-20 wt%.
Furthermore, in the composite solid electrolyte, the content of the inorganic ceramic powder is 70-85 wt%, the content of the lithium salt is 5-15 wt%, and the content of the organic solvent is 2-15 wt%.
Further, the inorganic ceramic powder is selected from at least one of LL ZSO, LL SBO, LL ZGO, LL ZTO and L TPO, wherein the chemical formula of LL ZSO is L i7La3Zr2-xSnxO12Wherein x is 0-1, and LL SBO has a chemical formula of L i6.25La3Sn1.25Bi0.75O12LL ZGO has a chemical formula of L i7La3Zr1.7Ge0.3O12LL ZTO has a chemical formula of L i6.75La3Zr1.75Ta0.25O12L TPO has a chemical formula of L iTa2PO8。
Further, the lithium salt is selected from at least one of lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium hexafluorophosphate, lithium bisoxalato borate, lithium oxalato difluoroborate, lithium perchlorate, and lithium tetrafluoroborate.
Further, the organic solvent is selected from one or more of 1-methyl-3-ethylimidazole dicyanimide, 1, 2-dimethyl-3-propylimidazole chloride, 1-ethyl-2-methylpyrazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethane sulfimide salt, N-butylpyridine bistrifluoromethane sulfimide salt, trimethylpropylammonium bistrifluoromethane sulfimide salt, N-methyl-N-propylpiperidine, 1-propyl-3-methylimidazole bistrifluoromethane sulfimide salt, 1-butyl-3-methylimidazole bistrifluoromethane sulfimide salt, N-methyl, butylpiperidine bistrifluoromethane sulfimide salt, trimethyl phosphate and triethyl phosphate.
Further, the inorganic ceramic powder is nano-particles, and the particle size range is 300-800 nm.
The invention also provides a preparation method of the composite solid electrolyte, which comprises the following steps:
s1, mixing inorganic ceramic powder, lithium salt and an organic solvent to form a composite electrolyte;
and S2, carrying out molding operation on the composite electrolyte to obtain the composite solid electrolyte.
Further, in step S1, mixing is performed by a ball milling method; in step S2, the composite electrolyte is subjected to a molding operation using a sheet pressing method.
Based on the composite solid electrolyte, the invention further provides a lithium ion battery comprising the composite solid electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
the composite solid electrolyte provided by the embodiment of the invention takes a composite electrolyte material of inorganic ceramic powder and lithium salt as a framework supporting structure, takes an organic solvent adsorbed in the framework as a common ion conducting material, can effectively promote the dissociation of the lithium salt, and improves the free L i in the electrolyte+In turn, improves the ionic conductivity of the electrolyte at room temperature as well as at elevated temperatures.
The preparation method of the composite solid electrolyte provided by the embodiment of the invention comprises the following steps: the composite solid electrolyte is prepared by taking inorganic ceramic powder, lithium salt and an organic solvent as raw materials, mixing the raw materials and then carrying out molding operation.
The lithium ion battery provided by the embodiment of the invention comprises the following components: the composite solid electrolyte with the beneficial effects is applied to the lithium ion battery, so that the lithium ion battery has good electrical property and cycle performance, and the coulomb efficiency of the lithium ion battery after 100 cycles can be kept at 96-99%.
Drawings
Features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a diagram showing an electrochemical cycle at a high temperature of a simulated battery assembled with a composite solid electrolyte according to one embodiment of the present invention;
FIG. 2 is a diagram showing the electrochemical cycle at high temperature of a simulated cell assembled with the composite solid-state electrolyte according to the second embodiment;
FIG. 3 is a diagram showing the electrochemical cycle at high temperature of a simulated cell assembled with the composite solid-state electrolyte according to the third example;
FIG. 4 is a diagram showing the electrochemical cycle at high temperature of a simulated cell assembled with the composite solid-state electrolyte according to the fourth example;
FIG. 5 is a diagram showing the electrochemical cycle at high temperature of a simulated cell assembled with the composite solid-state electrolyte according to the fifth example;
fig. 6 is a diagram showing electrochemical cycles at high temperatures of a simulated cell assembled with the composite solid-state electrolyte according to the sixth example.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
The invention provides a novel composite solid electrolyte and a preparation method thereof based on the problem that the cycle performance of the existing solid electrolyte in the prior art is not ideal at a higher temperature, and the composite solid electrolyte still has good cycle performance at a higher temperature; and further provides a lithium ion battery comprising the composite solid electrolyte.
The embodiment of the invention firstly provides a composite solid electrolyte, which comprises inorganic ceramic powder, lithium salt and an organic solvent, wherein the inorganic ceramic powder and the lithium salt are doped to form a framework, and the organic solvent is adsorbed on the framework.
In a preferred scheme, in the composite solid electrolyte, the content of the inorganic ceramic powder is 70-90 wt%, the content of the lithium salt is 1-20 wt%, and the content of the organic solvent is 1-20 wt%. In a more preferable scheme, the content of the inorganic ceramic powder is 70-85 wt%, the content of the lithium salt is 5-15 wt%, and the content of the organic solvent is 2-15 wt%.
Wherein the inorganic ceramic powder may be at least one selected from LL ZSO, LL SBO, LL ZGO, LL ZTO, L TPOSpecifically, LL ZSO has a chemical formula of L i7La3Zr2-xSnxO12Wherein x is 0-1, and LL SBO has a chemical formula of L i6.25La3Sn1.25Bi0.75O12LL ZGO has a chemical formula of L i7La3Zr1.7Ge0.3O12LL ZTO has a chemical formula of L i6.75La3Zr1.75Ta0.25O12L TPO has a chemical formula of L iTa2PO8。
Further, the inorganic ceramic powder is nano-particles, and the preferable particle size range of the inorganic ceramic powder is 300-800 nm.
Among them, the lithium salt may be commercially available or may be synthesized by itself, and is not particularly limited herein. For example, it may be selected from at least one of lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium hexafluorophosphate, lithium bisoxalato borate, lithium oxalato difluoroborate, lithium perchlorate and lithium tetrafluoroborate.
Wherein the organic solvent is selected from organic solvents having specific physicochemical properties including low volatility, high polarity, good thermal stability, good physical and chemical stability, and different solubility by adjusting anion and cation, such as ionic liquid, and can be selected from 1-methyl-3-ethylimidazole dicyan imide, 1, 2-dimethyl-3-propyl imidazole chloride, 1-ethyl-2-methylpyrazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethane sulfimide salt, N-butylpyridinium bistrifluoromethane sulfimide salt, trimethylpropylammonium bistrifluoromethane sulfimide salt, N-methyl-N-propylpiperidine, 1-propyl-3-methylimidazole bistrifluoromethane sulfimide salt, N-propylphosphonium salt, N-methyl-N-propylpiperidine, 1-propyl-3-methylimidazole bistrifluoromethane sulfimide salt, N-methyl-N-propylphosphonium salt, N-methyl-, At least one of ionic liquid such as 1-butyl-3-methylimidazole bistrifluoromethanesulfonimide salt, N-methyl, butyl piperidine bistrifluoromethanesulfonimide salt, trimethyl phosphate, triethyl phosphate and the like.
The composite solid electrolyte provided in the above embodiment is a composite electrolyte material comprising inorganic ceramic powder and lithium salt as a framework support structure, and an organic solvent adsorbed in the framework as a common ion-conducting material, and can effectively promote dissociation of the lithium salt and improve free L i in the electrolyte+In turn, improves the ionic conductivity of the electrolyte at room temperature as well as at elevated temperatures. Specifically, the ionic conductivity of the composite solid electrolyte is 10 at the temperature of 25-150 DEG C-4～10-3In the range of S/cm, wherein the ionic conductivity at 150 ℃ is 9 × 10-4S/cm. in addition, the composite solid electrolyte provided in the above example has excellent electrochemical stability, oxidation potential greater than 5V (Vs L i/L i)+)。
The embodiment of the invention also provides a preparation method of the composite solid electrolyte, which comprises the following steps:
and S1, mixing the inorganic ceramic powder, the lithium salt and the organic solvent to form the composite electrolyte.
The lithium salt may be one used in the prior art for preparing lithium batteries, and may be at least one selected from lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium hexafluorophosphate, lithium bisoxalato borate, lithium oxalato difluoroborate, lithium perchlorate, and lithium tetrafluoroborate.
Further, the inorganic ceramic powder is at least one selected from LL ZSO, LL SBO, LL ZGO, LL ZTO and L TPO, wherein the chemical formula of LL ZSO is L i7La3Zr2-xSnxO12Wherein x is 0-1, and LL SBO has a chemical formula of L i6.25La3Sn1.25Bi0.75O12LL ZGO has a chemical formula of L i7La3Zr1.7Ge0.3O12LL ZTO has a chemical formula of L i6.75La3Zr1.75Ta0.25O12L TPO chemical formula L iTa2PO8. The addition of the inorganic ceramic powder helps to maintain the solid form of the electrolyte.
The organic solvent selected by the embodiment of the invention needs to be an organic solvent with the characteristics of low volatility, large polarity, good thermal stability, good physical and chemical stability, different dissolubility by adjusting anions and cations, and the like, such as ionic liquid. The thermal stability refers to that the electrolyte can stably exist under the high-temperature operation condition, does not generate phenomena of liquefaction, gasification or thermal decomposition and the like, and can be specifically prepared into a composite solid electrolyte by selecting a proper organic solvent according to the temperature requirement of the operation environment.
Specifically, the organic solvent may be selected from at least one of 1-methyl-3-ethylimidazole dicyanimide, 1, 2-dimethyl-3-propylimidazole chloride, 1-ethyl-2-methylpyrazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethane sulfonimide salt, N-butylpyridine bistrifluoromethane sulfonimide salt, trimethylpropylammonium bistrifluoromethane sulfonimide salt, N-methyl-N-propylpiperidine, 1-propyl-3-methylimidazole bistrifluoromethane sulfonimide salt, 1-butyl-3-methylimidazole bistrifluoromethane sulfonimide salt, N-methyl, butylpiperidine bistrifluoromethane sulfonimide salt, trimethyl phosphate, triethyl phosphate.
In step S1, the content of the organic solvent is 1-20 wt%, and when the content of the organic solvent is too high or too low, the viscosity of the mixture may not meet the molding requirement of the solid electrolyte. Further preferably, the content is in the range of 2 to 15 wt%.
In step S1, the content of the lithium salt is 1-20 wt%, and when the content of the lithium salt is higher than 20 wt%, the lithium salt is difficult to dissolve and the lithium salt residue phenomenon is likely to occur, and a more preferable content range is 5-15 wt%.
In step S1, the content of the inorganic ceramic powder is 70 to 90 wt%, and when the content of the inorganic ceramic powder is higher than 90 wt%, the mixture is easily cracked, and a more preferable content range is 70 to 85 wt%.
Further, in step S1, the raw materials may be mixed by various mixing methods, such as stirring, ultrasonic, ball milling, etc. Preferably, the mixing is carried out by a ball milling method, and the ball milling time is more than or equal to 0.5 h.
And S2, carrying out molding operation on the composite electrolyte to obtain the composite solid electrolyte.
In this step, the composite electrolyte is preferably subjected to a molding operation by a sheet-pressing method.
The preparation method of the composite solid electrolyte takes the inorganic ceramic powder, the lithium salt and the organic solvent as raw materials, and the raw materials are mixed and then moldedThe prepared composite solid electrolyte takes the composite electrolyte material of inorganic ceramic powder and lithium salt as a framework supporting structure, and takes an organic solvent absorbed in the framework as a common ion conducting material, so that the dissociation of the lithium salt can be effectively promoted, and the free L i in the electrolyte can be improved+In order to improve the ionic conductivity of the electrolyte at room temperature and at elevated temperature; meanwhile, because the composite solid electrolyte has high temperature resistance, the composite solid electrolyte can keep good electrochemical stability under high temperature.
The material of the positive electrode and the negative electrode is not limited herein, for example, the material of the positive electrode can be L iFePO4The negative electrode may be lithium metal.
As described above, the composite solid electrolyte provided by the embodiment of the invention can effectively promote the dissociation of lithium salt, and improve the free L i in the electrolyte+In order to improve the ionic conductivity of the electrolyte at room temperature and at elevated temperature; and the composite solid electrolyte can keep good electrochemical stability under high temperature condition. Therefore, the lithium ion battery assembled by other battery accessories and the composite solid electrolyte keeps normal working state at higher temperature.
The above-described composite solid electrolyte, the preparation method thereof, and the lithium ion battery of the present invention will be described below with reference to specific examples, and it will be understood by those skilled in the art that the following examples are merely specific typical examples of the above-described composite solid electrolyte, the preparation method thereof, and the lithium ion battery of the present invention, and are not intended to limit the entirety thereof.
Example one
LL ZTO is used as inorganic ceramic powder, lithium bistrifluoromethylsulfonyl imide is used as lithium salt, and N-butylpyridine bistrifluoromethylsulfonyl imide is used as organic solvent to prepare the composite solid electrolyte.
And step S1, weighing N-butylpyridine bis-trifluoromethanesulfonimide salt, lithium bis-trifluoromethanesulfonimide and LL ZTO according to the mass ratio of 5:15:80, putting the N-butylpyridine bis-trifluoromethanesulfonimide salt, the lithium bis-trifluoromethanesulfonimide and the LL ZTO into a ball milling tank, and performing ball milling for 30min to obtain the composite electrolyte.
Step S2: and tabletting the composite electrolyte material by using a tablet machine to obtain the composite solid electrolyte.
Example two
LL ZTO is used as inorganic ceramic powder, lithium bistrifluoromethylsulfonyl imide is used as lithium salt, and trimethyl phosphate is used as organic solvent to prepare the composite solid electrolyte.
And step S1, weighing trimethyl phosphate, lithium bistrifluoromethylsulfonyl imide and LL ZTO according to the mass ratio of 5:15:80, putting the weighed materials into a ball milling tank, and carrying out ball milling for 30min to obtain the composite electrolyte.
Step S2: and tabletting the composite electrolyte material by using a tablet machine to obtain the composite solid electrolyte.
EXAMPLE III
LL ZTO is used as inorganic ceramic powder, lithium bistrifluoromethylsulfonyl imide is used as lithium salt, and triethyl phosphate is used as organic solvent to prepare the composite solid electrolyte.
And step S1, weighing triethyl phosphate, lithium bistrifluoromethylsulfonyl imide and LL ZTO into a ball milling tank according to the mass ratio of 5:15:80, and ball milling for 30min to obtain the composite electrolyte.
Step S2: and tabletting the composite electrolyte material by using a tablet machine to obtain the composite solid electrolyte.
Example four
LL ZTO is used as inorganic ceramic powder, lithium bistrifluoromethylsulfonyl imide is used as lithium salt, and triethyl phosphate is used as organic solvent to prepare the composite solid electrolyte.
And step S1, weighing triethyl phosphate, lithium bistrifluoromethylsulfonyl imide and LL ZTO into a ball milling tank according to the mass ratio of 10:10:80, and ball milling for 30min to obtain the composite electrolyte.
Step S2: and tabletting the composite electrolyte material by using a tablet machine to obtain the composite solid electrolyte.
EXAMPLE five
L TPO is used as inorganic ceramic powder, lithium bistrifluoromethylsulfonyl imide is used as lithium salt, and triethyl phosphate is used as organic solvent to prepare the composite solid electrolyte.
And step S1, weighing triethyl phosphate, lithium bistrifluoromethylsulfonyl imide and L TPO according to the mass ratio of 5:15:80, putting the triethyl phosphate, the lithium bistrifluoromethylsulfonyl imide and the L TPO into a ball milling tank, and carrying out ball milling for 30min to obtain the composite electrolyte.
Step S2: and tabletting the composite electrolyte material by using a tablet machine to obtain the composite solid electrolyte.
EXAMPLE six
LL ZTO is used as inorganic ceramic powder, lithium bis (fluorosulfonyl) imide is used as lithium salt, and trimethyl phosphate is used as organic solvent to prepare the composite solid electrolyte.
And step S1, weighing trimethyl phosphate, lithium bis (fluorosulfonyl) imide and LL ZTO into a ball milling tank according to the mass ratio of 5:15:80, and ball milling for 30min to obtain the composite electrolyte.
Testing and analysis
The composite solid electrolyte obtained in the first to sixth embodiments and the Swagelok cell mold are assembled into a solid-state simulation battery, wherein the material of the positive electrode is selected from L iFePO4And the negative electrode is selected from lithium metal. The solid-state simulation battery is tested in a blue battery circulating system, and electrochemical circulation diagrams at high temperature of 150 ℃ are obtained and are respectively shown in figures 1-6. The electrochemical performance data obtained after 100 cycles of the test are shown in table 1:
TABLE 1 electrochemical Performance data after 100 cycles at 150 deg.C
Figure BDA0002471396290000081
As can be seen from table 1 and fig. 1 to 6, the solid state simulation batteries of the first to sixth examples can be charged and discharged at 150 ℃. It should be noted that, at the beginning of the test, a side reaction may occur at the interface between the electrode and the composite solid electrolyte to increase the internal resistance, which further causes a large capacity attenuation at the beginning of the cycle, and then the stable stage is entered, so in the data in table 1, the capacity retention rate of the solid-state simulation battery is calculated by the specific capacity at the 10 th cycle and the specific capacity after the 100 th cycle. Analyzing the test results, specifically as follows:
(1) a solid state simulated battery assembled from the composite solid state electrolyte prepared in example one: the coulomb efficiency is kept about 98 percent, and the initial specific capacity is about 120 mAh/g; after 100 cycles of charging and discharging, the specific capacity is about 97mAh/g, and the capacity retention rate is about 75 percent by taking the data of the 10 th cycle entering the cycle stable stage as the reference.
(2) A solid state simulated battery obtained from the composite solid state electrolyte assembly prepared in example two: the coulomb efficiency is kept about 96%, and the initial specific capacity is about 138 mAh/g; after 100 cycles of charging and discharging, the specific capacity is about 108mAh/g, and the capacity retention rate is about 81.8 percent by taking the data of the 10 th cycle entering the cycle stable stage as the reference.
(3) A solid state simulated battery assembled from the composite solid state electrolyte prepared in example three: the coulomb efficiency is kept at about 99 percent, and the initial specific capacity is about 140 mAh/g; after 100 cycles of charging and discharging, the specific capacity is about 130mAh/g, and the capacity retention rate is about 92.9 percent by taking the data of the 10 th cycle entering the cycle stable stage as the reference.
(4) A solid state simulation battery obtained by assembling the composite solid state electrolyte prepared in example four: the coulomb efficiency is kept at about 99 percent, and the initial specific capacity is about 96 mAh/g; after 100 cycles of charging and discharging, the specific capacity is about 73mAh/g, and the capacity retention rate is about 76.0 percent by taking the data of the 10 th cycle entering the cycle stable stage as the reference.
(5) A solid state simulated battery assembled from the composite solid state electrolyte prepared in example five: the coulomb efficiency is basically kept about 96 percent, and the initial specific capacity is about 55 mAh/g; after 100 cycles of charging and discharging, the specific capacity is about 35mAh/g, and the capacity retention rate is about 70.0 percent by taking the data of the 10 th cycle entering the cycle stable stage as the reference.
(6) Example six a solid state simulated battery was obtained from the composite solid state electrolyte assembly prepared: the coulomb efficiency is basically kept to be about 96 percent; after 10 cycles of charging and discharging, the stable cycle stage is started, and the specific capacity is about 26 mAh/g; after 100 cycles of charging and discharging, the specific capacity is about 16mAh/g, and the capacity retention rate is about 61.5 percent by taking the data of the 10 th cycle entering the cycle stable stage as the reference. The solid-state analog battery of this embodiment, which decays capacity faster at the beginning of the cycle, is possible because: lithium bis (fluorosulfonyl) imide is a lithium salt with better low-temperature performance; or side reaction occurs at the interface of the electrode and the composite solid electrolyte in the initial stage of circulation, so that the internal resistance is increased.
(7) The specific capacity values of the fourth to sixth examples are greatly different from those of the first to third examples, which are related to the difference between the materials and the dosage ratios adopted in the respective examples, but for the solid-state simulation batteries of the respective examples, the coulomb efficiencies after 100 cycles are all kept at 96-99%, the capacity retention rates are also high, and the batteries of the embodiments of the invention have excellent cycle performance at high temperature.
The above six embodiments and the test results can be combined to obtain: (a) batteries assembled by the composite solid electrolyte added with the organic solvent can stably run in a high-temperature environment (can be intuitively known through each electrochemical cycle diagram); (b) different lithium salts, inorganic ceramic powder or organic solvents and different raw material dosage ratios have different degrees of influence on the performance of the battery.
The above embodiments of the present invention provide a composite solid electrolyte and a preparation method thereof, where the composite solid electrolyte has good cycle performance at a higher temperature, and reference is made to the above analysis for details, which is not repeated. The examples then further provide for the use of the above-described composite solid-state electrolyte suitable for use in a lithium ion battery (in the form of a solid state simulated battery employed in the examples of the invention). The lithium ion battery containing the composite solid electrolyte can realize the aim of stable operation at high temperature, and has good promotion effect on the development of special equipment power batteries at high temperature.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.

Claims (10)

1. The composite solid electrolyte is characterized by comprising inorganic ceramic powder, lithium salt and an organic solvent, wherein the inorganic ceramic powder and the lithium salt are doped to form a framework, and the organic solvent is adsorbed on the framework.
2. The composite solid electrolyte according to claim 1, wherein the inorganic ceramic powder is contained in an amount of 70 to 90 wt%, the lithium salt is contained in an amount of 1 to 20 wt%, and the organic solvent is contained in an amount of 1 to 20 wt%.
3. The composite solid electrolyte according to claim 2, wherein the inorganic ceramic powder is contained in an amount of 70 to 85 wt%, the lithium salt is contained in an amount of 5 to 15 wt%, and the organic solvent is contained in an amount of 2 to 15 wt%.
4. The composite solid electrolyte as claimed in any one of claims 1 to 3, wherein the inorganic ceramic powder is at least one selected from LL ZSO, LL SBO, LL ZGO, LL ZTO and L TPO, and wherein LL ZSO has a chemical formula of L i7La3Zr2- xSnxO12Wherein x is 0-1, and LL SBO has a chemical formula of L i6.25La3Sn1.25Bi0.75O12LL ZGO has a chemical formula of L i7La3Zr1.7Ge0.3O12LL ZTO has a chemical formula of L i6.75La3Zr1.75Ta0.25O12L TPO has a chemical formula of L iTa2PO8。
5. The composite solid electrolyte according to any one of claims 1 to 3, wherein the lithium salt is at least one selected from the group consisting of lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium oxalato difluoro borate, lithium perchlorate and lithium tetrafluoroborate.
6. The composite solid electrolyte according to any one of claims 1 to 3, wherein the organic solvent is selected from the group consisting of 1-methyl-3-ethylimidazole dicyanimide, 1, 2-dimethyl-3-propylimidazole chloride, 1-ethyl-2-methylpyrazole tetrafluoroborate, 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, N-butylpyridinium bistrifluoromethylsulfonyl imide salt, trimethylpropylammonium bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpiperidine, 1-propyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-butyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidinium bistrifluoromethylsulfonyl imide salt, N-methyl-ethyl-3-imidazolium bistrifluoromethylsulfonyl imide salt, N-methyl-propyl-2-methyl-pyrazolium tetrafluoroborate, 1-ethyl-3-methylimidazole, At least one of trimethyl phosphate and triethyl phosphate.
7. The composite solid electrolyte of claim 4, wherein the inorganic ceramic powder is nanoparticles having a particle size in the range of 300 to 800 nm.
8. A method for preparing a composite solid electrolyte as claimed in any one of claims 1 to 7, comprising the steps of:
s1, mixing inorganic ceramic powder, lithium salt and an organic solvent to form a composite electrolyte;
and S2, carrying out molding operation on the composite electrolyte to obtain the composite solid electrolyte.
9. The production method according to claim 8, wherein in step S1, the mixing is performed by a ball milling method; in step S2, the composite electrolyte is subjected to a molding operation using a sheet pressing method.
10. A lithium ion battery comprising the composite solid electrolyte according to any one of claims 1 to 7.
CN202010349672.9A 2020-04-28 2020-04-28 Composite solid electrolyte, preparation method thereof and lithium ion battery Pending CN111403805A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021039834A1 (en) * 2019-08-30 2021-03-04 昭和電工株式会社 Lithium ion-conducting oxide
CN112467194A (en) * 2020-12-09 2021-03-09 中国科学院上海硅酸盐研究所 Organic-inorganic composite quasi-solid electrolyte and quasi-solid lithium battery
WO2022186160A1 (en) * 2021-03-01 2022-09-09 株式会社日本触媒 Electrolyte compact production method and electrolyte compact
WO2022230426A1 (en) * 2021-04-28 2022-11-03 昭和電工株式会社 Lithium ion conducting oxide and all solid battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105618134A (en) * 2016-01-07 2016-06-01 西南大学 Composite material utilizing ionic liquid to wrap carbon nanotube and preparation method of composite material and application of composite material as hydrogen evolution catalyst
CN105699455A (en) * 2016-03-23 2016-06-22 海南师范大学 Preparation method of ionic liquid modified carbon paste electrode
US20160285125A1 (en) * 2015-03-27 2016-09-29 Mason K. Harrup All-inorganic solvents for electrolytes
CN106040314A (en) * 2016-06-13 2016-10-26 中国科学院过程工程研究所 Preparation and application of coating catalyst using ionic liquid as binder
CN107464950A (en) * 2017-07-27 2017-12-12 中国科学院化学研究所 A kind of high salt concentration solid electrolyte and application
CN109755637A (en) * 2018-12-29 2019-05-14 浙江南都电源动力股份有限公司 Oxide ceramics composite solid electrolyte, preparation method and its application
CN110336073A (en) * 2019-07-04 2019-10-15 北京协同创新研究院 A kind of solid electrolyte and preparation method thereof, solid state battery and electronic equipment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160285125A1 (en) * 2015-03-27 2016-09-29 Mason K. Harrup All-inorganic solvents for electrolytes
CN105618134A (en) * 2016-01-07 2016-06-01 西南大学 Composite material utilizing ionic liquid to wrap carbon nanotube and preparation method of composite material and application of composite material as hydrogen evolution catalyst
CN105699455A (en) * 2016-03-23 2016-06-22 海南师范大学 Preparation method of ionic liquid modified carbon paste electrode
CN106040314A (en) * 2016-06-13 2016-10-26 中国科学院过程工程研究所 Preparation and application of coating catalyst using ionic liquid as binder
CN107464950A (en) * 2017-07-27 2017-12-12 中国科学院化学研究所 A kind of high salt concentration solid electrolyte and application
CN109755637A (en) * 2018-12-29 2019-05-14 浙江南都电源动力股份有限公司 Oxide ceramics composite solid electrolyte, preparation method and its application
CN110336073A (en) * 2019-07-04 2019-10-15 北京协同创新研究院 A kind of solid electrolyte and preparation method thereof, solid state battery and electronic equipment

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021039834A1 (en) * 2019-08-30 2021-03-04 昭和電工株式会社 Lithium ion-conducting oxide
JP2021038099A (en) * 2019-08-30 2021-03-11 昭和電工株式会社 Lithium ion-conducting oxide
CN114402469A (en) * 2019-08-30 2022-04-26 昭和电工株式会社 Lithium ion conductive oxide
CN112467194A (en) * 2020-12-09 2021-03-09 中国科学院上海硅酸盐研究所 Organic-inorganic composite quasi-solid electrolyte and quasi-solid lithium battery
WO2022186160A1 (en) * 2021-03-01 2022-09-09 株式会社日本触媒 Electrolyte compact production method and electrolyte compact
WO2022230426A1 (en) * 2021-04-28 2022-11-03 昭和電工株式会社 Lithium ion conducting oxide and all solid battery

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Application publication date: 20200710