CN112768758A - Solid electrolyte, preparation method thereof, all-solid-state lithium ion battery and manufacturing method thereof - Google Patents

Solid electrolyte, preparation method thereof, all-solid-state lithium ion battery and manufacturing method thereof Download PDF

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CN112768758A
CN112768758A CN202110107970.1A CN202110107970A CN112768758A CN 112768758 A CN112768758 A CN 112768758A CN 202110107970 A CN202110107970 A CN 202110107970A CN 112768758 A CN112768758 A CN 112768758A
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lithium
solid
electrolyte
solid electrolyte
ion battery
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杨涛
唐泽勋
商士波
李捷帆
赵栋
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Hunan Sangrui New Material Co ltd
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Soundon New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention provides a solid electrolyte and a method for preparing the same, an all-solid lithium ion battery and a method for manufacturing the same, the solid electrolyte comprising: the electrolyte layer comprises one or more of lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate and lithium lanthanum titanium oxide; the coating layer contains a lithium-containing transition metal oxide. According to the solid electrolyte provided by the invention, the coating layer containing the lithium transition metal oxide is arranged on the electrolyte layer, the coating layer has good compatibility with the electrolyte layer, high ionic conductivity and good compatibility with the electrode material, so that the lithium ion conduction at the interface between the solid electrolyte and the electrode material can be improved, the interface impedance is effectively reduced, and the electrical performance of the solid lithium ion battery is improved.

Description

Solid electrolyte, preparation method thereof, all-solid-state lithium ion battery and manufacturing method thereof
Technical Field
The invention relates to the technical field of all-solid-state lithium ion batteries, in particular to a solid electrolyte and a preparation method thereof, and an all-solid-state lithium ion battery and a manufacturing method thereof.
Background
With the rapid development of the lithium ion battery technology, the lithium ion battery is widely applied in the fields of electric automobiles, portable electronic equipment and the like, so that the rapid development of the electric automobiles and the portable electronic equipment is promoted, and in the development process, people put forward higher requirements on the energy density and the safety of the lithium ion battery. At present, the electrolyte adopted by a large-scale commercial lithium ion battery is an organic electrolyte which is a very combustible substance, and when the lithium ion battery is in some extreme conditions (such as high temperature and overcharge), the combustion and even explosion of the organic electrolyte can be caused; in addition, organic electrolytes are also susceptible to decomposition and deterioration at high voltages. Therefore, it is urgently needed to develop an electrolyte which can enable the lithium ion battery to meet the energy density requirement and has higher safety.
In recent years, the solid electrolyte is nonflammable and has high electrochemical stability, so that the energy density of a cell can be greatly improved by coating the solid electrolyte on an electrode, and an all-solid lithium ion battery containing the solid electrolyte can meet the requirements of high safety and high energy density, so that the solid electrolyte becomes one of the hot points of research.
Solid state electrolytes of the prior art include polymer solid electrolytes, oxide-based, sulfide-based and halide solid electrolytes. Among them, oxide-based solid electrolytes have been widely studied because of their simple preparation, relatively low cost, and high stability.
At present, the oxide-based solid electrolyte and other types of solid electrolytes have great advantages in safety, and the ionic conductivity can reach or even exceed the level of a liquid electrolyte, but the compatibility between the solid electrolyte and an electrode material is poor, the interface impedance is high, and the further application of the solid electrolyte is limited.
Disclosure of Invention
In view of the above problems, the present invention provides a solid electrolyte and a method for preparing the same, an all-solid lithium ion battery and a method for manufacturing the same, which solves the problems of poor compatibility between the solid electrolyte and the electrode material and high interfacial resistance in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
in a first aspect, the present invention provides a solid-state electrolyte comprising:
an electrolyte layer comprising one or more of lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, and lithium lanthanum titanium oxide;
and the coating layer is coated on the electrolyte layer and contains lithium-containing transition metal oxide.
In some embodiments of the invention, the electrolyte layer comprises lithium aluminum titanium phosphate having the following general chemical formula:
Li1+xAlxTi2-x(PO4)3；
wherein x is a mole fraction, and x is more than 0 and less than 2.
In some embodiments of the invention, the lithium-containing transition metal oxide is Li2CoTi3O8。
In some embodiments of the present invention, the lithium-containing transition metal oxide is coated in an amount of 0.5 to 5.0% of the amount of the lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, or lithium lanthanum titanium oxide contained in the electrolyte layer.
In some embodiments of the invention, the particle size D of the lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate and lithium lanthanum titanium oxide contained in the electrolyte layer50Not more than 3 μm.
In a second aspect, the present invention also provides a method for preparing the solid electrolyte described in any one of the above embodiments, the method comprising the steps of:
1) mixing materials contained in the electrolyte layer with a transition metal source, a titanium source, a lithium source and a carbon source to obtain a mixture;
2) and calcining the mixture to obtain the solid electrolyte.
In some embodiments of the invention, the transition metal source is selected from at least one of lithium cobaltate, titanium dioxide and titanium carbide;
the lithium source is selected from at least one of lithium carbonate, lithium nitrate and lithium hydroxide;
the carbon source is at least one selected from the group consisting of acetylene black, carbon black and graphite.
In some embodiments of the invention, the temperature of the calcination is 700-1200 ℃ and the time of the calcination is 6-12 h.
In a third aspect, the present invention also provides an all-solid-state lithium ion battery comprising a positive electrode, a solid-state electrolyte and a negative electrode, wherein the solid-state electrolyte is the solid-state electrolyte described in any one of the above embodiments.
In a fourth aspect, the present invention further provides a method for manufacturing an all-solid-state lithium ion battery, including the steps of:
1) mixing the solid-state electrolyte described in any of the above embodiments with a binder to obtain a slurry;
2) coating the slurry on a positive electrode and/or a negative electrode;
3) assembling the anode and the cathode in the step 2) to obtain the all-solid-state lithium ion battery.
The embodiment provided by the invention has at least the following beneficial effects:
1) according to the solid electrolyte provided by the invention, the coating layer containing the lithium transition metal oxide is arranged on the electrolyte layer, the coating layer has good compatibility with the electrolyte layer, high ionic conductivity and good compatibility with the electrode material, so that the lithium ion conduction at the interface between the solid electrolyte and the electrode material can be improved, the interface impedance is effectively reduced, and the electrical performance of the solid lithium ion battery is improved.
2) According to the preparation method of the solid electrolyte, the coating layer can be generated on the surface of the electrolyte layer in situ, so that the prepared solid electrolyte has good compatibility with the electrolyte layer; in addition, the method is simple to operate, low in cost and suitable for industrial production.
3) The all-solid-state lithium ion battery provided by the invention contains the solid electrolyte, so that the all-solid-state lithium ion battery has high energy density and better safety performance.
4) The manufacturing method of the all-solid-state lithium ion battery can rapidly manufacture and obtain the all-solid-state lithium ion battery.
In addition to the technical problems addressed by the present invention, the technical features constituting the technical solutions, and the advantageous effects brought by the technical features of the technical solutions described above, other technical problems that can be solved by the solid electrolyte and the method for preparing the same, the all-solid lithium ion battery and the method for manufacturing the same, other technical features included in the technical solutions, and advantageous effects brought by the technical features of the present invention will be described in further detail in the detailed description.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a solid electrolyte prepared in example 1 of the present invention;
FIG. 2 is a graph showing Electrochemical Impedance Spectroscopy (EIS) of solid electrolytes produced in example 1 of the present invention and comparative example 1;
fig. 3 is a graph showing cycle-capacity retention rates of all solid-state lithium ion batteries manufactured in example 1 of the present invention and comparative example 1.
Detailed Description
The embodiments or implementation modes in the present specification are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments may be referred to each other.
In the description of the present specification, reference to the description of the terms "one embodiment", "some embodiments", "an illustrative embodiment", "an example", "a specific example", or "some examples", etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
The present invention firstly provides a solid electrolyte comprising: the electrolyte layer and the coating layer coated on the electrolyte layer.
The electrolyte layer contains one or more of Lithium Lanthanum Zirconium Oxide (LLZO), Lithium Aluminum Titanium Phosphate (LATP) and Lithium Lanthanum Titanium Oxide (LLTO), and the oxide solid electrolyte not only has higher lithium ion migration number, but also has better stability at high temperature, thereby improving the safety performance of the lithium ion battery. In addition, the oxide solid electrolyte and the coating layer of the lithium-containing transition metal oxide have good compatibility, and the coating layer of the lithium-containing transition metal oxide has good structural stability, so that the stability of the solid electrolyte can be further improved; and the coating layer containing the lithium transition metal oxide has higher lithium ion conductivity and good compatibility with the electrode material, so that the lithium ion conductivity at the interface where the solid electrolyte is contacted with the electrode material can be improved, the impedance at the interface can be effectively reduced, and the electrical property of the lithium ion battery can be improved.
In some embodiments of the present invention, the particle size D of the lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate and lithium lanthanum titanium oxide contained in the electrolyte layer50Not more than 3 μm. If the particle size is too large, the ionic conductivity and the coating effect are affected.
In some embodiments of the invention, LLZO may be selected to be Li7La3Zr2O12。
In some embodiments of the invention, the LATP may be formed from the general chemical formula Li1+xAlxTi2-x(PO4)3Wherein x is a mole fraction and can range in value from 0 < x < 2; in some embodiments, the LATP may be selected from Li1.3Al0.3Ti1.7(PO4)3And Li1.6Al0.6Ti1.4(PO4)3。
In some embodiments of the invention, LLTO may be formed from the chemical formula LiaLa2/(3-a)TiO3Wherein a is a mole fraction, and the numerical range may be 0 < a < 3.
As described above, the coating layer containing a lithium transition metal oxide has good structural stability, and can further improve the stability of the solid electrolyte. Wherein, the transition metal in the coating layer can be one or more selected from Co, Ti, Ni, Nb, Fe and Mn, and Ti and Co are preferred.
In some embodiments of the invention, the lithium-containing transition metal oxide may be Li2CoTi3O8。
Further, in order to improve the stability of the solid electrolyte and the compatibility of the solid electrolyte with the electrode material interface, the coating amount of the lithium-containing transition metal oxide is generally 0.5 to 5.0% of the amount of the lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate or lithium lanthanum titanium oxide contained in the electrolyte layer.
Illustratively, the above coating amount may be, but is not limited to, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%.
The present invention further provides a method of preparing a solid electrolyte according to any one of the above embodiments, comprising the steps of:
1) mixing materials contained in the electrolyte layer with a transition metal source, a titanium source, a lithium source and a carbon source to obtain a mixture;
2) and calcining the mixture to obtain the solid electrolyte.
In some embodiments of the present invention, the transition metal source may be selected from at least one of lithium cobaltate, titanium dioxide and titanium carbide, preferably lithium cobaltate and titanium dioxide.
The lithium source may be at least one selected from lithium carbonate, lithium nitrate and lithium hydroxide, preferably lithium carbonate.
The carbon source may be selected from at least one of acetylene black, carbon black and graphite, and is preferably acetylene black.
In some embodiments of the invention, the temperature of the calcination is 700-.
In some embodiments of the invention, the molar ratio of transition metal in the transition metal source, titanium in the titanium source, lithium in the lithium source, and carbon in the carbon source is 4:12:4: 3.
According to the preparation method of the solid electrolyte, the coating layer can be generated on the surface of the electrolyte layer in situ, so that the prepared solid electrolyte has good compatibility with the electrolyte layer; in addition, the method is simple to operate, low in cost and suitable for industrial production.
The invention also provides an all-solid-state lithium ion battery, which comprises a positive electrode, a solid electrolyte and a negative electrode, wherein the solid electrolyte is the solid electrolyte in any one of the embodiments.
In some embodiments of the present invention, the active component in the positive electrode may be selected from positive electrode materials such as lithium cobaltate, lithium iron phosphate, and nickel cobalt manganese. While the negative electrode typically employs a metallic lithium plate.
The all-solid-state lithium ion battery provided by the invention contains the solid electrolyte, so that the all-solid-state lithium ion battery has high energy density and better safety performance.
In addition, the invention also provides a manufacturing method of the all-solid-state lithium ion battery, which comprises the following steps:
1) mixing the solid-state electrolyte of any of the above embodiments with a binder to obtain a slurry;
2) coating the slurry on a positive electrode and/or a negative electrode;
3) assembling the anode and the cathode in the step 2) to obtain the all-solid-state lithium ion battery.
Hereinafter, the all solid-state lithium ion battery according to the present invention will be described in detail with reference to specific examples.
Unless otherwise specified, the chemical materials and instruments used in the following examples and comparative examples are all conventional chemical materials and conventional instruments, and are commercially available.
Example 1
The embodiment provides a preparation method of a solid electrolyte, which comprises the following steps:
1) weighing 9.6g of lithium carbonate, 3.06g of alumina, 27.2g of titanium dioxide and 69g of ammonium dihydrogen phosphate, uniformly mixing in a ball milling mode, calcining at 800 ℃ for 12h in an air atmosphere, cooling, and crushing to obtain LATP (Latin oxide phosphate), wherein the chemical formula of the LATP is Li1.3Al0.3Ti1.7(PO4)3；
2) 0.22g of lithium cobaltate and 1.1g of lithium cobaltate are weighed out7g of titanium dioxide, 0.08g of lithium carbonate and 0.01g of acetylene black are mixed with the prepared LATP uniformly in a ball milling mode, and the obtained mixture is calcined at 900 ℃ for 6 hours to obtain Li2CoTi3O8Coated LATP solid electrolyte, labeled C-LATP. Wherein Li2CoTi3O8The coating amount of (2) was 1%.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the solid electrolyte prepared in example 1.
The embodiment also provides a manufacturing method of the all-solid-state lithium ion battery, which comprises the following steps:
1) preparing a positive pole piece: reacting LiNi0.8Co0.1Mn0.1O2Mixing the positive electrode material, the superconducting carbon black and the PVDF binder according to the weight ratio of 94: 3, and preparing slurry by using NMP as a solvent according to a conventional process;
and coating the prepared slurry on an aluminum foil, and drying to obtain the positive pole piece.
2) Mixing the solid electrolyte prepared in the embodiment with a PVDF binder according to a weight ratio of 9:1, and preparing slurry by using NMP as a solvent according to a conventional process;
3) and coating the prepared slurry on a positive plate, and assembling the positive plate and a metal lithium plate serving as a negative electrode to obtain the all-solid-state lithium ion battery, wherein the battery is a 2032 type button battery.
Fig. 2 is a diagram of the electrochemical impedance of the solid electrolyte in this example, which is a typical nyquist curve, with the crossing half circles at low frequencies indicating the impedance of grain boundaries and bulk, and the slanted straight line being related to the warburg impedance.
Fig. 3 is a graph showing cycle duration-capacity retention of the all-solid-state lithium ion battery manufactured in this example. The all-solid-state ion battery is tested by adopting a blue test system at 25 ℃ (3.0-4.3V), the electrochemical test result is shown in figure 3, and as can be seen from figure 3, the capacity retention rate of 88 weeks at 0.5C circulation is 69.8%.
Similar results were obtained in subsequent examples using the same test methods.
Example 2
The embodiment provides a preparation method of a solid electrolyte, which comprises the following steps:
1) weighing 10.89g of lithium hydroxide, 4.68g of aluminum hydroxide, 27.2g of titanium dioxide and 79.2g of diammonium hydrogen phosphate, uniformly mixing in a ball milling mode, calcining at 700 ℃ for 10 hours in an air atmosphere, cooling, and crushing to obtain LATP (Latin oxide phosphate), wherein the chemical formula of the LATP is shown in the specification; li1.3Al0.3Ti1.7(PO4)3
2) 0.44g of lithium cobaltate, 2.34g of titanium dioxide, 0.16g of lithium carbonate and 0.02g of acetylene black are weighed and uniformly mixed with the prepared LATP in a ball milling mode, and the obtained mixture is calcined at 800 ℃ for 8 hours to obtain Li2CoTi3O8Coated LATP solid electrolyte. Wherein Li2CoTi3O8The coating amount of (2%).
The embodiment also provides a manufacturing method of the all-solid-state lithium ion battery, which comprises the following steps:
1) preparing a positive pole piece: subjecting LiCoO to condensation2Mixing the positive electrode material, the superconducting carbon black and the PVDF binder according to the weight ratio of 94: 3, and preparing slurry by using NMP as a solvent according to a conventional process;
and coating the prepared slurry on an aluminum foil, and drying to obtain the positive pole piece.
2) Mixing the solid electrolyte prepared in the embodiment with a PVDF binder according to a weight ratio of 9:1, and preparing slurry by using NMP as a solvent according to a conventional process;
3) and coating the prepared slurry on a positive plate, and assembling the positive plate and a metal lithium plate serving as a negative electrode to obtain the all-solid-state lithium ion battery, wherein the battery is a 2032 type button battery.
Example 3
The embodiment provides a preparation method of a solid electrolyte, which comprises the following steps:
1) weighing 9.6g of lithium carbonate, 4.68g of aluminum hydroxide, 27.2g of titanium dioxide and 58.8g of phosphoric acid, uniformly mixing in a ball milling mode, calcining at 950 ℃ for 16h in air atmosphere, cooling, and breakingCrushing to obtain LATP with the chemical formula of Li1.3Al0.3Ti1.7(PO4)3；
2) Weighing 1.1g of lithium cobaltate, 5.85g of titanium dioxide, 0.4g of lithium carbonate and 0.125g of graphite, uniformly mixing the lithium cobaltate, the titanium dioxide, the lithium carbonate and the graphite with the prepared LATP in a ball milling mode, and calcining the obtained mixture at 800 ℃ for 9 hours to obtain Li2CoTi3O8Coated LATP solid electrolyte. Wherein Li2CoTi3O8The coating amount of (2) was 5%.
The embodiment also provides a manufacturing method of the all-solid-state lithium ion battery, which comprises the following steps:
1) preparing a positive pole piece: subjecting LiCoO to condensation2Mixing the positive electrode material, the superconducting carbon black and the PVDF binder according to the weight ratio of 94: 3, and preparing slurry by using NMP as a solvent according to a conventional process;
and coating the prepared slurry on an aluminum foil, and drying to obtain the positive pole piece.
2) Mixing the solid electrolyte prepared in the embodiment with a PVDF binder according to a weight ratio of 9:1, and preparing slurry by using NMP as a solvent according to a conventional process;
3) and coating the prepared slurry on a positive plate, and assembling the positive plate and a metal lithium plate serving as a negative electrode to obtain the all-solid-state lithium ion battery, wherein the battery is a 2032 type button battery.
Comparative example 1
The present comparative example provides a method of preparing a solid electrolyte, comprising the steps of:
1) weighing 9.6g of lithium carbonate, 3.06g of alumina, 27.2g of titanium dioxide and 69g of ammonium dihydrogen phosphate, uniformly mixing in a ball milling mode, calcining at 800 ℃ for 12h in an air atmosphere, cooling, and crushing to obtain LATP (Latin oxide phosphate), wherein the LATP is marked as B-LATP, and the chemical formula of the LATP is Li1.3Al0.3Ti1.7(PO4)3；
The present comparative example also provides a manufacturing method of an all-solid-state lithium ion battery, the manufacturing method including:
1) preparing a positive pole piece: reacting LiNi0.8Co0.1Mn0.1O2Mixing the positive electrode material, the superconducting carbon black and the PVDF binder according to the weight ratio of 94: 3, and preparing slurry by using NMP as a solvent according to a conventional process;
and coating the prepared slurry on an aluminum foil, and drying to obtain the positive pole piece.
2) Mixing the solid electrolyte prepared by the comparative example with PVDF binder according to the weight ratio of 9:1, and preparing slurry by using NMP as a solvent according to a conventional process;
3) and coating the prepared slurry on a positive plate, and assembling the positive plate and a metal lithium plate serving as a negative electrode to obtain the all-solid-state lithium ion battery, wherein the battery is a 2032 type button battery.
Fig. 2 is a diagram of electrochemical impedance of the solid electrolyte in this comparative example, which shows a typical nyquist curve, with crossed semicircles at low frequencies indicating the impedance of grain boundaries and bulk, and a tilted straight line relating to the warburg impedance.
Fig. 3 is a graph showing cycle-capacity retention of the all-solid lithium ion battery manufactured by the present comparative example. The all-solid-state ion battery is tested by adopting a blue test system at 25 ℃ (3.0-4.3V), the electrochemical test result is shown in figure 3, and the capacity retention rate of the all-solid-state ion battery after being cycled for 100 weeks at 0.5C is 21.3% as can be seen from figure 3.
In summary, as can be seen from the test results of comparative example 1 and comparative example 1, the solid electrolyte provided by the present invention has good compatibility with the electrode material, so that the lithium ion conduction at the interface where the solid electrolyte and the electrode material are in contact can be improved, the impedance at the interface can be effectively reduced, and the electrical performance of the lithium ion battery can be improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A solid state electrolyte, comprising:
an electrolyte layer comprising one or more of lithium lanthanum zirconium oxide, lithium aluminum titanium phosphate, and lithium lanthanum titanium oxide;
a coating layer coated on the electrolyte layer, wherein the coating layer contains lithium-containing transition metal oxide.
2. The solid electrolyte of claim 1, wherein the electrolyte layer comprises lithium aluminum titanium phosphate having the following chemical formula:
Li1+xAlxTi2-x(PO4)3；
wherein x is a mole fraction, and x is more than 0 and less than 2.
3. Solid-state electrolyte according to claim 1 or 2, characterized in that the lithium-containing transition metal oxide is Li2CoTi3O8。
4. The solid electrolyte according to claim 3, wherein the coating amount of the lithium-containing transition metal oxide is 0.5 to 5.0% of the amount of the lithium lanthanum zirconium oxide, the lithium aluminum titanium phosphate, or the lithium lanthanum titanium oxide contained in the electrolyte layer.
5. The solid state electrolyte of claim 1, wherein the particle size D of the lithium lanthanum zirconium oxide, the lithium aluminum titanium phosphate and the lithium lanthanum titanium oxide contained in the electrolyte layer50Not more than 3 μm.
6. A method of producing a solid-state electrolyte according to any one of claims 1 to 5, comprising the steps of:
1) mixing materials contained in the electrolyte layer with a transition metal source, a titanium source, a lithium source and a carbon source to obtain a mixture;
2) and calcining the mixture to obtain the solid electrolyte.
7. The production method according to claim 6, wherein the transition metal source is selected from at least one of lithium cobaltate, titanium dioxide, and titanium carbide;
the lithium source is selected from at least one of lithium carbonate, lithium nitrate and lithium hydroxide;
the carbon source is at least one selected from the group consisting of acetylene black, carbon black and graphite.
8. The preparation method as claimed in claim 6, wherein the calcination temperature is 700-1200 ℃, and the calcination time is 6-12 h.
9. An all-solid-state lithium ion battery comprising a positive electrode, a solid electrolyte and a negative electrode, wherein the solid electrolyte is the solid electrolyte according to any one of claims 1 to 5.
10. A method for manufacturing an all-solid-state lithium ion battery, characterized by comprising the steps of:
1) mixing the solid electrolyte of any one of claims 1-5 with a binder to obtain a slurry;
2) coating the slurry on a positive electrode and/or a negative electrode;
3) assembling the anode and the cathode in the step 2) to obtain the all-solid-state lithium ion battery.
CN202110107970.1A 2021-01-27 2021-01-27 Solid electrolyte, preparation method thereof, all-solid-state lithium ion battery and manufacturing method thereof Pending CN112768758A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113851705A (en) * 2021-09-27 2021-12-28 哈尔滨理工大学 Method for modifying all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black
CN114497711A (en) * 2022-01-26 2022-05-13 合肥国轩高科动力能源有限公司 Composite solid electrolyte and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113851705A (en) * 2021-09-27 2021-12-28 哈尔滨理工大学 Method for modifying all-solid-state lithium ion battery interface by using two-dimensional titanium carbide-acetylene black
CN114497711A (en) * 2022-01-26 2022-05-13 合肥国轩高科动力能源有限公司 Composite solid electrolyte and preparation method thereof

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