CN115863748A - Preparation method of solid electrolyte material - Google Patents
Preparation method of solid electrolyte material Download PDFInfo
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- CN115863748A CN115863748A CN202211537237.4A CN202211537237A CN115863748A CN 115863748 A CN115863748 A CN 115863748A CN 202211537237 A CN202211537237 A CN 202211537237A CN 115863748 A CN115863748 A CN 115863748A
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Abstract
The invention relates to a preparation method of a solid electrolyte material. In the invention, the inner core of the oxide solid electrolyte is coated by the hydrogen phosphate or the dihydrogen phosphate, so that the oxide solid electrolyte material with high ionic conductivity and high stability is obtained. The solid electrolyte material has simple preparation process and high production efficiency, and is very suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of new energy. More particularly, the present invention relates to an undoped or doped oxide solid electrolyte having high ionic conductivity prepared by a solid phase reaction method, and then coated with phosphate to obtain an oxide solid electrolyte having high stability.
Background
The safety of the traditional lithium ion battery cannot be better guaranteed due to the use of electrolyte, and the energy density of the lithium ion battery reaches the bottleneck. The all-solid-state battery uses lithium metal to replace graphite as a negative electrode, so that the energy density of the battery is greatly improved, and the solid electrolyte replaces the traditional electrolyte, so that the safety problem of the battery can be fundamentally solved, and therefore, the all-solid-state battery is widely concerned in the academic world and the industrial world.
One of the core technologies of all-solid batteries is the solid electrolyte. The solid electrolyte includes an oxide solid electrolyte, a sulfide solid electrolyte, and a polymer solid electrolyte. The oxide solid electrolyte has high conductivity (10) -4 S/cm), good thermal stability, wide electrochemical window, and the like.
The oxide solid electrolyte needs to be made into a nanometer grade in the process of being processed into a solid electrolyte sheet, so that the oxide solid electrolyte sheet is more beneficial to being processed into the solid electrolyte sheet. Since an excessive amount of lithium salt is added to compensate for the absence of lithium at high temperature during the preparation of the oxide solid electrolyte, lithium on the surface tends to form an insulating layer of lithium carbonate in the air, which lowers the ionic conductivity of the electrolyte.
Attention has been paid to the problem that oxide solid electrolytes are prone to side reactions in air. The prior art is provided with a technique of coating the surface of an oxide solid electrolyte with a coating layer. However, these coating layers cause a decrease in lithium ion conductivity, and the coating methods thereof have problems that the steps are complicated and practical application is difficult.
Disclosure of Invention
Problems to be solved by the invention
The corresponding process of the solid electrolyte obtained by the existing preparation method is quite complex and tedious and is not suitable for amplification, and meanwhile, the solid electrolyte is exposed in the air to easily form lithium carbonate, so that the surface impedance of the electrolyte is obviously improved, and the conductivity is obviously reduced. The conventional coating layer can also cause the reduction of the lithium ion conductivity, and the coating method has complicated steps and is difficult to be practically applied.
Means for solving the problems
In the present invention, a solid electrolyte material comprising an oxide solid electrolyte core and a coating layer coated on the surface of the core, which has both high ionic conductivity and high stability, is obtained by applying a coating agent solution to a doped or undoped oxide solid electrolyte powder.
The invention provides a preparation method of a solid electrolyte material, which is characterized in that the solid electrolyte material comprises a doped or undoped oxide solid electrolyte core and a coating layer coated on the surface of the doped or undoped oxide solid electrolyte core, and the preparation method comprises the following steps:
step S1: applying a coating agent solution to a doped or undoped oxide solid electrolyte powder and optionally performing heat treatment, thereby obtaining a solid electrolyte material comprising a doped or undoped oxide solid electrolyte core and a coating layer coated on the surface of the doped or undoped oxide solid electrolyte core,
wherein the coating agent is hydrogen phosphate or dihydrogen phosphate.
The production method according to the above, wherein when the surface of the doped or undoped oxide solid electrolyte powder comprises lithium carbonate, the coating layer comprises lithium phosphate formed by reaction of the coating agent with the lithium carbonate; when lithium carbonate is not included on the surface of the doped or undoped oxide solid electrolyte powder, the coating layer includes the coating agent.
The production method according to the above, wherein the oxide solid electrolyte is at least one selected from a garnet-type oxide solid electrolyte, a perovskite-type oxide solid electrolyte.
The production method as described above, wherein the garnet-type oxide solid electrolyte has a chemical composition of Li 7-3x A x La 3 Zr 2-y B y O 12 Wherein the doped element A is Ga and/or Al, the doped element B is one or more of Ta, nb, ca, sr, ba, mo and W, x is more than or equal to 0 and less than or equal to 1.0, and y is more than or equal to 0 and less than or equal to 1.0;
the perovskite type oxide solid electrolyte is LLTO.
The production method according to the above, wherein the hydrogen phosphate comprises diammonium hydrogen phosphate, and the dihydrogen phosphate comprises one or both of ammonium dihydrogen phosphate and lithium dihydrogen phosphate.
The production method according to the above, wherein the particle diameter of the doped or undoped oxide solid electrolyte powder is 0.01 to 10 μm, preferably 0.1 to 5 μm.
The production method as described above, wherein the thickness of the coating layer is 10 to 300nm, preferably 30 to 200nm.
The production method described above, wherein the mass ratio of the coating agent to the doped or undoped oxide solid electrolyte powder is (0.1 to 20.0): 100, preferably (1.0 to 10.0): 100.
The production method according to the above, wherein when the coating layer includes lithium phosphate, the heat treatment is performed; when the coating layer includes the coating agent, the heat treatment is not performed.
The production method according to the above, wherein the conditions of the heat treatment are: heat treatment is carried out at 300 to 800 ℃, preferably 500 to 700 ℃ for 4 to 8 hours, preferably 5 to 7 hours.
The preparation method according to the above, wherein the solvent used in the coating agent solution is one or more of water and alcohol compounds.
The production method described above, wherein the concentration of the coating agent solution is 10 to 70 mass%, preferably 30 to 50 mass%.
The preparation method as described above, further comprising step S0: mixing, sintering and crushing the raw materials of the doped or undoped oxide solid electrolyte to obtain the doped or undoped oxide solid electrolyte powder.
The production method according to the above, wherein the sintering is two-step sintering.
The production method according to the above, wherein the applying of the coating agent solution to the doped or undoped oxide solid electrolyte powder includes: and spraying the coating agent solution onto the doped or undoped oxide solid electrolyte powder.
ADVANTAGEOUS EFFECTS OF INVENTION
The technical scheme of the invention has the following beneficial effects:
(1) The prepared oxide solid electrolyte is coated by a wet method, so that the coating agent reacts with lithium carbonate on the surface, lithium carbonate on the surface of the oxide solid electrolyte is consumed, and lithium ion conductor lithium phosphate is formed, the stability of the oxide solid electrolyte in the air is improved, the occurrence of surface side reaction is reduced, the diffusion rate of lithium ions can be improved by the lithium phosphate, the interface impedance is reduced, and the industrial production and use are facilitated.
(2) The phosphate-coated oxide solid electrolyte material obtained by the method provided by the invention is easy to process into a solid electrolyte film, has high stability in air, can obviously improve the conductivity stability of the all-solid battery in the air, and is very suitable for large-scale production and use.
Drawings
FIG. 1 is a surface SEM image of lithium lanthanum zirconium oxide coated with lithium phosphate obtained in example 1;
FIG. 2 is a TEM image of the surface of lithium lanthanum zirconium oxide coated with lithium phosphate obtained in example 1;
FIG. 3 is an XRD pattern of the solid state electrolyte materials obtained in examples 1 to 2, comparative example 1 and comparative example 2;
fig. 4 is an EIS chart of the solid electrolyte material pellet test obtained in examples 1 to 2, comparative example 1 and comparative example 2.
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims, and embodiments obtained by appropriately combining different embodiments and technical means disclosed in the embodiments are also included in the technical scope of the present invention. All documents described in this specification are incorporated herein by reference.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end points of numerical values a and B.
In the present specification, "plurality" of "plural", and the like means a numerical value of 2 or more unless otherwise specified.
In this specification, the terms "substantially", "substantially" or "substantially" mean an error of less than 5%, or less than 3%, or less than 1% as compared to the relevant perfect or theoretical standard.
In the present specification, "%" denotes mass% unless otherwise specified.
In the present specification, if "room temperature" or "normal temperature" is mentioned, the temperature may be generally 10 to 37 ℃ or 15 to 35 ℃.
In the present specification, the meaning of "may" or "may" includes both the meaning of the presence or absence of both the aspect and the aspect of performing a certain treatment and the aspect of not performing a certain treatment.
In this specification, "optional" and "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The terms "comprises" and "comprising," and any variations thereof in the description and claims of this invention and the above-described drawings, are intended to cover a non-exclusive inclusion. For example, a process, method, or system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
In the present specification, reference to "some/preferred embodiments", "embodiments", and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
In general, an excessive amount of lithium salt is required in the process of preparing an oxide solid electrolyte material such as lithium lanthanum zirconium oxide by a solid-phase sintering method, which may result in residual lithium oxide on the surface of the oxide solid electrolyte, and lithium carbonate is easily formed if contacting with air, which may result in significantly increasing the surface resistance of the oxide solid electrolyte, which is not favorable for the application thereof. According to the invention, the oxide solid electrolyte is coated with the phosphate by a wet method, so that the phosphate reacts with lithium carbonate on the surface of lithium lanthanum zirconium oxide to form lithium phosphate, thereby not only improving the stability of the lithium phosphate in the air and reducing the occurrence of surface side reactions, but also improving the diffusion rate of lithium ions by the lithium phosphate, reducing the interface impedance and being more beneficial to industrial production and use.
In addition, in some preferred embodiments of the present invention, doping the oxide solid electrolyte with gallium, tantalum, etc. can effectively improve the ordering of lithium ions in the material structure and promote the formation of cubic phase of the oxide solid electrolyte (the lithium ion conductivity of cubic phase lithium lanthanum zirconium oxygen can reach 10) -4 S/cm or more).
Specifically, the solid electrolyte material of the present invention includes a doped or undoped oxide solid electrolyte core and a coating layer coated on the surface of the oxide solid electrolyte core.
In the present invention, the oxide solid electrolyte is at least one selected from garnet-type oxide solid electrolytes and perovskite-type oxide solid electrolytes.
In the present invention, the chemical composition of the garnet-type oxide solid electrolyte is Li 7-3x A x La 3 Zr 2-y B y O 12 Wherein the doping element A is Ga and/or Al, preferably Ga; the doping element B is one or more of Ta, nb, ca, sr, ba, mo and W, and Ta and Nb are preferred.
In the above formula, x and y are each an arbitrary number of 0 to 1.0, preferably 0.1 to 0.75, more preferably 0.25 to 0.5. For example, x and y can be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, etc., respectively. Wherein x and y may be equal or different, and the ratio therebetween is not particularly limited.
In some preferred embodiments of the invention, x is not 0 and the doping element a is Ga. In other preferred embodiments, y is different from 0 and the doping element B is Ta. In some more preferred embodiments, x and y are both not 0 and doping element a is Ga and doping element B is Ta. When gallium and/or tantalum are adopted to carry out co-doping on lithium lanthanum zirconium oxide, the gallium and/or tantalum can effectively improve lithium ion in a material structureThe order of the lithium lanthanum zirconium oxygen cubic phase promotes the formation of the lithium lanthanum zirconium oxygen cubic phase (the conductivity of the cubic phase lithium ion can reach 10) -4 S/cm or more) so that the lithium lanthanum zirconium oxygen lithium ion conductivity can be improved.
In the invention, the perovskite type oxide solid electrolyte is lithium lanthanum titanium oxide LLTO, a doping element A of the perovskite type oxide solid electrolyte is Ga and/or Al, a doping element B of the perovskite type oxide solid electrolyte is one or more of Ta, nb, ca, sr, ba, mo and W, and Ta and Nb are preferred. When the gallium and/or the tantalum are adopted to carry out doping treatment on the lithium lanthanum titanium oxide LLTO, the gallium and/or the tantalum can more effectively promote the uniformity of lithium lanthanum titanium oxide particles, the compactness of the lithium lanthanum titanium oxide particles is obviously improved, and therefore the lithium ion conductivity of the lithium lanthanum titanium oxide can be improved. The preparation method of the solid electrolyte material of the invention comprises the following steps:
step S1, applying a coating agent solution to a doped or undoped oxide solid electrolyte powder and optionally performing heat treatment, thereby obtaining a solid electrolyte material including a doped or undoped oxide solid electrolyte core and a coating layer coated on a surface of the doped or undoped oxide solid electrolyte core.
In the present invention, the coating agent is hydrogen phosphate or dihydrogen phosphate. The hydrogen phosphate salt may include diammonium hydrogen phosphate, and the dihydrogen phosphate salt may include one or both of ammonium dihydrogen phosphate and lithium dihydrogen phosphate.
In the invention, when the surface of the doped or undoped oxide solid electrolyte powder comprises lithium carbonate, the coating layer comprises lithium phosphate formed by the reaction of a coating agent and the lithium carbonate; when the surface of the doped or undoped oxide solid electrolyte powder does not include lithium carbonate, the coating layer includes a coating agent.
In the present invention, the thickness of the coating layer may be 10 to 300nm, preferably 30 to 200nm, and more preferably 50 to 100nm. For example, the coating layer may have a thickness of 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, 250nm, 300nm, or the like. If the thickness of the clad layer is too thin, it cannot function as a protective layer, and if the thickness of the clad layer is too thick, it will adversely affect the lithium ion conductivity of the oxide solid electrolyte.
In the present invention, the mass ratio of the coating agent to the doped or undoped oxide solid electrolyte powder may be (0.1 to 20): 100, preferably (1 to 10): 100, more preferably (2 to 8): 100. For example, the mass ratio can be 0.1, 100, 0.5. By adopting the coating agent and the oxide solid electrolyte powder in the mass ratio, the coating agent can be better coated on the surface of the oxide solid electrolyte, and the lithium ion conductivity of the oxide solid electrolyte is not influenced by too much coating.
The solvent used in the coating agent solution is one or more of water and alcohol compounds. The alcohol compound may include ethanol, methanol, isopropanol, and the like. Among them, water is preferred. The concentration of the coating agent solution may be 10 to 70 mass%, preferably 30 to 50 mass%. The concentration of the coating agent solution of the invention cannot be too high or too low, and the too high or too low can cause the coating agent solution not to form uniform small droplets containing the coating agent when being sprayed, thereby influencing the uniformity of subsequent coating layers.
In the present invention, the manner of applying the coating agent solution to the doped or undoped oxide solid electrolyte powder is not particularly limited. For example, the coating agent solution may be uniformly applied to the surface of the oxide solid electrolyte powder by spraying, dropping, or the like. After the application of the coating agent solution, drying may be performed at a temperature of 50 to 150 ℃. The coating agent solution is preferably uniformly applied to the surface of the oxide solid electrolyte powder in a spraying mode, because the coating agent is dissolved by using as little water as possible, the coating agent is dispersed into small drops during spraying, the small drops are coated on the surface of the oxide solid electrolyte, and then drying is carried out, so that the obtained coating layer is uniform.
In the present invention, when the coating layer includes lithium phosphate, the above-described heat treatment is performed; when the coating layer includes a coating agent, the heat treatment is not performed.
When the heat treatment is performed, after the oxide solid electrolyte is dried, the heat treatment may be performed at 300 to 800 ℃, preferably 500 to 700 ℃ for 4 to 8 hours, preferably 5 to 7 hours. By this heat treatment, the coating agent can be reacted with lithium carbonate on the surface of the oxide solid electrolyte to form a lithium phosphate coating layer.
The reaction formula for the coating agent being ammonium dihydrogen phosphate is shown below:
the lithium phosphate coating layer is formed on the surface of the oxide solid electrolyte, so that the stability of the oxide solid electrolyte in the air is improved, the surface side reaction is reduced, and the lithium phosphate can improve the diffusion rate of lithium ions, thereby reducing the interface impedance.
In some preferred embodiments, the heat-treated solid electrolyte material may be sieved to obtain a more uniform particle size solid electrolyte material.
The method for producing a solid electrolyte material of the present invention further includes step S0, which is a step of producing an oxide solid electrolyte powder.
In the present invention, the method for producing the oxide solid electrolyte powder of the core is not particularly limited, and a method commonly used in the art, for example, a solid-phase sintering method, a sol-gel method, a coprecipitation method, or the like, can be used. Among them, the solid-phase sintering method is preferable in view of simple process and easy operation. The preparation of the oxide solid electrolyte powder is illustrated in the present invention by taking a solid-phase sintering method including two-step sintering as an example.
Specifically, the oxide solid electrolyte powder can be obtained by mixing, first ball-milling, first sintering, second ball-milling, second sintering, crushing and sieving the raw materials.
Raw materials
In the present invention, the raw material is not particularly limited. When the oxide solid electrolyte is a garnet-type oxide solid electrolyte LLZO, as the Li compound, la compound, zr compound, optionally the a compound and B compound as the dopant compound as the raw materials, salts, oxides, hydroxides, and the like thereof may be used. The salts may include, among others, carbonates, nitrates, acetates, halides, and the like. For the Li compound, a lithium salt or lithium hydroxide monohydrate may be used. From the viewpoint of easiness of obtaining raw materials and cost, it is preferable to use salts thereof such as lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and the like. As the La compound, lanthanum hydroxide, lanthanum oxide, lanthanum nitrate, and the like can be used. For the Zr compound, zirconia, zirconium carbonate, zirconium nitrate, or the like can be used. For the La compound and the Zr compound, it is preferable to use their oxides, i.e., lanthanum oxide, zirconium oxide, from the viewpoint of production cost.
The compound a as the dopant compound may be appropriately selected depending on the kind of the dopant element. For example, when the doping element includes Ta, a tantalate such as lithium tantalate or the like may be preferably used. When the doping element includes Nb, a niobate, such as lithium niobate or the like, may be preferably used. Further, lithium tantalate or lithium niobate is also preferably used from the viewpoint of lithium element supplementation. When the doping element includes Ca, sr, ba, mo, or W, an oxide or hydroxide thereof, for example, calcium oxide, calcium hydroxide, strontium oxide, strontium hydroxide, barium oxide, barium hydroxide, molybdenum oxide, molybdenum hydroxide, tungsten oxide, tungsten hydroxide may be used.
For the B compound as the doping compound, when the doping element is Ga, gallium oxide, gallium chloride, or the like; when the doping element is Al, aluminum oxide, aluminum hydroxide, or the like can be used.
When the oxide solid electrolyte is a perovskite type oxide solid electrolyte LLTO, the Li compound, la compound, ti compound and optionally a dopant compound as raw materials are also not particularly limited, and salts, oxides, hydroxides, and the like thereof may be used. The salts may include, among others, carbonates, nitrates, acetates, halides, and the like. For the Li compound, a lithium salt or lithium hydroxide monohydrate may be used. From the viewpoint of easiness of obtaining raw materials and cost, it is preferable to use salts thereof such as lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and the like. As the La compound, lanthanum hydroxide, lanthanum oxide, lanthanum nitrate, or the like can be used. For the Ti compound, titanium oxide, titanium chloride, or the like can be used. For the La compound and the Ti compound, their oxides, i.e., lanthanum oxide, titanium oxide, are preferably used from the viewpoint of production cost. As for the doping compound, it can be appropriately selected depending on the specific doping element, and specific examples are the same as in the above-described garnet-type oxide solid electrolyte.
In some embodiments of the invention, the above-described feedstock may optionally be pretreated. The pretreatment includes a pulverization treatment followed by a baking or drying treatment to reduce the particle size of the raw material and to reduce the moisture content in the raw material, so that the raw material powder is more uniformly mixed and the adverse effect of the moisture in the raw material on the product properties is reduced and one-step sintering is enabled. The particle sizes of the raw materials pretreated by this method are 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, and even more preferably 1 μm or less.
As for the pulverization treatment, a pulverizer such as a jet mill or the like commonly used in the art can be used. The roasting can be carried out for 5 to 10 hours at the temperature of 800 to 1000 ℃. The drying can be carried out at 100-150 ℃ for 4-10 hours. Generally, a firing treatment is employed for the La compound; for the Li compound, zr compound, ti compound and optionally doping compound, a drying treatment is employed.
The raw materials are weighed according to the chemical formula of the doped or undoped oxide solid electrolyte. In general, li needs to be excessive to compensate for the loss of lithium during sintering. The Li compound may be used in an excess of usually 5 to 30% by mass, preferably 10 to 20% by mass. For example, in the case of an oxide solid electrolyte of Li 7-3x A x La 3 Zr 2-y B y O 12 (wherein x is 0 to 1.0 and y is 0 to 1.0), each raw material may be weighed in such a manner that the molar ratio of Li to La to Zr to A is 7 to 3x (wherein x is 0 to 1.0 and y is 0 to 1.0) in terms of the element content.
First ball milling step
The optionally pretreated raw materials are weighed in the molar stoichiometric ratio of the formula or preferably in a lithium excess of 5 to 30% by mass and mixed and ball-milled in a ball mill pot to give a mixture.
In the present invention, the conditions for ball milling are not particularly limited, and can be appropriately adjusted according to actual conditions. For example, the rotational speed of the ball mill can be from 100 to 800r/min, preferably from 200 to 500r/min, and the ball milling time can be from 4 to 30h, preferably from 10 to 24 h. The mass ratio of the grinding balls to the raw material in the ball mill pot, i.e., the ball-to-material mass ratio, may be (1-5): 1, preferably (1-3): 1.
In order to make the mixture uniform and the particle size of the mixture small, the grinding balls are preferably formed by compounding balls of different diameters. For example, a large ball having a diameter of about 7 to 9mm, a medium ball having a diameter of 4 to 6mm, and a small ball having a diameter of 1 to 3mm may be blended at a predetermined mass ratio. The mass ratio can be 1 (1-3) to (1-5), preferably 1 (1-2) to (2-3). The grinding balls are also not particularly limited, and grinding balls commonly used in the art may be used, and examples thereof may include zirconia balls, silicon nitride balls, brown corundum balls, and the like. Among them, zirconia balls are preferably used.
In addition, a proper amount of solvent can be added into the ball-milling mixture. The solvent can be organic solvent such as methanol, ethanol, isopropanol, etc. When the solvent is added, the mass ratio of the solvent to the material can be (1-3) to 1.
A first sintering step (also called calcination step)
After the ball milling step, the obtained mixture is calcined, namely, sintered for the first time, so that a calcined material is obtained. In the present invention, the purpose of the first sintering is to decompose the raw materials, remove moisture, and preliminarily synthesize an oxide solid electrolyte.
Specifically, when the oxide solid electrolyte is a garnet-type oxide solid electrolyte, the conditions for the first sintering are: calcining at 800-1000 deg.C, preferably 850-950 deg.C for 3-12 h, preferably 5-10 h. When the oxide solid electrolyte is a perovskite-type oxide solid electrolyte, the conditions for the first sintering are as follows: calcining at 900-1100 deg.C, preferably 950-1000 deg.C for 3-18 h, preferably 6-12 h.
Second ball milling step
In order to promote the formation of cubic phases and to improve the crystallinity of the resulting electrolyte material, it is preferred to perform a second ball milling step between calcination and sintering. The conditions of the second ball milling step may be the same as in the first ball milling.
A second sintering step
After the second ball milling step, the resulting blend is subjected to a second sintering. The purpose of the second sintering is to synthesize a cubic phase, high crystallinity oxide solid electrolyte.
When the oxide solid electrolyte is a garnet-type oxide solid electrolyte, the second sintering conditions are: sintering at 950-1250 deg.c, preferably 1000-1200 deg.c for 4-24 hr, preferably 6-18 hr.
When the oxide solid electrolyte is a perovskite-type oxide solid electrolyte, the second sintering conditions are as follows: sintering at 1050-1350 deg.c, preferably 1200-1300 deg.c, for 3-18 hr, preferably 6-12 hr.
In the invention, the oxide solid electrolyte powder is prepared by a solid phase reaction method, the production process is simplified, the production efficiency is improved, and the obtained product has more perfect crystal form and can increase the relative density of the product by calcining and sintering.
Crushing and sieving step
And crushing and sieving the product obtained in the sintering step to obtain the oxide solid electrolyte powder.
In the invention, the oxide solid electrolyte powder obtained by crushing and sieving has a small amount of primary particles, most of the primary particles are secondary particles formed by the agglomeration of the primary particles, the particle size distribution of the primary particles is 0.01-2 mu m, and the particle size of the secondary particles is 1-10 mu m.
The crusher and the crushing conditions in the present invention are not particularly limited, and a crusher commonly used in the art may be used and the crushing conditions may be appropriately adjusted as long as an oxide solid electrolyte powder having a desired particle diameter can be obtained.
The particle diameter of the oxide solid electrolyte powder as the core may be 0.01 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.1 to 2 μm.
In general, a large excess amount of lithium salt is required in the preparation of an oxide solid electrolyte by a solid-phase sintering method, which results in the remaining of lithium oxide on the surface of the oxide solid electrolyte, and if lithium carbonate or lithium hydroxide is easily formed in contact with air, they significantly increase the surface resistance of the oxide solid electrolyte, which is not favorable for its application. In the invention, the solid-phase reaction method is adopted to prepare the oxide solid electrolyte material, the cubic phase structure of the material is stabilized by double doping of gallium and tantalum, the conductivity of lithium ion is improved, meanwhile, a layer of phosphate is coated on the surface of the oxide solid electrolyte, lithium carbonate on the surface of lithium lanthanum zirconium oxygen is consumed, lithium phosphate of a lithium ion conductor is formed, the generation of surface lithium carbonate can be reduced, and the stability of the lithium lanthanum zirconium oxygen in the air is improved. At the same time. In addition, the raw materials used in the invention can be oxides, the price is low, the process is simple, the yield is high, and the preparation method is suitable for large-scale industrial production.
Examples
The present invention will be described in detail below by way of examples. The examples of embodiments are intended to be illustrative of the invention and are not to be construed as limiting the invention. Those skilled in the art will recognize that the specific techniques or conditions, not specified in the examples, are according to the techniques or conditions described in the literature of the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Pretreatment of raw materials
Firstly, raw material Li 2 CO 3 、La 2 O 3 、ZrO 2 Separately jet milling with La 2 O 3 Placing the mixture into a muffle furnace to roast the mixture for 8 hours at 900 ℃, and Li 2 CO 3 And ZrO 2 Drying in an oven at 120 deg.C for 12 hr. And after roasting and drying, carrying out vacuum packaging for later use.
Example 1
S0, 60.96g of lithium carbonate (excess 20% mass fraction), 5.37g of gallium trioxide, 112.0g of lanthanum oxide, 49.42g of zirconium oxide, and 12.66g of tantalum pentoxide were weighed out in a ball mill pot in a molar ratio of Li: ga: la: zr: ta of 5. Preparing a large zirconia ball (with the diameter of 8 mm), a medium zirconia ball (with the diameter of 5 mm) and a small zirconia ball (with the diameter of 1 mm) into a mixed zirconia ball according to the mass ratio of 1. Weighing 220g of mixed zirconia balls according to a ball material mass ratio of 1, putting the mixed zirconia balls into a ball milling tank, setting a ball milling rotating speed of 500r/min, positively rotating for 30min, spacing for 30min, reversely rotating for 30min, ball milling for 24h, putting the uniformly mixed slurry into a vacuum oven for drying at 100 ℃ for 8h, putting the dried mixture into a crucible, covering the crucible, putting the crucible into a muffle furnace, heating to 950 ℃ at a speed of 2 ℃/min, pre-sintering for 6h, crushing and sieving the calcined material, and then continuously ball milling the calcined material, the zirconia balls and solvent isopropanol for 24h according to a mixing program, and then carrying out vacuum drying. Then the dried material is put into the crucible again and then put into a muffle furnace and heated to 1175 ℃ at the speed of 2 ℃/min for sintering for 6 hours, and then the sintered material is crushed and sieved to obtain the gallium and tantalum double-doped lithium lanthanum zirconium oxygen powder with the grain diameter of 0.05-2 mu m. The primary particles of lithium lanthanum zirconium oxygen are about 0.05 to 2 μm, and the particle size of the particles formed by the agglomeration of the primary particles is about 0.1 to 10 μm.
S1, mixing ammonium dihydrogen phosphate: deionized water =1, 10g of completely dissolved solution is uniformly sprayed on the surface of 100g of double-doped lithium lanthanum zirconium oxygen powder, then the solution is uniformly mixed after being dried at 100 ℃, the mixture is put into a crucible and then put into a muffle furnace for heat treatment at 600 ℃ for 6h to obtain a coated lithium lanthanum zirconium oxygen solid electrolyte, the coated lithium lanthanum zirconium oxygen solid electrolyte comprises a lithium lanthanum zirconium oxygen core and a lithium phosphate layer coated on the surface of the lithium lanthanum zirconium oxygen core, and the chemical composition of the lithium lanthanum zirconium oxygen core is Li 5 Ga 0.5 La 3 Zr 1.5 Ta 0.25 O 12 The particle size of the lithium lanthanum zirconium oxygen primary particle is 0.05-2 mu m. The surface SEM image of the lithium phosphate coated lithium lanthanum zirconium oxide is shown in figure 1, and the surface TEM image is shown in figure 2. As can be seen from fig. 1 (a), the overall particle size of the lithium lanthanum zirconium oxide is about 0.1-10 μm, and the EDS spectrum in fig. 1 (b) shows that the surface coating layer contains P element, which, in combination with the amorphous phase layer shown in fig. 2, indicates that the surface of the lithium lanthanum zirconium oxide particles is coated with a layer of lithium phosphate. Fig. 2 shows that the thickness of the surface-coated lithium phosphate is about 20 nm.
Example 2
S0, 48.96g of lithium carbonate (excess 20% mass fraction), 10.35g of gallium sesquioxide, 107.93 g of lanthanum oxide, 40.82g of zirconium oxide, and 24.40g of tantalum pentoxide were weighed out in a ball mill pot in a molar ratio of Li: ga: la: zr: ta of 5. Preparing a large zirconia ball (with the diameter of 8 mm), a medium zirconia ball (with the diameter of 5 mm) and a small zirconia ball (with the diameter of 1 mm) into a mixed zirconia ball according to the mass ratio of 1. Weighing 230g of mixed zirconia balls according to the ball material mass ratio of 1, putting the mixed zirconia balls into a ball milling tank, setting the ball milling speed at 500r/min, positively rotating for 30min, spacing for 30min, and reversely rotating for 30min, after ball milling for 24h, putting the uniformly mixed slurry into a vacuum oven at 100 ℃ for drying for 8h, after drying, putting the mixed material into a crucible, covering the crucible, putting the crucible into a muffle furnace, heating to 950 ℃ at a speed of 2 ℃/min for presintering for 6h, then crushing and sieving the calcined material, the zirconia balls and a solvent according to the mixing program, continuously ball milling for 24h, and then carrying out vacuum drying according to the mixing program in the proportion of 1. Then the dried material is put into the crucible again and then put into a muffle furnace and heated to 1175 ℃ at the speed of 2 ℃/min for sintering for 6 hours, and then the sintered material is crushed and sieved to obtain the gallium and tantalum double-doped lithium lanthanum zirconium oxygen powder with the grain diameter of 0.1-10 mu m.
S1, mixing ammonium dihydrogen phosphate: deionized water =1, 10g of completely dissolved solution is uniformly sprayed on the surface of 100g of double-doped lithium lanthanum zirconium oxygen powder, then the solution is uniformly mixed after being dried at 100 ℃, the mixture is put into a crucible and then put into a muffle furnace for heat treatment at 600 ℃ for 6h to obtain a coated lithium lanthanum zirconium oxygen solid electrolyte, the coated lithium lanthanum zirconium oxygen solid electrolyte comprises a lithium lanthanum zirconium oxygen core and a lithium phosphate layer coated on the surface of the lithium lanthanum zirconium oxygen core, and the chemical composition of the lithium lanthanum zirconium oxygen core is Li 6 Ga 0.25 La 3 Zr 1.75 Ta 0.5 O 12 The particle size of the lithium lanthanum zirconium oxygen core is 0.1-10 mu m, and the surface is coated with a layer of lithium phosphate.
Example 3
S0, 14.98g of lithium carbonate (excess 20% mass fraction), 110.11g of lanthanum oxide, 91.58g of titanium oxide, and 13.33g of tantalum pentoxide were weighed out in a ball mill pot in a molar ratio of Li: la: ti: ta of 0.28. Preparing a large zirconia ball (with the diameter of 8 mm), a medium ball (with the diameter of 5 mm) and a small ball (with the diameter of 1 mm) into a mixed zirconia ball according to the mass ratio of (1). Weighing 230g of mixed zirconia balls according to the ball material mass ratio of 1, putting the mixed zirconia balls into a ball milling tank, setting the ball milling speed at 500r/min, positively rotating for 30min, spacing for 30min, and reversely rotating for 30min, after ball milling for 24h, putting the uniformly mixed slurry into a vacuum oven at 100 ℃ for drying for 8h, after drying, putting the mixed material into a crucible, covering the crucible, putting the crucible into a muffle furnace, heating to 1000 ℃ at a speed of 2 ℃/min for presintering for 6h, then crushing and sieving the calcined material, the zirconia balls and a solvent according to the mixing program, continuously ball milling for 24h, and then carrying out vacuum drying according to the mixing program in the proportion of 1. And then putting the dried material into the crucible again, putting the crucible into a muffle furnace, heating to 1350 ℃ at the speed of 2 ℃/min, sintering for 12 hours, crushing and sieving the sintered material to obtain the tantalum-doped lithium lanthanum titanium oxide powder.
S1, mixing ammonium dihydrogen phosphate: deionized water =1, 10g of completely dissolved solution is uniformly sprayed on the surface of 100g of lithium lanthanum titanium oxide powder, then the solution is dried at 100 ℃ and uniformly mixed, the dried solution is placed into a crucible and then is placed into a muffle furnace for heat treatment at 600 ℃ for 6 hours to obtain a coated lithium lanthanum titanium oxide solid electrolyte, the coated lithium lanthanum titanium oxide solid electrolyte comprises a lithium lanthanum titanium oxide inner core and a lithium phosphate layer coated on the surface of the lithium lanthanum titanium oxide inner core, and the chemical composition of the lithium lanthanum titanium oxide inner core is Li lanthanum titanium oxide 0.28 La 0.56 Ti 0.95 Ta 0.05 O 3 The particle size of the lithium lanthanum zirconium oxygen core is 0.1-10 mu m, and the surface is coated with a layer of lithium phosphate.
Example 4
The mass ratio of the capping agent to the doped or undoped oxide solid electrolyte powder in this example was 0.5.
Example 5
The mass ratio of the coating agent to the doped or undoped oxide solid electrolyte powder in this example was 10.
Example 6
The mass ratio of the coating agent to the doped or undoped oxide solid electrolyte powder in this example was 17.
Example 7
The temperature of the heat treatment in this example was 350 ℃ and the time was 7.5 hours, and the other preparation steps and conditions were the same as in example 1.
Example 8
The temperature of the heat treatment in this example was 750 ℃ and the time was 5 hours, and the other preparation steps and conditions were the same as in example 1.
Example 9
The concentration of the coating agent solution in this example was 30wt%, and other preparation steps and conditions were the same as in example 1.
Comparative example 1 undoped uncoated
S0, 67.75g of lithium carbonate (excess 20%), 116.4g of lanthanum oxide and 58.7g of zirconium oxide were weighed out in a ball mill pot together with 230g of isopropanol according to a Li: la: zr molar ratio of 7. Preparing a large zirconia ball (with the diameter of 8 mm), a medium zirconia ball (with the diameter of 5 mm) and a small zirconia ball (with the diameter of 1 mm) into a mixed zirconia ball according to the mass ratio of 1. Weighing 230g of mixed zirconia balls according to a ball material mass ratio of 1, putting the mixed zirconia balls into a ball milling tank, setting a ball milling rotation speed of 500r/min, positively rotating for 30min, spacing for 30min, and reversely rotating for 30min, after ball milling for 24h, putting the uniformly mixed slurry into a vacuum oven for drying at 100 ℃ for 8h, after drying, putting the mixed material into a crucible, covering the crucible, putting the crucible into a muffle furnace, heating to 950 ℃ at a speed of 2 ℃/min, pre-sintering for 6h, crushing and sieving the calcined material, the zirconia balls and the solvent according to a mixing program in a ratio of 1. Then the dried material is put into the crucible again and then put into a muffle furnace and heated to 1200 ℃ at the speed of 2 ℃/min for sintering for 6h, and then the sintered material is crushed and sieved to obtain the lithium lanthanum zirconium oxygen powder with the grain diameter of 0.1-10 mu m.
Comparative example 2 doped uncoated
S0, 48.96g of lithium carbonate (excess 20% mass fraction), 10.35g of gallium sesquioxide, 107.93 g of lanthanum oxide, 40.82g of zirconia, and 24.40g of tantalum pentoxide were weighed out in a ball mill pot in a molar ratio of Li: ga: la: zr: ta of 5. Preparing a large zirconia ball (with the diameter of 8 mm), a medium zirconia ball (with the diameter of 5 mm) and a small zirconia ball (with the diameter of 1 mm) into a mixed zirconia ball according to the mass ratio of 1. Weighing 220g of mixed zirconia balls according to a ball material mass ratio of 1, putting the mixed zirconia balls into a ball milling tank, setting a ball milling rotating speed of 500r/min, positively rotating for 30min, spacing for 30min, reversely rotating for 30min, ball milling for 24h, putting the uniformly mixed slurry into a vacuum oven for drying at 100 ℃ for 8h, putting the dried mixture into a crucible, covering the crucible, putting the crucible into a muffle furnace, heating to 950 ℃ at a speed of 2 ℃/min, pre-sintering for 6h, crushing and sieving the calcined material, and then continuously ball milling the calcined material, the zirconia balls and the solvent for 24h according to a mixing program in a ratio of 1. Then the dried material is put into the crucible again and then put into a muffle furnace and heated to 1175 ℃ at the speed of 2 ℃/min for sintering for 6 hours, and then the sintered material is crushed and sieved to obtain the gallium and tantalum double-doped lithium lanthanum zirconium oxygen powder with the grain diameter of 0.1-10 mu m.
Test example
XRD tests were carried out on the solid electrolyte materials prepared in examples 1-9 and comparative examples 1-2, and XRD spectra of typical examples 1-2 and comparative examples 1-2, and examples 1-2 and comparative examples 1-2 are shown in FIG. 3. It can be seen that the gallium and tantalum double-doped lithium lanthanum zirconium oxide powder is a cubic phase with high crystallinity, and the undoped lithium lanthanum zirconium oxide contains a great amount of mixed phases and has low crystallinity, which indicates that the doping of gallium and tantalum can promote the generation of the cubic phase to a great extent. However, lithium lanthanum zirconium oxide coated with lithium phosphate has a slightly poorer crystallinity than that of uncoated lithium lanthanum zirconium oxide because amorphous lithium phosphate is formed on the surface of lithium lanthanum zirconium oxide.
Preparation of samples for electrical Property testing
Tabletting: 2g of the lithium phosphate-coated lithium lanthanum zirconium oxide solid electrolyte powder obtained in examples 1 to 9 or the lithium lanthanum zirconium oxide powder obtained in comparative examples 1 to 2 were weighed, and an aqueous solution of a polyvinyl alcohol (PVA) binder (containing 10 mass% of PVA) prepared in advance was added to the sample powder in a mass ratio of 10 to 30%, and the mixture was ground in an agate mortar to uniformly mix the powder with the PVA solution. After complete drying, the powder is filled in a die and kept for 10min under the pressure of 200MPa to obtain a molded wafer with the diameter of 17 mm;
rubber discharging: the pressed molded piece was placed in an oven at 50 ℃ and the solvent in the binder was dried. Then vertically placing the forming sheet in an open crucible, heating to 450 ℃ in a muffle furnace at a heating rate of 0.5-2 ℃/min, preserving heat for 5h, and then preserving heat for 5h at 950 ℃ to remove glue, thereby obtaining a ceramic sheet;
polishing and slurry coating: and (3) polishing and polishing the double surfaces of the ceramic wafer subjected to glue discharge, coating a layer of silver paste, and drying to obtain a test sample.
(1) Impedance value:
the impedance values of the test samples of examples 1 to 9 and comparative examples 1 to 2 prepared by the above-described methods were measured by the ac impedance test method. Specifically, the test samples were placed in a Chenghua electrochemical workstation to test the AC impedance with the frequency set to 0.1-0.1 MHz and the voltage amplitude set to 5mV, as shown in example 1-2 and comparative example 1-2, with the test results shown in FIG. 4.
As can be seen from fig. 4, the impedance spectrum of comparative example 1 has the largest semicircle, the highest impedance, and the lowest lithium ion conductivity; the semicircle of the impedance spectrum of example 1 is small, and the semicircle of the impedance spectrum of example 2 and comparative example 2 is minimum, which shows that the impedance value of example 2 and comparative example 2 is lowest, the lithium ion conductivity is highest, and the test results of examples 3-9 are similar to those of examples 1-2.
(2) Lithium ion conductivity:
the lithium ion conductivities of the test samples of examples 1 to 9 and comparative examples 1 to 2 were obtained as follows:
ionic conductivity σ = h/RA
In the formula: h-sample thickness (cm);
r-sample impedance (Ω);
a-circular cross-sectional area (cm) of sample 2 )
The impedance values and lithium ion conductivities of the lithium phosphate coated lithium lanthanum zirconium oxide obtained in examples 1-9, the lithium lanthanum zirconium oxide powders obtained in comparative example 1 and comparative example 2 were calculated by a fitting method using Zview 2 as a fitting software, typically as in comparative examples 1-2 and examples 1-2, and the results are shown in table 1 and the results of examples 3-9 are similar to those of example 1.
TABLE 1 impedance fitting values and corresponding lithium ion conductivities (25 ℃ C.)
As can be seen from the results of table 1, the initial powder lithium ion conductivity was the highest as in example 2 and comparative example 2, and example 1 was slightly inferior, and comparative example 1 had the lowest initial lithium ion conductivity and the highest resistance value because it was not doped; the lithium ion conductivity was significantly decreased after three days of air exposure because the coating was not performed in comparative example 1 and comparative example 2, and was not significantly decreased after three days of air exposure because the coating layer was formed on the electrolyte surface in example 1 and example 2.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Industrial applicability
The solid electrolyte material prepared by the method has high lithium ion conductivity and low impedance value, and the surface side reaction of the solid electrolyte material in the air is greatly reduced, so that the solid electrolyte material has high stability. The solid electrolyte material has simple preparation process and high production efficiency, and is very suitable for large-scale industrial production.
Claims (15)
1. A production method of a solid electrolyte material, characterized in that the solid electrolyte material comprises a doped or undoped oxide solid electrolyte core and a coating layer coated on a surface of the doped or undoped oxide solid electrolyte core, the production method comprising:
step S1: applying a coating agent solution to a doped or undoped oxide solid electrolyte powder and optionally carrying out a heat treatment, thereby obtaining a solid electrolyte material comprising a doped or undoped oxide solid electrolyte core and a coating layer coated on the surface of the doped or undoped oxide solid electrolyte core,
wherein the coating agent is hydrogen phosphate or dihydrogen phosphate.
2. The production method according to claim 1, wherein when the surface of the doped or undoped oxide solid electrolyte powder comprises lithium carbonate, the coating layer comprises lithium phosphate formed by reaction of the coating agent with the lithium carbonate;
when lithium carbonate is not included on the surface of the doped or undoped oxide solid electrolyte powder, the coating layer includes the coating agent.
3. The production method according to claim 1 or 2, wherein the oxide solid-state electrolyte is selected from at least one of garnet-type oxide solid-state electrolytes, perovskite-type oxide solid-state electrolytes.
4. The production method according to claim 3, wherein the garnet-type oxide solid electrolyte has a chemical composition of Li 7-3x A x La 3 Zr 2-y B y O 12 Wherein the doped element A is Ga and/or Al, the doped element B is one or more of Ta, nb, ca, sr, ba, mo and W, x is more than or equal to 0 and less than or equal to 1.0, and y is more than or equal to 0 and less than or equal to 1.0;
the perovskite type oxide solid electrolyte is LLTO.
5. The production method according to any one of claims 1 to 4, wherein the hydrogen phosphate salt includes diammonium hydrogen phosphate, and the dihydrogen phosphate salt includes one or both of ammonium dihydrogen phosphate and lithium dihydrogen phosphate.
6. The production method according to any one of claims 1 to 5, wherein the particle diameter of the doped or undoped oxide solid electrolyte powder is 0.01 to 10 μm, preferably 0.1 to 5 μm.
7. The production method according to any one of claims 1 to 6, wherein the thickness of the coating layer is 10 to 300nm, preferably 30 to 200nm.
8. The production method according to any one of claims 1 to 7, wherein the mass ratio of the coating agent to the doped or undoped oxide solid electrolyte powder is (0.1 to 20.0): 100, preferably (1.0 to 10.0): 100.
9. The production method according to any one of claims 1 to 8, wherein the heat treatment is performed when the coating layer comprises lithium phosphate;
when the coating layer includes the coating agent, the heat treatment is not performed.
10. The production method according to any one of claims 1 to 9, wherein the heat treatment is performed under the conditions: heat treatment is carried out at 300 to 800 ℃, preferably 500 to 700 ℃ for 4 to 8 hours, preferably 5 to 7 hours.
11. The preparation method according to any one of claims 1 to 10, wherein the solvent used in the coating agent solution is one or more of water and an alcohol compound.
12. The production method according to claim 11, wherein the concentration of the coating agent solution is 10 to 70 mass%, preferably 30 to 50 mass%.
13. The production method according to any one of claims 1 to 12, further comprising a step S0: mixing, sintering and crushing the raw materials of the doped or undoped oxide solid electrolyte to obtain the doped or undoped oxide solid electrolyte powder.
14. The production method according to claim 13, wherein the sintering is two-step sintering.
15. The production method according to claim 1, wherein the applying a coating agent solution to a doped or undoped oxide solid electrolyte powder includes: and spraying the coating agent solution onto the doped or undoped oxide solid electrolyte powder.
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