CN109659603B - Superfine solid electrolyte and preparation method thereof - Google Patents
Superfine solid electrolyte and preparation method thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2300/0065—Solid electrolytes
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Abstract
The invention discloses an ultrafine solid electrolyte and a preparation method thereof. The particle size D10 of the electrolyte is 50-100 nm, D50 is 100-200 nm, D90 is 200-400 nm, and Dmax is less than or equal to 500 nm. The preparation method of the superfine solid electrolyte comprises the following steps: 1) weighing reaction raw materials according to the ion ratio of Li to Al to M to P of 1+ X to 2-X to 3, wherein X is more than or equal to 0 and less than or equal to 1, and then carrying out wet grinding in a dispersion system containing a thickening agent until the particle size is less than 1 mu M to obtain a spray precursor; 2) spray drying to obtain a sintering precursor; 3) sintering and sanding until the grain diameter Dmax is less than or equal to 500nm to obtain the superfine solid electrolyte. The electrolyte has good processability and composite property, high ionic conductivity and is suitable for battery application. The method has the advantages of simple preparation process, low raw material cost, environmental friendliness, high product yield and convenience for industrial production.
Description
Technical Field
The invention relates to the field of solid electrolytes of lithium ion batteries, lithium metal batteries, lithium sulfur batteries and lithium air batteries, in particular to an ultrafine multi-element solid electrolyte material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in portable electronic products and electric vehicles because of their advantages of high operating voltage, long cycle life, no memory effect, low self-discharge, and environmental friendliness. Currently, several countries, including china, have established strategic goals for further increasing the energy density of power cells to the mid-and long-term range of 300-400 watt-hours/kg. According to the calculation, the weight energy density limit of the liquid lithium ion power battery formed by the high-voltage layered transition metal oxide and the graphite which are adopted at present as the positive and negative electrode active materials is about 280 Wh/kg. After the silicon-based alloy is introduced to replace pure graphite as a negative electrode material, the energy density of the lithium ion power battery is expected to be over 300Wh/kg, and the upper limit of the energy density is about 350 Wh/kg. For further achievement of higher energy density targets, lithium metal batteries with metallic lithium as the negative electrode have become a necessity of choice. This is because the capacity of lithium metal is 3860mAh/g, which is about 10 times of that of graphite, and since it is a lithium source, the cathode material has a wide selection range, and may be an intercalation compound containing lithium or no lithium, or may be sulfur or sulfide, or even air, to form a lithium-sulfur and lithium-air battery with higher energy density, respectively. However, a series of technical problems of the lithium metal negative electrode in the liquid battery still lack an effective solution so far, such as more interface side reactions of the lithium metal and the liquid electrolyte, uneven and unstable SEI film distribution, poor cycle life, uneven deposition and dissolution of the lithium metal, uneven formation of lithium dendrites and pores, and safety problems. For the above reasons, many researchers are looking to solve the application problem of the lithium metal negative electrode to the use of the solid electrolyte. The main idea is to avoid side reactions that continuously occur in the liquid electrolyte, and simultaneously to utilize the mechanical and electrical properties of the solid electrolyte to inhibit the formation of lithium dendrites.
However, the main methods for preparing the solid electrolyte at present are a high-temperature solid phase method and a sol-gel method, wherein the high-temperature solid phase method has a simple process, but can cause poor mixing effect of precursors, high required phase forming temperature and serious energy consumption; for example, in non-patent literature (h.aono. et al, j.electrochem. soc.137(1990)1023), the solid-phase method for preparing a titanium aluminum lithium phosphate solid electrolyte causes a phenomenon that the product is seriously adhered to the crucible wall, and thus industrialization is difficult. In the patent literature, CN105609881A discloses a method for preparing a solid electrolyte material by using sol-gel, which can avoid the disadvantages of the high-temperature solid phase method, but the sol-gel requires the addition of organic or inorganic additives, and moreover, the process of drying the sol by distillation takes too long, which leads to the increase of production cost and is not suitable for industrial production. CN105406118A discloses a method for preparing solid electrolyte by spray drying, which adopts a simple manner of mixing precursor and solvent, the operation process cannot avoid the phenomenon of sticking the wall of the product, which affects the yield of the product, and the particle size of the finally prepared solid electrolyte is in the micron order, which results in poor processability and composite property, and increased resistance between the interface between the electrolyte and the particles, which is not beneficial to subsequent utilization. Therefore, the most preferable particle size range of the solid electrolyte should be 500nm or less.
Therefore, it is a technical problem in the field of lithium ion batteries, lithium sulfur batteries and lithium air batteries to develop a simple and efficient method for preparing ultrafine solid electrolyte materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an ultrafine solid electrolyte and a preparation method thereof. The superfine solid electrolyte particles are very fine, the D10 is 50-100 nm, the D50 is 100-200 nm, the D90 is 200-400 nm, and the Dmax is less than or equal to 500 nm. The preparation method of the superfine solid electrolyte has the characteristics of simplicity, high efficiency, low energy consumption and easy industrialization.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an ultrafine solid electrolyte having a particle size D10 of 50nm to 100nm, for example 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, but not limited to the recited values, and other values not recited within the range of values are equally applicable; d50 is 100nm to 200nm, such as 100nm, 120nm, 140nm, 160nm, 180nm or 200nm, but not limited to the recited values, and other values not recited within the range of values are also applicable; d90 is 200 nm-400 nm, such as 200nm, 220nm, 240nm, 260nm, 280nm, 300nm, 320nm, 340nm, 360nm, 380nm or 400nm, but not limited to the values listed, and other values not listed in the range of values are also applicable; dmax is ≦ 500nm, for example 500nm, 480nm, 460nm, 440nm, 420nm or 400nm, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
In a preferred embodiment of the present invention, in the ultrafine solid electrolyte, the ionic ratio Li to Al to M to P is 1+ X to 2 to X to 3, 0. ltoreq. X.ltoreq.1, for example, X is 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, but not limited to the values listed, and other values not listed in the numerical range are also applicable; wherein M is any one or a combination of at least two of Ti, Si, Ge, Sn and Zr, typical but not limiting combinations are: combinations of Ti and Si, Ge and Sn, Sn and Zr, Ti, Si and Ge, Sn and Zr, Ti, Si, Ge and Sn, and the like.
Preferably, the ultrafine solid electrolyte has a specific surface area of 1m2/g～20m2G, e.g. 1m2/g、2m2/g、3m2/g、4m2/g、5m2/g、6m2/g、7m2/g、8m2/g、9m2/g、10m2/g、11m2/g、12m2/g、13m2/g、14m2/g、15m2/g、16m2/g、17m2/g、18m2/g、19m2G or 20m2And/g, but are not limited to the values listed, and other values not listed in the range are equally applicable, preferably 1.5m2/g～8.0m2/g。
Preferably, the ultra-fine solid electrolyte has a lithium ion conductivity of 1.0 × 10 at 25 deg.C (room temperature)-2S/m～1.0×10-6S/m, e.g. 1.0X 10-2S/m、1.0×10-3S/m、1.0×10-4S/m、10-5S/m or 10-6S/m, etc., but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
The superfine solid electrolyte provided by the invention is of an NASCION type structure, the particle size Dmax of particles is less than or equal to 500nm, the superfine solid electrolyte has a superfine nano structure, good processing and coating performances and high ionic conductivity, can effectively reduce the interfacial resistance between the electrolyte and the electrodes, and is more suitable for application on batteries.
In a second aspect, the present invention provides a method for preparing the ultrafine solid electrolyte according to the first aspect, the method comprising the steps of:
(1) weighing reaction raw materials according to the ion ratio of Li to Al to M to P of 1+ X to 2-X to 3, wherein X is more than or equal to 0 and less than or equal to 1, and then carrying out wet grinding in a dispersion system containing a thickening agent until the particle size is less than 1 mu M to obtain a spray precursor;
(2) spray drying to obtain a sintering precursor;
(3) sintering and sanding until the particle size Dmax is less than or equal to 500nm to obtain the superfine solid electrolyte;
wherein, M is any one or the combination of at least two of Ti, Si, Ge, Sn and Zr.
In the present invention, the wet grinding in step (1) is carried out to a particle size of less than 1 μm, for example, 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm or 0.1 μm, but not limited to the values listed, and other non-listed values within the range of values are also applicable, and particles having a particle size of less than 1 μm are obtained by limited wet grinding for subsequent spray drying, and such particle sizes are more spherical in the course of spray drying and lower sintering phase formation temperature is required subsequently.
Compared with the conventional high-temperature solid phase method, the spray drying technology adopted by the invention adopts wet mixing on the aspect of a precursor, and compared with solid phase mixing, the reaction raw materials can be fully mixed and reach micron-grade mixing, so that the preparation of a pure-phase electrolyte is realized, the phase forming temperature is lower than that of the solid phase method, and the effect of saving energy is achieved; and moreover, the spray drying technology is adopted, and compared with sol-gel, the drying efficiency is higher, and the industrial production is facilitated.
In the method, the grain diameter D50 of the solid electrolyte after high-temperature sintering is about 7 mu m, the grain diameter is larger, and the subsequent processing is not facilitated, and the invention adopts a sand grinding process after high-temperature sintering cooperatively to obtain the nano-scale superfine solid electrolyte, wherein Dmax is less than or equal to 500 nm. It can be seen that in the preparation method provided by the invention, the wet grinding technology, the spray drying technology, the high-temperature sintering and the sand grinding are tightly combined and work together to ensure that the ultrafine solid electrolyte is obtained.
As a preferred embodiment of the present invention, in step (1), the thickener includes but is not limited to any one or a combination of at least two of polyethylene, polyvinyl alcohol, polyvinyl methyl ester, polyethylene glycol, polyvinyl pyrrolidone, polyurethane, sodium carboxymethylcellulose, polyethylene oxide, or polybutadiene, and typical but not limited combinations are: combinations of polyethylene and polyvinyl alcohol, combinations of polyvinyl methyl ester and polyethylene glycol, combinations of polyvinylpyrrolidone and polyurethane, combinations of polyethylene, polyvinyl alcohol and polyvinyl methyl ester, combinations of polyethylene glycol, polyvinylpyrrolidone and polyurethane, combinations of sodium carboxymethylcellulose, polyethylene oxide and polybutadiene, and the like.
Preferably, in step (1), the thickener is present in an amount of 0.05% to 10%, for example 0.05%, 0.5%, 1%, 2%, 5%, 7%, 9% or 10% by mass based on 100% by mass of the total mass of the reaction raw material and the thickener-containing dispersion, but the thickener is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, in the step (1), in the dispersion system containing the thickener, the dispersant is any one or a combination of at least two of deionized water, ethanol, ethylene glycol, isopropanol or acetone, and typical but non-limiting combinations are as follows: a combination of deionized water and ethanol, a combination of ethylene glycol and isopropanol, a combination of isopropanol and acetone, a combination of ionized water, ethanol and ethylene glycol, a combination of ethylene glycol, isopropanol and acetone, and the like.
According to the invention, due to the use of a proper amount of the thickening agent, the sintering precursor prepared by subsequent spray drying has high sphericity, the phenomenon of sticking the crucible wall can not occur during sintering, and the yield of the product is improved.
As a preferred technical solution of the present invention, in the step (1), the source compound of Li is any one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium oxide or lithium phosphate, and typical but non-limiting combinations are: combinations of lithium hydroxide and lithium carbonate, lithium carbonate and lithium oxide, lithium oxide and lithium phosphate, lithium hydroxide, lithium carbonate and lithium oxide, lithium carbonate, lithium oxide and lithium phosphate, and the like.
Preferably, in step (1), the source compound of Al is any one or a combination of at least two of aluminum oxide, aluminum phosphate, aluminum hydroxide, aluminum isopropoxide or aluminum nitrate, typically but not limited to a combination of: combinations of aluminum oxide and aluminum phosphate, aluminum phosphate and aluminum hydroxide, aluminum isopropoxide and aluminum nitrate, aluminum oxide, aluminum phosphate and aluminum hydroxide, aluminum isopropoxide and aluminum nitrate, and the like.
Preferably, the source compound of M in step (1) is any one or a combination of at least two of titanium dioxide, tetrabutyl titanate, germanium dioxide, silicon dioxide, tin dioxide or zirconium dioxide, and typical but non-limiting combinations are: combinations of titanium dioxide and tetrabutyl titanate, combinations of germanium dioxide and silicon dioxide, combinations of tin dioxide and zirconium dioxide, combinations of titanium dioxide, tetrabutyl titanate and germanium dioxide, combinations of silicon dioxide, tin dioxide and zirconium dioxide, and the like.
Preferably, the source compound of P in step (1) is any one or a combination of at least two of phosphoric acid, phosphorus pentoxide, ammonium phosphate, ammonium dihydrogen phosphate or diammonium hydrogen phosphate, typically but not limited to a combination of: combinations of phosphoric acid and phosphorus pentoxide, combinations of phosphorus pentoxide and ammonium phosphate, combinations of ammonium dihydrogen phosphate and diammonium hydrogen phosphate, combinations of phosphoric acid, phosphorus pentoxide, and ammonium phosphate, combinations of ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, and the like.
As a preferred embodiment of the present invention, in step (1), the slurry solid content in the wet grinding process is 15% to 50%, for example, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, in step (1), the stirring speed in the wet-milling process is 20Hz to 60Hz, such as 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz or 60Hz, but not limited to the enumerated values, and other non-enumerated values within the range of values are equally applicable, preferably 40Hz to 60 Hz;
preferably, in step (1), the stirring time in the wet-milling process is 6h to 15h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14 or 15h, but is not limited to the recited values, and other unrecited values within the range of values are also applicable.
Preferably, in step (1), the wet milling process is performed using a wet mill.
Preferably, in the step (1), in the wet grinding process, the wet grinding system is a dispersion system containing zirconium balls.
Preferably, in step (1), the diameter of the zirconium balls in the wet grinding system is 1 mm.
As a preferable technical solution of the present invention, in the step (2), the spray dryer used in the spray drying process is any one of an open spray dryer or an inert gas protected closed spray dryer.
Preferably, in step (2), if an open spray dryer is used in the spray drying process, the inlet temperature is 180 ℃ to 280 ℃, such as 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃ or 280 ℃, but not limited to the recited values, and other non-recited values in the range of values are also applicable; the exit temperature is from 80 ℃ to 120 ℃, for example 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, etc., but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, in step (2), if the closed spray dryer is protected by inert gas in the spray drying process, the inlet temperature is 120 ℃ to 160 ℃, such as 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable; the exit temperature is 60 ℃ to 80 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but is not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, in step (2), the atomizer used in the spray drying process is any one of or a combination of at least two of a centrifugal type, a two-fluid type or a four-fluid type atomizer, typically but not limited to a combination of: a combination of centrifugal and two-fluid atomizers, a combination of two-fluid and four-fluid atomizers, a combination of centrifugal, two-fluid and four-fluid atomizers.
In a preferred embodiment of the present invention, in the step (2), the powder obtained by the spray drying has a median particle diameter of 4 μm to 10 μm, for example, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, but is not limited to the above-mentioned values, and other values not shown in the numerical range are also applicable.
In a preferred embodiment of the present invention, in the step (3), the sintering temperature is 600 to 950 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃, but the sintering temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and preferably 700 to 900 ℃.
Preferably, in step (3), the sintering time is 4h to 12h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in step (3), the temperature is raised to the sintering at a rate of 1 ℃/min to 20 ℃/min, such as 1 ℃/min, 2 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min, 14 ℃/min, 16 ℃/min, 18 ℃/min, or 20 ℃/min, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, in the step (3), the sintering is performed under an air atmosphere and/or an oxygen atmosphere. The "air atmosphere and/or oxygen atmosphere" in the present invention means that the atmosphere may be air atmosphere, oxygen atmosphere, or a mixed atmosphere of air and oxygen.
In a preferred embodiment of the present invention, in the step (3), the sand milling process is performed in a sand mill, and the rotation speed of the sand mill is preferably 2000rpm to 3000rpm, for example, 2000rpm, 2200rpm, 2400rpm, 2600rpm, 2800rpm, 3000rpm, or the like, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, in the step (3), in the sanding process, the sanding time is 4h to 10h, such as 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, in the step (3), in the sanding process, the sanding system is a dispersion system containing zirconium balls.
Preferably, in step (3), the diameter of the zirconium balls in the sanding system is any one of 0.1mm, 0.2mm and 0.3 mm.
Preferably, in step (3), the dispersant in the sanding system is any one or a combination of at least two of deionized water, ethanol, acetone or isopropanol, and typical but non-limiting combinations are as follows: a combination of deionized water and ethanol, a combination of ethanol and acetone, a combination of acetone and isopropanol, a combination of ionized water, ethanol, and acetone, a combination of ionized water, ethanol, acetone, and isopropanol, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the superfine solid electrolyte D10 provided by the invention is 50-100 nm, D50 is 100-200 nm, D90 is 200-400 nm, Dmax is less than or equal to 500nm, and the specific surface area can reach 20m2The lithium ion conductivity can reach 1.83 multiplied by 10-2S/m, and has superfine nanometer structure, good processing and coating performance, high ionic conductivity, and capacity of reducing the interface resistance between the electrode and the electrolyte, and is especially suitable for use in lithium ion cell, lithium sulfur cell, lithium air cell and other fields.
(2) The preparation method provided by the invention combines the high-energy ball milling technology of wet milling, the spray drying technology, the high-temperature sintering and the sand milling in a system containing the thickening agent to prepare the superfine solid electrolyte with various excellent properties. The method has the advantages of simple preparation process, low raw material cost, high finished product yield, environmental friendliness and convenience for industrial production.
Drawings
FIG. 1 is a scanning electron microscope photograph of an ultrafine solid electrolyte prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of an ultrafine solid electrolyte prepared in example 1 of the present invention;
FIG. 3 is a normal temperature AC impedance diagram of the ultrafine solid electrolyte prepared in example 1 of the present invention;
FIG. 4 is a graph showing AC impedance at different temperatures of the ultrafine solid electrolyte prepared in example 1 of the present invention;
FIG. 5 is a photograph of an ultrafine solid electrolyte obtained in comparative example 1 of the present invention;
fig. 6 is an electrochemical impedance spectrum of the solid electrolyte obtained in comparative example 2 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
The embodiment provides a method for preparing an ultrafine solid electrolyte, which comprises the following steps:
(1) according to the ionic proportion Li: al: ti: weighing a certain amount of lithium carbonate, aluminum oxide, titanium dioxide and ammonium dihydrogen phosphate when P is 1.4:0.4:1.6:3, adding the reactant raw materials into a wet grinder containing 1mm zirconium balls, then adding pure water, adjusting the solid content to 40%, firstly stirring for 2 hours at a stirring speed of 15Hz, then adding a thickening agent (polyvinylpyrrolidone) with the mass fraction of 5%, then stirring for 2 hours at a stirring speed of 15Hz, and then stirring for 6 hours at a stirring speed of 60Hz to obtain spray precursor slurry with the particle size of less than 1 mu m;
(2) spray drying the spray precursor slurry by using a two-fluid spray dryer, wherein the inlet temperature is 260 ℃, and the outlet temperature is controlled at 85 ℃, so that a sintering precursor with spherical micro-morphology is obtained;
(3) placing the sintering precursor in a box-type atmosphere furnace, introducing oxygen with the flow of 50ml/min, heating to 850 ℃ at the heating rate of 3 ℃/min, preserving the heat for 5h, and naturally cooling to room temperature to obtain large-particle solid electrolyte; and finally, sanding the large-particle solid electrolyte at the rotational speed of 2400rpm for 2h by respectively sanding zirconium balls with the particle sizes of 0.3mm and 0.1mm to obtain a final product with the particle size Dmax of 150nm, namely the superfine solid electrolyte named as LATP-900-RT.
Fig. 1 is a scanning electron microscope picture of the ultrafine solid electrolyte prepared in example 1 of the present invention, and it can be seen from fig. 1 that the particle size of the synthesized electrolyte particles is within 100nm, which illustrates that after sanding, the particles of the solid electrolyte are of a nano structure, which is advantageous for subsequent processing.
FIG. 2 is an X-ray diffraction pattern of the ultrafine solid electrolyte prepared in example 1 of the present invention, and it can be seen from FIG. 2 that the material has distinct NASICON structural peaks and no other miscellaneous peaks are found, indicating that the synthesized solid electrolyte has a high purity and the peak intensity becomes weak and broad, and indirectly demonstrating that the grains of the solid electrolyte are small.
FIG. 3 is a normal temperature AC impedance diagram of the ultrafine solid electrolyte prepared in example 1 of the present invention, and the lithium ion conductivity calculated using the AC impedance diagram of FIG. 3 is 1.83X 10-4S/cm, which shows that the synthesized electrolyte has very high ionic conductivity.
Fig. 4 is a graph of the ac impedance of the resultant electrolyte at different temperatures, illustrating the gradual rise in lithium ion conductance as the temperature increases.
Example 2
The embodiment provides a method for preparing an ultrafine solid electrolyte, which comprises the following steps:
(1) according to the ionic proportion Li: al: ti: weighing a certain amount of lithium hydroxide, aluminum nitrate, titanium dioxide and ammonium dihydrogen phosphate when P is 1.3:0.3:1.7:3, adding the reactant raw materials into a wet grinder containing 1mm zirconium balls, then adding pure water, adjusting the solid content to 50%, firstly stirring for 1.5h at the speed of 18Hz, then adding a thickening agent (carboxymethyl cellulose) with the mass fraction of 8%, continuously stirring for 3h while keeping the rotation speed unchanged, then increasing the rotation speed to 50Hz, and stirring for 8h to obtain spray precursor slurry with the particle size of less than 1 mu m;
(2) spray drying the spray precursor slurry by using a centrifugal spray dryer, wherein the inlet temperature is 280 ℃, the outlet temperature is controlled at 110 ℃, and a sintering precursor with spherical micro-morphology is obtained by spraying;
(3) placing the sintered precursor in a box-type atmosphere furnace, introducing oxygen, heating to 750 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 10 hours, and naturally cooling to room temperature to obtain large-particle solid electrolyte; and finally, sanding the large-particle solid electrolyte, wherein the sanding speed is 2200rpm, so that a final product with the particle size Dmax less than or equal to 400nm, namely the superfine solid electrolyte, can be obtained.
Example 3
The embodiment provides a method for preparing an ultrafine solid electrolyte, which comprises the following steps:
(1) according to the ionic proportion Li: al: ge: weighing a certain amount of lithium hydroxide, aluminum nitrate, germanium dioxide and ammonium dihydrogen phosphate when P is 1.3:0.3:1.7:3, adding the reactant raw materials into a wet grinder containing 1mm zirconium balls, then adding pure water, adjusting the solid content to 40%, firstly stirring at a low speed for 2h at a stirring speed of 15Hz, then adding a thickening agent (polyethylene glycol) with the mass fraction of 10%, stirring for 3h, then increasing the rotating speed to 45Hz, and after 10h, obtaining spray precursor slurry with the particle size of less than 1 mu m;
(2) spray drying the spray precursor slurry by using a four-fluid spray dryer, wherein the inlet temperature is 260 ℃, the outlet temperature is controlled at 110 ℃, and a sintering precursor with spherical micro-morphology is obtained by spraying;
(3) placing the sintering precursor in a box-type atmosphere furnace, introducing oxygen, heating to 950 ℃ at the heating rate of 3 ℃/min, preserving the heat for 5 hours, and naturally cooling to room temperature to obtain large-particle solid electrolyte; and finally, sanding the large-particle solid electrolyte, wherein the rotating speed is 2400rpm, and obtaining a final product with the particle size Dmax being less than or equal to 400nm, namely the superfine solid electrolyte.
Example 4
The embodiment provides a method for preparing an ultrafine solid electrolyte, which comprises the following steps:
(1) according to the ionic proportion Li: al: zr: weighing a certain amount of lithium oxide, aluminum nitrate, zirconium dioxide and diammonium hydrogen phosphate according to the proportion that P is 2:1:1:3, adding the reactant raw materials into a wet grinder containing 1mm zirconium balls, then adding pure water, adjusting the solid content to 15%, firstly stirring at low speed of 20Hz for 2h, then adding a thickening agent (polyethylene acid methyl ester) with the mass fraction of 10%, then stirring at low speed of 30Hz for 2h, and then stirring at high speed of 60Hz for 2h to obtain spraying precursor slurry with the particle size of less than 1 mu m;
(2) spray drying the spray precursor slurry by using a two-fluid spray dryer, wherein the inlet temperature is 180 ℃, the outlet temperature is controlled at 80 ℃, and a sintering precursor with spherical micro-morphology is obtained by spraying;
(3) placing the sintering precursor in a box-type atmosphere furnace, introducing oxygen with the flow of 50ml/min, heating to 900 ℃ at the heating rate of 1 ℃/min, preserving the heat for 4h, and naturally cooling to room temperature to obtain large-particle solid electrolyte; and finally, sanding the large-particle solid electrolyte, namely sanding the large-particle solid electrolyte for 2 hours in a sand mill at the rotating speed of 2000rpm by using a zirconium ball with the diameter of 0.3mm, and sanding the large-particle solid electrolyte for 8 hours at the rotating speed of 3000rpm by using a zirconium ball with the diameter of 0.1mm to obtain a final product with the particle size Dmax of less than or equal to 300nm, namely the superfine solid electrolyte.
Example 5
The embodiment provides a method for preparing an ultrafine solid electrolyte, which comprises the following steps:
(1) weighing a certain amount of lithium phosphate, tin dioxide and phosphorus pentoxide according to an ion ratio Li, Sn and P of 1:2:3, adding the reactant raw materials into a wet grinder containing 1mm zirconium balls, then adding pure water, adjusting the solid content to 50%, firstly stirring at a low speed of 30Hz for 2h, then adding a thickening agent (polyurethane) with the mass fraction of 0.05%, then stirring at a low speed of 30Hz for 3h, and then stirring at a high speed of 50Hz for 7h to obtain spraying precursor slurry with the particle size of less than 1 mu m;
(2) spray drying the spray precursor slurry by using a two-fluid spray dryer, wherein the inlet temperature is 260 ℃, the outlet temperature is controlled at 120 ℃, and a sintering precursor with spherical micro-morphology is obtained by spraying;
(3) placing the sintering precursor in a box-type atmosphere furnace, introducing oxygen with the flow of 50ml/min, heating to 700 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 12h, and naturally cooling to room temperature to obtain large-particle solid electrolyte; and finally, sanding the large-particle solid electrolyte, namely sanding for 3 hours in a sand mill at the rotating speed of 2000rpm by using a zirconium ball with the diameter of 0.3mm, and sanding for 4 hours at the rotating speed of 2500rpm by using a zirconium ball with the diameter of 0.1mm to obtain a final product with the particle size Dmax of less than or equal to 250nm, namely the superfine solid electrolyte.
Example 6
This example provides a method for preparing an ultra-fine solid electrolyte, which is described with reference to example 3, except that:
in the step (1), adding a thickening agent (polyethylene oxide) with the mass fraction of 3%;
in the step (2), spray drying is carried out on the spray precursor slurry by adopting an inert gas protection four-fluid spray dryer, wherein the inlet temperature is 120 ℃, and the outlet temperature is controlled at 70 ℃;
in the step (3), the temperature is raised to 600 ℃ for sintering.
Finally obtaining the final product with the grain diameter Dmax less than or equal to 300nm, namely the superfine solid electrolyte.
Example 7
This example provides a method for preparing an ultra-fine solid electrolyte, which is described with reference to example 3, except that:
in the step (1), a thickening agent (sodium carboxymethyl cellulose) with the mass fraction of 1% is added;
in the step (2), spray drying is carried out on the spray precursor slurry by adopting an inert gas protection four-fluid spray dryer, wherein the inlet temperature is 140 ℃, and the outlet temperature is controlled at 60 ℃;
finally obtaining the final product with the grain diameter Dmax less than or equal to 280nm, namely the superfine solid electrolyte.
Example 8
This example provides a method for preparing an ultra-fine solid electrolyte, which is described with reference to example 3, except that:
in the step (1), 7 mass percent of thickening agent (polybutadiene) is added;
in the step (2), spray drying is carried out on the spray precursor slurry by adopting an inert gas protection four-fluid spray dryer, wherein the inlet temperature is 160 ℃, and the outlet temperature is controlled at 80 ℃;
finally obtaining the final product with the grain diameter Dmax less than or equal to 280nm, namely the superfine solid electrolyte.
Comparative example 1
The specific procedure of this comparative example is as in example 1, except that: no thickener is used in step (1).
Fig. 5 is a photograph of the ultra-fine solid electrolyte product obtained after sintering without using a thickener, and it can be seen that the product is difficult to collect due to the phenomenon of sticking to the crucible, which greatly affects the production efficiency and productivity.
Comparative example 2
The specific procedure of this comparative example is as in example 1, except that: and (4) a sand grinding process is not used in the step (3).
Fig. 6 is an Electrochemical Impedance Spectroscopy (EIS) graph of the solid electrolyte product obtained in this comparative example without sanding, and it can be seen that the ion conductivity of the unground solid electrolyte product is much greater than that of the sanded ultrafine solid electrolyte product obtained in comparative example 1 (fig. 3).
As can be seen from the above examples 1-8 and comparative examples 1-2, the method of the present invention combines the wet milling technology, the spray drying technology, the high temperature sintering and the sand milling, and the matching with the thickening agent to prepare the ultrafine solid electrolyte of the present invention, wherein Dmax of the solid electrolyte is less than or equal to 500nm, the specific surface area is large, the lithium ion conductivity is high, the processability and the composite performance are good, and the method is very suitable for being used on batteries. The comparative examples, which did not use the thickening agent or the sanding technique, could not obtain the ultra-fine solid electrolyte having various excellent properties according to the present invention.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (34)
1. The superfine solid electrolyte is characterized in that the grain diameter D10 of the superfine solid electrolyte is 50 nm-100 nm, D50 is 100 nm-200 nm, D90 is 200 nm-400 nm, and Dmax is less than or equal to 500 nm; in the superfine solid electrolyte, the ionic ratio Li to Al to M to P is 1+ X to 2-X to 3, X is more than or equal to 0 and less than or equal to 1, wherein M is any one or the combination of at least two of Ti, Si, Ge, Sn and Zr.
2. The ultrafine solid electrolyte according to claim 1, wherein the ultrafine solid electrolyte has a specific surface area of 1m2/g～20m2/g。
3. The ultrafine solid electrolyte according to claim 2, wherein the ultrafine solid electrolyte has a specific surface area of 1.5m2/g～8.0m2/g。
4. The ultrafine solid electrolyte according to claim 1, wherein the ultrafine solid electrolyte has a lithium ion conductivity of 1.0 x 10 at 25 ℃-2S/m～1.0×10-6S/m。
5. The method for preparing the ultrafine solid electrolyte according to any one of claims 1 to 4, wherein the method comprises the steps of:
(1) weighing reaction raw materials according to the ion ratio of Li to Al to M to P of 1+ X to 2-X to 3, wherein X is more than or equal to 0 and less than or equal to 1, and then carrying out wet grinding in a dispersion system containing a thickening agent until the particle size is less than 1 mu M to obtain a spray precursor;
(2) spray drying to obtain a sintering precursor;
(3) sintering and sanding until the particle size Dmax is less than or equal to 500nm to obtain the superfine solid electrolyte;
wherein, M is any one or the combination of at least two of Ti, Si, Ge, Sn and Zr.
6. The method according to claim 5, wherein in the step (1), the thickener comprises any one or a combination of at least two of polyethylene, polyvinyl alcohol, polyvinyl methyl ester, polyethylene glycol, polyvinyl pyrrolidone, polyurethane, sodium carboxymethyl cellulose, polyethylene oxide, or polybutadiene.
7. The method according to claim 5, wherein in the step (1), the mass fraction of the thickener is 0.05 to 10% based on 100% by mass of the total mass of the reaction raw material and the dispersion containing the thickener.
8. The method according to claim 5, wherein in the step (1), in the dispersion system containing the thickener, the dispersant is any one or a combination of at least two of deionized water, ethanol, ethylene glycol, isopropanol or acetone.
9. The method according to claim 5, wherein in step (1), the source compound of Li is any one of lithium hydroxide, lithium carbonate, lithium oxide or lithium phosphate or a combination of at least two thereof.
10. The method as claimed in claim 5, wherein in step (1), the source compound of Al is any one or a combination of at least two of aluminum oxide, aluminum phosphate, aluminum hydroxide, aluminum isopropoxide or aluminum nitrate.
11. The method according to claim 5, wherein the source compound of M in step (1) is any one or a combination of at least two of titanium dioxide, tetrabutyl titanate, germanium dioxide, silicon dioxide, tin dioxide or zirconium dioxide.
12. The method of claim 5, wherein the source compound of P in step (1) is any one of phosphoric acid, phosphorus pentoxide, ammonium phosphate, ammonium dihydrogen phosphate or diammonium hydrogen phosphate, or a combination of at least two thereof.
13. The method according to claim 5, wherein in step (1), the slurry solids content in the wet milling process is between 15% and 50%.
14. The method according to claim 5, wherein in step (1), the stirring speed in the wet milling process is 20Hz to 60 Hz.
15. The method according to claim 5, characterized in that in step (1), the stirring time in the wet milling process is 6-15 h.
16. The method according to claim 5, wherein in the step (1), the wet grinding process is performed by using a wet grinder.
17. The method of claim 5, wherein in the step (1), in the wet grinding process, the wet grinding system is a dispersion system containing zirconium balls.
18. The method of claim 17, wherein in step (1), the diameter of the zirconium balls in the wet milling system is 1 mm.
19. The method according to claim 5, wherein in the step (2), the spray dryer used in the spray drying process is any one of an open spray dryer or an inert gas shielded closed spray dryer.
20. The method according to claim 19, wherein in the step (2), if an open spray dryer is used in the spray drying process, the inlet temperature is 180 ℃ to 280 ℃ and the outlet temperature is 80 ℃ to 120 ℃.
21. The method according to claim 19, wherein in the step (2), if the closed spray dryer is protected by inert gas, the inlet temperature is 120-160 ℃ and the outlet temperature is 60-80 ℃.
22. The method according to claim 5, wherein in step (2), the atomizer used in the spray drying process is any one of or a combination of at least two of a centrifugal type, a two-fluid type or a four-fluid type atomizer.
23. The method according to claim 5, wherein in the step (2), the median particle diameter of the powder obtained by spray drying is 4-10 μm.
24. The method according to claim 5, wherein the sintering temperature in step (3) is 600 ℃ to 950 ℃.
25. The method of claim 24, wherein in step (3), the sintering temperature is 700 ℃ to 900 ℃.
26. The method according to claim 5, wherein in the step (3), the sintering time is 4-12 h.
27. The method according to claim 5, wherein in the step (3), the temperature raising rate for raising the temperature to the sintering temperature is 1 ℃/min to 20 ℃/min.
28. The method according to claim 5, wherein in step (3), the sintering is performed under an air atmosphere and/or an oxygen atmosphere.
29. The method of claim 5, wherein in step (3), the sanding process is performed in a sand mill.
30. The method of claim 29, wherein the rotational speed of the sand mill is 2000rpm to 3000 rpm.
31. The method of claim 5, wherein in the step (3), the sanding process is carried out for 4-10 h.
32. The method of claim 5, wherein in the step (3), the sand grinding process is carried out by using a dispersion system containing zirconium balls.
33. The method of claim 32, wherein in step (3), the zirconium balls in the sanding system have a diameter of any one of 0.1mm, 0.2mm, or 0.3 mm.
34. The method of claim 32, wherein in step (3), the dispersing agent in the sanding system is any one or a combination of at least two of deionized water, ethanol, acetone, or isopropanol.
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| WO2021125344A1 (en) * | 2019-12-20 | 2021-06-24 | Ｄｏｗａエレクトロニクス株式会社 | Amorphous lithium ion-conductive oxide powder, method for producing same, and method for producing lithium ion-conductive oxide powder having nasicon crystal structure |
| CN111786015A (en) * | 2020-08-05 | 2020-10-16 | 长沙理工大学 | Novel composite anode and manufacturing method of all-solid-state lithium battery |
| CN111786014A (en) * | 2020-08-05 | 2020-10-16 | 长沙理工大学 | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof |
| CN112768755B (en) * | 2021-01-04 | 2022-05-20 | 长沙矿冶研究院有限责任公司 | Preparation method of NASION type solid electrolyte aluminum-containing phosphate |
| CN113224378B (en) * | 2021-04-27 | 2023-02-28 | 长江大学 | Lithium battery, solid electrolyte, and preparation method and application thereof |
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