CN111509222A - Halide solid electrolyte material and preparation method and application thereof - Google Patents
Halide solid electrolyte material and preparation method and application thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
- H01M2300/008—Halides
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Abstract
The invention relates to a halide solid electrolyte material, a preparation method and application thereof, wherein the halide solid electrolyte material is represented by the following formula L iaM1‑yCyX3+a+myWherein M is selected from one or more of Sc, Y and L a series elements, C is selected from one or more of Al, Ga, In, Bi, Sb, Fe, Co, Ni, Cu, Zn, Cr, Zr, Ag, Cd, Cs, Mg, Ca, Sr and Ba, X is selected from one or more of F, Cl, Br and I, a is more than or equal to 1 and less than or equal to 6, Y is more than or equal to 0.1 and less than or equal to 1.0, and M is the difference of chemical valence between C and M, the invention provides L IaM1‑yCyX3+a+myThe solid electrolyte material has high ionic conductivity and good humid air stability.
Description
Technical Field
The invention relates to a solid electrolyte material, in particular to a halide solid electrolyte material, a preparation method and application thereof.
Background
Along with the rapid development in recent years, various types of solid electrolyte materials such as sulfide electrolyte materials, oxide electrolyte materials, halide electrolytes and the like have been developed, wherein the halide electrolyte materials such as L i3YCl6、Li3InCl6The material and the high-voltage anode are stable and soft, are easy to form and process, and are expected to be applied to industry. However, most halide electrolytes have poor stability to humid air, and easily absorb water in the air to cause structural change and even hydrolysis, so that the ionic conductance of the material is rapidly attenuated. The development of halide electrolyte materials with better humid air/water stability is a key issue for further applications of this type of electrolyte.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a halide solid electrolyte material and a preparation method and application thereof.
An object of the present invention is to provide a halide solid state electrolyte material represented by the following formula,
LiaM1-yCyX3+a+my，
wherein M is selected from one or more of Sc, Y and L a series elements, C is selected from one or more of Al, Ga, In, Bi, Sb, Fe, Co, Ni, Cu, Zn, Cr, Zr, Ag, Cd, Cs, Mg, Ca, Sr and Ba, X is selected from one or more of F, Cl, Br and I, a is more than or equal to 1 and less than or equal to 6, Y is more than or equal to 0.1 and less than or equal to 1.0, and M is the difference of chemical valence between C and M.
According to some preferred embodiments of the invention, M is selected from one or more of Y, Ho, Er and Sc; and/or C is selected from one or more of Al, Ga, In, Bi, Fe and Zn; and/or a is more than or equal to 2 and less than or equal to 4; and/or, y is more than or equal to 0.25 and less than or equal to 0.95.
In the present invention, said L iaM1-yCyX3+a+myThe material has high ionic conductivity and good humid air stability, and does not react with water in the air when exposed to humid air or forms stable L i after reacting with wateraM1- yCyX3+a+my·nH2Intermediate phase O, which is subsequently dehydrated and then recovered to L iaM1-yCyX3+a+myThe electrolyte material, and accordingly the ionic conductivity, can also be restored.
According to some preferred embodiments of the present invention, the halide solid state electrolyte material is represented by any of the following formulas, L i3Y0.5In0.5Cl6、Li3Y0.4In0.6Cl6、Li3Y0.3In0.7Cl6、Li3Y0.2In0.8Cl6、Li3Y0.1In0.9Cl6、Li3Y0.5Bi0.5Cl6、Li2Ho0.4Al0.05In0.5Fe0.05Cl5。
In some preferred embodiments of the present invention, the halide solid state electrolyte material can obtain an effect of improving ion conductivity in addition to an effect of improving moisture air/water stability.
According to some preferred embodiments of the present invention, the halide solid state electrolyte material is a glass phase, a glass-ceramic phase, or a crystalline phase.
The invention also aims to provide a preparation method of the halide solid electrolyte material, wherein the C is introduced into L i-M-X halide electrolyte material, and the L i-M-X halide electrolyte material is L iaMX3+aThe compositions shown, where 1. ltoreq. a.ltoreq.6, preferably 2. ltoreq. a.ltoreq.4, give compositions of the type L i-M-C-X, in order to achieve a higher ionic conductivity and better wet air/water stability.
The inventor of the invention researches in practice to find that the hydration phase transformation process of the halide electrolyte after being exposed to humid air can be changed by doping other types of central elements into the halide electrolyte material L i-M-X and regulating the coordination capacity between central atoms and halogen and water molecules, so that stable L i-M-X-nH is obtained2The O intermediate phase avoids L i-M-X element phase separation, and can be recovered to the original L i-M-X electrolyte material after subsequent dehydration treatment, so that the stability and operability of the halide L i-M-X electrolyte material in wet air are realized.
In the invention, the C with better humid air stability is introduced, the L i-C-X material consisting of the element does not have L i phase separation with the C element after being exposed to humid air, the L i-C-X material does not dissolve in water or react with water to form L i-C-X nH2And (3) products of O.
In the present invention, the reaction with water forms L i-C-X.nH2Products of O specifically include, but are not limited to, L i3InCl6·H2O、Li3BiCl6·8H2O、Li2BiCl5·6H2O,Li2ZnCl4·2H2O,LiZnCl3·3H2O、LiMgCl3·7H2O、Li2.28Mn0.86Cl4·4H2O、LiCuCl3·2H2O、Li3ReCl6·12H2O. the L i-C-X material does not exhibit L i phase separation from the C element after exposure to humid air and includes but is not limited to L i6FeCl8、Li2FeCl4、Li2CdCl4、Li3GaCl6。
According to some preferred embodiments of the present invention, the L i-M-X halide electrolyte material has an ionic conductivity greater than 1 × 10-6S/cm。
The above-described halide electrolyte materials of the present invention can be prepared according to conventional techniques in the art.
According to some preferred embodiments of the present invention, the material is prepared by mixing the required raw materials or precursors according to a certain ratio and then grinding; or further adopting organic solvent codissolving recrystallization method, heating eutectic method, and method for making raw material granules contact in insoluble hydrocarbon organic solvent to obtain the compound with corresponding phase state.
According to some preferred embodiments of the present invention, NH is added during the mixing of the desired raw materials or precursors4Cl、I2L iI or S is used as a cosolvent, a fluxing agent or a ligand of a complex compound, and has the advantages of reducing the reaction temperature, forming a complex intermediate and the like, and being beneficial to the acquisition of products.
Another object of the present invention is to provide the use of the halide electrolyte material in a lithium secondary battery, preferably, as an electrode additive in a lithium secondary battery, or as an electrolyte in the preparation of a lithium secondary battery, using L i as described in the present inventionaM1-yCyX3+aThe electrolyte material can improve the ion transport speed of the electrode and is compatible with the existing electrode material of the lithium secondary battery.
Still another object of the present invention is a lithium secondary battery having at least one of a positive electrode layer, an electrolyte layer and a negative electrode layer containing one or more of the above-mentioned halide electrolyte materials; preferably, the lithium secondary battery includes a liquid-phase lithium secondary battery, a semi-solid-state lithium secondary battery, and an all-solid-state lithium secondary battery. In the present invention, the lithium secondary battery may be prepared according to a conventional method in the art.
According to the invention, the stability and operability of the halide L i-M-X electrolyte material in humid air are realized by doping L i-M-X material with one or more elements C with better humid air stability and regulating the coordination capacity between central atoms, halogen and water molecules by using the method, wherein the L i-M-X material has high ion conductivity but poor humid air stability, L i with both high ion conductivity and better humid air stability is obtainedaM1-yCyX3+a+myA solid electrolyte material.
The method and the obtained solid electrolyte material at least obtain a new material, the technical effect that the material has higher lithium ion conductivity and better humid air stability, and the technical effect that the material has chemical and electrochemical stability, so that the aim of storing or applying the halide electrolyte in a dry room and in an atmospheric environment is fulfilled.
Drawings
FIG. 1 is L i obtained in comparative example 1aMX3+a(M ═ Y, X ═ Cl, a ═ 3) XRD pattern of the solid electrolyte material.
FIG. 2 is L i obtained in comparative example 1aMX3+a(M ═ Y, X ═ Cl, a ═ 3) XRD patterns of solid electrolyte materials after exposure to humid air and subsequent dehydration reactions at 260, 500 degrees celsius.
FIG. 3 shows the glass-ceramic phase L i obtained in example 1aM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9) XRD patterns of the solid electrolyte materials.
FIG. 4 shows L i obtained in example 1 and comparative example 1aM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.2, 0.4, 0.5, 0.8, 0.9) and L iaMX3+a(M ═ Y, X ═ Cl, a ═ 3) XRD patterns of solid electrolyte materials dehydrated at 260 degrees celsius when exposed to humid air for 12 hours.
FIG. 5 shows L i obtained in example 1 and comparative example 1aM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.2, 0.5, 0.8) and L iaMX3+a(M ═ Y, X ═ Cl, a ═ 3) graph showing change in ion conductivity before and after exposure of solid electrolyte material to humid air
FIG. 6 shows L i obtained in example 1 and comparative example 1aM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.2, 0.4, 0.5, 0.8, 0.9) and L iaMX3+a(M ═ Y, X ═ Cl, a ═ 3) ion conductivity recovery after exposure of the solid electrolyte material to humid air.
FIG. 7 shows the glass-ceramic phase L i obtained in example 2aM1-yCyX3+a+my(M ═ Y, C ═ Bi, X ═ Cl, M ═ 0, a ═ 3, and Y ═ 0.5) impedance test curves obtained after the solid electrolyte material was exposed to humid air and dehydrated by heating.
FIG. 8 shows the glass-ceramic phase L i obtained in example 5aM1-yCyX3+a+my(M ═ Ho, C ═ Al, In, Fe, X ═ Cl, M ═ 0, a ═ 2, y ═ 0.6) solid electrolyte materials and their resistance change curves obtained after exposure to humid air and dry annealing at 450 ℃.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The raw materials used in the invention can be conveniently bought in domestic product markets.
In the examples of the present invention, the following X-ray diffraction was measured using copper K α radiation and synchrotron radiation source and the ion conductivity was measured using ac impedance by weighing 150 mg of electrolyte material in a glove box, then compressing it in a die cell at a pressure of 350MPa, then measuring the thickness of the electrolyte layer as L, then assembling it directly into a carbon/electrolyte/carbon symmetrical cell in the die cell, measuring the ac impedance of the cell under open circuit conditions, and calculating the impedance value as R using the formula σ L/(R · a), where σ is the ion conductivity, L is the thickness of the electrolyte layer, R is the impedance value, a is the electrode area of the electrolyte sheet, and the experiment of wet air stability was simulated in a dry box to adjust the corresponding humidity and air flow.
The raw materials involved in the embodiment of the invention are respectively lithium chloride, yttrium chloride, indium chloride, bismuth chloride, zinc chloride, holmium bromide, zinc bromide, erbium iodide, gallium iodide, aluminum chloride, ferric chloride, holmium chloride, lithium bromide and lithium iodide, and all the raw materials are analytically pure.
Example 1
This embodiment is L iaM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9) preparation of solid electrolyte materials and studies of humid air stability.
In a glove box, weighing:
1)3.81 g L iCl, 4.68 g YCl31.32 g of InCl3(y＝0.2)；
2)3.81 g L iCl, 4.1 g YCl31.99 g of InCl3(y＝0.3)；
3)3.81 g L iCl, 3.51 g YCl32.65 g of InCl3(y＝0.4)；
4)3.81 g L iCl, 2.93 g YCl33.31 g of InCl3(y＝0.5)；
5)3.81 g L iCl, 2.34 g YCl33.97 g of InCl3(y＝0.6)；
6)3.81 g L iCl, 1.76 g YCl34.63 g of InCl3(y＝0.7)；
7)3.81 g L iCl, 1.17 g YCl35.3 g of InCl3(y＝0.8)；
8)3.81 g L iCl, 0.59 g YCl35.96 g of InCl3(y＝0.9)；
Pouring the experimental proportions into a 100m L ball milling tank respectively for ball milling and mixing, wherein the ball-material ratio is 1:20, taking out the glove box after vacuum sealing, carrying out ball milling by adopting a planetary ball mill, the ball milling rotating speed is 550 revolutions per minute, the ball milling time is 10 hours, opening the glove box and scraping out the materials in the glove box after the ball milling is finished, pressing the ball-milled materials into 12 mm-sized pieces by adopting a tablet press, putting the 12 mm-sized pieces into a single-end quartz tube, sealing and taking out the single-end quartz tube by adopting a sealing film, sealing the single-end quartz tube by adopting a vacuum tube sealing mode, placing the vacuum tube in the muffle furnace for reaction at 260 ℃, keeping the temperature at 2 ℃ per minute, keeping the reaction time at 10 hours, cooling the tube, putting the tube into the glove box, opening the vacuum tube, and grinding the tubeaM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9) solid electrolyte materials.
Comparative example 1
This comparative example is L iaMX3+a(M ═ Y, X ═ Cl, a ═ 3) preparation of solid electrolyte material and study of stability in humid air, the same procedure as in example 1 was followed, except that the raw materials used in this comparative example were 3.81 g L iCl and 5.85 g YCl3。
FIG. 1 shows L i obtained in comparative example 1aMX3+a(M ═ Y, X ═ Cl, a ═ 3) the solid electrolyte material was pure L i3YCl6FIG. 2 shows L i obtained in comparative example 13YCl6The phase structure is converted into two phases after being exposed to humid air, which are L iCl. H2O and YCl6H2O. the original L i can not be recovered after the subsequent dehydration at 260 ℃ or 550 ℃ at the same time3YCl6Phase structure the product after dehydration was L iCl and YOCl material.
FIG. 3 shows the glass-ceramic phase L i obtained in example 1aM1-yCyX3+a+my(M ═ Y, C ═ In, X ═ Cl, M ═ 0, a ═ 3, Y ═ 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9) XRD patterns of solid electrolyte materials, it can be seen that 0.3. ltoreq. y.ltoreq.0.9 all gave materials similar to L i3InCl6XRD peak position shifts along the high angle direction as the value of y increases, indicating that the unit cell becomes smaller as y increases, labeled L i respectively3Y0.7In0.3Cl6、Li3Y0.6In0.4Cl6、Li3Y0.5In0.5Cl6、Li3Y0.4In0.6Cl6、Li3Y0.3In0.7Cl6、Li3Y0.2In0.8Cl6、Li3Y0.1In0.9Cl6。
FIG. 4 shows L i obtained in example 13Y0.8In0.2Cl6、Li3Y0.6In0.4Cl6、Li3Y0.5In0.5Cl6、Li3Y0.2In0.8Cl6、Li3Y0.1In0.9Cl6L i, the higher the stability of the obtained material to humid air, the more the phase structure can be restored to the original structure, from the change in XRD, the higher the stability of the obtained material to humid air, and the change in XRD before and after the exposure of the L i3YCl6 solid state electrolyte material to humid air, obtained in comparative example3YCl6The yield of L iCl and YOCl was predominantly achieved after humid air exposure and dehydration, as the value of y increased, the yield of L iCl by-product from the resulting material after humid air exposure and dehydration decreased, when y reached 0.5, only a small amount of L iCl was found to be produced, most of the XRD peaks were consistent with the initial unexposed sample, when y reached 0.8 and above, no L iCl by-product was seen, and all XRD peaks were consistent with the initial unexposed sample.
FIG. 5 shows L i obtained in example 13Y0.8In0.2Cl6、Li3Y0.5In0.5Cl6、Li3Y0.2In0.8Cl6And L i obtained in comparative example 13YCl6Ion conductivity of the solid electrolyte material before and after exposure to humid air is shown in the figure, L i is shown when the ion conductivity is measured at 25 degree centigrade3YCl6The room-temperature ion conductivity of the product before exposure to humid air reaches 7 × 10-5S/cm; the ionic conductivity of the product was reduced to 6 x 10 after wet air exposure and dehydration-7S/cm. differ by a factor of 100. y is 0.2, the room temperature ionic conductivity is 7 × 10 before and after exposure to air-4And 2 × 10-5S/cm, the difference between the front and the rear is 35 times, when the ion conductance is increased to 0.5, the ion conductance of the front and the rear is respectively 1.5 × 10-3And 4 × 10-4S/cm, with a difference of only 4 times before and after, and further, when the value of y is increased to 0.8, the room temperature ionic conductivity is 1.23 × 10 before and after exposure to air, respectively-3And 1.0 × 10-3S/cm, the ion conductivity curves substantially coincide. On the other hand, as y increases, not only does the wet air stability become good, but the room temperature ionic conductivity also becomes higher. The introduction of In the present embodiment can additionally obtain the effect of improving the ionic conductivity of the material.
FIG. 6 shows L i obtained in example 13Y0.8In0.2Cl6、Li3Y0.6In0.4Cl6、Li3Y0.5In0.5Cl6、Li3Y0.2In0.8Cl6、Li3Y0.1In0.9Cl6And L i obtained in comparative example 13YCl6A graph of the change in ionic conductivity before and after exposure of the solid state electrolyte material to humid air. The ionic conductivity was tested at 25 degrees celsius. As can be seen from the graph, as the value of y increases, the higher the retention of the ion conductivity of the resulting electrolyte material, indicating better moisture air stability.
The specific English meaning of Chinese in the attached figure is shown in Table 1
TABLE 1 attached drawings Chinese and English reference
| English language | Chinese character |
| intensity | Strength of |
| Degree | Angle of rotation |
| reheated | Reheating |
| After humidity exposure | After exposure to moisture |
| 3-5％humidity air exposed-reheat | Exposing to 3-5% humidity and then reheating for dehydration |
Example 2
This embodiment is L iaM1-yCyX3+a+my(M ═ Y, C ═ Bi, X ═ Cl, M ═ 0, a ═ 3, and Y ═ 0.5) preparation of solid electrolyte materials and wet air stability studies.
3.81 g L iCl and 2.93 g YCl were weighed in a glove box respectively34.73 g of BiCl3(M is Y, C is Bi, X is Cl, M is 0, a is 3, Y is 0.5), the above experimental proportions are respectively poured into a 100M L ball milling tank for ball milling and mixing, the ball material ratio is 1:20, the glove box is taken out after vacuum sealing, the ball milling is carried out by a planetary ball mill, the ball milling speed is 550 rpm, the ball milling time is 10 hours, the glove box is opened and the material in the glove box is scraped out after the ball milling is finished, the ball milled material is pressed into 12 mm-sized pieces by a tablet press, and the pieces are put into a single head for placingSealing and taking out the quartz tube by using a sealing film, sealing the quartz tube by using a vacuum tube sealing mode, placing the quartz tube in a muffle furnace to react at 260 ℃, wherein the temperature rising speed and the temperature reduction degree are both 2 ℃ per minute, the reaction time is 10 hours, cooling the quartz tube, placing the quartz tube in a glove box, opening the quartz tube and grinding the quartz tube into powder to obtain a glass-ceramic phase L iaM1-yCyX3+a+my(M ═ Y, C ═ Bi, X ═ Cl, M ═ 0, a ═ 3, and Y ═ 0.5) solid electrolyte material fig. 7 is a glass-ceramic phase L i obtained in example 2aM1-yCyX3+a+my(M ═ Y, C ═ Bi, X ═ Cl, M ═ 0, a ═ 3, and Y ═ 0.5) impedance test curves obtained after the solid electrolyte material was exposed to humid air and dehydrated by heating. The material was calculated to maintain an ionic conductivity of 0.05mS/cm after exposure to humid air.
Example 3
This embodiment is L iaM1-yCyX3+a+my(M ═ Ho, C ═ Zn, X ═ Br, M ═ 1, a ═ 2, y ═ 0.5) preparation of solid electrolyte materials and humid air stability studies.
In a glove box, 5.21 g L iBr and 6.07 g HoBr were weighed33.37 g of ZnBr (M ═ Ho, C ═ Zn, X ═ Br, M ═ 1, a ═ 2, y ═ 0.5), pouring the above experimental proportions into a single-head quartz tube respectively, sealing and taking out by using a sealing film, then sealing by using a vacuum tube-sealing mode and placing to react with 550 ℃ in a muffle furnace, the temperature rise speed and the temperature fall are both 2 ℃ per minute, the reaction time is 10 hours, after cooling, placing the tube into a glove box, opening and grinding into powder to obtain the glass-ceramic phase L iaM1-yCyX3+a+my(M ═ Ho, C ═ Al, X ═ Cl, M ═ 1, a ═ 2, and y ═ 0.6) solid electrolyte material.
Example 4
This embodiment is L iaM1-yCyX3+a+my(M ═ Er, C ═ Ga, X ═ I, M ═ 0, a ═ 2, and y ═ 0.6) preparation of solid electrolyte materials and wet air stability studies.
In a glove box, 12.1 g L iI and 6.6 g ErI were weighed respectively38.1 g of GaI3(M＝Er，C＝Ga, X, I, m, 2, y, 0.6, pouring the above experimental proportions into a 100m L ball milling tank respectively for ball milling and mixing, wherein the ball material ratio is 1:20, taking out the glove box after vacuum sealing, ball milling by a planetary ball mill at the ball milling speed of 550 revolutions per minute for 10 hours, opening the glove box after ball milling, scraping out the materials in the glove box, pressing the ball milled materials into 12 mm-sized pieces by a tablet press, putting the pieces into a single-end quartz tube, sealing and taking out by a sealing film, sealing by a vacuum sealing tube, placing the sealed materials to react with 260 ℃ in a muffle furnace, reacting at the temperature rise speed and the temperature drop speed of 2 ℃ per minute for 10 hours, cooling the tube, putting the cooled tube into the glove box, opening the sealed materials, and grinding the sealed materials into glass-ceramic phase L I, and obtaining the glass-ceramic phase L IaM1-yCyX3+a+my(M ═ Er, C ═ Ga, X ═ I, M ═ 0, a ═ 2, and y ═ 0.6) solid electrolyte materials.
Example 5
This embodiment is L iaM1-yCyX3+a+my(M ═ Ho, C ═ Al, In, Fe, X ═ Cl, M ═ 0, a ═ 2, y ═ 0.6) preparation of solid electrolyte materials and wet air stability studies.
In a glove box, 2.55 g L iCl and 3.25 g HoCl were weighed respectively30.1 g AlCl33.3 g of InCl30.24 g FeCl3(M ═ Ho, C ═ Al, In, Fe, X ═ Cl, M ═ 0, a ═ 2, y ═ 0.6.) the above experimental proportions are poured into a single-head quartz tube respectively, sealed by a sealing film and taken out, then sealed by vacuum tube sealing and placed to react with 550 ℃ In a muffle furnace, the temperature rise speed and the temperature fall speed are both 2 ℃ per minute, the reaction time is 10 hours, the tube is cooled and then placed into a glove box, and ground into powder, thus obtaining the glass-ceramic phase L iaM1-yCyX3+a+my(M ═ Ho, C ═ Al, In, Fe, X ═ Cl, M ═ 0, a ═ 2, and y ═ 0.6) solid electrolyte materials.
FIG. 8 shows the glass-ceramic phase L i obtained in example 5aM1-yCyX3+a+my(M ═ Ho, C ═ Al, In, Fe, X ═ Cl, M ═ 0, a ═ 2, y ═ 0.6) solid electrolyte material andresistance change curves obtained after exposure to humid air and dry annealing at 450 degrees celsius. It can be seen that the ion conductivity of the material after wet air exposure and subsequent drying annealing is not much changed from the original ion conductivity.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A halide solid state electrolyte material represented by the following formula,
LiaM1-yCyX3+a+my，
wherein M is selected from one or more of Sc, Y and L a series elements, C is selected from one or more of Al, Ga, In, Bi, Sb, Fe, Co, Ni, Cu, Zn, Cr, Zr, Ag, Cd, Cs, Mg, Ca, Sr and Ba, X is selected from one or more of F, Cl, Br and I, a is more than or equal to 1 and less than or equal to 6, Y is more than or equal to 0.1 and less than or equal to 1.0, and M is the difference of chemical valence between C and M.
2. The halide solid state electrolyte material according to claim 1,
m is selected from one or more of Y, Ho, Er and Sc; and/or C is selected from one or more of Al, Ga, In, Bi, Fe and Zn; and/or a is more than or equal to 2 and less than or equal to 4; and/or, y is more than or equal to 0.25 and less than or equal to 0.95.
3. The halide solid state electrolyte material according to claim 1 or 2, wherein the halide solid state electrolyte material is represented by any one of the following formulae,
Li3Y0.5In0.5Cl6、Li3Y0.4In0.6Cl6、Li3Y0.3In0.7Cl6、Li3Y0.2In0.8Cl6、Li3Y0.1In0.9Cl6、Li3Y0.5Bi0.5Cl6、Li2Ho0.4Al0.05In0.5Fe0.05Cl5。
4. the halide solid state electrolyte material according to any one of claims 1 to 3, wherein the halide solid state electrolyte material is a glass phase, a glass-ceramic phase, or a crystalline phase.
5. The method of producing a halide solid electrolyte material as claimed in any one of claims 1 to 4, wherein the C is introduced into L i-M-X halide electrolyte material, and the L i-M-X halide electrolyte material is L iaMX3+aThe composition shown, wherein 1. ltoreq. a.ltoreq.6, preferably 2. ltoreq. a.ltoreq.4.
6. The method of claim 5, wherein the L i-M-X halide electrolyte material has an ionic conductivity greater than 1 × 10-6S/cm。
7. The preparation method according to claim 5 or 6, characterized in that the preparation method is prepared by mixing the required raw materials or precursors according to the proportion and then grinding; or further adopting organic solvent codissolving recrystallization method, heating eutectic method, and method for making raw material granules contact in insoluble hydrocarbon organic solvent to obtain the compound with corresponding phase state.
8. The method of claim 7, wherein NH is added during the mixing of the desired raw materials or precursors4Cl、I2L iI or S as a co-solvent, fluxing agent or ligand for the complex.
9. Use of the halide electrolyte material according to any one of claims 1 to 4 in a lithium secondary battery, preferably as an electrode additive in a lithium secondary battery or as an electrolyte in the manufacture of a lithium secondary battery.
10. A lithium secondary battery characterized in that at least one of a positive electrode layer, an electrolyte layer and a negative electrode layer of the battery contains one or more halide electrolyte materials according to any one of claims 1 to 4; preferably, the lithium secondary battery includes a liquid-phase lithium secondary battery, a semi-solid-state lithium secondary battery, and an all-solid-state lithium secondary battery.
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