CN107403955B - Double-type anti-perovskite lithium ion solid electrolyte and preparation method and application thereof - Google Patents

Double-type anti-perovskite lithium ion solid electrolyte and preparation method and application thereof Download PDF

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CN107403955B
CN107403955B CN201710661140.7A CN201710661140A CN107403955B CN 107403955 B CN107403955 B CN 107403955B CN 201710661140 A CN201710661140 A CN 201710661140A CN 107403955 B CN107403955 B CN 107403955B
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lithium ion
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lithium
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邵国胜
王卓
徐红杰
轩敏杰
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Zhengzhou New Century Material Genome Engineering Research Institute Co ltd
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Abstract

The invention relates to a double-type anti-perovskite lithium ion solid electrolyte and a preparation method and application thereof, belonging to the technical field of lithium ion batteries. The lithium ion solid electrolyte of the present invention has a chemical formula as shown below: li3+aMpAmBn(XxYy)1‑bWherein a is more than or equal to-0.25 and less than or equal to 0.25; b is more than or equal to 0 and less than or equal to 0.5; p is more than or equal to 0 and less than or equal to 0.5, m is more than 0 and less than or equal to 1.25, and n is more than 0 and less than or equal to 1.25; x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; m is any one of Ca, Ba, Mg, Al and Ti; A. b is any two of O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br and I; x, Y are each independently selected from one of a halogen or a negative monovalent ion cluster or vacancy. The lithium ion solid electrolyte has a double-type anti-perovskite structure, and has a stable structure and good lithium ion transmission performance.

Description

Double-type anti-perovskite lithium ion solid electrolyte and preparation method and application thereof
Technical Field
The invention relates to a double-type anti-perovskite lithium ion solid electrolyte and a preparation method and application thereof, belonging to the technical field of lithium ion batteries.
Background
The lithium ion battery generally comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and an electrolyte, wherein the electrolyte used by the lithium ion battery uses an organic solvent, and the organic solvent is very easy to burn. The electrolyte used in the lithium ion battery is also very likely to form lithium dendrites on the surface of the negative electrode, resulting in internal short circuits of the battery and a large amount of heat release in a short time. In order to avoid the occurrence of lithium dendrites to the maximum extent, it is general to provide a safety device or structure for suppressing a short circuit of the battery in the battery to avoid a sharp increase in the internal temperature of the battery.
The all-solid electrolyte is used for replacing the liquid organic electrolyte, and is expected to be fundamentallyThe potential safety hazard of flammability of the lithium battery is solved, and the problem of formation of lithium dendritic crystals between the electrolyte and the metal lithium electrode interface is solved. However, the ionic conductance of the liquid electrolyte is taken as a standard (the lithium ion conductance is more than 1mScm-1) Achieving rapid transport of Li ions in solid electrolytes remains extremely challenging.
The lithium ion conductivity of the oxide solid electrolyte in the prior art is generally low and is generally lower than 1mScm-1Such as Li-Ti-phosphate type Li1.3M0.3Ti1.7(PO4)3(M is Al or Sc) solid electrolyte, and lithium ion conductivity at 25 ℃ is 0.7mScm at most-1Garnet type Li7La3Zr2O12Solid electrolyte with lithium ion conductivity of 0.774mScm at 25 deg.C-1，Li2.88PO3.73N0.14The lithium ion conductivity is 2.3 (+ -0.7) multiplied by 10 under the condition of the temperature of 25 DEG C-3mScm-1The diffusion activation energy was 0.55 (+ -0.02) eV.
In recent years, with the progress of research work relating to sulfide solid electrolytes, some sulfur-based solid electrolytes exhibit higher lithium ion conductivity. Wherein, tetragonal system Li10GeP2S12Is recognized as one of the best solid electrolytes at the present stage. Under the condition of room temperature, the lithium ion conductivity can exceed 10mScm-1The diffusion activation energy is between 0.22 and 0.285 eV. However, the materials only have one-dimensional lithium ion transport channels along the c-axis direction, and the activation energy of transverse diffusion is too high, about 0.62eV, so that the ion transport performance of the electrolyte greatly depends on the orientation distribution of crystal grains in the electrolyte, and the ion conductivity of the electrolyte can be fully exerted only when the c-axis direction of most crystal grains is close to the ion transport direction. In Li10GeP2S12On the basis of (2) Li having a similar structure9.54Si1.74P1.44S11.7Cl0.3The quinary solid electrolyte is synthesized in 2016, and the introduction of Cl ion modifies the original one-dimensional channel into three-dimensional lithium ion channel to raise the lithium ion conductivity greatlyReported to reach 25mScm at room temperature-1Much larger than the lithium ion conductivity in liquid electrolytes. However, this material is unstable in electrochemical properties when in contact with metallic Li, thus preventing its practical application in all-solid-state battery technology.
Materials with perovskite structures or anti-perovskite structures generally have more ideal properties, such as lower activation energy, higher conductivity and the like, and very low electronic conductivity, and more importantly, the materials have good stability, are very stable when meeting lithium, also have certain thermal stability and have better application space. However, the ion conductivity of the current perovskite-type or anti-perovskite-type solid electrolyte still remains to be improved.
Disclosure of Invention
The invention aims to provide a double-type anti-perovskite lithium ion solid electrolyte with high lithium ion conductivity.
The invention also aims to provide a preparation method and application of the double-type anti-perovskite lithium ion solid electrolyte.
In order to achieve the purpose, the technical scheme of the lithium ion solid electrolyte is as follows:
a double-type anti-perovskite lithium ion solid electrolyte having a chemical formula as shown below: li3+aMpAmBn(XxYy)1-bWherein a is more than or equal to-0.25 and less than or equal to 0.25; b is more than or equal to 0 and less than or equal to 0.5; p is more than or equal to 0 and less than or equal to 0.5, m is more than 0 and less than or equal to 1.25, and n is more than 0 and less than or equal to 1.25; x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; m is any one of Ca, Ba, Mg, Al and Ti; A. b is any two of O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br and I; x, Y is selected from one of halogen, negative monovalent ion group or vacancy, the halogen is any one of Cl, Br and I; the negative monovalent ion group is OH-、BH4 -、NH2 -、CH3 -、CN-、MgX3 -、CaX3 -One kind of (1).
The lithium ion solid electrolyte is double-type calciumThe titanium ore type compound contains two elements of O, S, Se, Te, N, P, Si, C, Sb, Bi, F, Cl, Br and I at the A, B position in the structure. The space group of the structure is Fm
Figure BDA0001370598150000021
(space group number 225) with Li6A、Li6B octahedral structure units located at the corners of the cubic inverse perovskite; x, Y are filled in the center of the cube. At this time, p may or may not be equal to 0. a may or may not be equal to 0. The solid electrolyte of the invention has thermodynamic stability, and the crystal lattice size is mainly formed by Li6A and Li6The contribution of the X site element is relatively weak, determined by the ionic bond length between A-Li or B-Li in the B octahedron. While the ionic bond length between A-Li or B-Li is determined by the electronegativity of the non-metal ions (A and B), the stronger the electronegativity, the shorter the corresponding bond length. When the sublattice positions of A and B are occupied by oxygen, the lattice dimension is the smallest, the heat formation of the compound is the largest, and the Li ion conductivity is the lowest.
Preferably, X is 0 and Y is 1, and only one element or group of X and Y remains.
In the double-type anti-perovskite solid electrolyte of the present invention, the material having a non-stoichiometric ratio can further improve the ionic conductivity on the basis of the double-type anti-perovskite structure.
Reducing the content of elements or groups at the X position may further facilitate the rate of lithium ion transport. When the stoichiometry of the element at the X position deviates from 1, a is 0, 0< b is less than or equal to 0.5, and A, B is any two of O, S, Se, Te, N, P, I, Cl and Br. At this time, if m + n is 1, A, B bitols remain at normal stoichiometry, and only X bitols deviate from stoichiometry. If m + n > 1, the stoichiometry of the element at position A, B is higher than normal stoichiometry. Preferably, p ═ 0, and the compound structure does not contain a metal element. Appropriate addition of larger octahedral Li6The content of the non-metal B in B can realize ultra-fast lithium ion transportation.
In the above-described lithium ion solid electrolyte, the stoichiometric number of lithium may deviate from the normal stoichiometry, i.e., a ≠ 0. At this time, the lithium ion solid electrolyte is classified into two cases of lithium-poor and lithium-rich, and in these two cases, the transport manner of lithium ions in the solid electrolyte is different.
The lithium ion conductivity in the solid electrolyte is determined by its diffusion coefficient, while the long-range diffusion coefficient of lithium ions is determined by the diffusion coefficient of lithium ions in Li6Migration on the a octahedron is controlled. In such systems, there are mainly two main types of Li ion transport modes: (a) under the condition of low lithium ion concentration, Li+Migration occurs along lithium vacancies on the vertex angle of the octahedron, and the diffusion activation energy is usually larger at the moment; (b) under the condition of higher lithium ion concentration, abundant Li+With Li6Li on A octahedron+Formation of Li+-Li+Paired in dumbbell shape and with Li at the other end of octahedron+Bulk migration occurs when the diffusion activation energy is small, often only one tenth of the transport mode (a). Thus, the low temperature diffusion coefficient is governed primarily by the lithium ion concentration, and the diffusion activation energy required to overcome its migration on octahedra. Since the diffusion activation energy is inversely related to the number of Li ions around the non-metal ion (A or B) in the octahedron, for example when Li6When A in the A octahedron is surrounded by more Li ions, the smaller the diffusion barrier is, the better the lithium ion conductivity is. Therefore, when the lithium ion concentration in the solid electrolyte is higher than that in the standard stoichiometry, the lithium-rich ions can diffuse more easily, and the diffusion activation energy can be reduced by about 10 times.
When the stoichiometry of the element at the X position deviates from 1, a is not equal to 0, b is more than 0 and less than or equal to 0.5, and A, B is any two of O, S, Se, Te, N, P, I, Cl and Br. At this time, the stoichiometric number of lithium deviates from the normal stoichiometry, and particularly under lithium-rich conditions, lithium ions diffuse more easily, and the activation energy for diffusion is very small. At this time, if m + n is 1, A, B bitols remain at normal stoichiometry, and only X bitols deviate from stoichiometry. If m + n > 1, the stoichiometry of the element at position A, B is higher than normal stoichiometry. Preferably, p ═ 0, and the compound structure does not contain a metal element. Appropriate addition of larger octahedral Li6The content of the non-metal B in B can realize ultra-fast lithium ion transportation.
In the case of lithium enrichment, additional lithium (Li) is dissociatedSeed remains adsorbed to Li6A or Li6Around the A/B bit in B. More lithium ions are gathered near the A/B position, so that the average interaction between Li and A/B is further reduced, and the diffusion activity of the lithium ions is enhanced. In addition, the Li-Li interaction can effectively reduce the Li ion diffusion distance between octahedrons, obviously reduce the diffusion potential barrier and show ultra-fast lithium ion conductivity.
In the lithium ion solid electrolyte of the present invention, a trace amount of high valence metal ion M such as Ca is appropriately added2+、Ba2+、Mg2+、Al3+、Ti4+The lithium ion transport channel can be further optimized, and the transmission of various metal ions can be realized simultaneously. In the above-mentioned various schemes, a proper quantity of metal ions can be added, i.e. it can ensure that p is greater than 0 and less than or equal to 0.5. Preferably, 0< p.ltoreq.0.05, i.e. the stoichiometric content of the metal element M is not more than 5%.
When metal ions do not need to be added, p is 0, and the structure is optimized only by the coordination of other elements, so that the transmission rate of lithium ions is ensured. Li not containing metal element M3+aMpAmBnY1-bThe octahedral structural unit formed by the AB element in (p ═ 0) and Li can provide a good channel for the transmission of lithium ions, so that the lithium ion battery has very good lithium ion conductivity. At this time, the compound still has better lithium ion conductivity without lithium enrichment.
For compounds in which the stoichiometric number of each element does not deviate from the standard stoichiometry without addition of metal ions, a is 0, b is 0, P is 0, m + N is 1, and A, B is any two of O, S, Se, Te, N, P, I, Cl, and Br. Such as Li3O0.5S0.5I、Li3N0.5Cl0.5I、Li3N0.5F0.5I、Li3P0.5Cl0.5I, having a standard double-type anti-perovskite structure.
In the compound to which no metal ion is added, the element at the X-position may be absent, and in this case, X is 0 and y is 0; -0.125 ≦ a ≦ 0.125, p ≦ 0; 0< m <1.25, 0< n <1.25, A and B are respectively one of Si, C, S and O. Preferably, 0< m <1, 0< n <1.
Preferably, the double-type anti-perovskite Li3+aO0.5S0.5+aCl1-a(a is 0.125), the lithium is enriched, the mixed discharge of S and Cl ions (S is used for Cl) is realized, the lithium ion diffusion barrier is only 0.026-0.053eV, and the lithium ion diffusion barrier is only tetragonal Li10GeP2S12One tenth to one fifth of the (best solid electrolyte at present) diffusion barrier is very low.
MgX3 -、CaX3 -Is a negative monovalent radical formed by Mg or Ca and halogen.
The lithium ion solid electrolyte is one of crystal, vitreous body and amorphous. The lithium ion solid electrolyte is a typical ionic compound system, so the ionic chemical environment in the glass state (especially a relaxation glass state) is similar to the crystal state, the application of the glass state electrolyte is beneficial to the low-temperature preparation of the electrolyte (such as a mechanical alloying method and a vacuum coating method), the relatively high hole concentration in the glass body is beneficial to the diffusion of lithium ions, the ionic conductivity is possibly better, and therefore, the solid electrolyte is preferably the glass body.
The technical scheme of the preparation method of the double-type anti-perovskite lithium ion solid electrolyte is as follows:
the preparation method of the double-type anti-perovskite lithium ion solid electrolyte comprises the following steps:
1) ball-milling the raw materials for 3-10h under the protection of vacuum or inert gas or anhydrous proton solvent to obtain a precursor;
2) and (3) preserving the heat of the precursor for 5-16h at the temperature of 150-500 ℃ under the protection of vacuum or inert gas to obtain the material.
Pressing the precursor obtained in the step 1) into a green body. And (3) carrying out heat preservation in the step 2), and then cooling to room temperature or carrying out quenching treatment. The quenching treatment is ice water quenching. The heat preservation is carried out in a muffle furnace or a vacuum tube furnace. The raw materials are compounds of corresponding elements in the preparation of corresponding solid electrolytes. Such as oxides or halides or sulfides. Specifically, lithium oxide, lithium chloride, lithium iodide, and lithium sulfide are exemplified.
Preferably, the inert gas in step 1) and step 2) is nitrogen or argon.
The anhydrous proton solvent is one of N-dimethylformamide, absolute ethyl alcohol, acetone, heptane and ethyl acetate.
The rotation speed of the ball mill is 250-350 rpm. During ball milling, standing for 5-10min every 20-30 min. Preferably, the mixture is kept standing for 5min every 20min of ball milling.
The lithium ion solid electrolyte can be prepared by the methods in the prior art, such as a melting method, a mechanical alloying method, a powder metallurgy method, a vacuum coating method or a chemical vapor deposition method.
The other preparation method of the double-type anti-perovskite lithium ion solid electrolyte comprises the following steps:
a) ball-milling the raw materials for 3-10h under the protection of vacuum or inert gas or anhydrous proton solvent,
obtaining a precursor;
b) pressing the precursor at 20-320 deg.C under 1-50MPa for 2-30 min.
Preferably, the inert gas in step a) and step b) is nitrogen or argon.
The anhydrous proton solvent is one of N-dimethylformamide, absolute ethyl alcohol, acetone, heptane and ethyl acetate.
The rotation speed of the ball milling is 250-350rpm, and the ball milling is performed for 5-10min after 20-30min of ball milling. Preferably, the mixture is kept standing for 5min every 20min of ball milling.
The technical scheme of the application of the double-type anti-perovskite lithium ion solid electrolyte is as follows:
the application of the double-type anti-perovskite lithium ion solid electrolyte in a lithium ion battery comprises an electrode plate, wherein the electrode plate comprises a current collector and an electrode material layer coated on the surface of the current collector, the electrode material layer comprises an electrode material and an electrode material additive, and the electrode material additive is the double-type anti-perovskite lithium ion solid electrolyte
In specific application, the mass content of the lithium ion solid electrolyte in the electrode material layer is 0-20%.
The invention has the beneficial effects that:
the lithium ion solid electrolyte has a double-type anti-perovskite structure, has a stable structure and good lithium ion transmission performance, and has good electrochemical performance and safety performance when used as a solid electrolyte of a lithium ion battery. The lithium ion solid electrolyte has very high ion conductivity which can exceed 25mScm at most-1And has good application prospect.
Drawings
Fig. 1 is an XRD test pattern of the lithium ion solid electrolyte in example 1;
fig. 2 is a schematic structural view of a lithium ion solid electrolyte in example 1;
fig. 3 is a schematic structural view of a lithium ion solid electrolyte of example 1 and comparative examples 1, 2, 3, 4, in which (a) is a schematic structural view of the lithium ion solid electrolytes of comparative examples 1 and 3, (b) is a schematic structural view of the lithium ion solid electrolyte of comparative example 4, (c) is a schematic structural view of the lithium ion solid electrolyte of comparative example 2, and (d) is a schematic structural view of the lithium ion solid electrolyte of example 1;
fig. 4 is a schematic view of diffusion activation energy of the lithium ion solid electrolyte in example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The chemical composition of the lithium ion solid electrolyte of this example was Li3O0.5S0.5I, the structure is shown in figure 2.
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) with a molar ratio of 1:1:22O), lithium sulfide (Li)2S), lithium iodide (LiI) powder are dried in a vacuum drying oven for 24 hours, and then in a glove box under the protection of argon atmosphereLithium oxide (Li)2O), lithium sulfide (Li)2S) and lithium iodide (LiI) are uniformly mixed, the mixture is put into a ball milling tank, 15 zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 150 ℃ for 16h, and slowly cooling to room temperature after heat treatment to obtain powder Li3O0.5S0.5A solid electrolyte of I.
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 2%.
The XRD spectrum of the solid electrolyte prepared in this example is shown in fig. 1.
Example 2
The chemical composition of the lithium ion solid electrolyte of this example was Li3O0.5S0.5I。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) with a molar ratio of 1:1:22O), lithium sulfide (Li)2S), lithium iodide (LiI) powder are dried in a vacuum drying oven for 24 hours, and then lithium oxide (Li) is dried in a glove box under the protection of argon atmosphere2O), lithium sulfide (Li)2S) and lithium iodide (LiI) are uniformly mixed, the mixture is put into a ball milling tank, 15 zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling,setting the rotation speed of the ball mill to 350rpm, ball-milling the ball mill for 20min, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from a ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, and slowly cold-pressing the powder into a ceramic blank with the diameter of 16mm, namely Li3O0.5S0.5A solid electrolyte of I.
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 5%.
Example 3
The chemical composition of the lithium ion solid electrolyte of this example was Li3O0.5S0.75I0.5。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) with a molar ratio of 1:1.5:12O), lithium sulfide (Li)2S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24 hours, then in a glove box, under the protection of argon atmosphere, lithium oxide, lithium sulfide and lithium iodide are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from a ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, putting the powder into a quartz glass tube, sealing, vacuumizing, carrying out heat treatment in a muffle furnace at the heat treatment temperature of 250 ℃ for 5 hours, completely melting the powder after the heat treatment, and then using ice waterQuenching treatment is carried out to obtain vitreous body powder, namely Li3O0.5S0.75I0.5The solid electrolyte of (1).
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the negative plate comprises a negative current collector and a negative material layer coated on the negative current collector, the negative material layer comprises a negative material and a negative material additive, the negative material is graphite, the negative material additive is the lithium ion solid electrolyte, and the mass content of the negative material additive in the negative material layer is 10%.
Example 4
The chemical composition of the lithium ion solid electrolyte of this example was Li3O0.5S0.75I0.5。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) with a molar ratio of 1:1.5:12O), lithium sulfide (Li)2S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24 hours, then in a glove box, under the protection of argon atmosphere, lithium oxide, lithium sulfide and lithium iodide are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) under the protection of argon atmosphere, taking out the precursor obtained in the step 1) from the ball milling tank, and slowly cold-pressing the precursor into a ceramic blank with the diameter of 16mm, namely Li3O0.5S0.75I0.5The solid electrolyte of (1).
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the negative plate comprises a negative current collector and a negative material layer coated on the negative current collector, the negative material layer comprises a negative material and a negative material additive, the negative material is graphite, the negative material additive is the lithium ion solid electrolyte, and the mass content of the negative material additive in the negative material layer is 10%.
Example 5
The chemical composition of the lithium ion solid electrolyte of this example was Li3.125O0.5S0.625I0.875。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) in a molar ratio of 1:1.25:1.752O), lithium sulfide (Li)2S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24 hours, then in a glove box, under the protection of argon atmosphere, lithium oxide, lithium sulfide and lithium iodide are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 200 ℃ for 16h, and slowly cooling to room temperature after heat treatment to obtain powder Li3.125O0.5S0.625I0.875The solid electrolyte of (1).
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the negative plate comprises a negative current collector and a negative material layer coated on the negative current collector, the negative material layer comprises a negative material and a negative material additive, the negative material is graphite, the negative material additive is the lithium ion solid electrolyte, and the mass content of the negative material additive in the negative material layer is 20%.
Example 6
The chemical composition of the lithium ion solid electrolyte of this example was Li3.125O0.5S0.625I0.875。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) in a molar ratio of 1:1.25:1.752O), lithium sulfide (Li)2S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24 hours, then in a glove box, under the protection of argon atmosphere, lithium oxide, lithium sulfide and lithium iodide are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from a ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, and slowly cold-pressing the powder into a ceramic blank with the diameter of 16mm, namely Li3.125O0.5S0.625I0.875The solid electrolyte of (1).
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the negative plate comprises a negative current collector and a negative material layer coated on the negative current collector, the negative material layer comprises a negative material and a negative material additive, the negative material is graphite, the negative material additive is the lithium ion solid electrolyte, and the mass content of the negative material additive in the negative material layer is 20%.
The chemical compositions of the lithium ion solid electrolytes of examples 7 to 14 are shown in the following table, and the preparation methods thereof are the same as those of example 1 except for specific reference.
TABLE 1 chemical compositions of lithium ion solid electrolytes of examples 7 to 14
Examples Chemical composition of solid electrolyte
7 Li2.99Ba0.01O0.5S0.75I0.5
8 Li2.99Ca0.01O0.5S0.75I0.5
9 Li3.125Ba0.01O0.5S0.625I0.875
10 Li3.125Ca0.01O0.5S0.625I0.875
11 Li3N0.5Cl0.5I
12 Li3N0.5F0.5I
13 Li3P0.5Cl0.5I
14 Li3C0.5S0.5
Note: reference is made to the processes in examples 1 to 6, in which Li3N0.5Cl0.5In the preparation of I, N is Li3N raw material introducing materialIn the material. Li3N0.5F0.5I、Li3P0.5Cl0.5The preparation method of I can refer to the previous steps, and the univalent anions are introduced into the material by using lithium compounds of the univalent anions as raw materials.
Comparative example 1
The chemical composition of the lithium ion solid electrolyte of this example was Li3OCl, structure shown in FIG. 3 (a).
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) with a molar ratio of 1:12O) and lithium chloride (LiCl) powder are dried in a vacuum drying oven for 24 hours, then in a glove box, under the protection of argon atmosphere, lithium oxide and lithium chloride are uniformly mixed, the mixture is filled into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 280rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 3h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, cold-pressing the powder into a ceramic blank with the diameter of 16mm, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 230 ℃ for 10h, and slowly cooling to room temperature after the heat treatment to obtain a ceramic body, namely the solid electrolyte of the LiOCl.
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 10%.
Comparative example 2
The chemical composition of the lithium ion solid electrolyte of this example was Li3SI, as shown in FIG. 3 (c).
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) mixing lithium sulfide (Li) with a molar ratio of 1:12S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24h, and then lithium sulfide (Li) is added in a glove box under the protection of argon atmosphere2S) and lithium iodide (LiI) are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 280rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 220 ℃ for 10h, slowly cooling to room temperature after heat treatment, and obtaining the powder which is Li3Solid electrolyte of SI.
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 10%.
Comparative example 3
The chemical composition of the lithium ion solid electrolyte of this example was Li3OI。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium oxide (Li) with a molar ratio of 1:12O) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24h, and then lithium oxide (Li) is added in a glove box under the protection of argon atmosphere2O) and lithium iodide (LiI) are evenly mixed and put into a ball milling tank, and a plurality of zirconia ball milling balls with the diameter of 10mm are added into the ball milling tank to seal the ball milling tank. Taking the sealed ball milling pot out of the glove boxPlacing the mixture into an omnibearing planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 280rpm, ball milling the mixture for 20min every time by the ball mill, and standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 260 ℃ for 8h, slowly cooling to room temperature after heat treatment, and obtaining the powder which is Li3Solid electrolyte of OI.
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 10%.
Comparative example 4
The chemical composition of the lithium ion solid electrolyte of this example was Li3SCl。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) mixing lithium sulfide (Li) with a molar ratio of 1:12S) and lithium chloride (LiCl) powder are dried in a vacuum drying oven for 24 hours, and then lithium sulfide (Li) is added in a glove box under the protection of argon atmosphere2S) and lithium chloride (LiCl) are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 260rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 6h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 300 ℃ for 10h, slowly cooling to room temperature after heat treatment, and thus obtaining the precursorThe powder is Li3Solid electrolyte of SCl.
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 10%.
Comparative example 5
The chemical composition of the lithium ion solid electrolyte of this example was Li3S1.25I0.5。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium sulfide (Li) with a molar ratio of 2.5:12S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24h, and then lithium sulfide (Li) is added in a glove box under the protection of argon atmosphere2S) and lithium iodide (LiI) are uniformly mixed, the mixture is put into a ball milling tank, 15 zirconia balls with the diameter of 10mm are added into the ball milling tank, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from a ball milling tank under the protection of argon atmosphere, weighing a certain amount of powder, putting the powder into a quartz glass tube, sealing, vacuumizing, carrying out heat treatment in a muffle furnace at the heat treatment temperature of 500 ℃ for 5h, completely melting the powder after the heat treatment, and then quenching with ice water to obtain vitreous body powder, namely Li3S1.25I0.5The solid electrolyte of (1).
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 10%.
Comparative example 6
The chemical composition of the lithium ion solid electrolyte of this example was Li3.125S1.125I0.875。
The preparation method of the lithium ion solid electrolyte of the embodiment includes the following steps:
1) lithium sulfide (Li) with a molar ratio of 1.125:0.8752S) and lithium iodide (LiI) powder are dried in a vacuum drying oven for 24h, and then lithium sulfide (Li) is added in a glove box under the protection of argon atmosphere2S) and lithium iodide (LiI) are uniformly mixed, the mixture is put into a ball milling tank, a plurality of zirconia ball milling balls with the diameter of 10mm are added, and the ball milling tank is sealed. Taking the sealed ball milling tank out of the glove box, putting the ball milling tank into an all-directional planetary ball mill for ball milling, setting the rotating speed of the ball mill to be 350rpm, ball milling the ball mill for 20min each time, standing and cooling for 5 min; the total ball milling time is 10h, and a precursor is obtained after ball milling;
2) taking out the precursor obtained in the step 1) from the ball milling tank under the protection of argon atmosphere, carrying out heat treatment in a vacuum tube furnace at the heat treatment temperature of 430 ℃ for 10h, and slowly cooling to room temperature after heat treatment to obtain powder Li3.125S1.125I0.875The solid electrolyte of (1).
The application of the lithium ion solid electrolyte in the lithium ion battery is as follows: the lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive material layer coated on the positive current collector, the positive material layer comprises a positive material and a positive material additive, the positive material additive is the lithium ion solid electrolyte, and the mass content of the positive material additive in the positive material layer is 10%.
Test examples
1) XRD test
The solid electrolyte obtained in example 1 was subjected to XRD measurement, and the XRD characteristic pattern obtained by the measurement is shown in fig. 1.
Comparing the XRD pattern of the solid electrolyte obtained by the test with the pattern obtained by theoretical calculation, the XRD of the crystal obtained by the experiment in the embodiment is completely consistent with the calculation result.
2) Calculation and analysis
By a material genome engineering method, under the theoretical framework of a Density Functional (DFT) method and first-principle molecular dynamics (AIMD), the thermodynamic stability and ion transport performance of the same-group or adjacent-group elements on the solid electrolyte can be systematically researched.
Li in example 13O0.5S0.5I and Li in example 103N0.5Cl0.5I all belong to a double-type calcium-resistant state ore structure. With Li3O0.5S0.5I is an example, and the structure is shown in FIG. 2, which has Li6O and Li6S octahedral structural units, which are connected alternately to form a structural frame of the material, and large size I-The ions are filled in the crystal lattice gaps, and the effect of improving the structural stability is achieved.
The double-type anti-perovskite is provided with Fm
Figure BDA0001370598150000141
(225) Symmetry is obviously different from the symmetry Pm of the traditional anti-perovskite
Figure BDA0001370598150000142
(221) (e.g. Li)3OCl), double-type anti-perovskite is a solid electrolyte with a brand new system.
According to XRD measurement data, the corresponding lattice constant size relation is as follows: li3OCl<Li3OI<Li3OI<Li3O0.5S0.5I<Li3N0.5Cl0.5And I, showing that the characteristic peak position of XRD is shifted left overall.
For the standard chemical formula Li3AB, calculate the structure tolerance factor according to the Goldschmidt calculation:
Figure BDA0001370598150000143
such as a watch2, Li3The key to whether form AB can form the monocalcite structure is whether the structure tolerance factor t is in the range of 0.8-1. As shown in Table 2, Li3OCl and Li3The tolerance factors for OI are 0.85 and 0.98, respectively, so that they can form a standard anti-perovskite structure, as shown in FIG. 3 (a); for Li3SCl, tolerance factor 0.7, less than 0.8, thus representing a layered structure, as shown in fig. 3 (b); for Li3SI, tolerance factor 0.81, slightly greater than 0.8, despite deformation, remains overall with the anti-perovskite structural features, as shown in fig. 3 (c); for Li3O0.5S0.5I(Li3OI+Li3SI) was 0.895, and thus exhibited a bimodal monocalcite structure, as shown in fig. 3 (d).
TABLE 2 structural tolerance factor for each of the substances
Figure BDA0001370598150000151
In the dual-type monocalcite solid electrolyte, two diffusion modes of Li exist mainly. With Li3O0.5S0.5I is an example, as shown in fig. 4: (a) under Li-poor conditions, diffusing along Li vacancies; the corresponding diffusion activation energy was 0.026-0.17eV, as shown in FIGS. 4(b) and (e); (d) under Li-rich conditions, Li-Li paired dumbbell transport. Under Li-rich conditions, the diffusion activation energy continued to decrease, only 0.053-0.055eV, as shown in FIGS. 4(c) and (f). The diffusion activation energy is greatly reduced, and the number of Li ions in the nearest neighbor of O/S is directly connected with the increase of the number of Li ions. As the number of Li ions around O/S increases, the binding force of O/S to Li ions is weakened, and thus the Li ion activity is remarkably enhanced.
For the solid electrolyte to which a trace amount of a high-valence metal ion is added, Li as in example 72.99Ba0.01O0.5S0.75I0.5And Li in example 93.125Ba0.01O0.5S0.625I0.875The structure can further optimize the Li ion diffusion channel, can simultaneously realize the conduction of multiple metal ions, and is favorable for further improving the solid stateThe performance of the battery.
3) Lithium ion conductivity test
Lithium ion solid electrolytes of examples 1 to 13 and comparative examples 1 to 6 were respectively tested for lithium ion conductivity at different temperatures, and the test results were subjected to normalization processing, and the results are shown in table 3.
TABLE 3 lithium ion conductivity and diffusion activation energy Ea of the lithium ion solid electrolytes of examples 1 to 13 and comparative examples 1 to 6
Figure BDA0001370598150000161
As can be seen from the data in table 3, the structural modification by adding a small amount of high-valence metal ions while deviating from the similar chemical composition can greatly improve the order of magnitude of the lithium ion conductivity of the lithium ion solid electrolyte having the double-type anti-perovskite structure.

Claims (5)

1. A double-type anti-perovskite lithium ion solid electrolyte, characterized in that the lithium ion solid electrolyte has a chemical formula as shown below: li3+aMpAmBn（XxYy）1-bWherein a =0.125, p =0.01, m =0.5, n =0.625, x =0.875, y =0, b = 0; m is any one of Ca, Ba, Mg, Al and Ti; A. b is any two of O, S, Se and Te; x is selected from halogen, and the halogen is any one of Cl, Br and I.
2. The double-type anti-perovskite lithium ion solid electrolyte according to claim 1, wherein the lithium ion solid electrolyte is one of crystalline and amorphous.
3. A method for preparing a double-type anti-perovskite lithium ion solid electrolyte as claimed in claim 1, comprising the steps of:
1) ball-milling the raw materials for 3-10h under the protection of vacuum or inert gas or anhydrous proton solvent to obtain a precursor;
2) and (3) preserving the heat of the precursor for 5-16h at the temperature of 150-500 ℃ under the protection of vacuum or inert gas to obtain the material.
4. A method for preparing a double-type anti-perovskite lithium ion solid electrolyte as claimed in claim 1, comprising the steps of:
a) ball-milling the raw materials for 3-10h under the protection of vacuum or inert gas or anhydrous proton solvent to obtain a precursor;
b) pressing the precursor at 20-320 deg.C under 1-50MPa for 2-30 min.
5. The application of the double-type anti-perovskite lithium ion solid electrolyte as claimed in claim 1 in a lithium ion battery, wherein the lithium ion battery comprises an electrode sheet, the electrode sheet comprises a current collector and an electrode material layer coated on the surface of the current collector, the electrode material layer comprises an electrode material and an electrode material additive, and the electrode material additive is the lithium ion solid electrolyte as claimed in claim 1.
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