CN113889662B - 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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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a halide solid electrolyte material and a preparation method and application thereof. The chemical general formula of the halide solid electrolyte material provided by the invention is LiaA 1‑x‑y M x N y X 3+a‑x+y Wherein a is more than or equal to 1 and less than or equal to 6; x is more than or equal to 0.02 and less than or equal to 0.9; y is more than or equal to 0.02 and less than or equal to 0.9; a is selected from Al 3+ 、Ga 3+ 、In 3+ 、Fe 3+ 、Y 3+ 、Sc 3+ One or more kinds of metals having a valence of +3 La; m is selected from Cu 2+ 、Zn 2+ 、Cd 2+ 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ One or more of (a); n is selected from Zr 4+ 、Hf 4+ 、Ti 4+ One or more of (a); x is selected from F ‑ 、Cl ‑ 、Br ‑ 、I ‑ One or more of (a). The halide solid electrolyte material provided by the invention can obviously reduce the diffusion impedance of lithium ions in the electrolyte material, improve the shuttle capability and transmission speed of the lithium ions in the electrolyte lattice, and improve the conductivity of the lithium ions.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a halide solid electrolyte material and a preparation method and application thereof.
Background
Since the self-introduction of lithium ion batteries, they have been widely used in various portable electronic products, electric vehicles, and other fields. However, recent new energy automobile safety accidents frequently occur, and the traditional lithium ion battery mainly needs flammable organic solvent as electrolyte, so that great potential safety hazards exist, and the conventional improvement method cannot thoroughly solve the problems. In contrast, solid-state lithium ion batteries using solid-state electrolytes have a safety advantage. The solid electrolyte is adopted, so that the safety problem of the lithium ion battery can be fundamentally solved, the manufacturing and packaging process is expected to be greatly simplified, and the energy density, reliability and design freedom of the battery are improved. Among various novel battery systems, solid-state batteries are the next-generation technology closest to the industrialization, and in order to meet the demand for high-performance solid-state batteries, electrolytes having high ionic conductivity are very critical materials.
The inorganic electrolyte with the highest ionic conductivity belongs to a sulfide system at present, and can reach or even exceed the level of the commercial electrolyte at present in the aspect of ionic conductivity. However, the raw material cost of sulfide is high, the preparation conditions are harsh, the sulfide cannot be stably matched with a lithium metal cathode or a high-voltage anode, and the battery assembly needs to be carried out in a high-cost drying chamber so as to avoid decomposition caused by contact with water and oxygen in the air. Compared with sulfide, oxide electrolyte represented by Lithium Lanthanum Zirconium Oxygen (LLZO) can match a high-voltage positive electrode and a lithium metal negative electrode, but the interface contact impedance of the positive electrode and the negative electrode is large, and the high ionic conductivity of the oxide electrolyte can be realized under the harsh preparation conditions of high temperature and high pressure (c)>1 mS/cm). Halide Li 3 AX 6 (X is Cl or Br) is a solid electrolyte material which is recently paid attention to, and has the advantages of high ionic conductivity, good anode material compatibility and the like. However, li 3 AX 6 The phase structure, ionic conductivity and stability of the metal negative electrode are influenced by the type and radius of the metal ions A, in order to maintain the structureStability and high ionic conductivity, A is selected from trivalent metal ions with ionic radius of 0.65-0.92, and mainly comprises In 3+ And rare earth ions, which are contained in the earth crust in a small amount and are expensive, and the mutual substitution among trivalent ions is difficult to effectively adjust the lithium ion/hole ratio, improve the lithium ion diffusion channel and improve the ionic conductivity.
Disclosure of Invention
The invention aims to overcome the defects of high cost, high diffusion resistance in an electrolyte material and limited lithium ion conductivity of the existing halide solid electrolyte material, and further provides a halide solid electrolyte material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a halide solid electrolyte material has a chemical general formula of LiaA 1-x-y M x N y X 3+a-x+y Wherein a is more than or equal to 1 and less than or equal to 6; x is more than or equal to 0.02 and less than or equal to 0.9; y is more than or equal to 0.02 and less than or equal to 0.9; a is selected from Al 3+ 、Ga 3+ 、In 3+ 、Fe 3+ 、Y 3+ 、Sc 3+ One or more of + 3-valent La metals; m is selected from Cu 2+ 、Zn 2+ 、Cd 2+ 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ One or more of; n is selected from Zr 4 + 、Hf 4+ 、Ti 4+ One or more of; x is selected from F - 、Cl - 、Br - 、I - One or more of (a).
It is understood that the metal element represented by a In the chemical formula may be one or more of Al, ga, in, fe, Y, sc, and La series elements; the metal element represented by M can be one or more of Cu, zn, cd, mg, ca, sr and Ba; the metal element represented by N can be one or more of Zr, hf and Ti; x represents one or more of F, cl, br and I. It is understood that the metal represented by A has a valence of +3 in the chemical formula, the metal represented by M has a valence of +2 in the chemical formula, the metal represented by N has a valence of +4 in the chemical formula, and the halogen element represented by X has a valence of-1 in the chemical formula. La-based metals of the present invention include, but are not limited to, la (lanthanum), ce (cerium), pr (praseodymium), nd (neodymium), pm (promethium), sm (samarium), eu (europium), gd (gadolinium), tb (terbium), dy (dysprosium), ho (holmium), er (erbium), tm (thulium), yb (ytterbium), lu (lutetium).
Preferably, A is selected from Ga 3+ 、In 3+ 、Fe 3+ 、Y 3+ 、Sc 3+ 、Ho 3+ 、Er 3+ 、Lu 3+ 、Yb 3+ One or more of; and/or M is selected from Mg 2+ 、Zn 2+ 、Cu 2+ One or more of; and/or N is selected from Zr 4+ And/or Hf 4+ ；
And/or a is more than or equal to 2.2 and less than or equal to 3.8; and/or x is more than or equal to 0.1 and less than or equal to 0.5; and/or y is more than or equal to 0.1 and less than or equal to 0.7.
Preferably, A is selected from Fe 3+ N is selected from Hf 4+ 。
Preferably, the halide solid state electrolyte material is in the form of any one of a glass phase, a glass-ceramic phase, or a crystalline phase.
The invention also provides a preparation method of the halide solid electrolyte material, which comprises the following steps:
1) Mixing the raw materials according to the formula proportion to obtain a mixture;
2) And grinding and sintering the mixture to obtain the halide solid electrolyte material.
In the invention, the halide solid electrolyte material can be prepared by any one of a ball milling method, a solid-phase sintering method and a heating eutectic method for the mixture, and preferably, the mixture is prepared by a grinding and sintering method.
The ionic conductivity of the halide solid electrolyte material prepared by the invention is more than 1 x 10 -5 S/cm。
Preferably, the mixture is ground in the step 2) by adopting a ball milling mode, the ball milling speed is 100-500 r/min, and the ball milling time is 1-50h; preferably, the ball milling rotating speed is 200-450 r/min, and the ball milling time is 2-40h.
The grinding step is carried out under an inert atmosphere;
the sintering temperature is 200-600 ℃, the heat preservation time is 1-40h, preferably, the sintering temperature is 250-550 ℃, and the heat preservation time is 2-30h.
Optionally, the temperature rising rate in the sintering step can be 1-3 ℃/min, and the temperature reduction rate after the heat preservation is finished can be 1-3 ℃/min.
Preferably, the step 2) further comprises a step of grinding the sintered material after sintering.
Preferably, the raw materials can be mixed in step 1) by using an agate mortar, so that the raw materials can be uniformly mixed. Optionally, the material weighing step and the mixing step in the invention are both carried out in an inert gas atmosphere.
Preferably, the first and second liquid crystal materials are,
the raw materials In the step 1) are a lithium source, an A source, an M source and an N source, wherein the lithium source is lithium halide, and the A source is one or more selected from Al halide, ga halide, in halide, fe halide, Y halide, sc halide and La metal halide;
the M source is selected from one or more of Cu halide, zn halide, cd halide, mg halide, ca halide, sr halide and Ba halide;
the N source is selected from one or more of Zr halide, hf halide and Ti halide. It is understood that the above metal halides include metal iodides, metal bromides, metal chlorides, and metal fluorides. Taking metal chloride as an example, the lithium source is lithium chloride, and the A source is one or more selected from aluminum chloride, gallium chloride, indium chloride, ferric chloride, yttrium chloride, scandium chloride and La metal chlorides;
the M source is selected from one or more of copper chloride, zinc chloride, cadmium chloride, magnesium chloride, calcium chloride, strontium chloride and barium chloride;
the N source is selected from one or more of zirconium chloride, hafnium chloride and titanium chloride.
The invention also provides a lithium secondary battery, which comprises a positive electrode layer, an electrolyte layer and a negative electrode layer, wherein at least one of the positive electrode layer, the electrolyte layer and the negative electrode layer contains the halide solid electrolyte material or the halide solid electrolyte material prepared by the preparation method.
Preferably, the lithium secondary battery includes a liquid-phase lithium secondary battery, a semi-solid lithium secondary battery, and an all-solid lithium secondary battery.
The invention has the beneficial effects that:
1. the halide solid electrolyte material provided by the invention introduces specific bivalent and quadrivalent ions in electrolyte components simultaneously, and utilizes the valence difference between the bivalent ions and the quadrivalent ions and the trivalent ions, and the bivalent ions and the quadrivalent ions substitute for the trivalent ions to cause the change of the number of lithium ions and holes in crystal lattices (substitution process: M) 2+ +Li + →A 3+ + a hole; n is a radical of hydrogen 4+ + hole → A 3+ +Li + ) Specifically, the substitution of divalent ions for trivalent ions increases lithium ions and decreases holes, while the substitution of tetravalent ions for trivalent ions increases holes and decreases lithium ions, and the ratio of lithium ions/holes can be flexibly and effectively adjusted through the interaction and coordination of the two ions; in addition, divalent ions and tetravalent ions are simultaneously introduced into a trivalent ion lattice site, the divalent ions, the tetravalent ions and the trivalent ions are mixed and arranged in the lattice, local difference of electron cloud arrangement is generated, the potential difference can form driving force for lithium ion diffusion, and then rapid shuttling of the lithium ions in the lattice is promoted. The combined action of the two aspects can obviously reduce the diffusion impedance of lithium ions in the electrolyte material, improve the shuttling capacity and the transmission speed of the lithium ions in the electrolyte crystal lattice, improve the conductivity of the lithium ions and further improve the multiplying power performance and the quick charging capacity of the battery. Meanwhile, the use of scarce and expensive trivalent ions is reduced, so that the raw material cost of the electrolyte material is reduced, and the practical application value of the electrolyte material is improved.
2. The invention provides a halide solid electrolyte material, further, A is selected from Ga 3+ 、In 3+ 、Fe 3+ 、Y 3+ 、Sc 3 + 、Ho 3+ 、Er 3+ 、Lu 3+ 、Yb 3+ One or more of; m is selected from Mg 2+ 、Zn 2+ 、Cu 2+ One or more of (a); n is selected from Zr 4+ And/or Hf 4+ (ii) a A is more than or equal to 2.2 and less than or equal to 3.8; x is more than or equal to 0.1 and less than or equal to 0.5; y is more than or equal to 0.1 and less than or equal to 0.7. The invention can further improve the ionic conductivity of the material by further limiting the element types of the metals A, M and N.
3. The invention provides a halide solid electrolyte material, further, A is selected from Fe 3+ N is selected from Hf 4+ The specific A and N elements are limited, and the ion conductivity of the material can be obviously improved by interaction with other elements.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a halide solid electrolyte material, which comprises the following steps:
1) Under the protection of argon atmosphere, 3.425 g LiCl and 1.404 g FeCl are weighed 3 0.549 g MgCl 2 4.621 g HfCl 4 (ii) a Grinding the materials in an agate mortar for 10min to obtain a mixture;
2) Pouring the mixture into a 100mL ball milling tank, wherein the ball-material ratio is 20The junction temperature is 450 ℃, the heat preservation time is 6h, after the heat preservation is finished, the quartz tube is cooled to the room temperature, then the quartz tube is placed into a glove box and opened, the obtained material is ground for 30min by using an agate mortar, and the glass-ceramic phase halide solid electrolyte material Li is obtained 2.8 Fe 0.3 Mg 0.2 Hf 0.5 Cl 6.1 。
Example 2
The embodiment provides a preparation method of a halide solid electrolyte material, which comprises the following steps:
1) Under the protection of argon atmosphere, 2.546 g LiCl and 0.961 g GaCl are weighed 3 0.372 g ZnCl 2 6.121 g HfCl 4 (ii) a Grinding the materials in an agate mortar for 10min to obtain a mixture;
2) Pouring the mixture into a 100mL ball milling tank, wherein the ball-to-material ratio is 20:1, sealing, ball milling is carried out by adopting a planetary ball mill, the ball milling speed is 500 r/min, the ball milling time is 1h, opening the ball milling tank under the protection of argon after the ball milling is finished, scraping the material out, pressing the ball-milled material into pieces with the size of 12mm by adopting a tablet press, putting the pieces into a single-head quartz tube, sealing by adopting a vacuum tube sealing mode, placing the single-head quartz tube into a muffle furnace for high-temperature sintering, wherein the sintering temperature is 200 ℃, the heat preservation time is 1h, cooling to room temperature after the heat preservation is finished, then placing the quartz tube into a glove box, opening, grinding the obtained material by using an agate mortar for 30min, and obtaining the glass-ceramic phase halide solid electrolyte material Li 2.2 Ga 0.2 Zn 0.1 Hf 0.7 Cl 5.8 。
Example 3
The embodiment provides a preparation method of a halide solid electrolyte material, which comprises the following steps:
1) Under the protection of argon atmosphere, 3.192 g LiCl and 2.100 g YCl are weighed 3 2.410 g of CuCl 2 2.297 g HfCl 4 (ii) a Grinding the materials in an agate mortar for 10min to obtain a mixture;
2) Pouring the mixture into a 100mL ball milling tank, wherein the ball-material ratio is 20The rotating speed is 100 revolutions per minute, the ball milling time is 50 hours, after the ball milling is finished, the ball milling tank is opened under the protection of argon atmosphere, the materials are scraped out, the ball milled materials are pressed into pieces with the size of 12mm by a tablet press, the pieces are placed into a single-end quartz tube, then the single-end quartz tube is sealed in a vacuum tube sealing mode and placed in a muffle furnace for high-temperature sintering, the sintering temperature is 600 ℃, the heat preservation time is 40 hours, after the heat preservation is finished, the materials are cooled to the room temperature, then the quartz tube is placed into a glove box and opened, the obtained materials are ground for 30 minutes by an agate mortar, and the glass-ceramic phase halide solid electrolyte material Li can be obtained 2.1 Y 0.3 Cu 0.5 Hf 0.2 Cl 4.8 。
Example 4
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.865 g LiCl and 1.972 g FeCl are weighed in step 1) under the protection of argon atmosphere 3 1.243 g ZnCl 2 2.920 g HfCl 4 (ii) a And (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example is a glass-ceramic phase with a chemical formula of Li 3 Fe 0.4 Zn 0.3 Hf 0.3 Cl 6 。
Example 5
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that in step 1), under the protection of an argon atmosphere, 0.715 g of LiCl and 1.824 g of ScCl are weighed 3 0.821 g ZnCl 2 1.930 g HfCl 4 4.710 g LiBr; and (3) putting the materials in an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.95 Sc 0.5 Zn 0.25 Hf 0.25 Cl 3.7 Br 2.25 。
Example 6
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.224 g of LiCl and 2.26 g of LiCl are weighed in step 1) under the protection of argon atmosphere1 g YbCl 3 1.078 g MgCl 2 3.017 g ZrCl 4 0.420 g LiF; and (3) putting the materials in an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.85 Yb 0.25 Mg 0.35 Zr 0.4 F 0.5 Cl 5.4 。
Example 7
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.537 g of LuCl is weighed in step 1) under the protection of argon atmosphere 3 0.571 g ZnCl 2 1.342 g HfCl 4 4.549 g LiBr; and (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.5 Lu 0.6 Zn 0.2 Hf 0.2 Cl 3 Br 2.5 。
Example 8
This example provides a method for preparing a halide solid state electrolyte material, which is different from example 1 only in that 0.447 g of LiCl and 1.499 g of HoCl are weighed in step 1) under the protection of argon atmosphere 3 0.813 g HoBr 3 0.203 g of CuCl 2 3.003 g HfBr 4 And 4.034 grams LiI; and (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.7 Ho 0.5 Cu 0.1 Hf 0.4 Cl 2 Br 2 I 2 。
Example 9
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 2.073 g LiCl and 2.509 g ErBr are weighed in step 1) under the protection of argon atmosphere 3 1.250 g ZnCl 2 1.514 g of TiF 4 And 2.654 grams LiBr; and (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte prepared in this exampleThe material is a glass-ceramic phase with a chemical general formula of Li 2.6 Er 0.3 Zn 0.3 Ti 0.4 F 1.6 Cl 3.1 Br。
Example 10
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that in step 1), under the protection of argon atmosphere, 1.600 g LiCl and 5.217 g LuBr are weighed 3 0.233 g of CaCl 2 0.332 g SrCl 2 1.343 g HfCl 4 And 1.275 grams LiBr; and (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example is a glass-ceramic phase with a chemical formula of Li 2.5 Lu 0.6 Ca 0.1 Sr 0. 1 Hf 0.2 Cl 3 Br 2.5 。
Example 11
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 0.693 g LiCl and 2.544 g LuBr are weighed in step 1) under the protection of argon atmosphere 3 1.124 g of CdCl 2 2.620 g HfCl 4 And 3.019 grams LiBr; and (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example is a glass-ceramic phase with a chemical formula of Li 2.5 Lu 0.3 Cd 0.3 Hf 0.4 Cl 3 Br 2.6 。
Example 12
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.162 g LiCl and 3.806 g InCl are weighed in step 1) under the protection of argon atmosphere 3 1.195 g BaCl 2 And 1.837 grams HfCl 4 (ii) a And (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.6 In 0.6 Ba 0.2 Hf 0.2 Cl 5.6 。
Example 13
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 6.041 g LiCl and 2.875 g ScCl are weighed in step 1) under the protection of argon atmosphere 3 0.324 g ZnCl 2 And 0.761 g HfCl 4 (ii) a And (3) putting the materials in an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 6 Sc 0.8 Zn 0.1 Hf 0.1 Cl 9 。
Example 14
This example provides a method for preparing a halide solid state electrolyte material, which is different from example 1 only in that 1.499 g of LiCl and 4.344 g of InCl are weighed in step 1) under the protection of argon atmosphere 3 1.071 g ZnCl 2 2.746 g of ZrCl 4 And 0.341 grams LiBr; and (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example is a glass-ceramic phase with a chemical formula of LiIn 0.5 Zn 0.2 Zr 0.3 Cl 4 Br 0.1 。
Example 15
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.441 g LiCl and 3.590 g InCl are weighed in step 1) under the protection of argon atmosphere 3 0.369 g of ZnCl 2 And 2.600 grams HfCl 4 (ii) a And (3) putting the materials in an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example is a glass-ceramic phase with a chemical formula of Li 3 In 0.6 Zn 0.1 Hf 0.3 Cl 6.2 。
Example 16
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 4.255 g of LiCl and 2.337 g of ScCl are weighed in step 1) under the protection of argon atmosphere 3 1.838 g of MgCl 2 0.900 g ZrCl 4 And 0.671 g LiBr; placing the above materials in a containerAnd grinding in an agate mortar for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.8 Sc 0.4 Mg 0.5 Zr 0.1 Cl 5.2 Br 0.2 。
Example 17
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.199 g of LiCl and 0.266 g of GaCl are weighed in step 1) under the protection of argon atmosphere 3 0.206 g ZnCl 2 And 6.330 g ZrCl 4 (ii) a And (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example is a glass-ceramic phase with a chemical formula of Li 2.5 Ga 0.05 Zn 0.05 Zr 0.9 Cl 6.35 。
Example 18
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that in step 1), under the protection of argon atmosphere, 2.368 g LiCl and 0.650 g ErCl are weighed 3 3.644 g ZnCl 2 0.190 g HfCl 4 And 3.147 grams LiBr; and (3) putting the materials in an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 3.1 Er 0.08 Zn 0.9 Hf 0.02 Cl 4 Br 1.22 。
Example 19
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 3.897 g LiCl and 1.992 g LaCl are weighed in step 1) under the protection of argon atmosphere 3 1.083 g MgCl 2 3.028 g of ZrCl 4 (ii) a And (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.83 La 0.25 Mg 0.35 Zr 0.4 Cl 5.88 。
Example 20
This example provides a method for preparing a halide solid state electrolyte material, which is different from example 1 only in that 2.113 g of LiCl and 3.942 g of GdCl are weighed in step 1) under the protection of argon atmosphere 3 0.680 g ZnCl 2 1.597 g HfCl 4 And 1.668 grams LiI; and (3) putting the materials in an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li 2.5 Gd 0.6 Zn 0.2 Hf 0.2 Cl 5 I 0.5 。
Comparative example 1
This comparative example provides a method for producing a halide solid electrolyte material, which differs from example 1 only in that 3.944 g of LiCl and 6.056 g of YCl were weighed in the step 1) under the protection of an argon atmosphere 3 (ii) a And (3) putting the materials into an agate mortar for grinding for 10min to obtain a mixture. The halide solid electrolyte material prepared in this comparative example was a glass-ceramic phase having a chemical formula of Li 3 YCl 6 。
Test example
The ion conductivity of the electrolyte materials prepared in the above examples and comparative examples was tested as follows: 100mg of electrolyte powder was weighed, placed in an insulating outer cylinder, pressure-molded at a pressure of 300MPa, subjected to an AC impedance spectroscopy test, and the ionic conductivity of the electrolyte material was calculated from the impedance values, with the test results shown in Table 1.
TABLE 1 Properties of the electrolyte Material
As can be seen from table 1, in the invention, divalent and tetravalent ions are introduced into electrolyte components simultaneously, so that the microstructure of halide is flexibly adjusted, the Li/hole ratio is optimized, the rapid shuttling of lithium ions in crystal lattices is promoted, the effect of greatly improving the conductivity of halide ions can be realized, the use of rare and expensive trivalent ions is reduced, the preparation cost of halide is reduced, a new technical route and a solution are provided for the practical application of halide materials, and the types and practical application values of halide solid electrolyte materials are enriched.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A halide solid electrolyte material is characterized in that the chemical general formula of the electrolyte material is LiaA 1-x- y M x N y X 3+a-x+y Wherein a is more than or equal to 1 and less than or equal to 6; x is more than or equal to 0.02 and less than or equal to 0.9; y is more than or equal to 0.02 and less than or equal to 0.9; a is selected from Ga 3+ 、In 3+ 、Fe 3+ 、Y 3+ 、Sc 3+ One or more kinds of metals having a valence of +3 La; m is selected from Cu 2+ 、Zn 2+ 、Cd 2+ 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ One or more of (a); n is selected from Zr 4+ 、Hf 4+ 、Ti 4+ One or more of (a); x is selected from F - 、Cl - 、Br - 、I - One or more of;
the bivalent ions represented by M replace the trivalent ions represented by A to increase lithium ions and reduce holes, the tetravalent ions represented by N replace the trivalent ions represented by A to increase holes and reduce lithium ions, and the bivalent ions, the tetravalent ions and the trivalent ions are mixed and arranged in the crystal lattice to generate local difference of electron cloud arrangement.
2. The halide solid state electrolyte material according to claim 1, which is characterized byCharacterized in that A is selected from Ga 3+ 、In 3+ 、Fe 3+ 、Y 3 + 、Sc 3+ 、Ho 3+ 、Er 3+ 、Lu 3+ 、Yb 3+ One or more of (a); and/or, M is selected from Mg 2+ 、Zn 2+ 、Cu 2+ One or more of; and/or N is selected from Zr 4+ And/or Hf 4+ ；
And/or a is more than or equal to 2.2 and less than or equal to 3.8; and/or x is more than or equal to 0.1 and less than or equal to 0.5; and/or, y is more than or equal to 0.1 and less than or equal to 0.7.
3. The halide solid electrolyte material of claim 2, wherein A is selected from the group consisting of Fe 3+ N is selected from Hf 4+ 。
4. A halide solid state electrolyte material according to any one of claims 1 to 3, wherein the halide solid state electrolyte material is in the form of any one of a glass phase, a glass-ceramic phase or a crystalline phase.
5. A method for producing a halide solid electrolyte material as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
1) Mixing the raw materials according to the formula proportion to obtain a mixture;
2) And grinding and sintering the mixture to obtain the halide solid electrolyte material.
6. The method for preparing the halide solid electrolyte material according to claim 5, wherein the mixture is ground in the step 2) by ball milling at a rotation speed of 100-500 rpm for 1-50h;
the grinding step is carried out under an inert atmosphere;
the sintering temperature is 200-600 ℃, and the heat preservation time is 1-40h.
7. The method for producing a halide solid electrolyte material according to claim 5 or 6, further comprising a step of grinding the sintered material after the sintering in step 2).
8. The method for producing a halide solid state electrolyte material according to claim 5,
the raw materials In the step 1) are a lithium source, an A source, an M source and an N source, wherein the lithium source is lithium halide, and the A source is one or more selected from Ga halide, in halide, fe halide, Y halide, sc halide and La metal halide;
the M source is selected from one or more of Cu halide, zn halide, cd halide, mg halide, ca halide, sr halide and Ba halide;
the N source is selected from one or more of Zr halide, hf halide and Ti halide.
9. A lithium secondary battery comprising a positive electrode layer, an electrolyte layer and a negative electrode layer, characterized in that at least one of the positive electrode layer, the electrolyte layer and the negative electrode layer contains the halide solid state electrolyte material according to any one of claims 1 to 4 or the halide solid state electrolyte material produced by the production method according to any one of claims 5 to 8.
10. The lithium secondary battery according to claim 9, wherein the lithium secondary battery comprises a liquid-phase lithium secondary battery, a semi-solid lithium secondary battery, and an all-solid lithium secondary battery.
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