CN113889662A - Halide solid electrolyte material and preparation method and application thereof - Google Patents

Halide solid electrolyte material and preparation method and application thereof Download PDF

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CN113889662A
CN113889662A CN202111153803.7A CN202111153803A CN113889662A CN 113889662 A CN113889662 A CN 113889662A CN 202111153803 A CN202111153803 A CN 202111153803A CN 113889662 A CN113889662 A CN 113889662A
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halide
electrolyte material
equal
solid electrolyte
halide solid
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CN113889662B (en
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周宇楠
陈少杰
曹晓菊
李瑞杰
黄海强
王磊
刘景超
王志文
李生
张琪
袁文森
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Svolt Energy Technology Co Ltd
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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
    • H01M10/056—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
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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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 invention provides a halide solid electrolyte material, wherein the chemical general formula of the electrolyte material is LiaA1‑x‑yMxNyX3+a‑x+yWherein 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 Al3+、Ga3+、In3+、Fe3+、Y3+、Sc3+One or more kinds of metals having a valence of +3 La; m is selected from Cu2+、Zn2+、Cd2+、Mg2+、Ca2+、Sr2+、Ba2+One or more of; n is selected from Zr4+、Hf4+、Ti4+One or more of; 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

Halide solid electrolyte material and preparation method and application thereof
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 introduction of lithium ion batteries, the lithium ion batteries 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 of high-performance solid-state batteries, electrolytes with 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 the ionic conductivityEven beyond current commercial electrolyte levels. However, the cost of raw materials of sulfide is high, the preparation conditions are harsh, the sulfide can not 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 only under the harsh preparation conditions of high temperature and high pressure ((>1 mS/cm). Halide Li3AX6(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, Li3AX6The phase structure, ionic conductivity and metal cathode stability are influenced by the type and radius of A metal ions, and In order to maintain the structural stability and high ionic conductivity, A is mainly selected from trivalent metal ions with the ionic radius between 0.65 and 0.92 and mainly comprises In3+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 LiaA1-x-yMxNyX3+a-x+yWherein 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 Al3+、Ga3+、In3+、Fe3+、Y3+、Sc3+One or more kinds of metals having a valence of +3 La; m is selected from Cu2+、Zn2+、Cd2+、Mg2+、Ca2+、Sr2+、Ba2+One or more of; n is selected from Zr4 +、Hf4+、Ti4+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 Ga3+、In3+、Fe3+、Y3+、Sc3+、Ho3+、Er3+、Lu3+、Yb3+One or more of; and/or, M is selected from Mg2+、Zn2+、Cu2+One or more of; and/or N is selected from Zr4+And/or Hf4+；
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 Fe3+N is selected from Hf4+。
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 10-5S/cm。
Preferably, the mixture is ground in the step 2) by adopting a ball milling mode, the ball milling speed is 100-; preferably, the ball milling speed is 200-.
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 2-30 h.
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 may be mixed in step 1) using an agate mortar in order to uniformly mix the raw materials. 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 series 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 selected from one or more of aluminum chloride, gallium chloride, indium chloride, ferric trichloride, 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+→A3++ a hole; n is a radical of4++ hole → A3++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 a lattice, local difference of electron cloud arrangement is generated, and the potential difference can diffuse lithium ions to formThe driving force, in turn, promotes rapid shuttling of lithium ions between crystal lattices. The combined action of the two aspects can obviously reduce the diffusion impedance of lithium ions in the electrolyte material, improve the shuttle capacity and 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 charge 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 Ga3+、In3+、Fe3+、Y3+、Sc3 +、Ho3+、Er3+、Lu3+、Yb3+One or more of; m is selected from Mg2+、Zn2+、Cu2+One or more of; n is selected from Zr4+And/or Hf4+(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 present invention can further enhance the ionic conductivity of the material by further limiting the elemental species of the metal A, M, N.
3. The invention provides a halide solid electrolyte material, further, A is selected from Fe3+N is selected from Hf4+The invention can obviously improve the ionic conductivity of the material by limiting specific A and N elements to interact 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) 3.425 g LiCl and 1.404 g FeCl were weighed in an argon atmosphere30.549 g MgCl24.621 g HfCl4(ii) a Grinding the materials in an agate mortar for 10min to obtain a mixture;
2) pouring the mixture into a 100mL ball mill with a ball-to-material ratio of 20:1, sealing, ball milling by a planetary ball mill at a ball milling speed of 400 r/min for 20 h, opening the ball mill under the protection of argon after ball milling, scraping the material, pressing the ball-milled material into 12 mm-sized pieces by a tablet press, placing the pieces into a single-end quartz tube, sealing by a vacuum tube sealing method, placing the single-end quartz tube into a muffle furnace for high-temperature sintering at 450 ℃ for 6h, cooling to room temperature after heat preservation, placing the quartz tube into a glove box, opening the glove box, and grinding the obtained material by an agate mortar for 30min to obtain the glass-ceramic phase halide solid electrolyte material Li2.8Fe0.3Mg0.2Hf0.5Cl6.1。
Example 2
The embodiment provides a preparation method of a halide solid electrolyte material, which comprises the following steps:
1) 2.546 g LiCl and 0.961 g GaCl were weighed out under the protection of argon atmosphere30.372 g ZnCl26.121 g HfCl4(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 20:1, sealing, ball milling by using a planetary ball mill at the ball milling rotation speed of 500 r/min for 1h, opening the ball milling tank under the protection of argon after ball milling, scraping the material out, pressing the ball-milled material into 12 mm-sized pieces by using a tablet press, putting the 12 mm-sized pieces into a single-end quartz tube, sealing by using a vacuum tube sealing mode, placing the single-end quartz tube in a muffle furnace for high-temperature sintering at 200 ℃,the heat preservation time is 1h, 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 an agate mortar, and the glass-ceramic phase halide solid electrolyte material Li is obtained2.2Ga0.2Zn0.1Hf0.7Cl5.8。
Example 3
The embodiment provides a preparation method of a halide solid electrolyte material, which comprises the following steps:
1) 3.192 g LiCl and 2.100 g YCl are weighed in under the protection of argon atmosphere32.410 g of CuCl22.297 g HfCl4(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 20:1, sealing, performing ball milling by using a planetary ball mill at the ball milling rotation speed of 100 revolutions per minute for 50 hours, 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 12 mm-sized pieces by using a tablet press, placing the pieces into a single-end quartz tube, sealing by using a vacuum tube sealing mode, placing the single-end quartz tube into a muffle furnace for high-temperature sintering at the sintering temperature of 600 ℃ for 40 hours, cooling to room temperature after the heat preservation is finished, placing the quartz tube into a glove box, opening the glove box, and grinding the obtained material by using an agate mortar for 30 minutes to obtain the glass-ceramic phase halide solid electrolyte material Li2.1Y0.3Cu0.5Hf0.2Cl4.8。
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 atmosphere31.243 g ZnCl22.920 g HfCl4(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 Li3Fe0.4Zn0.3Hf0.3Cl6。
Example 5
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 0.715 g LiCl and 1.824 g ScCl are weighed in step 1) under the protection of argon atmosphere30.821 g ZnCl21.930 g HfCl44.710 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 Li2.95Sc0.5Zn0.25Hf0.25Cl3.7Br2.25。
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 LiCl and 2.261 g YbCl are weighed in step 1) under the protection of argon atmosphere31.078 g MgCl23.017 g ZrCl40.420 g LiF; 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 Li2.85Yb0.25Mg0.35Zr0.4F0.5Cl5.4。
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 atmosphere30.571 g ZnCl21.342 g HfCl44.549 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 Li2.5Lu0.6Zn0.2Hf0.2Cl3Br2.5。
Example 8
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 0.447 g of LiCl and 1 are weighed in step 1) under the protection of argon atmosphere499 g of HoCl30.813 g HoBr30.203 g of CuCl23.003 g HfBr4And 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 Li2.7Ho0.5Cu0.1Hf0.4Cl2Br2I2。
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 atmosphere31.250 g ZnCl21.514 g of TiF4And 2.654 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 Li2.6Er0.3Zn0.3Ti0.4F1.6Cl3.1Br。
Example 10
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 1.600 g of LiCl and 5.217 g of LuBr are weighed in step 1) under the protection of argon atmosphere30.233 g of CaCl20.332 g SrCl21.343 g HfCl4And 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 was a glass-ceramic phase having the chemical formula Li2.5Lu0.6Ca0.1Sr0. 1Hf0.2Cl3Br2.5。
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 atmosphere31.124 g of CdCl22.620 g HfCl4And 3.019 grams LiBr; putting the materials into an agate mortar for grindingGrinding for 10min to obtain mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li2.5Lu0.3Cd0.3Hf0.4Cl3Br2.6。
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 atmosphere31.195 g BaCl2And 1.837 g HfCl4(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 Li2.6In0.6Ba0.2Hf0.2Cl5.6。
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 of LiCl and 2.875 g of ScCl are weighed in step 1) under the protection of argon atmosphere30.324 g ZnCl2And 0.761 g HfCl4(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 Li6Sc0.8Zn0.1Hf0.1Cl9。
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 atmosphere31.071 g ZnCl22.746 g of ZrCl4And 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 was a glass-ceramic phase having a chemical formula of LiIn0.5Zn0.2Zr0.3Cl4Br0.1。
Example 15
This implementationExample a method for producing a halide solid state electrolyte material is provided, which differs from example 1 only in that 3.441 g LiCl and 3.590 g InCl are weighed in step 1) under the protection of an argon atmosphere30.369 g of ZnCl2And 2.600 grams HfCl4(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 Li3In0.6Zn0.1Hf0.3Cl6.2。
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 atmosphere31.838 g MgCl20.900 g ZrCl4And 0.671 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 Li2.8Sc0.4Mg0.5Zr0.1Cl5.2Br0.2。
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 atmosphere30.206 g ZnCl2And 6.330 g ZrCl4(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 Li2.5Ga0.05Zn0.05Zr0.9Cl6.35。
Example 18
This example provides a method for preparing a halide solid electrolyte material, which is different from example 1 only in that 2.368 g of LiCl and 0.650 g of ErCl are weighed in step 1) under the protection of argon atmosphere33.644 g ZnCl20.190 g HfCl4And 3.147 grams LiBr; placing the materials in agate grinderGrinding in a bowl for 10min to obtain a mixture. The halide solid electrolyte material prepared in this example was a glass-ceramic phase having the chemical formula Li3.1Er0.08Zn0.9Hf0.02Cl4Br1.22。
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 atmosphere31.083 g MgCl23.028 g ZrCl4(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 Li2.83La0.25Mg0.35Zr0.4Cl5.88。
Example 20
This example provides a method for producing a halide solid 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 atmosphere30.680 g ZnCl21.597 g HfCl4And 1.668 g 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 Li2.5Gd0.6Zn0.2Hf0.2Cl5I0.5。
Comparative example 1
This comparative example provides a method for producing a halide solid electrolyte material, which is different from example 1 only in that 3.944 g of LiCl and 6.056 g of YCl were weighed out under the protection of an argon atmosphere in step 1)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 Li3YCl6。
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
Figure BDA0003288024670000091
Figure BDA0003288024670000101
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 LiaA1-x- yMxNyX3+a-x+yWherein 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 Al3+、Ga3+、In3+、Fe3+、Y3+、Sc3 +One or more kinds of metals having a valence of +3 La; m is selected from Cu2+、Zn2+、Cd2+、Mg2+、Ca2+、Sr2+、Ba2+One or more of; n is selected from Zr4+、Hf4+、Ti4+One or more of; x is selected from F-、Cl-、Br-、I-One or more of (a).
2. The halide solid state electrolyte material of claim 1, wherein A is selected from Ga3+、In3+、Fe3+、Y3 +、Sc3+、Ho3+、Er3+、Lu3+、Yb3+One or more of; and/or, M is selected from Mg2+、Zn2+、Cu2+One or more of; and/or N is selected from Zr4+And/or Hf4+；
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 state electrolyte material of claim 1 or 2, wherein a is selected from Fe3+N is selected from Hf4 +。
4. The 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 a halide solid electrolyte material as claimed in claim 5, wherein the mixture is ground in step 2) by ball milling at a rotation speed of 100 and 500 rpm for 1-50 h;
the grinding step is carried out under an inert atmosphere;
the sintering temperature is 200-600 ℃, and the heat preservation time is 1-40 h.
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 production method of a halide solid state electrolyte material according to any one of claims 5 to 7, characterized in that,
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 series 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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115528298A (en) * 2022-08-12 2022-12-27 中山大学 Sodium ion halide solid electrolyte material and preparation method and application thereof
CN115732751A (en) * 2022-11-28 2023-03-03 蜂巢能源科技(无锡)有限公司 Halide solid electrolyte material, preparation method thereof and lithium ion battery
CN115799621A (en) * 2022-09-09 2023-03-14 南开大学 Composite halide solid electrolyte membrane and solid battery prepared from same
WO2024037397A1 (en) * 2022-08-16 2024-02-22 中国科学技术大学 Halide all-solid-state battery material, preparation method therefor, and application thereof

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3407412A1 (en) * 2017-05-24 2018-11-28 Basf Se Ionically conductive compounds and related uses
CN111316485A (en) * 2018-01-05 2020-06-19 松下知识产权经营株式会社 Positive electrode material and battery
CN111509222A (en) * 2020-04-15 2020-08-07 国联汽车动力电池研究院有限责任公司 Halide solid electrolyte material and preparation method and application thereof
CN111566853A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Positive electrode material and battery using same
CN111566756A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Solid electrolyte material and battery
WO2020188915A1 (en) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
CN111868994A (en) * 2017-11-07 2020-10-30 密执安州立大学董事会 Solid-state battery electrolyte with improved stability to cathode materials
CN112216863A (en) * 2020-09-03 2021-01-12 北京当升材料科技股份有限公司 Halogenated solid electrolyte material, flexible solid electrolyte membrane, lithium battery and preparation method of flexible solid electrolyte membrane
WO2021186833A1 (en) * 2020-03-18 2021-09-23 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery in which same is used
CN113454735A (en) * 2019-02-28 2021-09-28 松下知识产权经营株式会社 Electrolyte material and battery using the same

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3407412A1 (en) * 2017-05-24 2018-11-28 Basf Se Ionically conductive compounds and related uses
CN111868994A (en) * 2017-11-07 2020-10-30 密执安州立大学董事会 Solid-state battery electrolyte with improved stability to cathode materials
CN111316485A (en) * 2018-01-05 2020-06-19 松下知识产权经营株式会社 Positive electrode material and battery
CN111566853A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Positive electrode material and battery using same
CN111566756A (en) * 2018-01-26 2020-08-21 松下知识产权经营株式会社 Solid electrolyte material and battery
CN113454735A (en) * 2019-02-28 2021-09-28 松下知识产权经营株式会社 Electrolyte material and battery using the same
WO2020188915A1 (en) * 2019-03-15 2020-09-24 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery using same
WO2021186833A1 (en) * 2020-03-18 2021-09-23 パナソニックＩｐマネジメント株式会社 Solid electrolyte material and battery in which same is used
CN111509222A (en) * 2020-04-15 2020-08-07 国联汽车动力电池研究院有限责任公司 Halide solid electrolyte material and preparation method and application thereof
CN112216863A (en) * 2020-09-03 2021-01-12 北京当升材料科技股份有限公司 Halogenated solid electrolyte material, flexible solid electrolyte membrane, lithium battery and preparation method of flexible solid electrolyte membrane

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115528298A (en) * 2022-08-12 2022-12-27 中山大学 Sodium ion halide solid electrolyte material and preparation method and application thereof
WO2024037397A1 (en) * 2022-08-16 2024-02-22 中国科学技术大学 Halide all-solid-state battery material, preparation method therefor, and application thereof
CN115799621A (en) * 2022-09-09 2023-03-14 南开大学 Composite halide solid electrolyte membrane and solid battery prepared from same
CN115799621B (en) * 2022-09-09 2024-01-16 南开大学 Composite halide solid electrolyte membrane and solid battery prepared from same
CN115732751A (en) * 2022-11-28 2023-03-03 蜂巢能源科技(无锡)有限公司 Halide solid electrolyte material, preparation method thereof and lithium ion battery

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