CN113772729A - Based on UCl3Framework conductor of type lattice, preparation method and application - Google Patents

Based on UCl3Framework conductor of type lattice, preparation method and application Download PDF

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CN113772729A
CN113772729A CN202111056096.XA CN202111056096A CN113772729A CN 113772729 A CN113772729 A CN 113772729A CN 202111056096 A CN202111056096 A CN 202111056096A CN 113772729 A CN113772729 A CN 113772729A
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chloride
ball milling
bromide
mixed powder
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CN113772729B (en
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姚宏斌
殷逸臣
杨竞天
罗锦达
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University of Science and Technology of China USTC
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01G35/00—Compounds of tantalum
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract

The present disclosure provides a method based on UCl3The preparation method of the frame conductor comprises the step of adding AX and MX in an inert atmosphere3、ZX4Mixing the raw material powder to obtain mixed powder I; carrying out solid-phase ball milling reaction on the mixed powder I under the inert atmosphere to obtain a compound with a chemical formula AxMyZzX3A frame conductor; or under inert atmosphere, adding AX and MX3、TX5Mixing the raw material powder to obtain mixed powder II; carrying out solid-phase ball milling reaction on the mixed powder II under the inert atmosphere to obtain a compound with a chemical formula AaMbTcX3A frame conductor. The method provided by the disclosure has the advantages of simple process and short synthesis time, and the obtained powder can obtain higher room-temperature ionic conductivity without high-temperature sintering after cold press molding.

Description

Based on UCl3Framework conductor of type lattice, preparation method and application
Technical Field
The present disclosure relates to solid state electricityThe technical field of pools, in particular to a pool based on UCl3A framework conductor of a type crystal lattice, a preparation method and application.
Background
Compared with the traditional liquid lithium ion battery, the solid lithium metal battery has the advantages of high safety, high energy density, long cycle life and the like. As a key component of solid-state lithium metal batteries, the performance of lithium ion solid electrolytes largely determines the cycling stability, energy density, and service life of the battery.
The related technology shows that the metal halide solid electrolyte has higher room-temperature ionic conductivity, wider electrochemical window and good interface compatibility with the oxide cathode material. However, most of the metal halide solid electrolytes in the related art adopt metal ions which are easily reduced to construct a conductive framework, which is thermodynamically unstable with lithium metal and causes the interface to be continuously deteriorated during cycling, thereby being unsuitable for a long-life, high-rate solid lithium metal battery.
Disclosure of Invention
In view of the above technical problems, the present disclosure provides a method for generating a UCl-based data packet3A framework conductor for a crystal lattice, a method for its production and its use, which at least partially solve at least one of the above-mentioned problems.
In order to solve the technical problem, the technical scheme of the disclosure is as follows:
as an aspect of the present disclosure, there is provided a UCl-based system3A method for preparing a framework conductor of a type lattice comprises the following steps:
under inert atmosphere, adding AX and MX3、ZX4Mixing the raw material powder to obtain mixed powder I;
carrying out solid-phase ball milling reaction on the mixed powder I under the inert atmosphere to obtain a compound with a chemical formula AxMyZzX3A frame conductor; or
Under inert atmosphere, adding AX and MX3、TX5Mixing the raw material powder to obtain mixed powder II;
under the inert atmosphere, carrying out solid phase ball on the mixed powder IIGrinding reaction to obtain the compound of formula AaMbTcX3A frame conductor;
wherein the content of the first and second substances,
a comprises Li+、Na+、K+、Ag+、Cu+One of the ions;
m comprises La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+One or more of ions;
z comprises Zr4+、Hf4+One or more of ions;
t comprises Ta5+、Nb5+One or more of ions;
x comprises F-、Cl-、Br-、I-One or more of ions;
x，y，z，a，b，c≥0；x+3y+4z＝3，a+3b+5c＝3。
according to an embodiment of the present disclosure, the AX comprises one of lithium chloride, sodium chloride, silver chloride, cuprous chloride, lithium bromide, sodium bromide, potassium bromide, silver bromide, cuprous bromide;
said MX3The material comprises one or more of lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, lanthanum bromide, cerium bromide, praseodymium bromide, neodymium bromide, samarium bromide, europium bromide, gadolinium bromide and terbium bromide;
said ZX4Comprises one or more of zirconium chloride, hafnium chloride, zirconium bromide and hafnium bromide;
the TX5Including one or more of tantalum chloride, niobium chloride, tantalum bromide, and niobium bromide.
According to an embodiment of the present disclosure, the AX, MX are reacted under an inert atmosphere3、ZX4Mixing the raw material powders to obtain mixed powder I comprising:
under the inert atmosphere, adding AX and MX3、ZX4According to the frame conductor AxMyZzX3Transformation ofMixing according to a stoichiometric ratio to obtain the mixed powder I;
under inert atmosphere, adding AX and MX3、TX5Mixing the raw material powders to obtain mixed powder II comprising:
under the inert atmosphere, adding AX and MX3、TX5The raw material powder is arranged according to the frame conductor AaMbTcX3The chemical formula (II) to obtain the mixed powder II.
According to the embodiment of the disclosure, in the solid-phase ball milling reaction, the mass ratio of the mixed powder I or the mixed powder II to ball milling beads is 1 to (20-30).
According to an embodiment of the present disclosure, before the subjecting the mixed powder I to the solid-phase ball milling reaction or before the subjecting the mixed powder II to the solid-phase ball milling reaction, further comprising:
the ball milling tank and the ball milling beads are sequentially subjected to ultrasonic cleaning by using deionized water and absolute ethyl alcohol, and are dried under the conditions that the temperature is 60-100 ℃ and the vacuum degree is-0.1 to-0.05 MPa.
According to embodiments of the present disclosure, the ball milling bead diameter in the solid phase ball milling reaction includes one or more of 10mm, 8mm, and 5 mm;
the inert gas comprises nitrogen or argon.
As a second aspect of the present disclosure, there is provided a frame conductor prepared by the above method.
As a third aspect of the present disclosure, there is provided a solid electrolyte prepared using the above-described frame conductor.
As a fourth aspect of the present disclosure, there is provided a solid-state lithium pair battery comprising the above-described solid electrolyte.
As a fifth aspect of the present disclosure, there is provided an all solid-state lithium metal battery including the above solid electrolyte.
According to an embodiment of the present disclosure, by combining AX, MX3、ZX4The raw material powder is mixed and then is subjected to solid phase ball milling reaction to prepare AxMyZzX3Frame conductor or lead frameAX、MX3、TX5The raw material powder is mixed and then is subjected to solid phase ball milling reaction to prepare AaMbTcX3Frame conductor, obtained AxMyZzX3Frame conductor and AaMbTcX3The frame conductors are all based on UCl3The ionic conductivity of the framework conductor of the type lattice can reach 0.1-5.0 mS cm under the room temperature condition-1And has good interface compatibility at the positive electrode and the lithium metal interface.
According to the embodiment of the disclosure, the simple solid-phase ball-milling reaction is adopted, so that the frame conductor of the monovalent ions with higher room-temperature conductivity can be obtained, the preparation process does not need high-temperature treatment, irritant gas is not generated, and the production energy consumption and the environmental pollution are greatly reduced. In addition, the preparation process has short preparation period and high repeatability.
Drawings
FIG. 1 schematically shows a UCl3A typical framework schematic of the crystal structure.
FIG. 2 schematically illustrates a UCl-based scheme provided by an embodiment of the present disclosure3An X-ray diffraction pattern of lithium/sodium lanthanum zirconium chloride or lithium/sodium lanthanum tantalum chloride in a lattice framework conductor.
FIG. 3 schematically illustrates a UCl-based scheme provided by an embodiment of the present disclosure3Electrochemical ac impedance spectroscopy of lithium/sodium lanthanum tantalum chloride in lattice framework conductors.
Fig. 4 schematically shows a cycling voltage curve of a lithium lanthanum tantalum chloride based solid-state lithium symmetric battery provided by an embodiment of the disclosure.
Fig. 5 schematically shows a charge-discharge curve of an all solid-state lithium metal battery based on lithium lanthanum tantalum chloride provided by an embodiment of the disclosure.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
Currently, many researches on solid electrolyte materials are conducted on oxide, sulfide and polymer-based lithium ion solid electrolyte material systems. The oxide solid electrolyte has a wide electrochemical window, but its harder lattice makes the contact with the electrode worse, causing larger interfacial resistance accompanied by lower lithium ion conductivity and higher grain boundary resistance, and thus is not suitable for preparing a high-power solid lithium metal battery. The sulfide solid electrolyte has ion conductivity comparable to or even exceeding that of a liquid electrolyte, but the application of the sulfide solid electrolyte in a high-energy-density lithium metal battery is limited by a narrow electrochemical window, and the problem of interface stability needs to be solved through complex doping modification. The polymer-based solid electrolyte generally has good contact property and lithium metal stability, but has poor oxidation resistance and low room-temperature conductivity, is difficult to match with a high-voltage positive electrode, and limits the application of the polymer-based solid electrolyte in a high-energy-density lithium metal solid-state battery.
Research shows that the metal halide solid electrolyte has higher room-temperature ionic conductivity, wider electrochemical window and good interface compatibility with oxide cathode materials. However, most of the metal halide solid electrolytes in the related art adopt metal ions which are easily reduced to construct a conductive framework, which is thermodynamically unstable with lithium metal and causes the interface to be continuously deteriorated during cycling, thereby being unsuitable for a long-life, high-rate solid lithium metal battery.
In order to solve the above technical problems, the present disclosure provides a method based on UCl3The preparation method of the framework conductor of the crystal lattice can regulate and control the concentration of different univalent ions and crystal lattice vacancy concentration through simple solid-phase ball milling reaction based on UCl3Universal monovalent ion framework conductor A of crystal latticexMyZzX3Or AaMbTcX3. The method has the advantages of simple process and high repeatability, and the prepared frame conductor has high room-temperature ionic conductivity.
Further, having the above chemical formula (Li/Na)xLayZrzCl3) Or ((Li/Na)aLabTacCl3) Has carrier/vacancy concentration adjustability, and can not cause UCl in a large-range regulation3Collapse of the lattice framework. In the method, the lithium/sodium content is regulated and controlled based on a solid-phase ball milling reaction, so that the conductivity of a target product at normal temperature reaches 0.1-5.0 mS cm-1. The prepared lithium lanthanum tantalum chloride is used as a solid electrolyte in a lithium metal battery, so that the stable deposition/desorption of metal lithium is facilitated, and a solid electrolyte lithium metal interface is gradually stabilized.
According to an embodiment of the present disclosure, there is provided a UCl-based system3A method for preparing a framework conductor of a type lattice comprises the following steps:
under inert atmosphere, adding AX and MX3、ZX4Mixing the raw material powder to obtain mixed powder I;
carrying out solid-phase ball milling reaction on the mixed powder I under inert atmosphere to obtain a chemical formula AxMyZzX3The frame conductor of (1); or
Under inert atmosphere, adding AX and MX3、TX5Mixing the raw material powder to obtain mixed powder II;
carrying out solid-phase ball milling reaction on the mixed powder II under inert atmosphere to obtain a chemical formula AaMbTcX3The frame conductor of (1);
wherein the content of the first and second substances,
a comprises Li+、Na+、K+、Ag+、Cu+One of the ions;
m comprises La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3++One or more of ions;
z comprises Zr4+、Hf4+One or more of ions;
t comprises Ta5+、Nb5+One or more of ions;
x comprises F-、Cl-、Br-、I-One or more of ions;
x，y，z，a，b，c≥0；x+3y+4z＝3，a+3b+5c＝3。
examples according to the disclosureExample by mixing AX, MX3、ZX4The raw material powder is mixed and then is subjected to solid phase ball milling reaction to prepare AxMyZzX3Frame conductor or by connecting AX, MX3、TX5The raw material powder is mixed and then is subjected to solid phase ball milling reaction to prepare AaMbTcX3Frame conductor, obtained AxMyZzX3Frame conductor and AaMbTcX3The frame conductors are all based on UCl3The ionic conductivity of the framework conductor of the type lattice is 0.1-5.0 mS cm at room temperature-1And has good interface compatibility at the positive electrode and the lithium metal interface.
According to the embodiment of the disclosure, the simple solid-phase ball-milling reaction is adopted, so that the frame conductor of the monovalent ions with higher room-temperature conductivity can be obtained, the preparation process does not need high-temperature treatment, irritant gas is not generated, and the production energy consumption and the environmental pollution are greatly reduced. In addition, the preparation process has short preparation period and high repeatability.
According to the embodiment of the present disclosure, the mixed powder I or the mixed powder II is supplied into a zirconia ball mill pot and tightly sealed, and a solid-phase ball milling reaction is performed.
According to an embodiment of the present disclosure, the AX, MX3、ZX4And TX5The purity of the powder is more than 99%.
According to an embodiment of the present disclosure, the AX, MX3、ZX4And TX5The amount of the powder is 1-100 mmol, and the raw materials can be prepared by the method in a wide range, so that the applicability is good.
According to an embodiment of the present disclosure, AX comprises one of lithium chloride, sodium chloride, silver chloride, cuprous chloride, lithium bromide, sodium bromide, potassium bromide, silver bromide, cuprous bromide;
MX3comprises lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, lanthanum bromide, cerium bromide, praseodymium bromide, neodymium bromide, samarium bromide, europium bromide, gadolinium bromide and gadolinium bromideOne or more of terbium;
ZX4comprises one or more of zirconium chloride, hafnium chloride, zirconium bromide and hafnium bromide;
TX5including one or more of tantalum chloride, niobium chloride, tantalum bromide, and niobium bromide.
According to an embodiment of the present disclosure, AX, MX are reacted under an inert atmosphere3、ZX4Mixing the raw material powders to obtain mixed powder I comprising:
under inert atmosphere, adding AX and MX3、ZX4According to the frame conductor AxMyZzX3The chemical formula (4) to obtain mixed powder I.
According to an embodiment of the disclosure, AX, MX3、ZX4According to the frame conductor AxMyZzX3In a stoichiometric ratio of (A) to (B), e.g. AX, MX3、ZX4According to (10 Xx) mmol of AX and (10 Xy) mmol of MX3And (10 xz) mmol of ZX4Mixing the components in the ratio.
According to an embodiment of the present disclosure, AX, MX are reacted under an inert atmosphere3、TX5Mixing the raw material powders to obtain mixed powder II comprising: under inert atmosphere, adding AX and MX3、TX5The raw material powder is arranged according to the frame conductor AaMbTcX3The chemical formula (II) to obtain a mixed powder II.
According to an embodiment of the disclosure, AX, MX3、TX5The raw material powder is arranged according to the frame conductor AaMbTcX3In a stoichiometric ratio of (A) and (B), for example, AX and MX3、TX5According to (20 × a) mmol of AX and (20 × b) mmol of MX3And (20 × c) mmol of TX5Mixing the components in the ratio.
According to the embodiment of the disclosure, in the solid-phase ball milling reaction, the mass ratio of the mixed powder I or the mixed powder II to the ball milling beads is 1 to (20-30).
According to the embodiment of the present disclosure, in the solid phase ball milling reaction, the mass ratio of the mixed powder I to the ball milling beads may be, for example, 1: 20, 1: 25, 1: 30, and the like.
According to the embodiment of the present disclosure, in the solid phase ball milling reaction, the mass ratio of the mixed powder II to the ball milling beads may be, for example, 1: 20, 1: 25, 1: 30, and the like.
According to the embodiment of the disclosure, in the ball milling process, if the powder mixed powder I or the mixed powder II is too much, the ball milling beads are too few, the ball milling amount is insufficient, and the reaction product is not uniform. If the powder is less, the ball milling beads are more, a large amount of powder can be adhered to the ball milling beads, so that the amount of the collected powder is less, and raw materials are wasted. Therefore, the mass ratio of the mixed powder I or the mixed powder II to the ball milling beads is limited to 1 to (20-30), so that the waste of the mixed powder I or the mixed powder II can be reduced and the yield can be improved under the condition of ensuring the ball milling effect.
According to the embodiment of the present disclosure, in the solid-phase ball-milling reaction, the time of the solid-phase ball-milling reaction is set to 6 to 20 hours; the rotation speed is set to 300-450 rpm.
According to the embodiment of the disclosure, the time for the solid phase ball milling reaction can be 6h, 12h, 18h, 20h and the like.
The rotational speed of the ball milling reaction in the solid phase may be, for example, 300 revolutions per minute, 350 revolutions per minute, 425 revolutions per minute, 450 revolutions per minute, and so on, according to embodiments of the present disclosure.
According to the embodiment of the disclosure, in the solid-phase ball-milling reaction, the solid-phase ball-milling reaction program comprises forward rotation, intermittent rotation, reverse rotation and intermittent rotation, and the operation is cycled in this order.
According to the embodiment of the present disclosure, the solid phase ball milling reaction program may be set to, for example, 2 minutes for forward rotation, 21 minutes for intermittent rotation, 2 minutes for reverse rotation, and 1 minute for intermittent rotation, and the operation may be cycled in this order.
According to the embodiment of the present disclosure, before the mixed powder I is subjected to the solid-phase ball milling reaction or before the mixed powder II is subjected to the solid-phase ball milling reaction, the method further includes: the ball milling tank and the ball milling beads are sequentially subjected to ultrasonic cleaning by using deionized water and absolute ethyl alcohol, and are dried under the conditions that the temperature is 60-100 ℃ and the vacuum degree is-0.1 to-0.05 MPa.
According to the embodiment of the disclosure, the drying time of the ball milling pot and the ball milling beads is at least 6 hours, such as 6 hours, 6.5 hours, 7 hours, 8 hours and the like.
According to an embodiment of the present disclosure, the temperature for drying the ball milling pot and the ball milling beads may be, for example, 60 ℃, 75 ℃, 85 ℃, 90 ℃, 100 ℃, or the like; the degree of vacuum may be, for example, -0.1MPa, -0.08MPa, -0.05MPa, or the like.
According to the embodiment of the disclosure, the moisture in the ball milling tank and the ball milling beads can cause the moisture absorption of raw materials and intermediate products, so that the state of the final product is influenced, and even the moisture absorption and deliquescence of the final product can be caused; and the existence of trace moisture can influence ion migration and can influence the judgment of the ion migration of the material body. Therefore, the ball milling tank and the ball milling beads are cleaned, and the ball milling tank and the ball milling beads are dried after being dehydrated by adopting absolute ethyl alcohol, so that trace moisture in the ball milling tank can be fully removed, and the normal operation of reaction is ensured.
According to embodiments of the present disclosure, the ball milling bead diameter in the solid phase ball milling reaction includes one or more of 10mm, 8mm, and 5 mm.
According to the embodiment of the present disclosure, for example, only ball milling beads of one diameter of 10mm may be included in the solid phase ball milling reaction, ball milling beads of two diameters of 10mm and 8mm may be included, ball milling beads of three diameters of 10mm, 8mm and 5mm may be included, and the like.
For example, the solid phase ball milling reaction may include ball milling beads of three diameters, 10mm, 8mm and 5mm, in a weight ratio of 2: 3: 5.
According to the embodiment of the disclosure, the ball milling reaction is carried out by adopting the ball milling beads with different sizes, the larger ball milling beads are beneficial to damaging the agglomerated product in the reaction process, and the smaller ball milling beads can be fully contacted with the powder and provide the energy required by the reaction, so that the reaction is promoted to be more uniform.
According to an embodiment of the present disclosure, the inert gas includes nitrogen or argon.
According to embodiments of the present disclosure, the purity of the nitrogen or argon is greater than or equal to 99.999%.
According to an embodiment of the present disclosure, there is provided a frame conductor prepared by the above method.
According to an embodiment of the present disclosure, there is provided a solid electrolyte prepared using the above frame conductor.
According to an embodiment of the present disclosure, there is provided a solid-state lithium pair battery including the above-described solid electrolyte.
According to an embodiment of the present disclosure, there is provided an all solid-state lithium metal battery including the above solid electrolyte.
The present disclosure is further illustrated by the following specific examples, which are not intended to limit the scope of the present disclosure.
In the following examples, unless otherwise specified, the methods used are conventional in the art, and the materials, reagents, detection devices, and the like used are commercially available.
FIG. 1 schematically shows a UCl3A typical frame diagram of the crystal structure, in which (a) in fig. 1 is a top view and (b) in fig. 1 is a test chart.
FIG. 1, UCl3Nine-coordinate triple-cap triangular prism unit [ MX ] in crystal structure9]A one-dimensional pore canal with six-order symmetry is formed by enclosing monovalent ion A+(Li+/Na+/K+/Ag+/Cu+Etc.) can be conducted rapidly within the pore channel. Confirmation of MX by search in crystallography database3(including LaCl)3、CeCl3、PrCl3、NdCl3、SmCl3、EuCl3、GdCl3、TbCl3、LaBr3、CeBr3、PrBr3、NdBr3Halides of isolanthanide metals) are all UCl3And (5) structure.
Materials, reagents, instruments and the like involved in the examples will be briefly described below.
Lithium chloride (LiCl, Aladdin, anhydrous grade, 99.9%), sodium chloride (NaCl, Aladdin, 99.9%), lanthanum chloride (LaCl)3Aladdin, anhydrous grade, 99.9%), tantalum chloride (TaCl)5Aladdin, anhydrous grade, 99.9%), zirconium chloride (ZrCl)4Alfa Aesar, anhydrous grade, 98%).
Example 1
Provides a method based on UCl3Method for preparing framework conductor of type lattice, this example to prepare Li0.3875La0.475Ta0.2375Cl3The frame conductor is taken as an example, and the preparation method comprises the following steps:
under the atmosphere of high-purity nitrogen, lithium chloride, lanthanum chloride and tantalum chloride powder are mixed according to the molar ratio of 3.875: 4.750: 2.375 to obtain mixed powder II, wherein the corresponding dosage of the lithium chloride, the lanthanum chloride and the tantalum chloride powder is 0.1643g, 1.1650g and 0.8508g respectively.
The zirconia ball milling tank and the ball milling beads are sequentially cleaned by deionized water and absolute ethyl alcohol, and are dried for at least 6 hours in a vacuum oven with the temperature of 75 ℃ and the vacuum degree of-0.1 MPa, so that trace moisture in the ball milling tank is fully removed.
Adding the mixed powder I into a ball milling tank in a high-purity nitrogen atmosphere, adding ball milling beads into the ball milling tank according to the mass ratio of the mixed powder I to the ball milling beads being 1: 25, strictly sealing, and then placing the ball milling tank in a planetary ball mill for solid-phase ball milling reaction. Wherein, the added ball milling beads comprise three types of 10mm, 8mm and 5mm in diameter, and are mixed according to the weight ratio of 2: 3: 5. The time of the solid phase ball milling reaction was set to 18 hours, the reaction speed was set to 425 rpm, and the reaction program was set to 2 minutes for normal rotation, 1 minute for pause, 2 minutes for reverse rotation, and 1 minute for pause, and the above sequence was repeated.
During the solid-phase ball-milling reaction, every 6 hours, the ball-milling tank is opened in a nitrogen-filled glove box for mixing, so that the sufficient and uniform reaction is ensured, and Li can be obtained after the reaction is finished0.3875La0.475Ta0.2375Cl3A frame conductor.
Example 2
Provides a method based on UCl3Preparation of framework conductor of type lattice, this example to prepare Na0.4423La0.3654Ta0.2923Cl3The frame conductor is taken as an example, and the preparation method comprises the following steps:
under the atmosphere of high-purity argon, mixing sodium chloride, lanthanum chloride and tantalum chloride powder according to the molar ratio of 4.423: 3.654: 2.923 to obtain mixed powder II, wherein the corresponding dosage of the sodium chloride, the lanthanum chloride and the tantalum chloride powder is 0.2585g, 0.8961g and 1.0472g respectively.
The zirconia ball milling tank and the ball milling beads are sequentially cleaned by deionized water and absolute ethyl alcohol, and are dried for at least 6 hours in a vacuum oven with the temperature of 60 ℃ and the vacuum degree of-0.08 MPa, so that trace moisture in the ball milling tank is fully removed.
Adding the mixed powder I into a ball milling tank in a high-purity argon atmosphere, and mixing the mixed powder I with ball milling beads according to a mass ratio of 1: 20, adding ball milling beads into a ball milling tank, strictly sealing, and then placing into a planetary ball mill for solid-phase ball milling reaction. Wherein, the added ball milling beads comprise three types of 10mm, 8mm and 5mm in diameter, and are mixed according to the weight ratio of 2: 3: 5. The time of the solid phase ball milling reaction was set to 18 hours, the reaction speed was set to 425 rpm, and the reaction program was set to 2 minutes for normal rotation, 1 minute for pause, 2 minutes for reverse rotation, and 1 minute for pause, and the above sequence was repeated.
During the solid-phase ball-milling reaction, every 6 hours, the ball-milling tank is opened in a nitrogen-filled glove box for mixing, so that the full and uniform reaction is ensured, and Na can be obtained after the reaction is finished0.4423La0.3654Ta0.2923Cl3A frame conductor.
Example 3
Provides a method based on UCl3Method for preparing framework conductor of type lattice, this example to prepare Li0.4636La0.4091Zr0.3273Cl3The frame conductor is taken as an example, and the preparation method comprises the following steps:
under the atmosphere of high-purity nitrogen, lithium chloride, lanthanum chloride and zirconium chloride powder are mixed according to the molar ratio of 4.636: 4.091: 3.273 to obtain mixed powder I, wherein the corresponding dosage of the sodium chloride, the lanthanum chloride and the zirconium chloride powder is 0.2948g, 1.5050g and 1.1440g respectively.
The zirconia ball milling tank and the ball milling beads are sequentially cleaned by deionized water and absolute ethyl alcohol, and are dried for at least 6 hours in a vacuum oven with the temperature of 100 ℃ and the vacuum degree of-0.09 MPa, so that trace moisture in the ball milling tank is fully removed.
Adding the mixed powder I into a ball milling tank in a high-purity nitrogen atmosphere, adding ball milling beads into the ball milling tank according to the mass ratio of the mixed powder I to the ball milling beads of 1: 30, strictly sealing, and then placing into a planetary ball mill for solid-phase ball milling reaction. Wherein, the added ball milling beads comprise three types of 10mm, 8mm and 5mm in diameter, and are mixed according to the weight ratio of 2: 3: 5. The time of the solid phase ball milling reaction was set to 18 hours, the reaction speed was set to 425 rpm, and the reaction program was set to 2 minutes for normal rotation, 1 minute for pause, 2 minutes for reverse rotation, and 1 minute for pause, and the above sequence was repeated.
During the solid-phase ball-milling reaction, every 6 hours, the ball-milling tank is opened in a nitrogen-filled glove box for mixing, so that the sufficient and uniform reaction is ensured, and Li can be obtained after the reaction is finished0.4636La0.4091Zr0.3273Cl3A frame conductor.
Example 4
Provides a method based on UCl3Preparation of framework conductor of type lattice, this example to prepare Na0.4636La0.4091Zr0.3273Cl3The frame conductor is taken as an example, and the preparation method comprises the following steps:
under the atmosphere of high-purity nitrogen, sodium chloride, lanthanum chloride and zirconium chloride powder are mixed according to the molar ratio of 4.636: 4.091: 3.273 to obtain mixed powder I, wherein the corresponding dosage of the sodium chloride, the lanthanum chloride and the zirconium chloride powder is 0.4064g, 1.5050g and 1.1440g respectively.
The zirconia ball milling tank and the ball milling beads are sequentially cleaned by deionized water and absolute ethyl alcohol, and are dried for at least 6 hours in a vacuum oven with the temperature of 75 ℃ and the vacuum degree of-0.1 MPa, so that trace moisture in the ball milling tank is fully removed.
Adding the mixed powder I into a ball milling tank in a high-purity nitrogen atmosphere, adding ball milling beads into the ball milling tank according to the mass ratio of the mixed powder I to the ball milling beads being 1: 25, strictly sealing, and then placing the ball milling tank in a planetary ball mill for solid-phase ball milling reaction. Wherein, the added ball milling beads comprise three types of 10mm, 8mm and 5mm in diameter, and are mixed according to the weight ratio of 2: 3: 5. The time of the solid phase ball milling reaction was set to 18 hours, the reaction speed was set to 425 rpm, and the reaction program was set to 2 minutes for normal rotation, 1 minute for pause, 2 minutes for reverse rotation, and 1 minute for pause, and the above sequence was repeated.
During the solid-phase ball-milling reaction, every 6 hours, the ball-milling tank is opened in a nitrogen-filled glove box for mixing, so that the full and uniform reaction is ensured, and Na can be obtained after the reaction is finished0.4636La0.4091Zr0.3273Cl3A frame conductor.
Performance detection
(1) The frame conductors prepared in examples 1-4 were characterized by X-ray diffraction.
FIG. 2 schematically illustrates a UCl-based scheme provided by an embodiment of the present disclosure3Lithium/sodium lanthanum zirconium chloride ((Li/Na) in lattice framework conductorsxLayZrzCl3) Or lithium/sodium lanthanum tantalum chloride ((Li/Na)aLabTacCl3) Wherein the horizontal axis is diffraction angle and the vertical axis is diffraction intensity.
As shown in FIG. 2, Li prepared in examples 1 to 4 was used0.3875La0.475Ta0.2375Cl3、Na0.4423La0.3654Ta0.2923Cl3、Li0.4636La0.4091Zr0.3273Cl3、Na0.4636La0.4091Zr0.3273Cl3And has UCl3Configurational LaCl3Comparing the standard X-ray diffraction pattern of the raw materials, and confirming the crystal structure of the obtained powder and the LaCl3The crystal structure of the starting material did not change significantly. Shows that the preparation method provided by the present disclosure can maintain LaCl3The original lattice structure.
(2) The ion conductivity test was carried out on the solid electrolyte prepared from the frame conductor prepared in examples 1 to 2.
FIG. 3 schematically illustrates an embodiment of the present disclosureFor based on UCl3Lithium/sodium lanthanum tantalum chloride ((Li/Na) in lattice framework conductor)aLabTacCl3) Electrochemical ac impedance spectroscopy.
Li prepared in examples 1-2 was used separately0.3875La0.475Ta0.2375Cl3、Na0.4423La0.3654Ta0.2923Cl3The powder is supplied to an MJP-Y type common cylindrical die (phi 10mm), a YLJ-15T-LD manual tablet press is used for applying 300-360 MPa pressure, and after cold pressing and maintaining for 1-2 minutes and die stripping, the solid electrolyte sheet with the thickness of 0.5-1.5 mm and the diameter of 10mm can be obtained. The upper and lower surfaces of the obtained solid electrolyte sheet were sputtered with gold ions using an SD-900M ion sputtering apparatus, and then the upper and lower surfaces were sandwiched by two blocking electrodes (stainless steel sheets) to connect Bio-Logic VMP3The electrochemical workstation performed an ionic conductivity ac impedance test in which the test frequency was 7MHz to 1Hz and the applied bias voltage was 200mV, and the results are shown in fig. 3.
As shown in fig. 3, the ion conductivity can be obtained by reading the intersection point of the ac impedance point line and the X axis and combining the calculation formula of the ion conductivity. Wherein the ion conductivity is calculated as T/(R × A), where T is the thickness of the electrolyte sheet (unit: cm), R is the measured resistance value (unit: Ω), and A is the area of the electrolyte sheet (unit: cm)2). For the reaction of Li0.3875La0.475Ta0.2375Cl3The electrolyte sheet obtained by powder cold pressing has a thickness of 0.097cm and an area of 0.785cm2Measuring the impedance value to be 39 omega, and calculating the obtained conductivity to be 3.17 mS/cm; for the reaction of Na0.4423La0.3654Ta0.2923Cl3The electrolyte sheet obtained by powder cold pressing has a thickness of 0.083cm and an area of 0.785cm2The measured impedance value was 32. omega. and the calculated conductivity was 3.30 mS/cm. Therefore, electrolyte sheets prepared using the frame conductors provided by the present disclosure have good ionic conductivity.
(3) Using the formula Li prepared in example 10.3875La0.475Ta0.2375Cl3The solid electrolyte of (1), assembling the solid lithium pair battery, and performing electrochemicalAnd (5) testing the chemical performance.
Fig. 4 schematically shows a cycling voltage curve of a lithium lanthanum tantalum chloride based solid-state lithium symmetric battery provided by an embodiment of the disclosure.
Prepared product with UCl3Lithium ion conductor powder Li of framework0.3875La0.475Ta0.2375Cl3Transferring into a dry argon-filled glove box, wherein the oxygen content and the water content in the glove box are both below 0.1 ppm; and then preparing the solid electrolyte sheet by adopting the method for preparing the solid electrolyte in the step (2). Solid-state lithium symmetric cells based on lithium lanthanum tantalum chloride electrolyte were assembled in CR-2032 type button cells using commercial lithium metal sheets as symmetric cell electrodes.
After assembly, electrochemical testing was performed using either the novalr or blue cell detection systems. In the test process, 0.05mA cm is firstly applied for 4-5 circles-2Current, 0.05mAh cm-2The small current and small volume circulation of the solution helps to stabilize the interface, and the current density is 0.2mA cm-2To a capacity of 1.0mAh cm-2The procedure of (3) was subjected to long cycle testing, the results of which are shown in FIG. 4.
As shown in fig. 4, it can be seen that the plateau value of the cycling voltage curve is about 70mV, and the voltage curve has good stability and cycle life, which indicates that the solid electrolyte provided by the present disclosure can reduce the potential for lithium deposition and deintercalation, and simultaneously exhibits a gradually stable solid electrolyte/lithium metal interface, thereby improving the energy density, stability and service life of the all-solid battery.
(4) With Li as prepared in example 10.3875La0.475Ta0.2375Cl3The solid electrolyte of (2) was assembled into a solid metal battery, and a charge and discharge test was performed.
Fig. 5 schematically shows a charging and discharging curve of an all-solid-state lithium metal battery based on lithium lanthanum tantalum chloride provided by an embodiment of the present disclosure, wherein the abscissa represents specific capacity, and the ordinate represents battery voltage.
By using a tube having UCl3Lithium ion conductor powder Li of framework0.3875La0.475Ta0.2375Cl3Transferred to dry argon gas chargeIn the glove box, LiNi which is a commercial nickel-cobalt-manganese ternary material is used0.5Co0.2Mn0.3O2(NCM523) is used as an anode active material, a certain amount of frame conductor powder and NCM 523/electrolyte/conductive carbon black mixed powder are sequentially supplied to an MJP-Y type common cylindrical die (phi 10mm), a YLJ-15T-LD manual tablet press is used for applying pressure of 200-360 MPa, cold pressing is carried out for 1-2 minutes, and after die stripping, the solid electrolyte (phi) NCM523 composite sheet with the thickness of 0.6-1.0 mm and the diameter of 10mm can be obtained. Then, a commercial lithium metal sheet is used as a negative electrode, and is attached to one side of the solid electrolyte of the composite sheet, and an all-solid-state lithium metal battery based on the lithium lanthanum tantalum chloride electrolyte, namely Li | | | NCM523, is assembled in a CR-2032 type button cell. In a 30 ℃ constant temperature test chamber, charging was performed at a rate of 0.2C, and discharging was performed at a rate of 0.1C, the results are shown in FIG. 5.
As shown in fig. 5, the all solid-state lithium metal battery based on lithium lanthanum tantalum chloride has good contact ratio of 3 charge-discharge curves and stable charge-discharge plateau in 3 charge-discharge cycles, which indicates that the solid electrolyte based on lithium lanthanum tantalum chloride has good interface stability and compatibility at the positive electrode and the lithium metal interface.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (10)

1. Based on UCl3A method for preparing a framework conductor of a type lattice comprises the following steps:
under inert atmosphere, adding AX and MX3、ZX4Mixing the raw material powder to obtain mixed powder I;
carrying out solid-phase ball milling reaction on the mixed powder I under the inert atmosphere to obtain a compound with a chemical formula AxMyZzX3A frame conductor; or
Under inert atmosphere, adding AX and MX3、TX5Mixing the raw material powder to obtain mixed powder II;
carrying out solid-phase ball milling reaction on the mixed powder II under the inert atmosphere to obtain a compound with a chemical formula AaMbTcX3A frame conductor;
wherein the content of the first and second substances,
a comprises Li+、Na+、K+、Ag+、Cu+One of the ions;
m comprises La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+One or more of ions;
z comprises Zr4+、Hf4+One or more of ions;
t comprises Ta5+、Nb5+One or more of ions;
x comprises F-、Cl-、Br-、I-One or more of ions;
x，y，z，a，b，c≥0；x+3y+4z＝3，a+3b+5c＝3。
2. the method of claim 1, wherein,
the AX comprises one of lithium chloride, sodium chloride, silver chloride, cuprous chloride, lithium bromide, sodium bromide, potassium bromide, silver bromide and cuprous bromide;
said MX3The material comprises one or more of lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, lanthanum bromide, cerium bromide, praseodymium bromide, neodymium bromide, samarium bromide, europium bromide, gadolinium bromide and terbium bromide;
said ZX4Comprises one or more of zirconium chloride, hafnium chloride, zirconium bromide and hafnium bromide;
the TX5Including one or more of tantalum chloride, niobium chloride, tantalum bromide, and niobium bromide.
3. The method of claim 1, wherein AX, MX are reacted under an inert atmosphere3、ZX4Mixing the raw material powders to obtain mixed powder I comprising:
under the inert atmosphere, adding AX and MX3、ZX4According to the frame conductor AxMyZzX3Mixing the components according to the stoichiometric ratio of the chemical formula (I) to obtain mixed powder I;
under inert atmosphere, adding AX and MX3、TX5Mixing the raw material powders to obtain mixed powder II comprising:
under the inert atmosphere, adding AX and MX3、TX5The raw material powder is arranged according to the frame conductor AaMbTcX3The chemical formula (II) to obtain the mixed powder II.
4. The method according to claim 1, wherein in the solid-phase ball milling reaction, the mass ratio of the mixed powder I or the mixed powder II to ball milling beads is 1: 20-30.
5. The method of claim 1, further comprising, prior to the subjecting the mixed powder I to the solid phase ball milling reaction or prior to the subjecting the mixed powder II to the solid phase ball milling reaction:
the ball milling tank and the ball milling beads are sequentially subjected to ultrasonic cleaning by using deionized water and absolute ethyl alcohol, and are dried under the conditions that the temperature is 60-100 ℃ and the vacuum degree is-0.1 to-0.05 MPa.
6. The method of claim 1, wherein the ball milling bead diameters in the solid phase ball milling reaction comprise one or more of 10mm, 8mm, and 5 mm;
the inert gas comprises nitrogen or argon.
7. A frame conductor prepared by the method of any one of claims 1 to 6.
8. A solid electrolyte prepared by using the frame conductor of claim 7.
9. A solid state lithium symmetric battery, wherein the solid state lithium symmetric battery comprises the solid electrolyte of claim 8.
10. An all solid-state lithium metal battery, wherein the all solid-state lithium metal battery comprises the solid electrolyte of claim 8.
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