CN120709482A - Fluoride oxide solid electrolyte and its preparation method and application - Google Patents
Fluoride oxide solid electrolyte and its preparation method and applicationInfo
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- CN120709482A CN120709482A CN202510883406.7A CN202510883406A CN120709482A CN 120709482 A CN120709482 A CN 120709482A CN 202510883406 A CN202510883406 A CN 202510883406A CN 120709482 A CN120709482 A CN 120709482A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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Abstract
The invention relates to a oxyfluoride solid electrolyte, a preparation method and application thereof. The chemical general formula of the oxyfluoride solid electrolyte material is Li xLayM1zM2wM3uO6 F, wherein M1 is tetravalent cation, M2 is pentavalent cation, M3 is hexavalent cation, 1< x+3y <5,0< x < 2,1/3< y <5/3;0 < z < 2, 0< w < 2, 0< u < 2, z+w+u=2, the density of the oxyfluoride solid electrolyte material is >90 percent, the purity of the oxyfluoride solid electrolyte material is >99 percent, the oxyfluoride solid electrolyte material is prepared by reacting a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source, an M3 source and a compound fluorine source, and the content of fluorine elements introduced by the compound fluorine source is excessive by 0.1-8 percent relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material. The high-density and high-purity oxyfluoride solid electrolyte material provided by the invention has the advantages of higher volume energy density, lower internal resistance and excellent ion conduction performance, is favorable for improving the rate capability, effectively slows down the capacity attenuation and prolongs the cycle life of the battery.
Description
Technical Field
The invention relates to the technical field of solid electrolyte materials, in particular to a oxyfluoride solid electrolyte, a preparation method and application thereof.
Background
With the increasing requirements of applications such as electric vehicles and portable electronic devices on the safety and energy density of lithium ion batteries, solid-state electrolytes are receiving a great deal of attention as alternatives to liquid electrolytes due to their excellent thermal stability, electrochemical stability and intrinsic safety. Among the numerous solid electrolyte systems, the oxyfluoride solid electrolyte exhibits good application prospects by virtue of its higher ionic conductivity and wider electrochemical window.
In the prior art, the preparation of the oxyfluoride solid electrolyte mostly adopts the processes of a high-temperature solid phase method, a mechanical ball milling method or a sol-gel method and the like. Although the method can obtain target materials to a certain extent, in practical application, the method still has a plurality of problems that firstly, the raw materials have larger particle size and low diffusion rate, sintering is required at a higher temperature, so that the problems of insufficient reaction, generation of impurity phases and the like are caused, the conductivity and purity of the final materials are influenced, secondly, volatile elements such as lithium, fluorine and the like are easy to lose in the high-temperature sintering process, the accuracy and structural stability of the composition of the materials are reduced, the electrolyte performance is further influenced, and further, the problems of insufficient reaction or limited fluorine fixing capability and the like of the traditional single fluorine source (such as LiF or LaF 3) are caused under the high-temperature condition, so that the reaction activity and the structural stability are difficult to be considered.
In addition, if the mixing uniformity of reactants is not fully controlled in the existing method, the lower density of the material is easily caused, the poor contact of particles is caused, the interface ion transmission impedance is increased, and the overall performance of the battery is influenced.
Therefore, development of a solid electrolyte material of oxyfluoride and a preparation method thereof, which can improve density and purity, reduce internal resistance and simplify process flow while controlling stability of fluorine content, is needed.
Disclosure of Invention
The invention aims at overcoming the defects existing in the prior art and provides a oxyfluoride solid electrolyte, a preparation method and application thereof. The oxyfluoride solid electrolyte material provided by the invention has high density and high purity, has higher volume energy density and lower internal resistance, has excellent ion conduction performance, is favorable for improving rate performance, effectively slows down capacity attenuation, and prolongs the cycle life of a battery.
In order to achieve the aim, in a first aspect, the invention provides a oxyfluoride solid electrolyte material, which has a chemical formula of Li xLayM1 zM2wM3uO6 F, wherein M1 is tetravalent cation, M2 is pentavalent cation, and M3 is hexavalent cation, 1< x+3y <5,0< x < 2,1/3< y <5/3;0 < z < 2, 0< w < 2, 0< u < 2, and z+w+u=2;
the density of the oxyfluoride solid electrolyte material is more than 90%, and the purity is more than 99%;
the oxyfluoride solid electrolyte material is prepared by the reaction of a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source, an M3 source and a composite fluorine source, and the content of fluorine introduced by the composite fluorine source is excessive by 0.1% -8% relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material.
Preferably, M1 is one or more of Zr, ti, hf, si, ge, sn, M2 is one or more of Nb, sb, bi, V, ta, and M3 is one or more of W, cr, mo, mn.
Preferably, the compound fluorine source is a combination of lanthanum fluoride and lithium fluoride.
In a second aspect, an embodiment of the present invention provides a method for preparing a oxyfluoride solid electrolyte material, including:
Mixing a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source and an M3 source to obtain a first mixture, placing the first mixture into first sintering equipment to perform first sintering, heating to 200-800 ℃ at a heating rate of 1-20 ℃ per minute, preserving heat for 1-8 hours, and then continuously heating to 800-1500 ℃ at a heating rate of 1-20 ℃ per minute, and preserving heat for 1-12 hours to obtain precursor powder;
Mixing the precursor powder with a composite fluorine source to obtain a second mixture, wherein the content of fluorine introduced by the composite fluorine source is 0.1% -8% excessive relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material;
transferring the second mixture into second sintering equipment for secondary sintering, heating to 600-1200 ℃ at a heating rate of 1-20 ℃ per minute under inert atmosphere, and preserving heat for 1-12 h to obtain the oxyfluoride solid electrolyte.
Preferably, M1 is one or more of Zr, ti, hf, si, ge, sn, M2 is one or more of Nb, sb, bi, V, ta, and M3 is one or more of W, cr, mo, mn.
Preferably, the D50 particle sizes of the lithium source, the lanthanum source, the M1 source, the M2 source, the M3 source and the composite fluorine source are all in the range of 100nm-1000nm.
Preferably, the compound fluorine source is a combination of lanthanum fluoride and lithium fluoride, wherein the stoichiometric ratio of the lanthanum fluoride to the lithium fluoride is (0-1/3): 0-1;
the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium oxalate and lithium acetate;
the lanthanum source comprises one or a combination of more of lanthanum oxide, lanthanum carbonate, lanthanum nitrate and lanthanum hydroxide;
the M1 source is a compound containing M1;
the M2 source is a compound containing M2;
the M3 source is a compound containing M3;
And the addition proportion of lithium fluoride and lanthanum fluoride in the composite fluorine source and the proportion of the lithium source and the lanthanum source in the first mixture are used for cooperatively determining the content of Li, la and F elements in the target stoichiometric ratio Li xLayM1zM2wM3uO6 F.
Preferably, the mixing equipment for mixing is selected from one or more of a VC efficient mixer, a planetary mixer, a vertical stirring tank and a high-energy ball mill;
The first sintering equipment and the second sintering equipment are respectively selected from any one of a box furnace, a tube furnace, a push plate furnace, a roller kiln and a rotary furnace.
Preferably, in the first sintering process, the process parameters are preferably as follows:
Heating to 400-600 ℃ at the heating rate of 2-8 ℃ per minute, preserving heat for 3-5 h, and then continuously heating to 900-1100 ℃ at the heating rate of 2-8 ℃ per minute, preserving heat for 5-7 h;
in the second sintering process, the process parameters are preferably as follows:
heating to 700-900 ℃ at a heating rate of 2-8 ℃ per min under an inert atmosphere, and preserving heat for 5-7 h, wherein the inert atmosphere comprises one or more of nitrogen, helium or argon;
The stoichiometric ratio of the lanthanum fluoride to the lithium fluoride is (0-0.3): 0.1-1;
The amount of elemental fluorine introduced by the composite fluorine source is in excess of 5% relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material.
In a third aspect, an embodiment of the present invention provides a lithium battery, including the oxyfluoride solid electrolyte material described in the first aspect, or including the oxyfluoride solid electrolyte material obtained by the preparation method described in the second aspect.
The oxyfluoride solid electrolyte material provided by the embodiment of the invention has the characteristics of high density and high purity, the density is more than 90%, the purity is more than 99%, more active ion channels can be carried in unit volume, the whole ion migration efficiency is improved, the interference of impurities on active substances is reduced due to the high purity, the lithium ion deintercalation is more efficient, the capacity attenuation is weakened, and the cycle life of the battery is prolonged. The content of fluorine element introduced by the composite fluorine source in the material is controlled in the range slightly higher than the metering ratio (0.1% -8%), so that the fluorine element can be ensured to fully participate in the construction of the crystal structure, and the loss generated by high-temperature volatilization in the preparation sintering process is effectively compensated, thereby improving the structural stability, electrochemical stability window and long-term cycle life of the material. Meanwhile, the compact structure enables the contact among particles to be tighter, reduces interface resistance, is beneficial to realizing stable charge and discharge performance under higher multiplying power, and meets the application requirements of high-performance solid-state lithium batteries.
Drawings
Fig. 1 is an X suspected diffraction (XRD) comparison of the solid electrolyte materials of example 1 and comparative example 1 provided in the examples of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
The embodiment of the invention provides a oxyfluoride solid electrolyte material, which has a chemical general formula of Li xLayM1zM2wM3uO6 F, wherein M1 is tetravalent cation, M2 is pentavalent cation, M3 is hexavalent cation, x+3y is 1< 5, x is 0< 2, y is 1/3< 5/3;0 < z is less than or equal to 2, w is 0< 2, u is 0< 2, and z+w+u=2.
The density of the oxyfluoride solid electrolyte material is more than 90 percent, and the purity is more than 99 percent.
The oxyfluoride solid electrolyte material is prepared by the reaction of a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source, an M3 source and a composite fluorine source, and the content of fluorine introduced by the composite fluorine source is excessive by 0.1% -8% relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material.
Wherein the composite fluorine source is a combination of lanthanum fluoride and lithium fluoride. M1 is one or more of Zr, ti, hf, si, ge, sn, M2 is one or more of Nb, sb, bi, V, ta, and M3 is one or more of W, cr, mo, mn.
The oxyfluoride solid electrolyte material provided by the embodiment of the invention has the characteristics of high density and high purity, the density is more than 90%, the purity is more than 99%, more active ion channels can be carried in unit volume, the whole ion migration efficiency is improved, the interference of impurities on active substances is reduced due to the high purity, the lithium ion deintercalation is more efficient, the capacity attenuation is weakened, and the cycle life of the battery is prolonged. The content of fluorine element introduced by the composite fluorine source in the material is controlled in the range slightly higher than the metering ratio (0.1% -8%), so that the fluorine element can be ensured to fully participate in the construction of the crystal structure, and the loss generated by high-temperature volatilization in the preparation sintering process is effectively compensated, thereby improving the structural stability, electrochemical stability window and long-term cycle life of the material. Meanwhile, the compact structure enables the contact among particles to be tighter, reduces interface resistance, is beneficial to realizing stable charge and discharge performance under higher multiplying power, and meets the application requirements of high-performance solid-state lithium batteries
The above oxyfluoride solid electrolyte material can be prepared by the following method. The method mainly comprises the following steps:
Step 110, mixing a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source and an M3 source to obtain a first mixture, placing the first mixture in first sintering equipment to perform first sintering, heating to 200-800 ℃ at a heating rate of 1-20 ℃ per minute, preserving heat for 1-8 h, and then continuously heating to 800-1500 ℃ at a heating rate of 1-20 ℃ per minute, and preserving heat for 1-12 h to obtain precursor powder.
Wherein, the D50 particle size ranges of the lithium source, the lanthanum source, the M1 source, the M2 source, the M3 source and the compound fluorine source are all 100nm-1000nm.
The lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium oxalate and lithium acetate.
The lanthanum source comprises one or a combination of more of lanthanum oxide, lanthanum carbonate, lanthanum nitrate and lanthanum hydroxide.
M1 is one or more of Zr, ti, hf, si, ge, sn, and the M1 source is a compound containing M1, and can specifically comprise an oxide, a hydroxide, a carbonate, an oxalate, an organic complex (such as isopropyl titanate, titanium tetrachloride) and the like of M1.
M2 is one or more of Nb, sb, bi, V, ta, and the M2 source is a compound containing M2, and can specifically comprise oxide, hydroxide, carbonate, oxalate, halide and the like of M2.
M3 is one or more of W, cr, mo, mn, and the M3 source is a compound containing M3, which can specifically comprise an oxide of M3, a salt containing M3 (such as sodium tungstate, ammonium molybdate, sodium chromate) or an acid containing M3 (such as molybdic acid, chromic acid), etc.
The composite fluorine source is a combination of lanthanum fluoride and lithium fluoride. Wherein the stoichiometric ratio of lanthanum fluoride to lithium fluoride is (0-1/3): 0-1, preferably (0-0.3): 0.1-1.
Further, in the first sintering process, the process parameters are preferably that the temperature is raised to 400-600 ℃ at the temperature rising rate of 2-8 ℃ per minute, the temperature is kept for 3-5 hours, and then the temperature is continuously raised to 900-1100 ℃ at the temperature rising rate of 2-8 ℃ per minute, and the temperature is kept for 5-7 hours.
In step 110, the particle sizes of the lithium source, lanthanum source, M1 source, M2 source and M3 source are all 100nm-1000nm, and the material has extremely large specific surface area, high surface atomic ratio and strong activity due to the small particle size, so that the sintered surface energy is greatly improved, the atomic diffusion rate is accelerated, and the diffusion path is reduced. In the sintering process, solid-phase chemical reaction occurs between raw materials, the larger particle contact area can increase the probability of reaction, quicken the reaction rate, and is beneficial to promoting the reaction, thereby causing the sintering activation energy to be smaller, quickening the reaction rate of the whole sintering, reducing the sintering temperature and time and improving the sintering efficiency and the product compactness.
And step 120, mixing the precursor powder with a composite fluorine source to obtain a second mixture.
Wherein the fluorine element content introduced by the composite fluorine source is in excess of 0.1% -8% relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material, preferably in excess of 5%.
The compound fluorine source added in the step 120 is a mixture of lanthanum fluoride (LaF 3) and lithium fluoride (LiF), fluoride ions are fixed by utilizing a high-stability framework of LaF 3, and meanwhile, the reaction activity is provided by utilizing LiF, so that a more stable fluorochemical environment can be obtained by the synergistic effect of the two. In lanthanum fluoride and lithium fluoride, the melting point of LiF is lower (848 ℃) and is preferentially melted to form a liquid phase in the subsequent second sintering process, the grain boundary of hard particles is wetted, the inter-particle friction is reduced, and the contact surface of the particles is increased to promote the reaction. LaF 3 stabilizes the grain boundary structure through its high melting point to prevent overgrowth of crystal grains, and LaF 3 fixes F - on lattice sites through strong ionic bonds (La-F bond energy is high) to inhibit volatilization of fluorine. Thus, the interaction of lithium fluoride and lanthanum fluoride lowers the reaction temperature and suppresses volatilization of fluorine element.
And 130, transferring the second mixture into second sintering equipment for secondary sintering, and heating to 600-1200 ℃ at a heating rate of 1-20 ℃ per minute under inert atmosphere, and preserving heat for 1-12 h to obtain the oxyfluoride solid electrolyte.
Further, in the second sintering process, the process parameters are preferably that the temperature is raised to 700-900 ℃ at a temperature rising rate of 2-8 ℃ per minute under an inert atmosphere, and the temperature is kept for 5-7 hours, wherein the inert atmosphere comprises one or a combination of more of nitrogen, helium or argon.
The mixing in the steps 110 and 120 may specifically include stirring mixing or ball milling mixing, and the mixing device used is one or more selected from a VC high-efficiency mixer, a planetary mixer, a vertical agitator tank, and a high-energy ball mill.
The first sintering device and the second sintering device in the steps 110 and 130 may be selected from any one of a box furnace, a tube furnace, a pusher furnace, a roller kiln, and a rotary furnace, respectively. The type of equipment used for the two sintering may be the same or different.
The addition ratio of lithium fluoride to lanthanum fluoride in the composite fluorine source and the ratio of the lithium source to the lanthanum source in the first mixture cooperate to determine the contents of Li, la and F elements in the target stoichiometric ratio Li xLayM1zM2wM3uO6 F. That is, in the invention, the stoichiometric ratio of each element in the finally prepared oxyfluoride solid electrolyte material is determined by the two-stage raw material addition, wherein Li element is derived from lithium fluoride (LiF) in the first-stage added lithium source and the second-stage composite fluorine source, la element is derived from lanthanum fluoride (LaF 3) in the first-stage lanthanum source and the second-stage composite fluorine source, and F element is provided by the composite fluorine sources (LiF and LaF 3) in total.
Therefore, when preparing raw materials, the addition amount of a lithium source and a lanthanum source in the raw materials in the first stage needs to be reasonably adjusted according to the stoichiometric ratio (Li xLayM1zM2wM3uO6 F) of a target material, and a proper amount of lithium fluoride and lanthanum fluoride is supplemented according to the notch part of the raw materials, so that the total content of Li, la and F elements meets the final proportioning requirement, and the content of F elements is ensured to be slightly excessive (0.1% -8%) relative to the stoichiometric ratio so as to compensate the fluorine volatilization loss in the high-temperature sintering process, thereby improving the component accuracy and the reaction suitability of the final product.
On the premise of defining the target stoichiometric ratio, the man skilled in the art can reasonably adjust the addition amount of the precursor raw material and the compound fluorine source by a conventional material proportioning design method so as to realize the final required element composition. The adjustment process is a conventional technical means in the art and can be completed without the need of creative labor.
According to the preparation method of the oxyfluoride solid electrolyte, provided by the invention, the nanoscale lithium source, the lanthanum source and the doped M1, M2 and M3 element raw materials are introduced, so that the mixed system has larger specific surface area and faster reaction kinetics, the mixing uniformity of the raw materials is obviously improved, the dense phase formation is completed at a lower sintering temperature and a shorter sintering time, and the energy consumption and the process complexity are effectively reduced. Furthermore, a composite fluorine source composed of LiF and LaF 3 is adopted, on one hand, the reaction activity is provided at the initial stage of sintering through LiF, liquid phase sintering is formed, the reaction rate and uniformity are enhanced, on the other hand, laF 3 is utilized to stabilize a fluoride structure, F - ions are fixed, and volatilization of fluorine element at high temperature is inhibited. The process is synergistically optimized, so that the material yield and the preparation stability are improved, the structural integrity and the chemical stability of the electrolyte are enhanced, and the process is suitable for the preparation requirement of large-scale solid electrolyte materials.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
First, in the present application, the particle diameter D50 of the material means the median particle diameter of the material, and may be the median value in order of volume, mass or number. The median particle size, ordered by number, is specifically employed in the examples of the present application to represent the particle size of the porous carbon matrix, ordered by number distribution, at 50%. Particle size D50 is a meaning well known in the art. The particle size D50 of the material provided in the embodiments of the present application may be measured by an apparatus and a conventional method known in the art, and specifically, in each embodiment of the present application, the particle size D50 is measured by using a Mastersizer 3000 type laser particle size analyzer, which is a company of malvern instruments, england.
Example 1
The embodiment of the invention provides a preparation method of a Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
According to the stoichiometric ratio required by Li 0.5La0.5Nb2O6, taking and mixing lithium carbonate with the particle size of 656nm, lanthanum trioxide with the particle size of 772nm and niobium pentoxide with the particle size of 729nm with the stoichiometric ratio of 1:1:4, and obtaining the first mixture with the total mass of 2 kg. Placing the first mixture into a box-type furnace, heating to 300 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 2 hours, then continuously heating to 1000 ℃ at the heating rate of 5 ℃ per minute, and preserving heat for 6 hours to obtain precursor powder.
Taking materials from lithium fluoride with the particle size D50 of 892nm and lanthanum fluoride with the particle size D50 of 717nm according to the stoichiometric ratio of 78:8:100, and ball-milling and mixing to obtain a second mixture. Transferring the second mixture into a tube furnace, introducing nitrogen to maintain nitrogen atmosphere, heating to 900 ℃ at a heating rate of 2 ℃ per minute, and preserving heat for 5 hours to obtain the Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte.
Example 2
The embodiment of the invention provides a preparation method of a Li 1.25La0.58Ti2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
According to the stoichiometric ratio required by Li 0.5La0.5Ti2O6, taking and mixing lithium carbonate with the particle size D50 of 656nm, lanthanum trioxide with the particle size D50 of 754nm and titanium dioxide with the particle size D50 of 382nm according to the stoichiometric ratio of 1:1:4, and obtaining the first mixture with the total mass of 2 kg. And placing the first mixture into a rotary furnace, heating to 300 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 2 hours, then continuously heating to 1000 ℃ at the heating rate of 5 ℃ per minute, and preserving heat for 6 hours to obtain precursor powder.
Taking materials from lithium fluoride with the particle size D50 of 892nm and lanthanum fluoride with the particle size D50 of 717nm and the precursor powder according to the stoichiometric ratio of 80:8:100, and ball-milling and mixing to obtain a second mixture. Transferring the second mixture into a tube furnace, introducing nitrogen to maintain nitrogen atmosphere, heating to 1000 ℃ at a heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain the Li 1.25La0.58Ti2O6 F oxyfluoride solid electrolyte.
Example 3
The embodiment of the invention provides a preparation method of a Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
According to the stoichiometric ratio required by Li 0.5La0.5Nb2O6, taking and mixing lithium carbonate with the particle size of 656nm, lanthanum trioxide with the particle size of 772nm and niobium pentoxide with the particle size of 729nm with the stoichiometric ratio of 1:1:4, and obtaining the first mixture with the total mass of 2 kg. Placing the first mixture into a box-type furnace, heating to 600 ℃ at a heating rate of 2 ℃ per minute, preserving heat for 2 hours, then continuously heating to 1000 ℃ at the heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain precursor powder.
Taking materials from lithium fluoride with the particle size D50 of 892nm and lanthanum fluoride with the particle size D50 of 717nm and the precursor powder according to the stoichiometric ratio of 80:8:100, and ball-milling and mixing to obtain a second mixture. Transferring the second mixture into a tube furnace, introducing argon to maintain an argon atmosphere, heating to 1000 ℃ at a heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain the Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte.
Example 4
The embodiment of the invention provides a preparation method of LiLa 0.66Ti 0.25Nb1.8O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
According to the stoichiometric ratio required by Li 0.5La0.5Ti 0.25Nb1.8O6, taking and mixing lithium carbonate with the particle size of 656nm, lanthanum trioxide with the particle size of 772nm, titanium dioxide with the particle size of 382nm and niobium pentoxide with the particle size of 729nm according to the stoichiometric ratio of 1:1:1:3.6, and obtaining the first mixture with the total mass of 2 kg. Placing the first mixture into a box-type furnace, heating to 600 ℃ at a heating rate of 2 ℃ per minute, preserving heat for 2 hours, then continuously heating to 1000 ℃ at the heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain precursor powder.
Taking materials from lithium fluoride with the particle size D50 of 892nm and lanthanum fluoride with the particle size D50 of 717nm according to the stoichiometric ratio of 11:10:100, and ball-milling and mixing to obtain a second mixture. Transferring the second mixture into a tube furnace, introducing argon to maintain an argon atmosphere, heating to 1000 ℃ at a heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain LiLa 0.66Ti 0.25Nb1.8O6 F oxyfluoride solid electrolyte.
Example 5
The embodiment of the invention provides a preparation method of a Li 1.25La0.58Mo0.66Nb1.2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
According to the stoichiometric ratio required by Li 0.5La0.5Mo0.66Nb1.2O6, taking and mixing lithium carbonate with the particle size of 656nm, lanthanum oxide with the particle size of 772nm, molybdenum oxide with the particle size of 582nm and niobium pentoxide with the particle size of 729nm according to the stoichiometric ratio of 1:1:2.67:2.4, and obtaining the first mixture with the total mass of 2 kg. Placing the first mixture into a box-type furnace, heating to 600 ℃ at a heating rate of 2 ℃ per minute, preserving heat for 2 hours, then continuously heating to 1000 ℃ at the heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain precursor powder.
Taking materials from lithium fluoride with the particle size D50 of 892nm and lanthanum fluoride with the particle size D50 of 717nm according to the stoichiometric ratio of 41:12:50, and ball-milling and mixing to obtain a second mixture. Transferring the second mixture into a tube furnace, introducing argon to maintain an argon atmosphere, heating to 1000 ℃ at a heating rate of 2 ℃ per minute, and preserving heat for 6 hours to obtain the Li 1.25La0.5Mo0.66Nb1.2O6 F oxyfluoride solid electrolyte.
Comparative example 1
The comparative example provides a preparation method of a conventional Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
lithium carbonate with the particle size D50 of 4.71um, lanthanum oxide with the particle size D50 of 2.64um, niobium pentoxide with the particle size D50 of 5.28um and lithium fluoride with the particle size D50 of 3.18um are taken and mixed according to the stoichiometric ratio of Li 1.25La0.58Nb2O6 F of 0.625:0.29:1:1.1 (10 percent of fluorine element excess), and the total mass is 2kg, so that a first mixture is obtained.
Placing the first mixture into a box furnace, heating to 500 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 5 hours, then continuously heating to 1200 ℃ at the heating rate of 5 ℃ per minute, and preserving heat for 8 hours to obtain the Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte.
Comparative example 2
The comparative example provides a preparation method of a conventional Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
Lithium carbonate with a particle size D50 of 4.71um, lanthanum oxide with a particle size D50 of 2.64um, niobium pentoxide with a particle size D50 of 5.28um, lithium fluoride with a particle size D50 of 892nm and lanthanum fluoride with a particle size D50 of 717nm are taken and mixed according to a stoichiometric ratio of 2.5:1:4:3.44:0.32 (10% excess fluorine element), and the total mass is 2kg, so that a first mixture is obtained.
Placing the first mixture into a box furnace, heating to 500 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 5 hours, then continuously heating to 1200 ℃ at the heating rate of 5 ℃ per minute, and preserving heat for 8 hours to obtain the Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte.
Comparative example 3
The comparative example provides a preparation method of a conventional Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
Lithium carbonate with a particle size of 656nm, lanthanum oxide with a particle size of 772nm, niobium pentoxide with a particle size of 729nm and lithium fluoride with a particle size of 892nm with a particle size of D50 are mixed according to a stoichiometric ratio of Li 1.25La0.58Nb2O6 F of 0.625:0.29:1:1.1 (10% excess fluorine element), and the total mass is 2kg, so that a first mixture is obtained.
Placing the first mixture into a box furnace, heating to 500 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 5 hours, then continuously heating to 1200 ℃ at the heating rate of 5 ℃ per minute, and preserving heat for 8 hours to obtain the Li 1.25La0.58Nb2O6 F oxyfluoride solid electrolyte.
Comparative example 4
The comparative example provides a preparation method of a Li 1.25La0.58Ti2O6 F oxyfluoride solid electrolyte, which specifically comprises the following steps:
Lithium carbonate with a particle size D50 of 4.71um, lanthanum trioxide with a particle size D50 of 2.64um, titanium dioxide with a particle size D50 of 2.18um and lithium fluoride with a particle size D50 of 3.18um are taken and mixed according to a stoichiometric ratio of Li 1.25La0.58Ti2O6 F of 0.625:0.29:1:1.1 (10% excess fluorine element), and the total mass is 2kg, so that a first mixture is obtained.
Placing the first mixture into a box furnace, heating to 500 ℃ at a heating rate of 5 ℃ per minute, preserving heat for 5 hours, then continuously heating to 1200 ℃ at the heating rate of 5 ℃ per minute, and preserving heat for 6 hours to obtain the Li 1.25La0.58Ti2O6 F oxyfluoride solid electrolyte.
The solid electrolytes of the above examples and comparative examples were subjected to X-ray diffraction (XRD) pattern test. The results are shown in FIG. 1.
As is evident from XRD pattern tests, only the diffraction peaks of the target phases appear in the oxyfluoride solid electrolytes prepared in the examples 1 and 3, no obvious impurity phase is detected, which indicates that the oxyfluoride solid electrolytes have higher phase purity, and impurity phases exist in the comparative examples 1-3. The preparation method provided by the invention can prepare the high-purity oxyfluoride solid electrolyte under the conditions of less fluorine loss and sintering temperature.
Further, purity data was obtained by calculating the content ratio of each phase by the "peak area fitting" method commonly used in the prior art. Recorded in table 1. Purity herein refers to crystal phase purity.
The compactness test is carried out by adopting the following method:
1. Preparing a sample, namely pressing the oxyfluoride solid electrolyte into a ceramic sheet by using a tablet press, sintering the ceramic sheet at 1000 ℃ for 5 hours to densify the ceramic sheet to obtain a densified ceramic sheet sample, and placing the obtained ceramic sheet sample in a drying oven for drying at 110 ℃ for 2 hours;
2. Measuring the mass W ( Air-conditioner ) of the oxyfluoride solid electrolyte in air using an analytical balance;
3. Placing a ceramic wafer sample on a sample rack, connecting the sample rack with an analytical balance to test the mass of the sample, and placing the sample rack in deionized water to obtain the mass W ( Water and its preparation method ) of the oxyfluoride solid electrolyte in the deionized water under the action of buoyancy;
According to the formula:
ρ=ρ( Water and its preparation method )×W( Air-conditioner )/(W( Air-conditioner )-W( Water and its preparation method ))
α=(ρ/ρ0)*100%
ρ is the bulk density of the oxyfluoride solid electrolyte ceramic wafer in grams per cubic centimeter (g/cm 3);
w ( Air-conditioner ) is the mass of the oxyfluoride solid electrolyte ceramic sheet in the air, and the unit is gram (g);
W ( Water and its preparation method ) is the mass of the oxyfluoride solid electrolyte ceramic sheet in deionized water, and the unit is gram (g);
ρ ( Water and its preparation method ) is the density of water in grams per cubic centimeter (g/cm 3);
ρ 0 is the theoretical density of the oxyfluoride solid state electrolyte ceramic sheet in grams per cubic centimeter (g/cm 3).
The ion conductivity test was performed as follows:
1. uniformly grinding oxyfluoride solid electrolyte powder, pressing the oxyfluoride solid electrolyte powder into ceramic sheets, and sintering the ceramic sheets at 1000 ℃ for 5 hours for densification to obtain densified ceramic sheet samples;
2. Sequentially polishing two round surfaces of the ceramic sheet obtained by sintering with 400-mesh, 1000-mesh and 3000-mesh sand paper to smooth, so that the surface of the whole round surface is smooth and clean without defects;
3. measuring the thickness L of the ceramic plate by using a digital display thickness gauge, measuring the diameter of the ceramic plate by using a vernier caliper, and further calculating to obtain the cross section area of the circular surface of the ceramic plate, wherein the cross section area is recorded as S;
4. Coating conductive silver paste on the surface of the polished solid electrolyte sheet sample, and then polishing off the conductive silver paste on the side surface of the solid electrolyte sheet;
5. Testing at the temperature of 25+/-2 ℃ and the humidity of less than 50%, opening a Zahner electrochemical workstation to set the parameter disturbance voltage to 10mV, and testing the impedance curve at the frequency of 0.1-106 Hz;
and fitting and calculating by using Zahner Analysis software to obtain a resistance R, and calculating according to an ion conductivity formula to obtain the room-temperature ion conductivity of the solid electrolyte.
Ion conductivity test formula:
σ=L/(R*S)
Wherein:
sigma is the ionic conductivity of the oxyfluoride solid electrolyte ceramic sheet, and the unit is Siemens per centimeter (S/cm);
L is the thickness of the oxyfluoride solid electrolyte ceramic sheet, and the unit is centimeter (cm)
R is the fitting impedance value of the oxyfluoride solid electrolyte ceramic chip, and the unit is ohm (omega)
S is the cross section area of the circular surface of the oxyfluoride solid electrolyte ceramic chip, and the unit is square centimeter (cm 2).
TABLE 1
According to table 1, as can be seen from the comparison of the density and purity of comparative examples 1-2 and examples 1-3, by applying the preparation method of the present invention, the nano-scale raw material and the composite fluorine source are applied in the preparation, so that the density of the material and the purity of the prepared powder can be greatly improved, and meanwhile, the ion conductivity of the material can be synchronously improved due to the higher density.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A oxyfluoride solid electrolyte material is characterized by having a chemical general formula of Li xLayM1zM2wM3uO6 F, wherein M1 is a tetravalent cation, M2 is a pentavalent cation, and M3 is a hexavalent cation, wherein 1< x+3y <5,0< x < 2,1/3< y <5/3;0 < z < 2, 0< w < 2, 0< u < 2, and z+w+u=2;
the density of the oxyfluoride solid electrolyte material is more than 90%, and the purity is more than 99%;
the oxyfluoride solid electrolyte material is prepared by the reaction of a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source, an M3 source and a composite fluorine source, and the content of fluorine introduced by the composite fluorine source is excessive by 0.1% -8% relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material.
2. The oxyfluoride solid state electrolyte material of claim 1, wherein M1 is one or more of Zr, ti, hf, si, ge, sn, M2 is one or more of Nb, sb, bi, V, ta, and M3 is one or more of W, cr, mo, mn.
3. The oxyfluoride solid state electrolyte material of claim 1, wherein the composite fluorine source is a combination of lanthanum fluoride and lithium fluoride.
4. A method for preparing the oxyfluoride solid electrolyte material of claims 1 to 3, comprising:
Mixing a nanoscale lithium source, a lanthanum source, an M1 source, an M2 source and an M3 source to obtain a first mixture, placing the first mixture into first sintering equipment to perform first sintering, heating to 200-800 ℃ at a heating rate of 1-20 ℃ per minute, preserving heat for 1-8 hours, and then continuously heating to 800-1500 ℃ at a heating rate of 1-20 ℃ per minute, and preserving heat for 1-12 hours to obtain precursor powder;
Mixing the precursor powder with a composite fluorine source to obtain a second mixture, wherein the content of fluorine introduced by the composite fluorine source is 0.1% -8% excessive relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material;
transferring the second mixture into second sintering equipment for secondary sintering, heating to 600-1200 ℃ at a heating rate of 1-20 ℃ per minute under inert atmosphere, and preserving heat for 1-12 h to obtain the oxyfluoride solid electrolyte.
5. The method according to claim 4, wherein M1 is one or more of Zr, ti, hf, si, ge, sn, M2 is one or more of Nb, sb, bi, V, ta, and M3 is one or more of W, cr, mo, mn.
6. The method for preparing a solid electrolyte material of oxyfluoride according to claim 4, wherein the D50 particle size ranges of the lithium source, the lanthanum source, the M1 source, the M2 source, the M3 source and the composite fluorine source are all 100nm-1000nm.
7. The method of claim 4, wherein the composite fluorine source is a combination of lanthanum fluoride and lithium fluoride, wherein the stoichiometric ratio of lanthanum fluoride to lithium fluoride is (0-1/3): 0-1;
the lithium source comprises one or more of lithium carbonate, lithium hydroxide, lithium oxalate and lithium acetate;
the lanthanum source comprises one or a combination of more of lanthanum oxide, lanthanum carbonate, lanthanum nitrate and lanthanum hydroxide;
the M1 source is a compound containing M1;
the M2 source is a compound containing M2;
the M3 source is a compound containing M3;
And the addition proportion of lithium fluoride and lanthanum fluoride in the composite fluorine source and the proportion of the lithium source and the lanthanum source in the first mixture are used for cooperatively determining the content of Li, la and F elements in the target stoichiometric ratio Li xLayM1zM2wM3uO6 F.
8. The method for producing a solid electrolyte material of oxyfluoride according to claim 4, wherein the mixing equipment for mixing is one or more selected from the group consisting of a VC high-efficiency mixer, a planetary mixer, a vertical agitator tank, and a high-energy ball mill;
The first sintering equipment and the second sintering equipment are respectively selected from any one of a box furnace, a tube furnace, a push plate furnace, a roller kiln and a rotary furnace.
9. The method for preparing a solid state oxyfluoride electrolyte material according to claim 4, wherein the process parameters during the first sintering process are preferably:
Heating to 400-600 ℃ at the heating rate of 2-8 ℃ per minute, preserving heat for 3-5 h, and then continuously heating to 900-1100 ℃ at the heating rate of 2-8 ℃ per minute, preserving heat for 5-7 h;
in the second sintering process, the process parameters are preferably as follows:
heating to 700-900 ℃ at a heating rate of 2-8 ℃ per min under an inert atmosphere, and preserving heat for 5-7 h, wherein the inert atmosphere comprises one or more of nitrogen, helium or argon;
The stoichiometric ratio of the lanthanum fluoride to the lithium fluoride is (0-0.3): 0.1-1;
The amount of elemental fluorine introduced by the composite fluorine source is in excess of 5% relative to the stoichiometric ratio of fluorine required in the oxyfluoride solid electrolyte material.
10. A lithium battery comprising the oxyfluoride solid electrolyte material according to any one of claims 1 to 3, or comprising the oxyfluoride solid electrolyte material obtained by the production method according to any one of claims 4 to 8.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113224379A (en) * | 2021-04-27 | 2021-08-06 | 西南交通大学 | Fluorine-doped F-LLTO composite solid electrolyte, preparation method and application |
| CN113937352A (en) * | 2021-12-17 | 2022-01-14 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Composite solid electrolyte, preparation method thereof and battery |
| CN118872114A (en) * | 2022-03-10 | 2024-10-29 | 株式会社电装 | Solid electrolyte for secondary battery and secondary battery |
| US20240363896A1 (en) * | 2022-02-14 | 2024-10-31 | Grirem Hi-Tech Co., Ltd. | Grain boundary- and surface-doped lithium-lanthanum-zirconium composite oxide electrolyte, preparation method therefor, and application thereof |
| CN119320170A (en) * | 2024-09-03 | 2025-01-17 | 东北大学 | Novel preparation method of solid electrolyte with high ionic conductivity |
-
2025
- 2025-06-29 CN CN202510883406.7A patent/CN120709482A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113224379A (en) * | 2021-04-27 | 2021-08-06 | 西南交通大学 | Fluorine-doped F-LLTO composite solid electrolyte, preparation method and application |
| CN113937352A (en) * | 2021-12-17 | 2022-01-14 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Composite solid electrolyte, preparation method thereof and battery |
| US20240363896A1 (en) * | 2022-02-14 | 2024-10-31 | Grirem Hi-Tech Co., Ltd. | Grain boundary- and surface-doped lithium-lanthanum-zirconium composite oxide electrolyte, preparation method therefor, and application thereof |
| CN118872114A (en) * | 2022-03-10 | 2024-10-29 | 株式会社电装 | Solid electrolyte for secondary battery and secondary battery |
| CN119320170A (en) * | 2024-09-03 | 2025-01-17 | 东北大学 | Novel preparation method of solid electrolyte with high ionic conductivity |
Non-Patent Citations (1)
| Title |
|---|
| AKIHISA AIMI等: "High Li-Ion Conductivity in Pyrochlore-Type Solid Electrolyte Li2-xLa(1+x)/3M2O6F (M = Nb, Ta)", CHEMISTRY OF MATERIALS, vol. 36, 28 March 2024 (2024-03-28), pages 3717 - 3725 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120978181A (en) * | 2025-10-21 | 2025-11-18 | 溧阳天目先导电池材料科技有限公司 | A method for preparing a fluoride oxide solid electrolyte, and the fluoride oxide solid electrolyte. |
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