CN113130976A - Garnet type solid electrolyte and preparation method thereof - Google Patents

Garnet type solid electrolyte and preparation method thereof Download PDF

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Publication number
CN113130976A
CN113130976A CN201911395547.5A CN201911395547A CN113130976A CN 113130976 A CN113130976 A CN 113130976A CN 201911395547 A CN201911395547 A CN 201911395547A CN 113130976 A CN113130976 A CN 113130976A
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electrolyte
modifier
solid electrolyte
mixing
garnet
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吴剑文
李山山
凌仕刚
沙金
朱卫泉
苏迎春
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Tianjin Guoan MGL New Materials Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • 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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    • H01M2300/0091—Composites in the form of mixtures
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention discloses a garnet type solid electrolyte which is prepared by calcining a matrix and a modifier, wherein the modifier comprises an anion modifier and a cation modifier, the conductivity of lithium ions can be enhanced by doping a non-metal element and a plurality of metal elements into a lithium lanthanum zirconium oxygen based solid electrolyte material, the stability of the material is improved, and the calcining temperature is reduced to be below 1000 ℃.

Description

Garnet type solid electrolyte and preparation method thereof
Technical Field
The invention designs a preparation method of a solid electrolyte, in particular to a garnet type solid electrolyte co-doped with anions and cations and a preparation method thereof, belonging to the field of solid electrolyte materials of lithium ion batteries.
Background
The lithium ion battery is an important energy storage device in a plurality of fields such as lithium ion battery communication electronic products, mobile computers, portable entertainment equipment, daily electric tools, new energy automobiles, energy storage and the like. With the rapid development of industries such as electronic products, new energy automobiles, energy storage applications and the like, the market puts higher requirements on the energy density, the cycle performance and the safety performance of the lithium ion battery. The safety of the current power battery, particularly the safety performance of the high-energy density power battery, is still deficient.
The existing lithium ion battery uses liquid electrolyte, has flammability and poor thermal stability, and is easy to cause explosion accidents. The solid electrolyte material is used for replacing or partially replacing the liquid electrolyte material, so that the safety performance of the battery can be improved, the grouping efficiency of the power battery is improved in grouping, and the overall energy density of the battery pack is improved.
As solid electrolyte materials applied to lithium ion batteries, organic polymer electrolytes and inorganic electrolytes can be classified. Organic polymer electrolyte materials generally have a narrow electrochemical redox window, which greatly limits the application of high energy density. The inorganic electrolyte may include an oxide-based electrolyte and a sulfide-based electrolyte. Among them, sulfide electrolytes limit applications due to their sensitivity to water.
Oxide-based electrolytes can be classified into LiPON type, perovskite type, garnet type and glass ceramic type, having a 10 th degree of crystallinity-5To 10-3Ion conductivity of S/cm. Only the garnet-type oxide has both stability to a metallic lithium negative electrode and stability to a high-voltage positive electrode, and does not undergo redox reaction, so that fewer components can be used in the solid-state battery, and a greater battery energy density can be achieved.
There have been many studies on garnet-type electrolytes, but the garnet-type electrolytes still have the following problems: (1) lithium ion conductivity is limited at room temperature; (2) poor stability in air; (3) the lithium ions are greatly lost when the material is roasted at high temperature.
Disclosure of Invention
As a result of intensive studies to solve the above problems, the present inventors have found that doping a lithium lanthanum zirconium oxygen-based solid electrolyte material with a fluorine element and a metal element can enhance the conductivity of lithium ions, improve the stability of the material, lower the firing temperature during production, and obtain a high-purity cubic garnet phase, thereby completing the present invention.
Specifically, the present invention aims to provide the following:
the invention provides a garnet-type solid electrolyte which is prepared by calcining a matrix and a modifier, wherein the modifier comprises an anionic modifier and a cationic modifier.
In another aspect, the present invention provides a method for preparing the garnet-type solid electrolyte according to the first aspect of the present invention, the method comprising the steps of:
step 1, mixing raw materials to obtain mixed powder;
step 2, calcining the mixed powder to obtain a calcined product;
and 3, grinding the calcined product to obtain a sample.
The invention has the advantages that:
1) the garnet type solid electrolyte provided by the invention has few impure phases and high purity, the cubic phase crystal form occupation ratio is up to 98%, and the conductivity of lithium ions is high;
2) according to the garnet-type solid electrolyte provided by the invention, the stability of the electrolyte material is improved by doping anions;
3) according to the garnet-type solid electrolyte provided by the invention, the calcination temperature in the electrolyte preparation process is reduced to below 1050 ℃, even below 1000 ℃, such as 985 ℃ or 995 ℃ through the synergistic effect of anions and cations, so that the great loss of lithium ions during high-temperature calcination is effectively avoided;
4) the method for preparing the garnet type solid electrolyte provided by the invention does not need to be pressed and formed, does not need to be calcined for the second time, and is simple in process, easy to operate and convenient for industrial popularization.
Drawings
Figure 1 shows XRD patterns of examples and comparative samples;
FIG. 2 shows EIS plots of samples from examples 1-5;
FIG. 3 shows EIS plots of comparative samples in comparative examples 1-4.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a garnet-type solid electrolyte which is prepared by calcining a matrix and a modifier, wherein the modifier comprises an anionic modifier and a cationic modifier.
In a preferred embodiment, the matrix is a lithium lanthanum zirconium oxygen based solid consisting essentially of Li, La, Zr, and O.
Wherein the Li element is selected from Li-containing compounds including Li2O or decomposable to Li at a high temperature of 400 ℃, preferably 700 ℃, more preferably 900 ℃ or higher2O and compounds of volatile constituents, e.g. LiOH, LiNO3Or Li2CO3。
The La element is selected from La-containing compounds including La2O3Or decomposable to La at a high temperature of 400 ℃, preferably 700 ℃, more preferably 900 ℃ or higher2O3And compounds of volatile constituents, e.g. La (OH)3、La(NO3)3Or La2(CO3)3。
The Zr element is selected from Zr-containing compounds including ZrO2Or decomposable into ZrO at a high temperature of 400 deg.C, preferably 700 deg.C, more preferably 900 deg.C or higher2And compounds of volatile constituents, e.g. Zr (OH)4、Zr(NO3)4Or Zr3(CO3)O5(zirconium basic carbonate).
In a preferred embodiment, the cationic modifier is at least one of compounds containing a metal element represented by A, D, E.
The lithium lanthanum zirconium oxygen-based solid electrolyte composed of Li, La, Zr and O belongs to garnet type crystals and has two crystal forms of tetragonal phase and cubic phase. In the cubic structure, there are two kinds of Li+One is a tetrahedral gap 24d position, the other is a distorted octahedral gap 96h position, the octahedron and the tetrahedron are connected with each other in a coplanar manner to form a three-dimensional network channel for lithium ion diffusion transmission, and the occupied positions of the three-dimensional network channel are disordered by Li+Due to mutual repulsion between them.
In the tetragonal crystal phase structure, Li+Occupy three positions, respectively the tetrahedral interstitial 8a position, the two octahedral interstitial 16f position and the 32g position, Li in the tetragonal phase+The sites and vacancies are ordered, making ionic transition between adjacent sites difficult, resulting in cubic phase ion conductivity higher than that of the tetragonal phase.
However, the pure cubic phase structure is unstable at high temperatures and easily transforms into the tetragonal phase. However, since the garnet-type solid electrolyte is often prepared without high-temperature calcination, it is preferable to dope the lithium lanthanum zirconium oxygen-based solid electrolyte with a metal element in order to stabilize the cubic phase lattice.
On one hand, the metal element doping can utilize the conservation of electrovalence to control the lithium ion concentration in the lithium lanthanum zirconium oxygen-based solid electrolyte, effectively improve the lithium vacancy concentration in the structure, increase the disorder degree of lithium ion arrangement, and achieve the purposes of stabilizing cubic phase and optimizing ion conductivity; on the other hand, the framework structure can be regulated and controlled, and elements with different ionic radii are used for doping or replacing the framework structure, so that the size of a lithium ion channel in the unit cell is suitable for the migration of lithium ions.
In a preferred embodiment, the element a is one or more elements selected from B, Al, Ga, In, Fe, Co, and Ni, more preferably one or more elements selected from B, Al, Ga, and In, and still more preferably Ga.
Wherein, the doping of a small amount of A element can play a role in stabilizing the crystal form, reduce the calcining temperature and improve the purity and the ion conduction rate of the garnet type solid electrolyte. However, if the a element is doped too much, the extra a element may generate some new impurities with Li, La and O, which may hinder the growth of cubic phase crystal during the calcination process, thereby causing the ion conductivity of the garnet-type solid electrolyte to be decreased.
Preferably, the element a is selected from a group consisting of a compound containing a including an oxide of a or a compound consisting of a and J. Still more preferably, the a-containing compound does not contain an oxygen element and an element other than the nonmetal element represented by J. For example, AlF3，AlCl3、Al2O3、Ga2O3。
In a preferred embodiment, the D element is one or more elements selected from Nb, Ta, and V, more preferably one or more elements selected from Nb and Ta, and still more preferably a Ta element.
Preferably, the element D is selected from a D-containing compound comprising an oxide of D or a compound consisting of D and J. Further preferably, the D-containing compound does not contain an oxygen element and an element other than the nonmetal element represented by J. For example, TaF5、NbF5、Nb2O5、Ta2O5。
In a preferred embodiment, the E element is one or more elements selected from Cr, W and Mo, more preferably one or more elements selected from W and Mo, and still more preferably a W element.
The doping of the D element and the E element can change the internal structure of the crystal, increase the parameters of a cavity and a channel in the crystal, and reduce the resistance of lithium ions to diffusion and movement in the crystal.
Preferably, the element E is selected from E-containing compounds including oxides of E or compounds consisting of E and J. Further preferably, the E-containing compound does not contain an oxygen-scavenging element and a non-metallic element represented by JElements other than elements. For example WF6、MoF6、MoO3、WO3。
In a preferred embodiment, the anionic modifier is a compound containing a nonmetallic element represented by J.
The element J is one or more elements selected from F, Cl, Br and I, more preferably one or more elements selected from F and Cl, and still more preferably an element F.
The reason is that the anions of the F, Cl, Br and I elements have strong electronegativity, and the stability of the lithium lanthanum zirconium oxygen-based solid electrolyte can be improved by doping the anions into the lithium lanthanum zirconium oxygen-based solid electrolyte.
In addition, doping of a small amount of J element also enables preparation of a large amount of garnet-type solid electrolyte. In the process of preparing the garnet-type solid electrolyte, calcination is required. The larger the amount to be prepared, the more difficult the calcination, and when the thickness of the calcined powder exceeds 1 to 1.5cm, the failure of calcination may be caused, and thus it is difficult to realize mass production of the garnet-type solid electrolyte. However, the applicant of the present invention has found through a lot of experiments that the doping of a small amount of J element, especially F element, into the garnet-type solid electrolyte can realize kilogram-level mass production of the garnet-type solid electrolyte, and improve the production efficiency of the garnet-type solid electrolyte.
Preferably, the J element is selected from J-containing compounds, the J element being selected from compounds of J with Li, La, Zr, A, D or E. Further preferably, the J-containing compound does not contain an oxygen element and an element other than Li, La, Zr, a, D, or E. For example AlF3、LiF、ZrF4、LaF3。
In a preferred embodiment, the electrolyte material has an empirical composition formula Li2a-3x-y-2z-wAxLa3Zr2-y- zDyEzO8.5+a-wJwThe composition formula is shown in the specification, and the mixture ratio of the components except the O element is the material charging ratio of the substance amount of each element in the raw materials. In which the electrolyte material is a solution ofThe empirical composition formula can be verified by the mass change before and after the reaction.
Wherein the relationship of a, x, y, z and w in the composition formula is as follows:
3.0≤a≤4.0
0≤x≤0.3
0≤y≤0.5
0≤z≤0.3
0.1≤w≤0.6
0.15≤x+y+z≤0.9
0.4≤w+x+y+z≤1.0
in a further preferred embodiment, the relationship of a, x, y, z and w in the composition formula is:
3.2≤a≤3.8
0≤x≤0.25
0≤y≤0.4
0≤z≤0.25
0.1≤w≤0.6
0.15≤x+y+z≤0.9
0.4≤w+x+y+z≤1.0。
in a still further preferred embodiment, the relationship of a, x, y, z and w in the composition formula is:
a is 3.75, x is 0.2, y is 0.3, z is 0.1, and w is 0.2 (that is, the composition formula of the electrolyte is Li)6.2Ga0.2La3Zr1.6Ta0.3W0.1O12.05F0.2)；
Or a is 3.875, x is 0.2, y is 0.25, z is 0.15, and w is 0.4 (i.e., the composition formula of the electrolyte is Li)6.2Al0. 2La3Zr1.6Nb0.25W0.15O11.975F0.4)。
In a preferred embodiment, the electrolyte has a structure of a cubic garnet phase, a cubic phase unit cell parameter of 12.85 or more, more preferably 12.95 or more, and still more preferably 12.99 or more, and no other impurity phase is detected on an X-ray diffraction pattern.
In a preferred embodiment, the electrolyte has an ionic conductivity of 2 x 10-4-1.0×10-3S/cm, inOne step is preferably 4.75X 10-4-×9.43-4S/cm, more preferably 9.43X 10-4S/cm。
In a second aspect the present invention provides a method of preparing a garnet-type solid electrolyte, comprising the steps of:
step 1, mixing raw materials to obtain mixed powder;
in a preferred embodiment, the raw material includes a Li-containing compound, a La-containing compound, a Zr-containing compound.
Wherein the Li element is selected from Li-containing compounds including Li2O or decomposable to Li at a high temperature of 400 ℃, preferably 700 ℃, more preferably 900 ℃ or higher2O and compounds of volatile constituents, e.g. LiOH, LiNO3Or Li2CO3。
The La element is selected from La-containing compounds including La2O3Or decomposable to La at a high temperature of 400 ℃, preferably 700 ℃, more preferably 900 ℃ or higher2O3And compounds of volatile constituents, e.g. La (OH)3、La(NO3)3Or La2(CO3)3。
The Zr element is selected from Zr-containing compounds including ZrO2Or decomposable into ZrO at a high temperature of 400 deg.C, preferably 700 deg.C, more preferably 900 deg.C or higher2And compounds of volatile constituents, e.g. Zr (OH)4、Zr(NO3)4Or Zr3(CO3)O5(zirconium basic carbonate).
In a preferred embodiment, the feedstock further comprises a J-containing compound. The J is one or more elements selected from F, Cl, Br and I, more preferably one or more elements selected from F and Cl, and still more preferably an element selected from F.
Preferably, the J-containing compound is selected from compounds consisting of J and Li, La, Zr, a, D or E. Further preferably, the J-containing compound does not contain an oxygen element and an element other than Li, La, Zr, a, D, or E.
In a preferred embodiment, the feedstock further comprises at least one of a compound comprising a, a compound comprising D, a compound comprising E.
The element a is one or more elements selected from B, Al, Ga, In, Fe, Co, and Ni, more preferably one or more elements selected from B, Al, Ga, and In, and still more preferably Ga.
Preferably, the A-containing compound comprises an oxide of A or a compound consisting of A and J. Still more preferably, the a-containing compound does not contain an oxygen element and an element other than the nonmetal element represented by J. For example, AlF3，AlCl3、Al2O3、Ga2O3。
The D element is one or more of Nb, Ta, and V, more preferably one or more of Nb and Ta, and still more preferably Ta.
Preferably, the D-containing compound comprises an oxide of D or a compound consisting of D and J. Further preferably, the D-containing compound does not contain an oxygen element and an element other than the nonmetal element represented by J. For example, TaF5、NbF5、Nb2O5、Ta2O5。
The element E is selected from one or more elements selected from Cr, W and Mo, more preferably one or more elements selected from W and Mo, and still more preferably the element W.
Preferably, the E-containing compound comprises an oxide of E or a compound consisting of E and J. Further preferably, the E-containing compound does not contain an oxygen element and an element other than the nonmetal element represented by J. For example WF6、MoF6、MoO3、WO3。
In a preferred embodiment, in step 1, Li is expressed according to the empirical composition formula of the electrolyte2a-3x-y-2z- wAxLa3Zr2-y-zDyEzO8.5+a-wJwThe corresponding raw materials are respectively weighed according to the proportion of various elements in the raw materials.
Preferably, the relationship of a, x, y, z and w in the composition formula is:
3.0≤a≤4.0
0≤x≤0.3
0≤y≤0.5
0≤z≤0.3
0.1≤w≤0.6
0.15≤x+y+z≤0.9
0.4≤w+x+y+z≤1.0。
further preferably, the relationship of a, x, y, z and w in the composition formula is:
3.2≤a≤3.8
0≤x≤0.25
0≤y≤0.4
0≤z≤0.25
0.1≤w≤0.6
0.15≤x+y+z≤0.9
0.4≤w+x+y+z≤1.0
more preferably, the relationship of a, x, y, z and w in the composition formula is:
a is 3.75, x is 0.2, y is 0.3, z is 0.1, and w is 0.2 (that is, the composition formula of the electrolyte is Li)6.2Ga0.2La3Zr1.6Ta0.3W0.1O12.05F0.2)；
Or a is 3.875, x is 0.2, y is 0.25, z is 0.15, and w is 0.4 (i.e., the composition formula of the electrolyte is Li)6.2Al0. 2La3Zr1.6Nb0.25W0.15O11.975F0.4)。
In a preferred embodiment, in step 1, the mixing is ball milling.
In the invention, the raw materials comprise various raw materials, the particle size of each raw material is not necessarily the same, and the raw materials are difficult to be uniformly mixed by simple mechanical stirring and mixing. The ball milling mixing can apply certain extrusion force to the mixed materials in the mixing process to achieve the grinding effect, so that the mixed powder is uniform in particle size, the powder can be mixed more uniformly, and the prepared electrolyte is excellent in electrical property.
In a preferred embodiment, the type of ball milling is not particularly limited, and dry ball milling or wet ball milling may be used.
Compared with dry ball milling, the slurry obtained by wet ball milling is more uniform and the grinding efficiency is high. The reason is that the materials to be milled are sometimes adhered to the milling balls during dry milling, so that the milling efficiency is reduced, and the wet milling can avoid the phenomenon due to the addition of the mixed medium, so that the milling efficiency is improved.
In a preferred embodiment, the solvent added in the wet ball milling is selected from one or more of water, absolute ethyl alcohol, propyl alcohol and isopropyl alcohol. Since the slurry needs to be dried after wet ball milling, the solvent added in wet ball milling is preferably absolute ethyl alcohol in order to simplify the difficulty of subsequent drying operation.
In a preferred embodiment, in the ball milling, the milling balls are selected from one or more of alumina milling balls, zirconia milling balls, stainless steel milling balls, quartz sand milling balls.
Grinding balls are grinding media, and generally, the higher the density of the grinding balls, the stronger the grinding ability, and the higher the grinding efficiency. Therefore, in the present invention, the grinding balls are preferably zirconia grinding balls.
In a preferred embodiment, the grinding balls comprise big balls and small balls, and the ratio of the number of the big balls to the number of the small balls is preferably (1-6): 1, more preferably (3-4): 1, more preferably 3: 1.
This is because the impact and grinding action of the grinding balls can be fully exerted by mixing the grinding balls of different sizes in a certain proportion and loading the mixture into a ball mill for use. Wherein the large balls mainly play a role of impact, and the small balls mainly play a role of grinding.
Preferably, the large sphere has a diameter of 3 to 30mm, more preferably 5 to 20mm, and still more preferably 10 mm. The diameter of the small spheres is preferably 50% to 80%, more preferably 60% to 70%, and still more preferably 65% of the diameter of the large spheres.
In a preferred embodiment, the mass ratio of the grinding balls to the raw materials is (1-7): 1, more preferably (3-5): 1, more preferably 4: 1.
The mass ratio of the grinding balls to the raw materials influences the quality of the ground powder. If the loading of the grinding balls is too small, insufficient grinding will occur, and the resulting mixed powder will have uneven particle diameters. If the loading of the grinding balls is too much, the grinding efficiency is reduced, which is not favorable for the industrial production of the product. The inventor of the invention has found through a great deal of experiments that the ball milling effect is best when the ball-to-material ratio is 4: 1.
In a preferred embodiment, the ball milling is carried out as follows: mixing for 30min-4h at the rotation speed of 100-500 rpm.
Wherein, the higher the rotating speed, the longer the ball milling time, the better the uniformity of the raw material mixing, and the higher the dispersibility. However, excessive increase in the rotation speed and time is not significant in improving the mixing effect, and energy consumption is wasted, thereby increasing production cost.
In a further preferred embodiment, in step 1, the ball milling is carried out as follows: mixing is carried out for 1h-3h at the rotation speed of 150-.
In a still further preferred embodiment, in step 1, the ball milling is performed as follows: mix for 3h at 200 rpm.
In a preferred embodiment, after the ball milling is finished, the slurry is dried for 6 to 15 hours at the temperature of between 80 and 120 ℃ to obtain mixed powder.
In a further preferred embodiment, after the ball milling is finished, the slurry is dried for 8-12h at 90-110 ℃ to obtain mixed powder.
In a more preferred embodiment, after the ball milling is finished, the slurry is dried at 100 ℃ for 10 hours to obtain a mixed powder.
Step 2, calcining the mixed powder to obtain a calcined product;
in a preferred embodiment, in step 2, the calcination is carried out as follows: heating from room temperature to 985-1035 ℃ at the heating rate of 2-8 ℃/min, and keeping the temperature for 8-16 h.
Among them, the calcination temperature and calcination time have an important influence on the performance of the garnet-type solid electrolyte. If the calcination temperature is highToo low, too short calcination time, insufficient reaction and more impurities in the obtained electrolyte; if the calcination temperature is too high, a large amount of lithium is volatilized, and La is easily formed on the surface of the solid electrolyte2Zr2O7And the yield and the finished product conductivity are greatly influenced, the firing temperature is higher, and more energy is consumed.
The rate of temperature increase also affects the crystals of the calcined product, which in turn affects the electrical properties of the electrolyte produced. Too fast a temperature rise rate may lead to a subsequent reaction without complete decomposition of the lithium source, and the PH of the product after the reaction is too high to facilitate storage of the electrolyte material.
In a further preferred embodiment, in step 2, the calcination is carried out as follows: raising the temperature from room temperature to 995-1020 ℃ at the temperature raising rate of 3-6 ℃/min, and preserving the temperature for 10-14 h.
In a more preferred embodiment, in step 2, the calcination is carried out as follows: raising the temperature from room temperature to 1000 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 12 h.
In a preferred embodiment, the temperature reduction after calcination is not particularly limited, but is preferably carried out naturally to obtain a calcined product. The production process can be simplified by adopting natural cooling, and the method is convenient for commercial popularization.
And 3, grinding the calcined product to obtain a sample.
In the invention, the calcined product obtained after calcination is sintered into blocks, the particle size is larger and has a wide range and irregular particle appearance, so that the electrochemical performance of the solid electrolyte is difficult to control. Therefore, after calcination, the obtained calcined product needs to be ground again to obtain the high-conductivity cubic-phase garnet-type solid electrolyte.
In the present invention, the grinding in step 3 is not particularly limited, and the grinding may be performed manually using a millstone or mortar, or may be performed automatically using a grinder, such as a planetary ball mill, an attritor, a ball mill, or an air mill. Either wet or dry milling may be performed.
In order to reduce the cost of material synthesis preparation, air pulverization dry grinding is preferred in the invention, and the air pulverization uses low dew point dry air as a gas source to avoid surface deterioration of the material in the pulverization process.
And after the grinding is finished, obtaining an anion-cation modified garnet type solid electrolyte sample, wherein the particle size of the sample is 0.5-60 μm, more preferably 2-30 μm, and more preferably 4-15 μm.
Examples
Example 1
0.64mol (26.88g) of LiOH. H2O，0.15mol(48.87g)La2O3，0.175mol(21.56g)ZrO2，0.0125mol(3.323g)Nb2O5，0.01mol(0.840g)AlF3And 0.005mol (0.51g) of Al2O3Ball milling and mixing the materials, wherein the solvent is ethanol, the mixing time is 3h, the materials are dried for 10h at 100 ℃ after mixing to obtain mixed powder, 100.00g of the mixed powder is placed in a corundum crucible, the heating speed is 4 ℃ per minute, the temperature is increased to 985 ℃, the temperature is kept for 8h, the mixed powder is naturally cooled and then ground to obtain a product, and the product is marked as a sample 1.
Wherein, the weight of the corundum crucible before synthesis is 655.94g, the weight of the sintered material and the corundum crucible is 739.00g, the weight of the corundum crucible after synthesis is 655.93g, namely the weight of the material is 83.06g, the content of Al in ICP test in the sintered material is 6368ppm, the Al is basically consistent with the theoretical calculation result 6374ppm, the Al in the crucible is not obviously diffused into the material, and the weight loss in the synthesis process is only per mol LiOH H according to the calculation mode2O lost 1.5mol of H2O weight loss of 16.94g (theoretical weight loss of 16.944g), no other obvious volatilization weight loss of Li and F, metal elements can be considered not to have valence change reaction in the synthesis process, and analysis confirms that the composition formula is Li6.4Al0.2La3Zr1.75Nb0.25O11.975F0.3。
Example 2
0.6mol (25.20g) of LiOH. H2O，0.15mol(48.87g)La2O3，0.16mol(19.71g)ZrO2，0.015mol(6.629g)Ta2O5，0.02mol(0.518g)LiF，0.01mol(1.8g)Ga2O3，0.01mol(2.319g)WO3Ball milling and mixing the materials, wherein the solvent is ethanol, the mixing time is 3h, the materials are dried for 10h at 100 ℃ after mixing to obtain mixed powder, 100.00g of the mixed powder is placed in a corundum crucible, the temperature rise speed is 4 ℃ per minute, the temperature is raised to 1000 ℃, the temperature is kept for 12h, the mixed powder is naturally cooled and then ground to obtain a product, and the product is recorded as a sample 2.
Wherein, the weight of the corundum crucible before synthesis is 655.93g, the weight of the sintered material and the corundum crucible is 740.52g, the weight of the corundum crucible after synthesis is 655.92g, namely the weight of the material is 84.60g, the content of Al in the sintered material in an ICP test is 16ppm, the Al content is basically consistent with the theoretical calculation result of 0ppm, the Al in the crucible can not be obviously diffused into the material, and the weight loss in the synthesis process is only per mol LiOH.H according to the calculation mode2O lost 1.5mol of H2O weight loss is 15.40g (theoretical weight loss is 15.41g), other obvious volatilization weight loss of Li and F is not seen, the metal elements can be considered not to have valence change reaction in the synthesis process, and analysis confirms that the composition empirical formula is Li6.2Ga0.2La3Zr1.6Ta0.3W0.1O12.05F0.2。
Example 3
0.31mol (22.91g) of Li2CO3，0.15mol(48.87g)La2O3，0.16mol(19.71g)ZrO2，0.0125mol(3.323g)Nb2O5，0.0133mol(1.120g)AlF3，0.00333mol(0.340g)Al2O3，0.015mol(3.48g)WO3And performing ball milling and mixing on the mixed materials, wherein the solvent is water, the mixing time is 3h, the mixed materials are dried at 120 ℃ for 10h to obtain mixed powder, 98.00g of the mixed powder is placed in a corundum crucible, the heating speed is 4 ℃ per minute, the temperature is raised to 995 ℃, the heat preservation is performed for 12h, and the mixed powder is ground after natural cooling and is marked as a sample 3.
Wherein, the weight of the corundum crucible is 655.90g, the weight of the sintered material and the corundum crucible is 740.50g, the weight of the synthesized corundum crucible is 655.90g, namely the weight of the material is 84.60g, the content of Al in ICP test in the sintered material is 6290ppm, the Al content is basically consistent with the theoretical calculation result of 6270ppm, and the Al in the crucible is not obviously diffused into the material, and the weight loss in the synthesis process is calculatedOnly per mol Li2CO3Loss of 1mol CO2The weight loss is 13.40g (theoretical weight loss is 13.40g), other obvious volatilization weight loss of Li and F is not seen, the metal elements can be considered not to have valence change reaction in the synthesis process, and the composition empirical formula is Li by analysis6.2Al0.2La3Zr1.6Nb0.25W0.15O11.975F0.4。
Example 4
0.62mol (42.72g) of LiNO was added3，0.3mol(57.90g)La(OH)3，0.17mol(20.94g)ZrO2，0.02mol(0.518g)LiF，0.01mol(1.874g)Ga2O3，0.015mol(6.629g)Ta2O5And ball-milling and mixing the materials, carrying out solvent-free dry grinding for 5h, placing 100.00g of mixed powder in a corundum crucible, heating at the speed of 4 ℃ per minute to 1020 ℃ per minute, keeping the temperature for 12h, naturally cooling, and grinding to obtain a sample 4.
Wherein, the weight of the corundum crucible is 655.90g, the weight of the sintered material and the corundum crucible is 724.06g, the weight of the synthesized corundum crucible is 655.90g, namely the weight of the material is 68.16g, the content of Al in the sintered material in an ICP test is 30ppm, the Al content is basically consistent with the theoretical calculation result of 0ppm, the Al in the crucible can not be obviously diffused into the material, and only LiNO is used for weight loss in the synthesis process according to the calculation mode3And La (OH)3The weight loss is 13.40g (theoretical weight loss is 13.40g), other obvious volatilization weight loss of Li and F is not seen, the metal elements can be considered not to have valence change reaction in the synthesis process, and the composition empirical formula is Li by analysis6.4Ga0.2La3Zr1.7Ta0.3O12.05F0.2。
Example 5
0.67mol (28.14g) of LiOH. H2O，0.15mol(48.87g)La2O3，0.2mol(24.64g)ZrO2，0.015mol(1.260g)AlF3And ball-milling and mixing the materials, carrying out solvent-free dry grinding for 5h, placing 100.00g of mixed powder in a corundum crucible, heating at the speed of 4 ℃ per minute to 1035 ℃ per minute, keeping the temperature for 16h, naturally cooling, and grinding to obtain a sample 5.
Wherein, the weight of the corundum crucible is 655.90g, the weight of the sintered material and the corundum crucible is 738.30g, the weight of the synthesized corundum crucible is 655.89g, namely the weight of the material is 82.41g, the content of Al in the sintered material in an ICP test is 4792ppm, the content is basically consistent with the theoretical calculation result 4775ppm, the Al in the crucible is not obviously diffused into the material, and the weight loss in the synthesis process is only per molLiOH.H according to the calculation mode2O lost 1.5mol of H2O weight loss of 17.59g (theoretical weight loss of 17.58g) and no other obvious volatilization weight loss of Li and F, metal elements can be considered to have no valence change reaction in the synthesis process, and the composition empirical formula is Li by analysis6.7Al0.15La3Zr2O11.85F0.45。
Comparative example
Comparative example 1
0.75mol (31.43g) of LiOH. H2O，0.15mol(48.87g)La2O3，0.2mol(24.64g)ZrO2And ball-milling and mixing the materials, wherein the solvent is ethanol, the mixing time is 3h, drying the mixed materials at 100 ℃ for 10h to obtain mixed powder, placing 100.00g of the mixed powder in a corundum crucible, heating the mixed powder at the speed of 4 ℃ per minute to 1050 ℃, preserving the heat for 16h, naturally cooling and grinding the mixed powder to obtain a comparative sample 1. Wherein, the weight of the corundum crucible is 655.88g, the weight of the sintered material and the corundum crucible is 736.57g, the weight of the synthesized corundum crucible is 655.87g, the weight of the synthesized sample is 80.70g, the content of Al in the sintered material in an ICP test is 21ppm, the Al content is basically consistent with the theoretical calculation result of 0ppm, and the composition formula of the sample is Li by analysis7.5La3Zr2O12.25。
Comparative example 2
0.69mol (28.98g) of LiOH. H2O，0.15mol(48.87g)La2O3，0.2mol(24.64g)ZrO2，0.01mol(1.020g)Al2O3And ball-milling and mixing the materials, wherein the solvent is ethanol, the mixing time is 3h, drying the mixed materials at 100 ℃ for 10h to obtain mixed powder, placing 100.00g of the mixed powder in a corundum crucible, heating at the speed of 4 ℃ per minute to 1050 ℃, preserving heat for 16h, naturally cooling, and grinding to obtain a comparative sample 2.
Wherein, the weight of the corundum crucible is 655.87g, the weight of the sintered material and the corundum crucible is 737.86g, the weight of the synthesized corundum crucible is 655.87g, the weight of the synthesized sample is 81.99g, the content of Al in the sintered material in an ICP test is 6380ppm, the Al content is basically consistent with the theoretical calculation result of 6362ppm, and the sample composition formula is Li by analysis6.9Al0.2La3Zr2O12.25。
Comparative example 3
0.63mol (26.46g) of LiOH. H2O，0.15mol(48.87g)La2O3，2mol(24.64g)ZrO2And performing ball milling and mixing on 0.05mol (1.295g) of LiF mixture, wherein the solvent is ethanol, the mixing time is 3 hours, drying the mixture at 100 ℃ for 10 hours after mixing to obtain mixed powder, putting 100.00g of the mixed powder in a corundum crucible, heating the mixed powder to 1050 ℃ at a heating speed of 4 ℃ per minute, preserving the heat for 16 hours, naturally cooling, and grinding to obtain a comparative sample 3.
Wherein, the weight of the corundum crucible is 655.86g, the weight of the sintered material and the corundum crucible is 739.06g, the weight of the synthesized corundum crucible is 655.86g, the weight of the synthesized sample is 83.20g, the content of Al in the sintered material in an ICP test is 15ppm, the Al content is basically consistent with the theoretical calculation result of 0ppm, and the composition formula of the sample is Li by analysis6.8La3Zr2O11.65F0.5。
Comparative example 4
0.69mol (28.98g) of LiOH. H2O，0.15mol(48.87g)La2O3，0.2mol(24.64g)ZrO2，0.01mol(1.020g)Al2O3Ball-milling and mixing the materials, wherein the solvent is ethanol, the mixing time is 3h, the materials are dried for 10h at 100 ℃ after mixing to obtain mixed powder, the mixed powder is placed in a corundum crucible, the heating speed is 4 ℃ per minute, the heating is up to 1050 ℃, the heat preservation is 16h, the materials are naturally cooled and then ground, 2g of the mixed powder is placed in a tabletting mold with the diameter of 13mm, 5 tons of pressure are used for pressing into a sheet, the ceramic sheet is placed in the corundum crucible after demolding, the temperature is up to 1150 ℃ per minute, the heat preservation is 16h, a comparative sample 4 is obtained through natural cooling, the Al content in the sample is 6405ppm and basically consistent with the theoretical value of 6362ppm, and the sample composition formula is Li6.9Al0.2La3Zr2O12.25。
Examples of the experiments
Experimental example 1
XRD examination was performed on the samples obtained in examples 1 to 5 and comparative examples 1 to 4, and the results are shown in FIG. 1:
comparing the XRD patterns of the samples obtained in examples 1 to 5 and comparative examples 1 to 4 with the XRD pattern of the garnet-type solid electrolyte standard, it can be seen that the samples obtained in examples 1 to 5 have high purity of crystals, almost no impurity phase, and a cubic phase content ratio of 98% or more, while the samples obtained in comparative examples 1 to 4 have both cubic and tetragonal phases.
The unit cell parameters calculated by XRD are shown in table 1:
XRD analysis results of the samples of Table 1
Figure BDA0002346201610000191
As can be seen from table 1, in comparative example 1, the cubic phase in the lithium lanthanum zirconium oxygen-based solid electrolyte was 43% and the tetragonal phase was 54% in the case of no doping. In comparative sample 2 doped with only a single metal element and comparative sample 3 doped with only a single nonmetal element, the proportion of cubic phase is almost not different from that in comparative sample 1. Therefore, the cubic phase crystal lattice can be stabilized only under the synergistic action of the metal element and the nonmetal element, and the lithium ion conductivity in the electrolyte is improved.
The comparison between the comparative example 2 and the comparative example 4 shows that the pure material is difficult to prepare by the common powder bulk firing, but the cubic phase content can be improved by the tabletting firing, which shows that the paper firing temperature can be greatly reduced under the interaction of the added anions and cations, the firing condition is relaxed, and the cubic phase content in the sample is improved.
Experimental example 2
The samples obtained in examples 1 to 5 and comparative examples 1 to 4 were respectively loaded into a tabletting grinder having a diameter of 13mm, pressed into a ceramic sheet having a weight of 1g under a pressure of 5 tons, treated at a high temperature of 1195 ℃ for 24 hours, and the ceramic sheet was ground to a circular sheet having a diameter of 10mm and a thickness of 1.5mm, subjected to double-sided gold spraying and side polishing using an ion sputtering apparatus, and the ceramic sheet was tested for EIS using an electrochemical workstation and the ionic conductivity was calculated from the thickness and diameter of the ceramic sheet, and the test results thereof are shown in fig. 2 and 3:
as can be seen from fig. 2, in the samples 1, 2, 3, 4, and 5, since the device cannot completely read the semicircle, the straight line of the diffusion line portion and the horizontal axis focus of the EIS diagram are taken, the reading is read and recorded as the resistance value of the ceramic wafer, and the ion conductivity of the corresponding sample is obtained according to the calculation; the resistance values of the comparative samples 1, 2, 3 and 4 were obtained by fitting, and the ionic conductivities of the samples were obtained by substituting the calculations, the results of which are shown in table 2:
table 2 ceramic wafer conductivity results for the samples
Figure BDA0002346201610000201
As can be seen from Table 2, the conductivity of the unmodified comparative sample 1 was the lowest, only 0.0027X 10-4S/cm, the conductivity of the obtained comparative sample is not obviously changed when only a single metal is used for modification or only fluorine is used for modification. When the cation modifier and the anion modifier are added into the garnet type solid electrolyte at the same time, the conductivity of the prepared sample is obviously improved and can be increased from 0.0027 multiplied by 10-4The S/cm is increased to at least 4.75 multiplied by 10-4S/cm, can be increased to 9.43 multiplied by 10-4S/cm. Moreover, the effect of simultaneous modification of the three metals is obviously better than that of simultaneous modification of the two metals.
The present invention has been described above in connection with preferred embodiments, but these embodiments are merely exemplary and merely illustrative. On the basis of the above, the invention can be subjected to various substitutions and modifications, and the substitutions and the modifications are all within the protection scope of the invention.

Claims (10)

1. A garnet-type solid electrolyte characterized in that: the electrolyte is prepared by calcining a matrix and a modifier.
2. The electrolyte of claim 1, wherein: the matrix is a lithium lanthanum zirconium oxygen-based solid and mainly comprises Li, La, Zr and O.
3. The electrolyte of claim 1 or 2, wherein: the modifier includes an anionic modifier and a cationic modifier.
4. The electrolyte of claim 3, wherein: the anion modifier is a compound containing a nonmetal element represented by J, and the cation modifier is at least one of compounds containing a metal element represented by A, D, E;
wherein J, A, D, E respectively represent the following elements,
j is one or more elements selected from F, Cl, Br and I,
a is selected from one or more of B, Al, Ga, In, Fe, Co and Ni,
d is one or more elements selected from Nb, Ta and V,
e is one or more elements selected from Cr, W and Mo.
5. Electrolyte according to one of claims 1 to 3, characterized in that: the structure of the electrolyte is a cubic garnet phase.
6. Electrolyte according to one of claims 1 to 3, characterized in that: the electrolyte has high ionic conductivity.
7. A method for producing a garnet-type solid electrolyte, preferably for producing an electrolyte as claimed in one of claims 1 to 6, characterized in that: the method comprises the following steps:
step 1, mixing raw materials to obtain mixed powder;
step 2, calcining the mixed powder to obtain a calcined product;
and 3, grinding the calcined product to obtain a sample.
8. The method of claim 7, wherein: in the step 1, the mixing is ball milling mixing; the ball milling was carried out as follows: mixing for 30min-4h at the rotation speed of 100-500 rpm.
9. The method of claim 7, wherein: in step 2, the calcination is carried out as follows: heating from room temperature to 985-1035 ℃ at the heating rate of 2-8 ℃/min, and keeping the temperature for 8-16 h.
10. The method of claim 7, wherein: in step 3, the structure of the sample is a cubic garnet phase.
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