CN111276737B - Garnet type composite electrolyte material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a garnet type composite electrolyte material and a preparation method thereof, belonging to the field of new energy materials, wherein the garnet type composite electrolyte material is a core-shell structure which takes garnet type oxide as an inner core and coordination hydride as a shell layer; the preparation method of the garnet type composite electrolyte material comprises the following steps: under the protection of inert gas, the garnet-type oxide and the coordination hydride undergo an oxidation-reduction reaction under the action of ball milling to obtain the garnet-type composite electrolyte material. The garnet composite electrolyte material prepared by the invention has the advantages of high lithium ion conductivity, high voltage window and the like, can be applied to the preparation of all-solid-state lithium ion batteries, and has higher application value in the industrial production of all-solid-state lithium ion batteries.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a garnet type composite electrolyte material and a preparation method thereof.
Background
The all-solid-state lithium ion battery has the advantages of high energy density, difficult spontaneous combustion, no pollution, compatibility with a high-capacity metal lithium cathode and a high-voltage anode and the like, and has wide application in real life. The electrolyte material is used as one of important components of the all-solid-state lithium ion battery, and has great influence on the battery performance; the garnet-type oxide electrolyte material has the advantages of high ionic conductivity, environmental friendliness, high safety performance and the like, and is an all-solid-state lithium ion battery electrolyte material with development potential.
For garnet-type oxides of cubic structure Li7La3Zr2O12The frame is made of LaO8Dodecahedron (24c) and ZrO6Octahedral (16a) composition, Li+Tetrahedral sites (24d) occupying the framework gaps; when Li is in the formula+When the content of (B) is more than 3, Li+Excess of (2) can lead to Li in the network channels+Rearrangement of part of Li+Incorporation of loosely bound distorted octahedral sites with simultaneous introduction of Li at the otherwise tightly bound and fully occupied tetrahedral sites+Vacancies, form Li+Thereby conducting Li as an electrolyte material+。
Publication number CN108832173A discloses a garnet-type lithium ion solid electrolyte co-doped with gallium and molybdenum and a preparation method thereof, wherein the garnet-type lithium ion solid electrolyte has a general formula: li6.55-2xGa0.15La3Zr2-xMoxO12Wherein x is more than or equal to 0.05 and less than or equal to 0.25; the preparation method comprises the following steps: s1, weighing Li in stoichiometric ratio according to the general formula2CO3Powder of ZrO2Powder of Ga2O3Powder, La2O3Powder and MoO3Powder; s2, mixing all the powder together and grinding to form a first material to be molded; s3, pressing and forming the first material to be molded, and then calcining to obtain a precursor compound; s4, grinding the precursor compound to form a second material to be molded; and S5, pressing and forming the second material to be molded, and then sintering to obtain the gallium and molybdenum co-doped garnet type lithium ion solid electrolyte.
The publication No. CN110474098A discloses a garnet-type solid electrolyte material, a preparation method and an application thereof, wherein the garnet-type solid electrolyte material is a core-shell structure with a shell layer coating an inner core, and the shell layer is a garnet-type solid electrolyte material Li7-2xMgxLa3-4/3yTiyZr2O12Wherein x is 0.05-0.1, and y is 0.1-0.3; the inner core is made of high nickel material; the preparation method comprises the following steps: 1) according to the formula Li7-2xMgxLa3-4/3yTiyZr2O12Weighing a lithium source, a magnesium source, a lanthanum source, a titanium source and a zirconium source according to a molar ratio,adding deionized water, and stirring uniformly to obtain a solution I, wherein x is 0.05-0.1, and y is 0.1-0.3; 2) spray drying the solution I to obtain a material II; 3) roasting the material II in an air atmosphere to obtain a material III; 4) sanding the material III and the dispersing agent together in a sand mill to obtain slurry IV; 5) spray drying the slurry IV to obtain a material V; 6) and roasting the material V in an air atmosphere to obtain the garnet type solid electrolyte material.
The preparation method of the garnet-type solid electrolyte material has certain limitations. For example, the electrolyte material is prepared by prefabricating the electrolyte material into a ceramic material. However, the preparation of ceramic materials requires a long sintering time at temperatures exceeding 1000 ℃, which is time and energy consuming; in addition, the preparation process of the ceramic material is complex, the problems of uneven temperature distribution of the cavity of the sintering equipment and the like exist, and the preparation method is not suitable for preparing large-size ceramic solid electrolyte materials.
In order to solve the above problems, the present inventors mainly focused on lowering the sintering temperature of the solid electrolyte ceramic material by means of ion doping, but no solution was proposed to the problem of how to obtain a garnet-type oxide electrolyte material of an appropriate size. Therefore, developing a preparation method with mild reaction conditions, which is suitable for preparing the garnet-type composite electrolyte material with a suitable size (the length is more than or equal to 0 and less than or equal to 100mm, the width is more than or equal to 0 and less than or equal to 400mm, and the thickness is more than or equal to 0 and less than or equal to 300mm) has important significance for the development of all-solid-state lithium ion batteries.
Disclosure of Invention
The invention provides a garnet type composite electrolyte material, and an all-solid-state lithium ion battery prepared by using the garnet type composite electrolyte material has the characteristics of high lithium ion conductivity and high voltage window.
The garnet composite electrolyte material is a core-shell structure with a garnet oxide as an inner core and a coordination hydride as an outer shell.
The particle size range of the garnet composite electrolyte material is 50nm-10 mu m.
Said garnet typeThe molecular formula of the oxide is LiαGα’La3-βMβZr2-γRγO12；
Wherein G is one of Al, Fe, Ga and Ge; m is one of Sr and Rb; r is one of Ta, Nb, Sb and Mo; alpha is 3-7; alpha' is 0-0.8; beta is 0-0.8; and gamma is 0-0.8.
The complex hydride is LiBH4、LiNH2、(LiBH4)mNH3、(LiBH4)nNH3BH3And NH3BH3One of (1); wherein m is greater than or equal to 1/3 and less than or equal to 10, and n is greater than or equal to 1 and less than or equal to 10.
Preferably, the ratio of the garnet-type oxide to the complex hydride is 1:0.05 to 40.
The garnet composite electrolyte material has a cubic phase structure due to the existence of a plurality of uniformly dispersed metal and nonmetal elements, and Li is added+Vacancy transport of Li+The conductivity is improved.
The invention also provides a preparation method of the garnet type composite electrolyte material, which is simple to operate, does not need high-temperature sintering in the preparation process, and provides a preparation scheme for the solid garnet type composite electrolyte material.
A method for preparing a garnet-type composite electrolyte material, comprising: under the inert gas, the garnet-type oxide and the coordination hydride are subjected to oxidation-reduction reaction under the mechanical action to obtain the garnet-type composite electrolyte material.
Preferably, the inert gas is argon.
Preferably, the mechanical action is planetary ball milling; the ratio of the mass of the grinding balls to the total mass of the garnet oxide and the complex hydride in the planetary ball milling is 20-120: 1.
more preferably, the rotation speed of the ball mill is 200-600 rpm, and the time is 0.1-24 h.
The preparation method of the garnet composite electrolyte material comprises the following stepsThe garnet composite electrolyte material has an amorphous flexible layer due to star-type ball milling, so that the compactness of the garnet composite electrolyte material is improved, and Li is reduced+Barrier during migration, thereby further increasing Li+The garnet-type composite electrolyte material can still keep stable at higher voltage due to the stable crystal structure of the garnet-type oxide matrix, and has higher voltage window.
The invention also provides an application of the garnet composite electrolyte material, which comprises the following steps: filling garnet type composite electrolyte material powder into a die, and pressing at high pressure to obtain a garnet type composite electrolyte block material; the garnet composite electrolyte bulk material can be directly applied to the preparation of all-solid-state lithium ion batteries as a solid electrolyte.
Preferably, the pressure of the high-pressure pressing is 200-400 MPa.
The invention has the following beneficial effects:
(1) the coordination hydride adopted in the garnet-type composite electrolyte material provided by the invention has a wide range, different garnet-type oxides can be modified by adopting a method of compounding with the coordination hydride, and the prepared garnet-type composite electrolyte material has the advantages of high lithium ion conductivity, high voltage window and the like, and has great competitiveness in industrial production and application.
(2) The preparation method of the garnet composite electrolyte material provided by the invention has the advantages of mild conditions, simple process and high safety performance, and is suitable for industrial production.
(3) Compared with the traditional garnet type electrolyte material, the garnet type composite electrolyte material provided by the invention does not need to be sintered at high temperature in the application process, so that the energy consumption is greatly reduced, and meanwhile, the requirement on equipment is low because the temperature uniformity in the sintering process does not need to be controlled, and the preparation of a large-size solid electrolyte material is facilitated.
Drawings
FIG. 1 is a TEM image of a garnet-type composite electrolyte material (LLZTO-LBH) prepared in example 1 of the present invention.
FIG. 2 is a particle size distribution diagram of a garnet-type composite electrolyte material (LLZTO-LBH) prepared in example 1 of the present invention.
FIG. 3 is an XRD pattern of a garnet-type composite electrolyte material and a primary garnet-type oxide prepared in example 1 of the present invention; wherein a is the XRD pattern of the garnet-type composite electrolyte material; b is the XRD pattern of the garnet-type oxide.
Fig. 4 is an XPS spectrum of the garnet-type composite electrolyte material prepared in example 1 of the present invention.
Fig. 5 is an Electrochemical Impedance Spectroscopy (EIS) of the garnet-type composite electrolyte material prepared in example 1 of the present invention.
Fig. 6 is a Cyclic Voltammetry (CV) graph of the garnet-type composite electrolyte material prepared in example 1 of the present invention.
Fig. 7 is an XRD spectrum of the garnet-type composite electrolyte material prepared in example 2 of the present invention and the garnet-type oxide thereof; wherein a is the XRD pattern of the garnet-type composite electrolyte material prepared in example 2; b is the XRD pattern of the garnet-type oxide.
Fig. 8 is an Electrochemical Impedance Spectroscopy (EIS) of the garnet-type composite electrolyte material prepared in example 2 of the present invention.
Fig. 9 is an Electrochemical Impedance Spectroscopy (EIS) of the garnet-type composite electrolyte material prepared in example 3 of the present invention.
Detailed Description
The present invention is further illustrated, but is not intended to be limited, by the following examples, in which reference is made to commercially available materials.
Example 1
In a glove box under argon atmosphere, 0.911g of Li was weighed6.4La3Zr1.4Ta0.6O12And 0.089g LiBH4(wherein, Li6.4La3Zr1.4Ta0.6O12With LiBH4The molar ratio is 1: 4) sequentially loading into a ball milling tank, wherein the ball material ratio is 120:1, and ball milling beads are made of stainless steel; the mixture was run in a planetary ball mill at 300rpmAnd (4) carrying out rapid ball milling for 12h, taking out the obtained ball-milled product in an argon atmosphere glove box, recording as LLZTO-LBH, and carrying out subsequent electrochemical performance test.
As shown in FIG. 1, the garnet-type composite electrolyte material (LLZTO-LBH) prepared in example 1 has a layer of amorphous phase coated on the black dense garnet-type oxide, which improves the compactness of the garnet-type composite electrolyte material and reduces Li+Barrier during migration, thereby further increasing Li+Electrical conductivity.
As shown in FIG. 2, the particle size distribution of the garnet-type composite electrolyte material (LLZTO-LBH) prepared in example 1 was between 50nm and 10 μm.
As shown in fig. 3, a is an XRD pattern of the garnet-type composite electrolyte material (LLZTO-LBH) prepared in example 1; b is the original garnet-type oxide Li6.4La3Zr1.4Ta0.6O12An XRD pattern of (a); as can be seen from the figure, it is related to LiBH4Ball-milled composite material LLZTO-LBH and original Li6.4La3Zr1.4Ta0.6O12Compared with the method without generating new crystalline phase, the matrix structure of the electrolyte material is not changed.
As shown in fig. 4, the XPS spectrum of the garnet-type composite electrolyte material prepared in example 1 has 2 peak positions, and the corresponding binding energies are 191eV and 192eV, respectively, which indicates that the boron element is amorphous borate or amorphous boron oxide B2O3In the form of (A) is present in a garnet-type composite electrolyte material, and when used as an active material of the electrolyte material, the amorphous boron oxide B is present2O3On one hand, the amorphous borate can be used as a bonding agent to effectively reduce pores among matrix oxide particles; on the other hand, amorphous borate may favor Li+Thereby improving the composite electrolyte Li+Electrical conductivity.
As shown in FIG. 5, the Electrochemical Impedance Spectrum (EIS) of the garnet-type composite electrolyte material prepared in example 1 shows that the impedance curve in the high frequency region is a semicircle, and the intersection of the right end of the semicircle and the solid axis represents the bulk and the particle spaceThe total resistance, which is a diagonal line in the low frequency region, reflects the ion blocking phenomenon, and can be seen from the curve, Li of LLZTO-LBH at 30 deg.C+The conductivity can reach 5.02 x 10-S/cm; and Li6.4La3Zr1.4Ta0.6O12Li of (2)+The conductivity is only 7.45 multiplied by 10-9S/cm; further illustrates that the garnet-type composite electrolyte material prepared in example 1 has high Li+Electrical conductivity.
As shown in fig. 6, Cyclic Voltammetry (CV) curves of the garnet-type composite electrolyte material prepared in example 1; at 30 ℃, in the range of-0.5V to 6V, no other obvious redox current except the reaction peak of lithium deposition-stripping appears; as can be seen from the curves, the electrochemical stability window of the garnet-type composite electrolyte material prepared in example 1 can reach 6V (vs. Li/Li)+) This creates conditions for the preparation of high-voltage all-solid-state lithium ion batteries.
Example 2
In a glove box under argon atmosphere, 0.911g of Li was weighed6.4La3Zr1.4Ta0.6O12、0.089g LiBH4And 0.053gLiNH2(wherein, Li6.4La3Zr1.4Ta0.6O12With LiBH4、LiNH2The molar ratio is 1: 4: 2) sequentially loading into a ball milling tank, wherein the ball material ratio is 100:1, and ball milling beads are made of stainless steel; and (3) ball-milling the mixture in a planetary ball mill at the rotating speed of 351rpm for 12h, taking out the obtained ball-milled product in an argon atmosphere glove box, recording as LLZTO-B-N, and carrying out subsequent electrochemical performance test.
As shown in FIG. 7, A is the XRD pattern of the garnet-type composite electrolyte material (LLZTO-B-N) prepared in example 2; b is a primary garnet-type oxide (Li)6.4La3Zr1.4Ta0.6O12)2 XRD pattern, as can be seen from the figure, with LiBH4Compared with the original composite material, the composite material LLZTO-B-N obtained by ball milling does not generate new crystalline phase, and the matrix structure of the electrolyte material is not changed.
As shown in FIG. 8, the garnet-type composite prepared in example 2The impedance (EIS) curve of the electrolyte material, which is a semicircle in the high frequency region, the intersection point of the right end of the semicircle and the real axis represents the total resistance of the bulk phase and the particle gap, and an oblique line in the low frequency region reflects the ion blocking phenomenon, and can be known from the curve that the Li of LLZTO-B-N is at 30 DEG C+The conductivity can reach 1.19 multiplied by 10-4S/cm; and Li6.4La3Zr1.4Ta0.6O12Li of (2)+The conductivity is only 7.45 multiplied by 10-9S/cm。
Example 3
In a glove box under argon atmosphere, 0.928g of Li was weighed6.4Al0.2La3Zr2O12、0.072g LiBH4(wherein, Li6.4Al0.2La3Zr2O12With LiBH4The molar ratio is 1: 3) sequentially loading the materials into a ball milling tank, wherein the ball material ratio is 90:1, and ball milling beads are made of stainless steel; and (3) ball-milling the mixture in a planetary ball mill at the rotating speed of 290rpm for 20h, taking out the obtained ball-milled product in an argon atmosphere glove box, marking as LALZO-LBH, and carrying out subsequent electrochemical performance test.
As shown in FIG. 9, the impedance (EIS) curve of the garnet-type composite electrolyte material (LALZO-LBH) of example 3, in which the curve is a semicircle in the high frequency region, the intersection of the right end of the semicircle and the solid axis represents the total resistance of the bulk phase and the inter-particle space, and in which the curve is a diagonal line in the low frequency region, reflects the ion blocking phenomenon, is known from the curve that Li of LALZO-LBH is present at 30 ℃+The conductivity can reach 1.1 x 10-5S/cm; and Li6.4Al0.2La3Zr2O12Li of (2)+The conductivity is only 4.5 multiplied by 10-9S/cm。
Examples 4 to 15
Examples 4 to 15 are garnet-type composite materials obtained by ball-milling different garnet-type oxides and different complex hydrides, and electrochemical properties thereof, respectively.
Basically the same as the method adopted in the above examples 1 to 3, only the relative mass of the added reactants and the ball milling preparation parameters (including the ball milling rotation speed, the ball milling time and the ball-to-material ratio) are adjusted to respectively obtain different garnet typesThe garnet composite electrolyte material is formed by compounding an oxide and different coordination hydrides; table 1 shows different garnet-type composite electrolyte materials prepared by the ball milling process and Li at 30 ℃ respectively+Conductivity, visible, garnet-type oxides and LiBH4、LiNH2、(LiBH4)mNH3、(LiBH4)nNH3BH3、NH3BH3At least one of them has high Li at 30 deg.C+Electrical conductivity.
TABLE 1 different composite electrolyte materials prepared by ball milling process and Li at 30 deg.C+Electrical conductivity of
As shown in Table 1, garnet-type composite electrolyte materials were prepared by mixing garnet-type oxides (A) doped with different elements with different complex hydrides (B) according to the above-mentioned preparation method, and Li was added to the garnet-type composite electrolyte materials at 30 deg.C+The conductivity is higher (-10)-5S/cm order of magnitude) far greater than Li of garnet-type oxide single phase obtained by the same preparation method+Conductivity (. about.10)-9Of the order of S/cm).
Claims (9)
1. The garnet-type composite electrolyte material is characterized in that the garnet-type composite electrolyte material is of a core-shell structure with a garnet-type oxide as an inner core and coordination hydride as an outer shell;
the complex hydride is LiBH4、LiNH2、(LiBH4)mNH3、(LiBH4)nNH3BH3And NH3BH3One of (1); wherein m is greater than or equal to 1/3 and less than or equal to 10, and n is greater than or equal to 1 and less than or equal to 10.
2. The garnet-type composite electrolyte material as set forth in claim 1, wherein the particle diameter of the garnet-type composite electrolyte material is in the range of 50nm to 10 μm.
3. The garnet-type composite electrolyte material as set forth in claim 1, wherein the garnet-type oxide has a molecular formula of LiαGα’La3-βMβZr2-γRγO12；
Wherein G is one of Al, Fe, Ga and Ge; m is one of Sr and Rb; r is one of Ta, Nb, Sb and Mo; alpha is 3-7; alpha' is 0-0.8; beta is 0-0.8; and gamma is 0-0.8.
4. The garnet-type composite electrolyte material as set forth in claim 1, wherein the ratio of the garnet-type oxide to the complex hydride is 1:0.05 to 40.
5. A method for producing a garnet-type composite electrolyte material according to any one of claims 1 to 4, comprising: under the protection of inert gas, the garnet-type oxide and the coordination hydride are subjected to oxidation-reduction reaction under the mechanical action to obtain the garnet-type composite electrolyte material.
6. The method of claim 5, wherein the mechanical action is planetary ball milling.
7. The method for preparing the garnet-type composite electrolyte material as set forth in claim 6, wherein the ratio of the mass of the grinding balls in the planetary ball mill to the total mass of the garnet-type oxide and the complex hydride is 20 to 120: 1.
8. the method for preparing the garnet-type composite electrolyte material as set forth in claim 6, wherein the planetary ball mill has a rotation speed of 200-600 rpm for 0.1-24 hours.
9. Use of the garnet-type composite electrolyte material according to any one of claims 1 to 4 in a lithium ion battery.
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| CN112290082B (en) * | 2020-10-28 | 2021-11-26 | 贵州梅岭电源有限公司 | Surface treatment method of garnet type solid electrolyte |
| CN113078350A (en) * | 2021-03-26 | 2021-07-06 | 光鼎铷业(广州)集团有限公司 | Preparation method of rubidium-doped high-conductivity LLZTO/PEO composite solid electrolyte |
| CN113097562B (en) * | 2021-04-13 | 2024-04-05 | 无锡新锂耀辉能源科技有限公司 | Lithium borohydride-garnet type oxide composite solid electrolyte material and preparation method and application thereof |
| CN113991171B (en) * | 2021-10-22 | 2023-03-24 | 浙江大学 | Garnet type multi-element composite solid electrolyte and preparation method and application thereof |
| CN114421002A (en) * | 2022-01-04 | 2022-04-29 | 浙江大学 | Garnet oxide/coordination boron nitrogen hydride composite solid electrolyte and preparation method and application thereof |
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