CN113912120B - Method for improving stability of lithium lanthanum zirconium oxygen cubic phase - Google Patents

Method for improving stability of lithium lanthanum zirconium oxygen cubic phase Download PDF

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CN113912120B
CN113912120B CN202111184124.6A CN202111184124A CN113912120B CN 113912120 B CN113912120 B CN 113912120B CN 202111184124 A CN202111184124 A CN 202111184124A CN 113912120 B CN113912120 B CN 113912120B
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郑兴华
王其竞
郭昊轩
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
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    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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Abstract

The invention discloses a method for improving the stability of a lithium lanthanum zirconium oxygen cubic phase, which adopts MoO 3 Substitution of Li 7 La 3 Zr 2 O 12 Middle part ZrO 2 Li is prepared 7‑2x La 3 Zr 2‑x Mo x O 12 ，0<x is less than or equal to 0.1. With Li 7 La 3 Zr 2 O 12 In comparison with Li 7‑2x La 3 Zr 2‑x Mo x O 12 The electrolyte sheet is not easy to generate impurity phase, has garnet cubic phase with high purity, has high ion conductivity, simplifies the preparation process, and has good industrial production potential in the field of lithium ion batteries and medium-low temperature fuel cells.

Description

Method for improving stability of lithium lanthanum zirconium oxygen cubic phase
Technical Field
The invention belongs to the technical field of lithium ion batteries and medium-low temperature fuel cells, and particularly relates to a method for improving the stability of a lithium lanthanum zirconium oxygen cubic phase.
Background
In recent years, lithium ion batteries have been rapidly developed, which have been receiving a great deal of attention due to their high specific energy density, and have been used in various fields such as portable mobile devices, electric vehicles, energy storage power stations, and the like. Because organic electrolyte and gel polymer electrolyte are mostly adopted, the problems of poor electrochemical stability, inflammability, explosiveness and the like of the electrolyte are caused, and great attention is given to the safety performance of lithium batteries by people, and the problems also limit the use of lithium ion batteries greatly.
Compared with the liquid electrolyte, the solid electrolyte has the advantages of higher lithium ion conductivity, wider electrochemical window, good safety system, simplified design and the like, attracts attention of researchers, wherein the oxide inorganic solid electrolyte is a novel material with great application prospect, is suitable for new energy and lithium ion battery industries, and is used for improving the comprehensive performance of batteries by coating electrode materials with powder, coating a diaphragm with powder and the like, but has limitations.
Li 7 La 3 Zr 2 O 12 (LLZO) is a relatively common electrolyte of guava Dan Gutai, which has both tetragonal and cubic crystal structures,both frameworks are LaO 8 Dodecahedron and ZrO 6 Octahedral composition, differing in Li at the gaps + The arrangement modes are different. Li in the cubic phase due to the inclusion of more lithium vacancies in the cubic phase + Compared with tetragonal phase, the cubic phase has the advantages of much higher ionic conductivity, high stability to Li, high energy density, wide electrochemical window and the like.
Although cubic garnet Li 7 La 3 Zr 2 O 12 The electrolyte has high ionic conductivity but cubic phase Li 7 La 3 Zr 2 O 12 On the one hand, difficult to synthesize, literature (Ramaswamy Murugan, venkataraman Thangadurai, werner Weppner, fast Lithium Ion Conduction in Garnet-Type Li 7 La 3 Zr 2 O 12 Physical Inorganic Chemistry, doi: 10.1002/chip.200750009) reported that a cubic phase could be synthesized only by sintering at 1230℃for 6 hours; on the other hand, the garnet cubic phase is easy to be transformed into a tetragonal phase at high temperature, so that the stability of the garnet cubic phase is improved, and the simple synthesis becomes a hot spot and focus in academia and engineering world.
By combining with Li 7 La 3 Zr 2 O 12 Elemental doping with close Li, zr, la ion radii is an important strategy to improve cubic phase stability, replacing or doping ions can create charge-compensated vacancies or interstitials, reducing or increasing Li vacancy concentration while maintaining oxygen chemical equilibrium to stabilize the cubic phase. CN105742699a adopts lithium hydroxide, lanthanum hydroxide, zirconium oxide and aluminum oxide as raw materials to prepare cubic garnet LLZ ceramic, but XRD still has obvious impurity phase, which limits its application to a great extent. CN109301315a shows a solid electrolyte powder and a preparation method thereof, although ball milling after sintering reduces granularity, and heat treatment is performed in inert gas, an electrolyte powder with granularity in micro-nano level is obtained, but the electrolyte powder is not a cubic pure phase, and has certain impurity phase, which limits the application thereof. Document (Jiang Pengfeng, dan Yuancheng, li Kangmo, et al, progress of research on solid electrolyte Lithium Lanthanum Zirconium Oxide (LLZO) [ J)]Energy storage science and technology 2020, 9 (46): 217-231.) also indicates garnetThe solid electrolyte cubic phase has narrower stable temperature and is easy to be matched with CO in the air 2 、H 2 O reacts, reducing the cubic phase stability.
Disclosure of Invention
The invention aims to provide a method for improving the stability of a lithium lanthanum zirconium oxygen cubic phase, which is characterized in that a garnet LLZO-based solid electrolyte is prepared by a Mo doping traditional sintering method, so that the sintering temperature is obviously reduced, the production cost is reduced, the stability of the garnet cubic phase is improved, and the ionic conductivity of the garnet cubic phase is improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for improving the stability of a lithium lanthanum zirconium oxygen cubic phase, which comprises the following steps: by MoO 3 Substitution of Li 7 La 3 Zr 2 O 12 Middle part ZrO 2 Li is prepared 7-2x La 3 Zr 2-x Mo x O 12 ，0<x is less than or equal to 0.1. The method comprises the following steps:
(1) Mixing a lithium source, a lanthanum source, a zirconium source and a molybdenum source, adding absolute ethyl alcohol, ball milling for 10 hours, drying, and presintering for 2 hours at 900 ℃;
(2) Adding absolute ethyl alcohol again, ball milling for 10 hours, drying and sieving;
(3) Maintaining the pressure at 100MPa for 1-3min, calcining at 1100 ℃ for 2h, and cooling to obtain Li 7-2x La 3 Zr 2-x Mo x O 12 ，0<x≤0.1。
The lithium source is lithium carbonate, the zirconium source is zirconium dioxide, the lanthanum source is lanthanum oxide, and the molybdenum source is molybdenum trioxide.
The lanthanum oxide is pretreated and calcined at 900 ℃ for 2 hours.
The ball milling speed was 380rpm.
The invention has the beneficial effects that:
(1) In MoO 3 As a doping source, the cost is low, the sintering temperature is reduced, and the cost is greatly reduced;
(2) LLZO-based electrolyte prepared by doping a small amount of Mo has more stable cubic phase, is not easy to generate mixed phase, widens the temperature interval of the stable cubic phase, and optimizes the production condition of the electrolyte of the pomegranate Dan Gutai.
Drawings
FIG. 1 is an XRD pattern of the solid electrolyte sheets prepared in examples 1 to 3.
FIG. 2 is Li produced in example 3 6.8 La 3 Zr 1.9 Mo 0.1 O 12 SEM image of solid electrolyte sheet.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Li is mixed with 2 CO 3 、La 2 O 3 、ZrO 2 Weighing according to a stoichiometric ratio, adding absolute ethyl alcohol, ball milling for 10 hours at a rotating speed of 380rpm, drying the ball-milled slurry, and presintering in air at 900 ℃ for 2 hours to obtain a precursor;
(2) Ball milling the precursor again under the same conditions as in the step (1), drying after ball milling, grinding and sieving the obtained powder, and selecting a screen with 60 meshes to obtain corresponding powder;
(3) Weighing powder, maintaining the pressure at 100MPa for 3min, and calcining at 1200 ℃ for 2h; cooling to room temperature along with the furnace to prepare Li 7 La 3 Zr 2 O 12 An electrolyte sheet having a distinct tetragonal phase of miscibility;
(4) XRD and FSEM tests were performed on electrolyte sheets, and the gold spraying test was performed on Li 7 La 3 Zr 2 O 12 The solid electrolyte sheet has an alternating current impedance of 100Hz-1 MHz.
Example 2
This example prepares Li according to the following procedure 6.9 La 3 Zr 1.95 Mo 0.05 O 12 Electrolyte sheet 2:
(1) Li is mixed with 2 CO 3 、La 2 O 3 、ZrO 2 MoO (MoO) 3 Weighing according to stoichiometric ratio, adding absolute ethyl alcohol, ball-milling for 10h at 380rpm, drying the ball-milled slurry, presintering in air at 900 ℃ for 2h to obtainTo the precursor;
(2) Ball milling the precursor again under the same conditions as in the step (1), drying after ball milling, grinding and sieving the obtained powder, and selecting a screen with 60 meshes to obtain powder 2;
(3) Weighing powder, maintaining the pressure at 100MPa for 3min, and calcining at 1100 ℃ for 2h; cooling to room temperature along with the furnace to prepare garnet cubic phase pure phase Li 6.9 La 3 Zr 1.95 Mo 0.05 O 12 An electrolyte sheet;
(4) XRD and FSEM tests were performed on electrolyte sheets, and the gold spraying test was performed on Li 6.9 La 3 Zr 1.95 Mo 0.05 O 12 The solid electrolyte sheet has an alternating current impedance of 100Hz-1 MHz.
Example 3
This example prepares Li according to the following procedure 6.8 La 3 Zr 1.9 Mo 0.1 O 12 Electrolyte sheet 3:
(1) Li is mixed with 2 CO 3 、La 2 O 3 、ZrO 2 MoO (MoO) 3 Weighing according to a stoichiometric ratio, adding absolute ethyl alcohol, ball milling for 10 hours at a rotating speed of 380rpm, drying the ball-milled slurry, and presintering in air at 900 ℃ for 2 hours to obtain a precursor;
(2) Ball milling is carried out on the obtained precursor again, the conditions are the same as those of the step (1), drying is carried out after ball milling is finished, grinding and sieving are carried out on the obtained powder, and 60 meshes of screen mesh are selected to obtain powder 3;
(3) Weighing powder, maintaining the pressure at 100MPa for 3min, and calcining at 1150 ℃ for 2h; cooling to room temperature along with the furnace to prepare garnet cubic phase pure phase Li 6.8 La 3 Zr 1.9 Mo 0.1 O 12 An electrolyte sheet;
(4) XRD and FSEM tests were performed on electrolyte sheets, and the gold spraying test was performed on Li 6.8 La 3 Zr 1.9 Mo 0.1 O 12 The solid electrolyte sheet has an alternating current impedance of 100Hz-1 MHz.
FIG. 1 is an XRD pattern of the solid electrolyte sheets prepared in examples 1 to 3. It can be seen that the cubic phase of example 1 is not pure and there are more peaks; in example 2, with the introduction of Mo doped element, the impurity peak disappears and the pure cubic phase is converted; in example 3, the Mo content was further increased, and the diffraction peak corresponding to the cube was more remarkable.
FIG. 2 is Li produced in example 3 6.8 La 3 Zr 1.9 Mo 0.1 O 12 SEM image of solid electrolyte sheet. It can be seen that the Mo doping makes the particles more uniform and dense, which is beneficial to improving the ionic conductivity.
Figure DEST_PATH_IMAGE001
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (3)

1. A method for improving the stability of lithium lanthanum zirconium oxygen cubic phase is characterized by comprising the following steps: by MoO 3 Substitution of Li 7 La 3 Zr 2 O 12 Middle part ZrO 2 Li is prepared 7-2x La 3 Zr 2-x Mo x O 12 ，0<x is less than or equal to 0.1; the method comprises the following steps:
(1) Mixing a lithium source, a lanthanum source, a zirconium source and a molybdenum source, adding absolute ethyl alcohol, ball milling for 10 hours, drying, and presintering for 2 hours at 900 ℃;
(2) Adding absolute ethyl alcohol again, ball milling for 10 hours, drying and sieving; the ball milling rotating speed is 380rpm;
(3) Maintaining the pressure at 100MPa for 1-3min, calcining at 1100 ℃ for 2h, and cooling to obtain Li 7-2x La 3 Zr 2-x Mo x O 12 ，0<x≤0.1。
2. The method according to claim 1, characterized in that: the lithium source is lithium carbonate, the zirconium source is zirconium dioxide, the lanthanum source is lanthanum oxide, and the molybdenum source is molybdenum trioxide.
3. The method according to claim 2, characterized in that: the lanthanum oxide is pretreated and calcined at 900 ℃ for 2 hours.
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CN111732432A (en) * 2020-06-30 2020-10-02 上海国瓷新材料技术有限公司 Spherical lithium lanthanum zirconium oxygen powder material and composite solid electrolyte prepared from same

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CN105932327A (en) * 2016-05-16 2016-09-07 北京科技大学 Preparation method for cubic-phase lithium lanthanum zirconium oxide solid-state electrolyte nano material
CN107746206A (en) * 2017-10-31 2018-03-02 福州大学 A kind of High-energy-storage density dielectric material and preparation method thereof
CN108832173A (en) * 2018-06-27 2018-11-16 东北大学 Gallium and the carbuncle type lithium ion solid electrolyte of molybdenum codope and preparation method thereof
CN111732432A (en) * 2020-06-30 2020-10-02 上海国瓷新材料技术有限公司 Spherical lithium lanthanum zirconium oxygen powder material and composite solid electrolyte prepared from same

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