CN113912120A - Method for improving lithium lanthanum zirconium oxygen cubic phase stability - Google Patents

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

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CN113912120A
CN113912120A CN202111184124.6A CN202111184124A CN113912120A CN 113912120 A CN113912120 A CN 113912120A CN 202111184124 A CN202111184124 A CN 202111184124A CN 113912120 A CN113912120 A CN 113912120A
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郑兴华
王其竞
郭昊轩
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Fuzhou University
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Abstract

The invention discloses a method for improving the stability of a lithium lanthanum zirconium oxygen cubic phase, which adopts MoO3Substitution of Li7La3Zr2O12Middle part of ZrO2To obtain Li7‑2xLa3Zr2‑xMoxO12，0<x is less than or equal to 0.1. With Li7La3Zr2O12In contrast, Li7‑2xLa3Zr2‑xMoxO12The electrolyte sheet is not easy to generate impure phase, has high-purity garnet cubic phase, high ionic conductivity, simplified preparation process and good industrial production potential in the field of lithium ion batteries and medium and low temperature fuel cells.

Description

Method for improving lithium lanthanum zirconium oxygen cubic phase stability
Technical Field
The invention belongs to the technical field of lithium ion batteries and medium and low temperature fuel batteries, 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, and have been receiving wide 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. As most of organic electrolyte and gel polymer electrolyte are adopted, the electrolyte has the safety problems of poor electrochemical stability, flammability, explosiveness and the like, great attention of people to the safety performance of the lithium battery is attracted, and the use of the lithium ion battery is greatly limited due to the problems.
Compared with liquid electrolytes, solid electrolytes have the advantages of higher lithium ion conductivity, wider electrochemical window, good safety system, simplified design and the like, and attract the attention of researchers, wherein oxide inorganic solid electrolytes are novel materials with great application prospects and are suitable for the industries of new energy and lithium ion batteries, and CN112670561A, CN111916836A and CN109119573A improve the comprehensive performance of the batteries by coating electrode materials with powder, coating diaphragms with powder and the like, but still have limitations.
Li7La3Zr2O12(LLZO) is a relatively common garnet solid electrolyte having both tetragonal and cubic crystal structures with LaO backbones8Dodecahedron and ZrO6Octahedral constitution, differing by Li at the interstice+The arrangement is different. Li in cubic phase due to more lithium vacancies contained therein+Compared with the tetragonal phase, the phase is easier to migrate, so the cubic phase has the advantages of ion conductivity far higher than that of the tetragonal phase, high stability to Li, high energy density, wide electrochemical window and the like.
Although cubic phase garnet Li7La3Zr2O12The electrolyte has high ionic conductivity, but cubic phase Li7La3Zr2O12On the one hand, it is difficult to synthesize and is known in the literature (Ramaswamy Murugan, Venkataraman Thangdurai, Werner Weppner, Fast Lithium Ion reduction in Garnet-Type Li7La3Zr2O12Physical Inorganic Chemistry, doi: 10.1002/chi.200750009) reported that cubic phases could only be synthesized by sintering at 1230 ℃ for 6 hours; on the other hand, the garnet is easily transformed into a tetragonal phase at high temperature, so that the stability of the cubic phase of the garnet is improved and the simple synthesis becomes a hot spot and a focus of academic and engineering circles.
By reaction with Li7La3Zr2O12The doping of elements with similar Li, Zr and La ions is an important strategy for improving the stability of cubic phase, and the replacement or doping ions can generate charge compensation vacancies or gaps, reduce or increase the oxygen chemical balance while maintaining the oxygen chemical balanceThe cubic phase is stabilized by adding a concentration of Li vacancies. CN105742699A prepared cubic garnet LLZ ceramic by using lithium hydroxide, lanthanum hydroxide, zirconia and alumina as raw materials, but XRD still has obvious mixed phases, which greatly limits the application. CN109301315A provides a solid electrolyte powder and a preparation method thereof, although the granularity is reduced by ball milling after sintering, and the electrolyte powder with the granularity in the micro-nano grade is obtained by heat treatment in inert gas, the electrolyte powder is not a cubic phase pure phase, and has a certain impurity phase, thereby limiting the application thereof. Research progress in literature (Jianpengfeng, Shiyuan, Likanwan, et al. solid electrolyte Lithium Lanthanum Zirconium Oxygen (LLZO) [ J]Energy storage science and technology 2020, 9(46):217-2、H2The O reaction reduces 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, wherein a garnet-based LLZO-based solid electrolyte is prepared by a Mo-doped 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 purpose, the invention adopts the following technical scheme:
a method for improving the stability of a lithium lanthanum zirconium oxygen cubic phase comprises the following steps: by using MoO3Substitution of Li7La3Zr2O12Middle part of ZrO2To obtain Li7-2xLa3Zr2-xMoxO12，0<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 10h, drying and sieving;
(3) maintaining the pressure at 100MPa for 1-3min, calcining at 1100 ℃ for 2h, and cooling to obtain Li7-2xLa3Zr2-xMoxO12，0<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 calcined for 2 hours at 900 ℃.
The ball milling speed was 380 rpm.
The invention has the beneficial effects that:
(1) with MoO3As a doping source, the material is low in price, and the sintering temperature is reduced, so that the cost is greatly reduced;
(2) the LLZO-based electrolyte prepared by doping a small amount of Mo has more stable cubic phase and is not easy to generate impurity phase, the temperature range of the stable phase of the cubic phase is widened, and the production conditions of the garnet solid electrolyte are optimized.
Drawings
Fig. 1 is an XRD pattern of the solid electrolyte sheet obtained in examples 1-3.
FIG. 2 shows Li obtained in example 36.8La3Zr1.9Mo0.1O12SEM image of solid electrolyte sheet.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Mixing Li2CO3、La2O3、ZrO2Weighing according to a stoichiometric ratio, adding absolute ethyl alcohol, ball-milling for 10h at the rotating speed of 380rpm, drying the ball-milled slurry, and presintering for 2h at 900 ℃ in the air to obtain a precursor;
(2) performing ball milling on the precursor again under the same conditions as the step (1), drying after the ball milling is finished, grinding and sieving the obtained powder, and selecting a screen of 60 meshes to obtain corresponding powder;
(3) weighing the powder, maintaining the pressure for 3min at 100MPa, and calcining for 2h at 1200 ℃; cooling to room temperature along with the furnace to prepare the Li7La3Zr2O12An electrolyte sheet having a distinct tetragonal heterogeneous phase;
(4) XRD and FSEM tests are carried out on the electrolyte sheet, and Li is tested by gold spraying7La3Zr2O12A solid electrolyte sheet with an alternating impedance of 100Hz to 1 MHz.
Example 2
This example prepares Li according to the following procedure6.9La3Zr1.95Mo0.05O12Electrolyte sheet 2:
(1) mixing Li2CO3、La2O3、ZrO2And MoO3Weighing according to a stoichiometric ratio, adding absolute ethyl alcohol, ball-milling for 10h at the rotating speed of 380rpm, drying the ball-milled slurry, and presintering for 2h at 900 ℃ in the air to obtain a precursor;
(2) performing ball milling on the precursor again under the same conditions as those in the step (1), drying after the ball milling is finished, grinding and sieving the obtained powder, and selecting a screen of 60 meshes to obtain powder 2;
(3) weighing the powder, maintaining the pressure for 3min under 100MPa, and calcining for 2h at 1100 ℃; cooling to room temperature along with the furnace, and preparing to obtain garnet cubic phase pure phase Li6.9La3Zr1.95Mo0.05O12An electrolyte sheet;
(4) XRD and FSEM tests are carried out on the electrolyte sheet, and Li is tested by gold spraying6.9La3Zr1.95Mo0.05O12A solid electrolyte sheet with an alternating impedance of 100Hz to 1 MHz.
Example 3
This example prepares Li according to the following procedure6.8La3Zr1.9Mo0.1O12Electrolyte sheet 3:
(1) mixing Li2CO3、La2O3、ZrO2And MoO3Weighing according to a stoichiometric ratio, adding absolute ethyl alcohol, ball-milling for 10h at the rotating speed of 380rpm, drying the ball-milled slurry, and presintering for 2h at 900 ℃ in the air to obtain a precursor;
(2) performing ball milling on the obtained precursor again under the same conditions as the step (1), drying after the ball milling is finished, grinding and sieving the obtained powder, and selecting a screen of 60 meshes to obtain powder 3;
(3) weighing the powder, maintaining the pressure for 3min under 100MPa, and calcining for 2h at 1150 ℃; cooling to room temperature along with the furnace, and preparing to obtain garnet cubic phase pure phase Li6.8La3Zr1.9Mo0.1O12An electrolyte sheet;
(4) XRD and FSEM tests are carried out on the electrolyte sheet, and Li is tested by gold spraying6.8La3Zr1.9Mo0.1O12A solid electrolyte sheet with an alternating impedance of 100Hz to 1 MHz.
Fig. 1 is an XRD pattern of the solid electrolyte sheet obtained in examples 1-3. It can be seen that the cubic phase of example 1 is impure and there are more hetero-peaks; in the embodiment 2, with the introduction of the doped Mo element, the impurity peak disappears and is converted into a pure cubic phase; in example 3, the content of doped Mo is further increased, and the diffraction peak corresponding to the cube is more significant.
FIG. 2 shows Li obtained in example 36.8La3Zr1.9Mo0.1O12SEM image of solid electrolyte sheet. It can be seen that Mo is doped, so that the particles become more uniform and compact, and the ionic conductivity is favorably improved.
Figure DEST_PATH_IMAGE001
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (5)

1. A method for improving the stability of lithium lanthanum zirconium oxygen cubic phase is characterized in that: by using MoO3Substitution of Li7La3Zr2O12Middle part of ZrO2To obtain Li7-2xLa3Zr2-xMoxO12，0<x≤0.1。
2. The method of claim 1, wherein: 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 10h, drying and sieving;
(3) maintaining the pressure at 100MPa for 1-3min, calcining at 1100 ℃ for 2h, and cooling to obtain Li7-2xLa3Zr2-xMoxO12，0<x≤0.1。
3. The method of claim 2, wherein: 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.
4. The method of claim 3, wherein: the lanthanum oxide is calcined for 2 hours at 900 ℃.
5. The method of claim 2, wherein: the ball milling speed was 380 rpm.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105489929A (en) * 2015-11-24 2016-04-13 青岛能迅新能源科技有限公司 Method for coating through all-solid-state lithium-ion electrolyte material Li<7>La<3>Zr<2>O<12>
US20160133990A1 (en) * 2014-11-11 2016-05-12 Purdue Research Foundation Solid-state electrolytes and batteries made therefrom, and methods of making solid-state electrolytes
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
US20170104245A1 (en) * 2015-10-08 2017-04-13 Toyota Jidosha Kabushiki Kaisha All solid state battery
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
CN110444805A (en) * 2019-07-08 2019-11-12 电子科技大学 A kind of the cubic phase Garnet-type solid electrolyte material and its synthetic method of Er ions
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160133990A1 (en) * 2014-11-11 2016-05-12 Purdue Research Foundation Solid-state electrolytes and batteries made therefrom, and methods of making solid-state electrolytes
US20170104245A1 (en) * 2015-10-08 2017-04-13 Toyota Jidosha Kabushiki Kaisha All solid state battery
CN105489929A (en) * 2015-11-24 2016-04-13 青岛能迅新能源科技有限公司 Method for coating through all-solid-state lithium-ion electrolyte material Li<7>La<3>Zr<2>O<12>
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
CN110444805A (en) * 2019-07-08 2019-11-12 电子科技大学 A kind of the cubic phase Garnet-type solid electrolyte material and its synthetic method of Er ions
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DANIEL RETTENWANDER: "Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7−2xLa3Zr2−xMoxO12 (x = 0.1−0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+" *
PATRICK BOTTKE: "Ion Dynamics in Solid Electrolytes: NMR Reveals the Elementary Steps of Li+ Hopping in the Garnet Li6.5La3Zr1.75Mo0.25O12", CHEM. MATER *

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