CN116231053A - Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof - Google Patents

Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof Download PDF

Info

Publication number
CN116231053A
CN116231053A CN202310273634.3A CN202310273634A CN116231053A CN 116231053 A CN116231053 A CN 116231053A CN 202310273634 A CN202310273634 A CN 202310273634A CN 116231053 A CN116231053 A CN 116231053A
Authority
CN
China
Prior art keywords
powder
solid electrolyte
llzo
ball milling
drying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310273634.3A
Other languages
Chinese (zh)
Inventor
何鹏
路富刚
王策
林盼盼
林铁松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN202310273634.3A priority Critical patent/CN116231053A/en
Publication of CN116231053A publication Critical patent/CN116231053A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Conductive Materials (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides a Ga-LLZO solid electrolyte and a method for inhibiting abnormal growth of crystal grains thereof, and relates to the technical field of lithium batteries, wherein the method for inhibiting abnormal growth of crystal grains of the Ga-LLZO solid electrolyte comprises the following steps: by Li 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 Obtaining LLYZO powder; by Li 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 Obtaining Ga-LLZO powder; mixing the LLYZO powder and the Ga-LLZO powder, and performing ball milling and drying to obtain composite mother powder; and (3) performing pressure forming on the composite mother powder to form a lamellar structure, calcining, cooling to room temperature to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains, and avoiding the phenomenon of abnormal growth of the crystal grains.

Description

Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a Ga-LLZO solid electrolyte and a method for inhibiting abnormal growth of crystal grains thereof.
Background
The conventional lithium ion battery is approaching the energy limit, and the safety of the conventional lithium ion battery in the related application field of the power battery is questioned because the liquid organic electrolyte is adopted and has the risk of inflammability and explosiveness. The all-solid-state lithium battery adopts the solid electrolyte and the lithium metal cathode, has higher energy density and higher safety, and replaces the traditional lithium ion battery to become a future development trend.
The solid electrolyte is required to have a combination of excellent properties as a core component of an all-solid lithium battery. In recent years, ceramic electrolytes having garnet structures have excellent chemical stability and ion conductivity, and are outstanding among many types of electrolytes. Elemental doping is an important modification means of garnet-type LLZO electrolyte, wherein Ga-doped LLZO electrolyte exhibits the highest lithium ion conductivity, however, it has the problem of abnormal growth of crystal grains, resulting in brittleness of Ga-LLZO electrolyte, which limits its application in lithium batteries.
Disclosure of Invention
The invention solves the problems that Ga doped LLZO electrolyte in the prior art has high lithium ion conductivity, but the crystal grains are abnormal and coarse, the crystal grain quality is poor, and the application of the Ga doped LLZO electrolyte in lithium batteries is limited.
In order to solve the problems, the invention provides a method for inhibiting abnormal growth of Ga-LLZO solid electrolyte grains, which comprises the following steps:
step S1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 According to chemical formula Li 7 La 2.7 Yb 0.3 Zr 2 O 12 Weighing the molar ratio, performing primary ball milling and drying to obtain first premixed powder, and performing calcination, secondary ball milling and drying on the first premixed powder to obtain LLYZO powder;
step S2, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Weighing the molar ratio, performing primary ball milling and drying to obtain second premixed powder, and performing calcination, secondary ball milling and drying on the second premixed powder to obtain Ga-LLZO powder;
step S3, mixing the LLYZO powder and the Ga-LLZO powder, and ball-milling and drying to obtain composite mother powder;
and S4, performing pressure forming on the composite mother powder to form a lamellar structure, and cooling to room temperature after calcination treatment to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains.
Preferably, in step S3, the mass fraction of the LLYZO powder in the composite mother powder is 40% -50%.
Preferably, in step S1 and step S2, the primary ball milling process includes: grinding aid is added into the ball mill, and ball milling is carried out for 22-26 hours at the speed of 60-80 r/min.
Preferably, the grinding aid comprises isopropanol and zirconia.
Preferably, the secondary ball milling in step S1 and step S2 and the ball milling in step S3 include: and ball milling is carried out in a ball milling tank at a speed of 450-550r/min for 10-14h.
Preferably, in step S1, step S2 and step S3, the drying process includes: drying at 55-65deg.C for 5-7 hr.
Preferably, in step S1, the calcining includes: calcining the first premixed powder at 850-950 ℃ for 5-7 hours, heating to 1220-1240 ℃ and preserving heat for 0.4-0.6 hours, and cooling to room temperature at a speed of 4-5 ℃/min.
Preferably, in step S4, the press molding of the composite mother powder into a laminated structure includes: and forming the composite master batch into a laminated structure with the diameter of 12-14mm under the pressure of 180-220 MPa.
Preferably, in step S4, the calcining process includes: calcining at 980-1020 deg.C for 10-14 hr, at 1030-1070 deg.C for 16-120 hr, and at 1090-1130 deg.C for 22-26 hr.
The invention is thatCompared with the prior art, the method for inhibiting the abnormal growth of the Ga-LLZO solid electrolyte crystal grains has the advantages that the second phase LiYbO can be introduced by compounding LLYZO powder and the Ga-LLZO powder 2 The migration of grain boundaries of the Ga-LLZO solid electrolyte in the firing process is inhibited, so that the growth of crystal grains is inhibited, the Ga-LLZO solid electrolyte with fine and uniformly distributed crystal grains is finally obtained, the mechanical properties of the Ga-LLZO solid electrolyte are improved, and the LLYZO powder and the Ga-LLZO powder are simple in preparation method.
In order to solve the technical problems, the invention also provides the Ga-LLZO solid electrolyte, which is prepared by the method for inhibiting abnormal growth of the Ga-LLZO solid electrolyte crystal grains.
The Ga-LLZO solid electrolyte provided by the invention has finer grains and use strength, and is beneficial to practical application of the Ga-LLZO solid electrolyte.
Drawings
FIG. 1 is a flow chart of a method for inhibiting abnormal grain growth of Ga-LLZO solid electrolyte according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of Ga-LLZO solid electrolyte in an embodiment of the present invention;
FIG. 3 is a photograph of a fracture scanning electron microscope of a Ga-LLZO ceramic electrolyte in a comparative example of the present invention;
fig. 4 is a fracture scanning electron micrograph of a Ga-LLZO solid electrolyte in an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and thoroughly described below with reference to the accompanying drawings.
In the description of embodiments of the present application, the term "description of some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same implementations or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
As shown in fig. 1, an embodiment of the present invention provides a method for inhibiting abnormal grain growth of a Ga-LLZO solid electrolyte, which is characterized by comprising the steps of:
step S1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 According to chemical formula Li 7 La 2.7 Yb 0.3 Zr 2 O 12 Weighing the molar ratio, performing primary ball milling and drying to obtain first premixed powder, and performing calcination, secondary ball milling and drying on the first premixed powder to obtain LLYZO powder;
step S2, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Weighing the molar ratio, performing primary ball milling and drying to obtain second premixed powder, and performing calcination, secondary ball milling and drying on the second premixed powder to obtain Ga-LLZO powder;
step S3, mixing the LLYZO powder and the Ga-LLZO powder, and ball-milling and drying to obtain composite mother powder;
and S4, performing pressure forming on the composite mother powder to form a lamellar structure, and cooling to room temperature after calcination treatment to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains.
In this example, in order to compensate for the loss of Li in the preparation of the electrolyte, li is generally allowed to be slightly excessive. Specifically, this example Li 2 CO 3 The excessive amount is 15wt.%, so that the loss of Li can be compensated and the raw materials can be saved.
In some preferred embodiments, in step S3, the mass fraction of the LLYZO powder in the composite mother powder is 40% -50%, which does not affect the conductivity of the lithium battery, and can inhibit the abnormal growth of grains of the Ga-LLZO solid electrolyte during the firing process.
In some preferred embodiments, in step S1 and step S2, the one ball milling process includes: grinding aid is added into the ball mill, and ball milling is carried out for 22-26 hours at the speed of 60-80 r/min. Therefore, the raw materials are uniformly mixed, and the addition of the grinding aid can prevent particle agglomeration and improve the fluidity of the materials, so that the ball milling efficiency is improved and the milling time is shortened.
In some preferred embodiments, the grinding aid comprises isopropyl alcohol and zirconia. The materials are easy to obtain.
In some preferred embodiments, the secondary ball milling in step S1 and step S2 and the ball milling in step S3 include: in a ball milling tank, planetary ball milling is carried out for 10-14 hours at the speed of 450-550r/min, and the mixing is more uniform. Thus, the mixing is more uniform and finer.
In some preferred embodiments, in step S1, step S2 and step S3, the drying process includes: drying at 55-65deg.C for 5-7 hr. Thereby, the isopropanol in the grinding aid is completely volatilized.
In some preferred embodiments, in step S1, the calcining process comprises: calcining the first premixed powder at 850-950 ℃ for 5-7 hours, heating to 1220-1240 ℃ and preserving heat for 0.4-0.6 hours, and cooling to room temperature at a speed of 4-5 ℃/min. In the step S2, the calcination process only needs to calcine the first premixed powder for 5-7 hours at the temperature of 850-950 ℃. This is because Ga-LLZO powder Ga during sintering + Will enter [ La ] 3 Zr 2 O 12 ] 7- Li position in the skeleton can reduce sintering temperature after sintering into pure phase, so that sintering can be carried out at 850-950 ℃, while LLYZO powder is Yb during sintering 3+ Will enter [ La ] 3 Zr 2 O 12 ] 7- La or Zr in the framework is not obvious in effect of reducing sintering temperature after being sintered into pure phase, so that the pure phase can be obtained after calcining for 5-7 hours at 850-950 ℃, and then heating to 1220-1240 ℃ and preserving heat for 0.4-0.6 hours.
In some preferred embodiments, in step S4, press molding the composite master batch into a laminate structure includes: and forming the composite master batch into a laminated structure with the diameter of 12-14mm under the pressure of 180-220 MPa. The molding effect is good.
In some preferred embodiments, in step S4, the calcining process includes: calcining at 980-1020 deg.C for 10-14 hr, at 1030-1070 deg.C for 16-120 hr, and at 1090-1130 deg.C for 22-26 hr.
In this embodiment, the second phase LiYbO can be introduced by compounding LLYZO powder with the Ga-LLZO powder 2 The migration of grain boundaries of the Ga-LLZO solid electrolyte in the firing process is inhibited, so that the growth of crystal grains is inhibited, the Ga-LLZO solid electrolyte with fine and uniformly distributed crystal grains is finally obtained, the mechanical properties of the Ga-LLZO solid electrolyte are improved, and the LLYZO powder and the Ga-LLZO powder are simple in preparation method.
Another embodiment of the present invention also provides a Ga-LLZO solid electrolyte prepared by the method of inhibiting abnormal growth of crystal grains of a Ga-LLZO solid electrolyte.
The Ga-LLZO solid electrolyte disclosed in the embodiment has finer grains and use strength, and is beneficial to practical application of the Ga-LLZO solid electrolyte.
Example 1
The embodiment provides a method for inhibiting abnormal growth of Ga-LLZO solid electrolyte grains, comprising the following steps:
step 1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 According to chemical formula Li 7 La 2.7 Yb 0.3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling at a speed of 70r/min for 24 hours to obtain first mixed slurry, drying the first mixed slurry in an oven at 60 ℃ to obtain first premixed powder, calcining the first premixed powder at 900 ℃ for 6 hours, heating to 1230 ℃ for 0.5 hours, cooling to room temperature at a speed of 5 ℃/min to obtain LLYZO coarse powder, placing the LLYZO coarse powder, the isopropanol and the agate grinding balls in a ball milling tank, performing planetary ball milling at a speed of 500r/min for 12 hours, and drying at 60 ℃ to obtain LLYZO powder with fine and uniform granularity;
step 2, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling at a speed of 70r/min for 24 hours to obtain second mixed slurry, drying the second mixed slurry in an oven at 60 ℃ to obtain second premixed powder, calcining the second premixed powder at 900 ℃ for 6 hours, cooling to room temperature to obtain Ga-LLZO coarse powder, placing the Ga-LLZO coarse powder, the isopropanol and the agate grinding balls in a ball milling tank, performing planetary ball milling at a speed of 500r/min for 12 hours, and drying at 60 ℃ to obtain Ga-LLZO powder with fine and uniform granularity;
step 3, mixing the LLYZO powder and the Ga-LLZO powder to obtain premixed powder, placing the premixed powder, isopropanol and agate grinding balls into a ball milling tank, performing planetary ball milling for 12 hours at a speed of 500r/min, and drying at 60 ℃ to obtain composite mother powder with fine granularity and uniform mixing, wherein the mass fraction of the LLYZO powder in the composite mother powder is 45%;
and 4, pressing the composite mother powder into a thin wafer with the diameter of 13mm at the pressure of 200MPa, calcining in a muffle furnace, and naturally cooling to room temperature to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains.
As can be seen from FIG. 2 and FIG. 4, the XRD pattern and the fracture scanning electron microscope photograph of the Ga-LLZO solid electrolyte obtained in the present example show that the main phase of the Ga-LLZO solid electrolyte ceramic is c-LLZO and LiYbO is present 2 A second phase; as can be seen from fig. 4, the ceramic grains are fine and uniform, the grain combination is relatively compact, the average grain diameter is 2-5 microns, the abnormal growth phenomenon of the grains does not exist, and the fracture mode is through-grain and along-grain composite fracture, which indicates that the ceramic has good mechanical properties.
Comparative example
The preparation method of the Ga-LLZO solid electrolyte provided in the embodiment is different from that of the embodiment 1 only in that the raw material is Ga-LLZO powder only, and comprises the following steps:
step 1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling at a speed of 70r/min for 24 hours to obtain second mixed slurry, drying the second mixed slurry in an oven at 60 ℃ to obtain second premixed powder, calcining the second premixed powder at 900 ℃ for 6 hours, cooling to room temperature to obtain Ga-LLZO coarse powder, placing the Ga-LLZO coarse powder, the isopropanol and the agate grinding balls in a ball milling tank, performing planetary ball milling at a speed of 500r/min for 12 hours, and drying at 60 ℃ to obtain Ga-LLZO powder with fine and uniform granularity;
and 2, pressing the Ga-LLZO powder into a thin wafer with the diameter of 13mm at the pressure of 200MPa, calcining in a muffle furnace, and naturally cooling to room temperature to obtain the Ga-LLZO solid electrolyte.
As shown in fig. 3, it can be seen from fig. 3 that the Ga-LLZO solid electrolyte obtained in this comparative example has a crystal grain of millimeter scale, and the crystal grain is porous and loose, and has a phenomenon of abnormal growth.
Example 2
The embodiment provides a method for inhibiting abnormal growth of Ga-LLZO solid electrolyte grains, comprising the following steps:
step 1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 According to chemical formula Li 7 La 2.7 Yb 0.3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling for 26 hours at the speed of 60r/min to obtain first mixed slurry, putting the first mixed slurry into an oven for drying at 55 ℃ to obtain first premixed powder, and putting the first premixed powder into a condition of 850 DEG CCalcining for 7 hours, heating to 1220 ℃, preserving heat for 0.6 hours, cooling to room temperature at a speed of 4 ℃/min to obtain LLYZO coarse powder, placing the LLYZO coarse powder, isopropanol and agate grinding balls into a ball milling tank, performing planetary ball milling at a speed of 450r/min for 14 hours, and drying at 55 ℃ to obtain LLYZO powder with fine and uniform granularity;
step 2, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling at a speed of 60r/min for 26 hours to obtain second mixed slurry, drying the second mixed slurry in an oven at 55 ℃ to obtain second premixed powder, calcining the second premixed powder at 850 ℃ for 7 hours, cooling to room temperature to obtain Ga-LLZO coarse powder, placing the Ga-LLZO coarse powder, the isopropanol and the agate grinding balls in a ball milling tank, performing planetary ball milling at a speed of 450r/min for 14 hours, and drying at 55 ℃ to obtain Ga-LLZO powder with fine and uniform granularity;
step 3, mixing the LLYZO powder and the Ga-LLZO powder to obtain premixed powder, placing the premixed powder, isopropanol and agate grinding balls into a ball milling tank, performing planetary ball milling at the speed of 450r/min for 14h, and drying at the temperature of 55 ℃ to obtain composite mother powder with fine granularity and uniform mixing, wherein the mass fraction of the LLYZO powder in the composite mother powder is 40%;
and 4, pressing the composite mother powder into a thin wafer with the diameter of 12mm under the pressure of 180MPa, calcining in a muffle furnace, and naturally cooling to room temperature to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains.
Example 3
The embodiment provides a method for inhibiting abnormal growth of Ga-LLZO solid electrolyte grains, comprising the following steps:
step 1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 According to chemistryLi (lithium ion battery) 7 La 2.7 Yb 0.3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling for 22 hours at the speed of 80r/min to obtain first mixed slurry, drying the first mixed slurry in an oven at 65 ℃ to obtain first premixed powder, calcining the first premixed powder at 950 ℃ for 5 hours, heating to 1240 ℃ and preserving heat for 0.4 hours, cooling to room temperature at the speed of 5 ℃/min to obtain LLYZO coarse powder, placing the LLYZO coarse powder, the isopropanol and the agate grinding balls in a ball milling tank for ball milling for 10 hours at the speed of 550r/min, and drying at 65 ℃ to obtain LLYZO powder with fine and uniform granularity;
step 2, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Molar ratio weighing, li, to compensate for lithium loss during electrolyte sintering 2 CO 3 Adding isopropanol and zirconia grinding balls into raw materials for ball milling for one time, ball milling at the speed of 80r/min for 22 hours to obtain second mixed slurry, drying the second mixed slurry in an oven at 65 ℃ to obtain second premixed powder, calcining the second premixed powder at 950 ℃ for 5 hours, cooling to room temperature to obtain Ga-LLZO coarse powder, placing the Ga-LLZO coarse powder, the isopropanol and the agate grinding balls in a ball milling tank, performing planetary ball milling at the speed of 550r/min for 10 hours, and drying at 65 ℃ to obtain Ga-LLZO powder with fine and uniform granularity;
step 3, mixing the LLYZO powder and the Ga-LLZO powder to obtain premixed powder, placing the premixed powder, isopropanol and agate grinding balls into a ball milling tank, performing planetary ball milling for 10 hours at the speed of 550r/min, and drying at 65 ℃ to obtain composite mother powder with fine granularity and uniform mixing, wherein the mass fraction of the LLYZO powder in the composite mother powder is 50%;
and 4, pressing the composite mother powder into a thin wafer with the diameter of 14mm at the pressure of 220MPa, calcining in a muffle furnace, and naturally cooling to room temperature to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains.
Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the disclosure.

Claims (10)

1. A method for inhibiting abnormal growth of Ga-LLZO solid electrolyte grains is characterized by comprising the following steps:
step S1, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Yb 2 O 3 According to chemical formula Li 7 La 2.7 Yb 0.3 Zr 2 O 12 Weighing the molar ratio, performing primary ball milling and drying to obtain first premixed powder, and performing calcination, secondary ball milling and drying on the first premixed powder to obtain LLYZO powder;
step S2, li is 2 CO 3 、La 2 O 3 、ZrO 2 And Ga 2 O 3 According to chemical formula Li 6.25 Ga 0.25 La 3 Zr 2 O 12 Weighing the molar ratio, performing primary ball milling and drying to obtain second premixed powder, and performing calcination, secondary ball milling and drying on the second premixed powder to obtain Ga-LLZO powder;
step S3, mixing the LLYZO powder and the Ga-LLZO powder, and ball-milling and drying to obtain composite mother powder;
and S4, performing pressure forming on the composite mother powder to form a lamellar structure, and cooling to room temperature after calcination treatment to obtain the Ga-LLZO solid electrolyte with fine and uniform crystal grains.
2. The method for suppressing abnormal growth of Ga-LLZO solid electrolyte crystal grains according to claim 1, wherein in step S3, the mass fraction of the LLYZO powder in the composite mother powder is 40% to 50%.
3. The method for suppressing abnormal grain growth of Ga-LLZO solid electrolyte according to claim 1, wherein in step S1 and step S2, the one-time ball milling process comprises: grinding aid is added into the ball mill, and ball milling is carried out for 22-26 hours at the speed of 60-80 r/min.
4. The method for suppressing abnormal grain growth of a Ga-LLZO solid electrolyte according to claim 3, wherein the grinding aid comprises isopropyl alcohol and zirconia.
5. The method for suppressing abnormal grain growth of Ga-LLZO solid electrolyte according to claim 1, wherein the secondary ball milling in step S1 and step S2 and the ball milling in step S3 include: and ball milling is carried out in a ball milling tank at a speed of 450-550r/min for 10-14h.
6. The method for suppressing abnormal grain growth of Ga-LLZO solid electrolyte according to claim 1, wherein in step S1, step S2 and step S3, the drying process comprises: drying at 55-65deg.C for 5-7 hr.
7. The method for suppressing abnormal grain growth of Ga-LLZO solid electrolyte according to claim 1, wherein in step S1, the calcination process comprises: calcining the first premixed powder at 850-950 ℃ for 5-7 hours, heating to 1220-1240 ℃ and preserving heat for 0.4-0.6 hours, and cooling to room temperature at a speed of 4-5 ℃/min.
8. The method for suppressing abnormal grain growth of Ga-LLZO solid electrolyte according to claim 1, wherein in step S4, press-molding the composite mother powder into a laminated structure comprises: and forming the composite master batch into a laminated structure with the diameter of 12-14mm under the pressure of 180-220 MPa.
9. The method for suppressing abnormal grain growth of a Ga-LLZO solid electrolyte according to claim 1, wherein in step S4, the calcination process includes: calcining at 980-1020 deg.C for 10-14 hr, at 1030-1070 deg.C for 16-120 hr, and at 1090-1130 deg.C for 22-26 hr.
10. A Ga-LLZO solid electrolyte characterized by being prepared by the method for inhibiting abnormal grain growth of a Ga-LLZO solid electrolyte according to any one of claims 1 to 9.
CN202310273634.3A 2023-03-21 2023-03-21 Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof Pending CN116231053A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310273634.3A CN116231053A (en) 2023-03-21 2023-03-21 Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310273634.3A CN116231053A (en) 2023-03-21 2023-03-21 Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof

Publications (1)

Publication Number Publication Date
CN116231053A true CN116231053A (en) 2023-06-06

Family

ID=86571294

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310273634.3A Pending CN116231053A (en) 2023-03-21 2023-03-21 Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof

Country Status (1)

Country Link
CN (1) CN116231053A (en)

Similar Documents

Publication Publication Date Title
CN104557013B (en) Preparation method of transparent tetravalent chromium-doped yttrium aluminum garnet ceramics
CN108516820B (en) A kind of short route sintering process of tin indium oxide target material
CN107129293A (en) A kind of preparation method of Mg adjuvant systems YAG base transparent ceramics
CN107200575A (en) A kind of preparation method of Ca adjuvant systems YAG base transparent ceramics
CN112939601A (en) Electrolyte material, preparation method and application thereof
CN110759733B (en) Y0.5Dy0.5Ta0.5Nb0.5O4Tantalum ceramic material and preparation method thereof
CN101665356A (en) Zirconium-doped yttria base transparent ceramic and preparation method thereof
CN113637945A (en) Rolling preparation method of large-size molybdenum-niobium alloy target
CN101182199A (en) Y2O3-TiO2 series microwave dielectric ceramic and preparation method thereof
CN116231053A (en) Ga-LLZO solid electrolyte and method for inhibiting abnormal growth of crystal grains thereof
CN111056839A (en) Boron compound doped lithium lanthanum zirconium oxygen solid electrolyte and preparation method thereof
Wei et al. Fabrication of Yb 3+-doped YAG transparent ceramics by aqueous gelcasting
CN114230342B (en) Rare earth oxide doped modified Ga-LLZO solid electrolyte and preparation method thereof
CN114497714B (en) Preparation method of garnet type solid electrolyte with high ion conductivity
Ma et al. Improvement of the Li-ion conductivity and air stability of the Ta-doped Li 7 La 3 Zr 2 O 12 electrolyte via Ga co-doping and its application in Li–S batteries
CN112537958B (en) Lanthanum lithium zirconate solid electrolyte and preparation method thereof
CN115332619A (en) High-entropy oxide solid electrolyte material for solid battery and preparation method and application thereof
CN115413273B (en) Ceramic powder material, sintered body, and battery
KR102547097B1 (en) Method of preparing llzo solid electrolyte, llzo solid electrolyte and all solid state lithium ion battery comprising the same
CN114436638A (en) Iron-doped lithium zirconium phosphate ceramic solid electrolyte and preparation method thereof
CN114243004B (en) Garnet type solid electrolyte capable of effectively inhibiting lithium dendrites and preparation method thereof
CN115417660B (en) Eu (Eu) 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof
CN115417667B (en) Nd 2 O 3 Doped Na-beta (beta') -Al 2 O 3 Solid electrolyte ceramic material and preparation method thereof
CN113213931B (en) Preparation method of transparent ceramic optical fiber based on Isobam gel and melt spinning technology
CN114716242B (en) X8R type multilayer ceramic capacitor porcelain and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination