CN110256068B - Preparation method of LiNiLaZrMO solid electrolyte - Google Patents

Preparation method of LiNiLaZrMO solid electrolyte Download PDF

Info

Publication number
CN110256068B
CN110256068B CN201910481050.9A CN201910481050A CN110256068B CN 110256068 B CN110256068 B CN 110256068B CN 201910481050 A CN201910481050 A CN 201910481050A CN 110256068 B CN110256068 B CN 110256068B
Authority
CN
China
Prior art keywords
linilazrmo
oxide
compound
solid electrolyte
powder
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.)
Active
Application number
CN201910481050.9A
Other languages
Chinese (zh)
Other versions
CN110256068A (en
Inventor
刘小珍
陈捷
刘雨泽
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.)
Shanghai Institute of Technology
Original Assignee
Shanghai 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 Shanghai Institute of Technology filed Critical Shanghai Institute of Technology
Priority to CN201910481050.9A priority Critical patent/CN110256068B/en
Publication of CN110256068A publication Critical patent/CN110256068A/en
Application granted granted Critical
Publication of CN110256068B publication Critical patent/CN110256068B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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

Abstract

The invention relates to a preparation method of LiNiLaZrMO solid electrolyte, which comprises the following steps: la2O3、ZrO2Mixing the nickel compound, the M compound and the lithium salt, adding a dispersing agent, grinding and drying to obtain a precursor; roasting the precursor at 300-809 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrMO powder; and tabletting the LiNiLaZrMO powder by using a tabletting machine to obtain LiNiLaZrMO tablets, adding the LiNiLaZrMO powder into a roasting container, inserting the LiNiLaZrMO tablets into the LiNiLaZrMO powder, sintering at 1000-1159 ℃, and cooling to room temperature to obtain the LiNiLaZrMO solid electrolyte. Compared with the prior art, the invention has the advantages of simple preparation method, low synthesis temperature, energy conservation and the like.

Description

Preparation method of LiNiLaZrMO solid electrolyte
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a LiNiLaZrMO solid electrolyte.
Background
The all-solid-state lithium ion battery has the characteristics of high safety, long cycle life, high energy density, wide use temperature range and the like, so that the all-solid-state lithium ion battery becomes a hot point of current research, and the solid electrolyte is one of the core parts of the all-solid-state lithium ion battery. The preparation of the solid electrolyte is usually carried out by a high-temperature solid-phase synthesis method, the synthesis temperature is higher and is approximately more than 1600 ℃; higher synthesis temperature causes harsh preparation conditions, and is not favorable for expanded production and equipment type selection in the production process.
Chinese patent CN106684440A discloses a preparation method of libalazrrealo solid electrolyte; with La2O3、ZrO2、WO3Rare earth oxide, Al2O3And lithium-containing compound as raw materials, wherein the first roasting temperature is 810-990 ℃, and the second roasting temperature is 1160-1200 ℃; chinese patent CN106025349A discloses a LiBaLaZrREAlO solidPreparation method of bulk electrolyte with La2O3、ZrO2Rare earth oxide, Al2O3And lithium-containing compound as raw materials, wherein the first roasting temperature is 810-990 ℃, and the second roasting temperature is 1160-1200 ℃; chinese patent CN106159319A discloses a preparation method of LiBaLaZrAlREWO lithium ion solid electrolyte, wherein the first roasting temperature is 810-990 ℃, and the second roasting temperature is 1160-1200 ℃; and Chinese patent CN105977531A discloses a preparation method of LiBaLaZrAlREO lithium ion solid electrolyte, wherein the first roasting temperature is 810-990 ℃, and the second roasting temperature is 1160-1200 ℃. These patents have room for further reduction in firing temperatures; in the synthesis process, some preparation methods have complex preparation routes; and the lithium ion conductivity of the solid electrolyte obtained in these patents has room for further improvement.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of LiNiLaZrMO solid electrolyte.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of LiNiLaZrMO solid electrolyte is characterized by comprising the following steps:
(1) la2O3、ZrO2Mixing the nickel compound, the M compound and the lithium salt, adding a dispersing agent, grinding and drying to obtain a precursor;
(2) roasting the precursor in the step (1) at 300-809 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrMO powder;
(3) and (3) tabletting the LiNiLaZrMO powder in the step (2) by using a tabletting machine to obtain LiNiLaZrMO tablets, adding the LiNiLaZrMO powder into a roasting container, inserting the LiNiLaZrMO tablets into the LiNiLaZrMO powder, sintering at 1000-1159 ℃, and cooling to room temperature to obtain the LiNiLaZrMO solid electrolyte.
The prior art needs a high-temperature roasting temperature of 1600 ℃ and a high precursor treatment temperature, so as to obtain a better and satisfactory compact structure. According to the invention, a Ni element dopant capable of compacting ceramics is added, the lithium salt adopts a lithium salt capable of forming a low lowest eutectic point, and by utilizing the characteristics of the Ni element, each element in LiNiLaZrMO forms a compact structure, so that the temperature of the roasting treatment of a precursor is reduced to 300-809 ℃, and in the prior art, the roasting treatment of the precursor needs 810-990 ℃ to form a compact structure which meets the requirements preliminarily; and the subsequent roasting temperature of the invention is also greatly reduced.
Further, when an M compound is added in addition to LiNiLaZrO, the conductivity of the electrolyte can be improved due to the synergistic effect of the Ni compound and the M compound.
In the invention, the addition amounts of Ni element and M element are optimized, when the addition amount of Ni element is too large, impurities can be generated, the density of LiNiLaZrMO is reduced, and when the addition amount of Ni element is too small, the effect of improving the density of LiNiLaZrMO is not obvious; for the M element, when the addition amount of the M element is too large, impurities are generated, the density of the LiNiLaZrMO is reduced, and when the addition amount of the M element is too small, the effect of improving the density of the LiNiLaZrMO is not obvious; according to the invention, the density of the LiCuLaZrMO solid electrolyte is synergistically improved by optimizing the doping amount of Cu and M elements, so that a better conductive effect is obtained.
In the step (1), the La2O3、ZrO2The molar ratio of the nickel compound, the M compound and the lithium salt is 1.25-1.50: 1.60-2.00: 0.10-3.00: 0.01-0.67: 7.15-9.80.
Preferably, the La2O3、ZrO2The molar ratio of the nickel compound, the M compound and the lithium salt is 1.25-1.50: 1.60-2.00: 0.10-1.50: 0.01-0.67: 7.15-9.80.
The present invention can further lower the treatment temperature of the sample by further optimizing the content of the Ni element.
In the step (1), the M compound is one or more selected from calcium compounds, strontium compounds, barium compounds, tungsten oxides or rare earth oxides.
In the step (1), the calcium compound is selected from one or more of calcium carbonate, calcium sulfate, calcium nitrate, calcium acetate, calcium chloride, calcium hydroxide or calcium oxide; the strontium compound is selected from one or more of strontium chloride, strontium hydroxide, strontium carbonate, strontium sulfate, strontium nitrate or strontium acetate; the barium compound is selected from one or more of barium chloride, barium hydroxide, barium sulfate, barium carbonate, barium nitrate or barium acetate; the rare earth oxide is selected from one or more of cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, scandium oxide or yttrium oxide.
In the step (1), the nickel compound is selected from one or more of nickel nitrate, nickel sulfate, nickel hydroxide, nickel carbonate, nickel chloride or nickel oxide.
In the step (1), the lithium salt is selected from one or more of lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate, lithium oxide or lithium carbonate.
In the step (1), the dispersing agent is selected from one or more of ethylene glycol, propanol or isopropanol.
In the step (2), the roasting time of the precursor is 5-7 h.
In the step (3), the method for inserting the LiNiLaZrMO sheet into the LiNiLaZrMO powder comprises the following steps: laying a layer of LiNiLaZrMO powder, a layer of LiNiLaZrMO sheet and a layer of LiNiLaZrMO powder in sequence from top to bottom in a roasting container; the ratio of the total weight of the LiNiLaZrMO powder to the total weight of the LiNiLaZrMO sheet is 0.2-1.
In the step (3), the sintering time of the LiNiLaZrMO sheet and the LiNiLaZrMO powder is 5-12 h.
Compared with the prior art, the invention has the following advantages:
(1) the synthesis temperature for preparing the LiNiLaZrMO solid electrolyte is low, the roasting temperature of the roasting treatment of the precursor is only 300-809 ℃, the sintering temperature is only 1000-1159 ℃, and the requirements on roasting equipment are reduced;
(2) the roasting temperature and the sintering temperature of the roasting treatment of the precursor are reduced, so that the energy is saved;
(3) the lithium ion conductivity of the LiNiLaZrO solid electrolyte prepared by the invention is 3.71 multiplied by 10-4S•cm-1～3.67×10-3 S•cm-1And the conductivity is good.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The embodiment provides a preparation method of a LiNiLaZrMO solid electrolyte, which comprises the following steps:
(1) respectively weighing La2O3、ZrO2Putting the nickel compound, the M compound and the lithium salt into a ball milling tank, adding a certain amount of dispersing agent, ball milling for 2-9 h, and drying to obtain a precursor; wherein the nickel compound is one or more of nickel nitrate, nickel sulfate, nickel hydroxide, nickel carbonate, nickel chloride and nickel oxide; the M compound is one or a mixture of more than one of calcium compounds (calcium carbonate, calcium sulfate, calcium nitrate, calcium acetate, calcium chloride, calcium hydroxide and calcium oxide), strontium compounds (strontium chloride, strontium hydroxide, strontium carbonate, strontium sulfate, strontium nitrate and strontium acetate), barium compounds (barium chloride, barium hydroxide, barium sulfate, barium carbonate, barium nitrate and barium acetate), tungsten oxide and rare earth oxide (cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium oxide); the lithium salt is one or a mixture of more than one of lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate, lithium oxide and lithium carbonate; la2O3:ZrO2The nickel compound, the M compound and the lithium salt are in a molar ratio of 1.25-1.50: 1.60-2.00: 0.10-1.50: 0.01-0.67: 7.15-9.80, and the dispersing agent is one or a mixture of more than one of ethylene glycol, propanol and isopropanol.
(2) Putting the precursor into a crucible, firing for 5-7 h at 300-809 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrMO powder;
(3) and (2) pressing the LiNiLaZrMO powder into tablets by using a tablet press to obtain LiNiLaZrMO tablets, adding the LiNiLaZrMO powder into a crucible, inserting the LiNiLaZrMO tablets into the LiNiLaZrMO powder, sintering for 5-12 h at 1000-1159 ℃, and cooling to room temperature to obtain the LiNiLaZrMO solid electrolyte.
The lithium ion conductivity of the linilazrno solid electrolyte obtained in each example of the present invention was measured using Solartron1260+1287 electrochemical workstation, uk, see specification for Solartron1260+1287 electrochemical workstation.
In the following, a solid electrolyte of LiNiLaZrMO was prepared in accordance with the specific embodiment, and the conductivity and electrical properties were measured.
Example 1
Weighing 1.25 mol of La2O31.60 mol of ZrO2And respectively adding a certain amount of glycol into a 5L ball milling tank, adding 0.10 mol of nickel nitrate, 0.01 mol of calcium carbonate, 2.75 mol of lithium hydroxide and 4.43 mol of lithium nitrate, ball milling for 2h, and drying to obtain a precursor. And putting the precursor into a 3L crucible, burning for 5h at 300 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrCaO powder. And (3) tabletting the LiNiLaZrCaO powder by using a tabletting machine to obtain LiNiLaZrCaO tablets, adding the LiNiLaZrCaO powder into a crucible, inserting the LiNiLaZrCaO tablets into the LiNiLaZrCaO powder, sintering at 1000 ℃ for 5 hours, and cooling to room temperature to obtain the LiNiLaZrCaO solid electrolyte. The lithium ion conductivity of the obtained LiNiLaZrCaO solid electrolyte was 3.71X 10-4S·cm-1。
Example 2
Weighing 1.50 mol of La2O32.00 mol of ZrO21.00 mol of nickel oxide, 0.50 mol of nickel chloride, 0.02 mol of strontium chloride and 0.46 mol of WO30.19 mol Nd2O3And 9.80 mol of lithium carbonate are respectively put into a 5L ball milling tank, a certain amount of isopropanol is added, ball milling is carried out for 9h, and drying is carried out, thus obtaining the precursor. Placing the precursor into 3L crucible, and burning at 809 deg.CAnd (4) burning for 7h, cooling to room temperature, and grinding to obtain LiNiLaZrSrWNdO powder. And (2) pressing the LiNiLaZrSrWNdO powder into tablets by using a tablet press to obtain LiNiLaZrSrWNdO tablets, adding the LiNiLaZrSrWNdO powder into a crucible, inserting the LiNiLaZrSrWNdO tablets into the LiNiLaZrSrWNdO powder, sintering for 12 hours at 1159 ℃, and cooling to room temperature to obtain the LiNiLaZrSrWNdO solid electrolyte. The lithium ion conductivity of the obtained LiNiLaZrSrWNdO solid electrolyte was 1.85X 10-3S·cm-1。
Example 3
Weighing 1.38 mol of La2O31.80 mol of ZrO20.20 mol of nickel sulfate, 0.30 mol of nickel hydroxide, 0.30 mol of nickel carbonate, 0.01 mol of barium sulfate and 0.33 mol of WO3Respectively adding a certain amount of propanol into a 5L ball milling tank containing 6.28 mol of lithium carbonate and 2.20 mol of lithium hydroxide, carrying out ball milling for 5.5h, and drying to obtain a precursor. And putting the precursor into a 3L crucible, burning for 6h at 554 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrBaWO powder. And (3) tabletting the LiNiLaZrBaWO powder by using a tabletting machine to obtain LiNiLaZrBaWO tablets, adding the LiNiLaZrBaWO powder into a crucible, inserting the LiNiLaZrBaWO tablets into the LiNiLaZrBaWO powder, sintering for 8.5h at 1079 ℃, and cooling to room temperature to obtain the LiNiLaZrBaWO solid electrolyte. The lithium ion conductivity of the obtained LiNiLaZrBaWO solid electrolyte was 3.67X 10- 3S·cm-1。
Example 4
Weighing 1.32 mol of La2O31.70 mol of ZrO20.10 mol of nickel nitrate, 0.35 mol of nickel hydroxide, 0.03 mol of calcium oxide, 0.145 mol of Y2O3Adding a certain amount of propanol into a 5L ball milling tank respectively containing 4.93 mol of lithium chloride and 2.90 mol of lithium hydroxide, ball milling for 3.8h, and drying to obtain a precursor. And putting the precursor into a 3L crucible, burning for 5.5h at 427 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrCaYO powder. And (3) pressing the LiNiLaZrCaYO powder into tablets by using a tablet press to obtain LiNiLaZrCaYO tablets, adding the LiNiLaZrCaYO powder into a crucible, inserting the LiNiLaZrCaYO tablets into the LiNiLaZrCaYO powder, sintering at 1040 ℃ for 7 hours, and cooling to room temperature to obtain the LiNiLaZrCaYO solid electrolyte. ObtainedThe lithium ion conductivity of LiNiLaZrCaYO solid electrolyte is 7.97 multiplied by 10-4S·cm-1。
Example 5
Weighing 1.44 mol of La2O31.90 mol of ZrO21.15 mol of nickel carbonate and 0.31 mol of Dy2O30.20 mol Yb2O3And 6.75 mol of lithium hydroxide, 2.37 mol of lithium carbonate, 0.01 mol of lithium oxalate and 0.01 mol of lithium oxide are respectively added into a 5L ball milling tank, a certain amount of propanol is added, ball milling is carried out for 7.3h, and drying is carried out, thus obtaining the precursor. And putting the precursor into a 3L crucible, burning for 6.5h at 682 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrDyYbO powder. And (3) pressing the LiNiLaZrDyYbO powder into tablets by using a tablet press to obtain LiNiLaZrDyYbO tablets, adding the LiNiLaZrDyYbO powder into a crucible, inserting the LiNiLaZrDyYbO tablets into the LiNiLaZrDyYbO powder, sintering at 1119 ℃ for 10.3 hours, and cooling to room temperature to obtain the LiNiLaZrDyYbO solid electrolyte. The lithium ion conductivity of the obtained LiNiLaZrDyYbO solid electrolyte was 9.53X 10-4S·cm-1。
Example 6
Weighing 1.50 mol of La2O32.00 mol of ZrO21.00 mol of nickel oxide, 2.00 mol of nickel chloride, 0.02 mol of strontium chloride and 0.46 mol of WO30.19 mol Nd2O3And 9.80 mol of lithium carbonate are respectively put into a 5L ball milling tank, a certain amount of isopropanol is added, ball milling is carried out for 9h, and drying is carried out, thus obtaining the precursor. And putting the precursor into a 3L crucible, burning for 7h at 800 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrSrWNdO powder. And (3) pressing the LiNiLaZrSrWNdO powder into tablets by using a tablet press to obtain LiNiLaZrSrWNdO tablets, adding the LiNiLaZrSrWNdO powder into a crucible, inserting the LiNiLaZrSrWNdO tablets into the LiNiLaZrSrWNdO powder, sintering for 12 hours at 1000 ℃, and cooling to room temperature to obtain the LiNiLaZrSrWNdO solid electrolyte. The lithium ion conductivity of the obtained LiNiLaZrSrWNdO solid electrolyte was 4.10X 10-4S·cm-1。
By comparing examples 1 to 6 with the solid electrolyte in the prior art, it can be seen that the pretreatment temperature and the baking temperature of the electrolyte in this example are both low, and the lithium ion conductivity of the obtained solid electrolyte is equivalent to that in the prior art, so that the solid electrolyte in this example has significant advantages in terms of temperature resistance of the preparation equipment and energy saving requirements in the preparation process.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (8)

1. A preparation method of LiNiLaZrMO solid electrolyte is characterized by comprising the following steps:
(1) la2O3、ZrO2Mixing a nickel compound, an M compound and a lithium salt, adding a dispersing agent, grinding and drying to obtain a precursor, wherein the M compound is one or more selected from a calcium compound, a strontium compound, a barium compound, a tungsten oxide or a rare earth oxide;
(2) roasting the precursor in the step (1) at 300-682 ℃, cooling to room temperature, and grinding to obtain LiNiLaZrMO powder;
(3) tabletting the LiNiLaZrMO powder in the step (2) by using a tablet machine to obtain LiNiLaZrMO tablets, adding the LiNiLaZrMO powder into a roasting container, inserting the LiNiLaZrMO tablets into the LiNiLaZrMO powder, sintering at 1000-1159 ℃, and cooling to room temperature to obtain the LiNiLaZrMO solid electrolyte;
the La2O3、ZrO2The molar ratio of the nickel compound to the M compound to the lithium salt is 1.25-1.50: 1.60-2.00: 0.10-3.00: 0.01-0.67: 7.15-9.80, and the lithium salt capable of forming a low minimum eutectic point is used.
2. The method for preparing a solid electrolyte of LiNiLaZrMO according to claim 1, wherein in step (1), said La is added2O3、ZrO2The molar ratio of the nickel compound, the M compound and the lithium salt is1.25～1.50:1.60～2.00:0.10～1.50:0.01～0.67：7.15～9.80。
3. The method for preparing a LiNiLaZrMO solid electrolyte according to claim 1, wherein in step (1), said calcium compound is selected from one or more of calcium carbonate, calcium sulfate, calcium nitrate, calcium acetate, calcium chloride, calcium hydroxide and calcium oxide; the strontium compound is selected from one or more of strontium chloride, strontium hydroxide, strontium carbonate, strontium sulfate, strontium nitrate or strontium acetate; the barium compound is selected from one or more of barium chloride, barium hydroxide, barium sulfate, barium carbonate, barium nitrate or barium acetate; the rare earth oxide is selected from one or more of cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, scandium oxide or yttrium oxide.
4. The method for preparing a solid electrolyte of LiNiLaZrMO according to claim 1, wherein in step (1), said nickel compound is selected from one or more of nickel nitrate, nickel sulfate, nickel hydroxide, nickel carbonate, nickel chloride and nickel oxide.
5. The method for preparing a solid electrolyte of LiNiLaZrMO according to claim 1, wherein in step (1), said lithium salt is selected from one or more of lithium hydroxide, lithium nitrate, lithium chloride, lithium oxalate, lithium oxide and lithium carbonate.
6. The method for preparing a solid electrolyte of LiNiLaZrMO according to claim 1, wherein in step (1), the dispersant is selected from one or more of ethylene glycol, propanol or isopropanol.
7. The method for preparing LiNiLaZrMO solid electrolyte according to claim 1, wherein in step (2), the calcination time of the precursor is 5-7 h.
8. The method for preparing a solid electrolyte of LiNiLaZrMO according to claim 1, wherein in step (3), the method for inserting the LiNiLaZrMO sheet into the LiNiLaZrMO powder comprises: laying a layer of LiNiLaZrMO powder, a layer of LiNiLaZrMO sheet and a layer of LiNiLaZrMO powder in a roasting container from top to bottom in sequence; the ratio of the total weight of the LiNiLaZrMO powder to the total weight of the LiNiLaZrMO sheet is 0.2-1; the sintering time is 5-12 h.
CN201910481050.9A 2019-06-04 2019-06-04 Preparation method of LiNiLaZrMO solid electrolyte Active CN110256068B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910481050.9A CN110256068B (en) 2019-06-04 2019-06-04 Preparation method of LiNiLaZrMO solid electrolyte

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910481050.9A CN110256068B (en) 2019-06-04 2019-06-04 Preparation method of LiNiLaZrMO solid electrolyte

Publications (2)

Publication Number Publication Date
CN110256068A CN110256068A (en) 2019-09-20
CN110256068B true CN110256068B (en) 2022-02-11

Family

ID=67916635

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910481050.9A Active CN110256068B (en) 2019-06-04 2019-06-04 Preparation method of LiNiLaZrMO solid electrolyte

Country Status (1)

Country Link
CN (1) CN110256068B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021169387A (en) * 2020-04-15 2021-10-28 セイコーエプソン株式会社 Method for producing solid composition and method for producing functional ceramic molded body
KR20230135122A (en) * 2021-02-09 2023-09-22 신닛폰 덴코 가부시키가이샤 Additives to lithium ion secondary battery electrodes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016169142A (en) * 2015-03-10 2016-09-23 Tdk株式会社 Garnet-type lithium ion-conducting oxide and all solid lithium ion secondary battery
EP2905829B1 (en) * 2014-02-07 2017-06-21 Samsung SDI Co., Ltd. Positive active material, positive electrode and lithium battery including the positive active material, and method of manufacturing the positive active material
CN108155413A (en) * 2018-01-12 2018-06-12 北京科技大学 The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method
JP2019006634A (en) * 2017-06-26 2019-01-17 日立金属株式会社 Manufacturing method of solid electrolyte, and solid electrolyte
CN109643825A (en) * 2016-07-11 2019-04-16 密执安州立大学董事会 Ceramic garnet base ion-conductive material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2905829B1 (en) * 2014-02-07 2017-06-21 Samsung SDI Co., Ltd. Positive active material, positive electrode and lithium battery including the positive active material, and method of manufacturing the positive active material
JP2016169142A (en) * 2015-03-10 2016-09-23 Tdk株式会社 Garnet-type lithium ion-conducting oxide and all solid lithium ion secondary battery
CN105977528A (en) * 2015-03-10 2016-09-28 Tdk株式会社 Garnet-type li-ion conductive oxide and all-solid li-ion secondary battery
CN109643825A (en) * 2016-07-11 2019-04-16 密执安州立大学董事会 Ceramic garnet base ion-conductive material
JP2019006634A (en) * 2017-06-26 2019-01-17 日立金属株式会社 Manufacturing method of solid electrolyte, and solid electrolyte
CN108155413A (en) * 2018-01-12 2018-06-12 北京科技大学 The Li of divalent alkaline-earth metal and tantalum codope7La3Zr2O12Solid electrolyte material and preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
First-Principles Studies on Cation Dopants and Electrolyte|Cathode Interphases for Lithium Garnets;Lincoln J. Miara et. al;《Chemistry of Materials》;20150430;第27卷(第11期);第4040-4047页 *
Towards Mixed Ionic and Electronic Conducting Li-Stuffed Garnets;Alfred Junio Samson et. al;《Journal of The Electrochemical Society》;20180725;第165卷(第10期);第A2303-A2311页 *

Also Published As

Publication number Publication date
CN110256068A (en) 2019-09-20

Similar Documents

Publication Publication Date Title
CN112467119B (en) Preparation method and application of layered high-entropy oxide sodium-ion battery positive electrode material
CN112174664B (en) High-energy-storage and high-efficiency sodium niobate-based ceramic material and preparation method thereof
CN107681128B (en) Lithium ion battery anode material and preparation method thereof
CN106505193A (en) Monocrystalline nickel-cobalt lithium manganate cathode material and preparation method thereof and lithium ion battery
CN103130499B (en) A kind of preparation method of microwave dielectric ceramic materials
CN102195042A (en) High performance lithium ion battery anode material lithium manganate and preparation method thereof
CN108793987B (en) Lithium ion conductive oxide solid electrolyte and preparation method thereof
CN110885246A (en) High-conductivity solid electrolyte prepared by sol-gel method
KR101762275B1 (en) Method for preparing solid elecrolyte by low temperature sintering process and method for manufacturing all-solid-state lithium secondary battery comprising the same
CN103730654A (en) High-capacity high-stability lithium manganate positive electrode material and preparation method thereof
CN110922187B (en) Preparation method of garnet type lithium ion solid electrolyte for removing lithium carbonate
CN110256068B (en) Preparation method of LiNiLaZrMO solid electrolyte
CN101764212A (en) Method for preparing spinelle lithium titanate for lithium ion battery negative electrode material
CN103172364B (en) Preparation method of microwave dielectric ceramic material
CN104900887A (en) Double-perovskite type intermediate temperature solid oxide fuel cell anode material and preparation method
US20230088369A1 (en) Stable high conductivity oxide electrolyte
CN109659602A (en) A kind of hydrotalcite-modified lithium lanthanum zirconium oxygen solid electrolyte and preparation method thereof
CN114824303A (en) R-P type layered intermediate entropy perovskite structure cathode material and preparation method thereof
CN112490417A (en) Mg-Zr co-doped high-nickel ternary material and preparation method and application thereof
KR102200967B1 (en) Galium- gadolinium dopped solid electrolyte material for all-solid-state lithium secondary battery and method for preparing the same
CN110229003B (en) Preparation method and application of LiNiLaZrO solid electrolyte
CN110289445B (en) Preparation method of LiCuLaZrMO solid electrolyte
Cheng et al. Effects of Mg2+ addition on structure and electrical properties of gadolinium doped ceria electrolyte ceramics
CN103172365B (en) Preparation method of microwave dielectric ceramic material
CN110311172B (en) Preparation method and application of LiCuLaZrO solid electrolyte

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
GR01 Patent grant
GR01 Patent grant