CN105428706A - Praparation method for garnet type lithium lanthanum zirconate based solid electrolyte material - Google Patents

Praparation method for garnet type lithium lanthanum zirconate based solid electrolyte material Download PDF

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Publication number
CN105428706A
CN105428706A CN201510827934.7A CN201510827934A CN105428706A CN 105428706 A CN105428706 A CN 105428706A CN 201510827934 A CN201510827934 A CN 201510827934A CN 105428706 A CN105428706 A CN 105428706A
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solid electrolyte
lanthanum
solution
lithium
gel
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林展
刘培杨
李全国
高学会
刘磊
许阳阳
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Qingdao Nengxun New Energy Technology Co Ltd
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Qingdao Nengxun New Energy Technology Co Ltd
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    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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

Abstract

The present invention discloses a preparation method for a garnet type lithium lanthanum zirconate based solid electrolyte material. A molecular formula of the material is Li7La3Zr2O12. The preparation method comprises the following steps: (1) dissolving lithium acetate in aqueous solution of acetic acid; (2) dissolving lanthanum acetate and tetrabutyl zirconate in ethanol; (3) adding the solution in the step (2) into the solution in the step (1) with stirring, and aging the mixture for 8-10 hours to obtain gel; and (4) after drying the gel in the step (3) for 1-2 hours at a temperature of 80-100 DEG C, raising the temperature to 500-800 DEG C, burning the dried gel for 2-3 hours, and cooling the product naturally to obtain the garnet type lithium lanthanum zirconate based solid electrolyte material. Compared with an existing method, the method provided by the present invention has the advantages that the burning temperature can be decreased significantly, ignition loss of the lithium element is avoided, and the ionic conductivity of the method under a room temperature can reach 2.25*10-4S/cm.

Description

The preparation method of carbuncle type lithium lanthanum Zirconium-base solid electrolyte
Technical field
The invention belongs to technical field of lithium ion, be specifically related to the preparation method of carbuncle type lithium lanthanum Zirconium-base solid electrolyte.
Background technology
In recent years, there is serious security incident in high capacity lithium ion battery in electric automobile, aircraft auxiliary power, and the cause of these problems is relevant with adopting flammable organic solvent in lithium ion battery.Although by adding fire retardant, employing refractory ceramics barrier film, positive and negative pole material finishing, optimizing battery structure Design and optimization BMS, at battery core outer surface phase transformation fire proofing, improving the measures such as cooling system, the fail safe of existing lithium ion battery can be improved to a great extent, but these measures fundamentally cannot ensure the fail safe of high capacity cell system, particularly under the extreme service condition of battery, when there is safety issue in local cell unit.And adopt the inorganic solid electrolyte do not fired completely, then fundamentally can ensure the fail safe of lithium ion battery.
In order to overcome existing commercial liquid lithium ion battery institute problems faced, scientific research personnel is greatly developing the lithium ion battery based on solid electrolyte, and it has significant advantage.First, relative to liquid electrolyte, solid electrolyte is non-volatile, generally non-combustible, therefore adopts the solid state battery of solid electrolyte can have excellent fail safe.The second, because solid electrolytic mass-energy keeps stable in wide temperature range, therefore all-solid-state battery can work in wide temperature range, particularly under high temperature.3rd, some solid electrolytic confrontation moisture are insensitive, can keep good chemical stability for a long time in atmosphere, and therefore the manufacture whole process of solid state battery not necessarily needs the protection of inert atmosphere, can reduce the manufacturing cost of battery to a certain extent.Finally, some solid electrolyte material has very wide electrochemical window, this makes high-voltage electrode material be expected to application, thus improve battery energy density relative to the gel electrolyte of porous and the porous septum infiltrating liquid electrolyte, solid electrolyte is fine and close, and has higher intensity and hardness, can effectively stop the perverse of Li dendrite to be worn, therefore improve the fail safe of battery, also make metal Li become possibility as the use of negative pole simultaneously.
The people such as Weppner have the Li of garnet structure reported first in 2007 7la 3zr 2o 12solid electrolyte material, it at room temperature can have 10 -4the ionic conductivity of S/cm, very close to can be practical level.The more important thing is, Li 7la 3zr 2o 12electrochemical properties very stable, even if with lithium metal Long contact time, also can not the change of recurring structure or transmission performance, this makes it in assembling all-solid-state battery, have unique advantage.But, for preparation Li 7la 3zr 2o 12the research of this material carry out and insufficient, especially consider that the volatilization of elemental lithium in heat treatment process lacks control.The more important thing is that high-temperature heat treatment energy ezpenditure high maximum temperature reaches 1500 DEG C, the reaction time reaches more than 30 hours.For this reason, the target that a kind of more succinct directly method synthesis LLZO solid electrolyte is each researcher is studied.
In China Patent Publication No. CN104051782A, report the synthetic method of a kind of Li-La-Zr-O: first nitrate corresponding for Li, La, Zr element and a kind of organic solvent are mixed and made into gel, then obtain the presoma powder of dielectric substance in the drying do not waited to a few hours through several hours and heat treatment.Finally, powder compressing tablet is calcined 1 ~ 10 hour at 1000 DEG C ~ 1500 DEG C.Whole building-up process will through twice high-temperature process, accumulative tens of hours consuming time.Complexity and the inconvenience of its operation visible.
The synthetic method of a kind of LLTO is reported: first prepare presoma powder with solid phase method or gel method in China Patent Publication No. CN101325094A.And then distinguish Kaolinite Preparation of Catalyst and silicon solution, finally three is mixed also at high temperature heat drying and obtain composite granule.At 1100 DEG C ~ 1400 DEG C, sinter 1 ~ 10 hour after composite granule compressing tablet, finally obtain solid electrolyte finished product.The operation that its building-up process have passed through multiple step equally just synthesizes LLTO, and not only experimental period, building-up process energy consumption height production cost that is long but also that be was large.
The synthetic method of a kind of LLZO is reported at China Patent Publication No. CN103496740A.First high-temperature roasting lanthana at 900 DEG C, then by all raw materials high-energy ball milling 6 ~ 12 hours by a certain percentage.Finally by the pressure sintering number minute obtained target product LLZO at 800 DEG C ~ 1230 DEG C of the powder after ball milling.Although but its preparation method decreases synthesis step still inevitably need the ball milling of high temperature sintering and high energy consumption.
Summary of the invention
For prior art exist the problems referred to above, the present invention adopts sol-gel process to prepare carbuncle type lithium lanthanum Zirconium-base solid electrolyte, the method reaction temperature and, technique is simple.
The scheme that the present invention adopts for the above technical problem of solution is:
The preparation method of carbuncle type lithium lanthanum Zirconium-base solid electrolyte, the molecular formula of described material is Li 7la 3zr 2o 12, step is as follows:
(1) lithium acetate is dissolved in aqueous acetic acid;
(2) lanthanum acetate and tetrabutyl zirconate are dissolved in ethanol;
(3) under agitation join in the solution of step (1) by the solution of step (2), ageing 8-10 hour, obtains gel;
(4) gel of step (3) after dry 1-2 hour, is warming up to 500-800 DEG C of calcining 1-3 hour, naturally cools, obtain described carbuncle type lithium lanthanum Zirconium-base solid electrolyte at 80-100 DEG C.
Preferably, in step (1), the concentration of lithium acetate is 0.5-1.5mol/L
Preferably, in step (1), the concentration of acetic acid is 1-5mol/L.
Preferably, in step (2), the concentration of tetrabutyl zirconate is 0.5-1.5mol/L.
Preferably, in step (2), the mol ratio of lanthanum and zirconium is 3:2.
Preferably, be (7-7.2) by the mol ratio of lithium and lanthanum: 3, the solution of step (2) is joined in the solution of step (1).
Preferably, 500-800 DEG C is risen to the speed of 5-30 DEG C/min.
The present invention adopts sol-gel process successfully to prepare carbuncle type Li 7la 3zr 2o 12, compared with the conventional method, the present invention obviously can reduce calcining heat, and avoid elemental lithium burning at high temperature to lose, the ionic conductance under its normal temperature can up to 2.25 × 10 -4s/cm.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of carbuncle type lithium lanthanum Zirconium-base solid electrolyte prepared by the embodiment of the present invention.
Embodiment
For making content of the present invention, technical scheme and advantage clearly understand, set forth the present invention further below in conjunction with specific embodiment, these embodiments are only for illustration of the present invention, and the present invention is not limited only to following examples.
Embodiment 1
(1) lithium acetate being dissolved in the degree of depth is in the aqueous acetic acid of 1mol/L, and the concentration of lithium acetate is 0.5mol/L;
(2) be dissolved in ethanol by lanthanum acetate and tetrabutyl zirconate, the concentration of tetrabutyl zirconate is 0.5mol/L, and the mol ratio of lanthanum and zirconium is 3:2;
(3) under agitation, be 7:3 by the mol ratio of lithium and lanthanum, join in the solution of step (1) by the solution of step (2), ageing 8 hours, obtains gel;
(4) gel of step (3) after dry 2 hours, is proceeded to Muffle furnace at 100 DEG C, be warming up to 700 DEG C of calcinings 1 hour with the speed of 6 DEG C/min, naturally cool in stove, obtain pressed powder.
Embodiment 2
(1) lithium acetate being dissolved in the degree of depth is in the aqueous acetic acid of 2mol/L, and the concentration of lithium acetate is 1mol/L;
(2) be dissolved in ethanol by lanthanum acetate and tetrabutyl zirconate, the concentration of tetrabutyl zirconate is 1mol/L, and the mol ratio of lanthanum and zirconium is 3:2;
(3) under agitation, be 7.1:3 by the mol ratio of lithium and lanthanum, join in the solution of step (1) by the solution of step (2), ageing 9 hours, obtains gel;
(4) gel of step (3) after dry 2 hours, is proceeded to Muffle furnace at 100 DEG C, be warming up to 800 DEG C of calcinings 2 hours with the speed of 20 DEG C/min, naturally cool in stove, obtain pressed powder.
Embodiment 3
(1) lithium acetate being dissolved in the degree of depth is in the aqueous acetic acid of 5mol/L, and the concentration of lithium acetate is 1.5mol/L;
(2) be dissolved in ethanol by lanthanum acetate and tetrabutyl zirconate, the concentration of tetrabutyl zirconate is 1.5mol/L, and the mol ratio of lanthanum and zirconium is 3:2;
(3) under agitation, be 7.2:3 by the mol ratio of lithium and lanthanum, join in the solution of step (1) by the solution of step (2), ageing 10 hours, obtains gel;
(4) gel of step (3) after dry 1 hour, is proceeded to Muffle furnace at 100 DEG C, be warming up to 550 DEG C of calcinings 3 hours with the speed of 15 DEG C/min, naturally cool in stove, obtain pressed powder.
XRD collection of illustrative plates as Fig. 1 can be found out, products therefrom is the Li of garnet structure 7la 3zr 2o 12, the ionic conductivity under normal temperature is respectively 1.01 × 10 -4s/cm, 2.25 × 10 -4s/cm, 1.14 × 10 -4s/cm.
Last it is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. the preparation method of carbuncle type lithium lanthanum Zirconium-base solid electrolyte, the molecular formula of described material is Li 7la 3zr 2o 12, step is as follows:
(1) lithium acetate is dissolved in aqueous acetic acid;
(2) lanthanum acetate and tetrabutyl zirconate are dissolved in ethanol;
(3) under agitation join in the solution of step (1) by the solution of step (2), ageing 8-10 hour, obtains gel;
(4) gel of step (3) after dry 1-2 hour, is warming up to 500-800 DEG C of calcining 1-3 hour, naturally cools, obtain described carbuncle type lithium lanthanum Zirconium-base solid electrolyte at 80-100 DEG C.
2. method according to claim 1, is characterized in that, in step (1), the concentration of lithium acetate is 0.5-1.5mol/L.
3. method according to claim 1, is characterized in that, in step (1), the concentration of acetic acid is 1-5mol/L.
4. method according to claim 1, is characterized in that, in step (2), the concentration of tetrabutyl zirconate is 0.5-1.5mol/L.
5. method according to claim 1, is characterized in that, in step (2), the mol ratio of lanthanum and zirconium is 3:2.
6. method according to claim 1, is characterized in that, is (7-7.2): 3, is joined in the solution of step (1) by the solution of step (2) by the mol ratio of lithium and lanthanum.
7. method according to claim 1, is characterized in that, step (4) rises to 500-800 DEG C with the speed of 5-30 DEG C/min.
CN201510827934.7A 2015-11-24 2015-11-24 Praparation method for garnet type lithium lanthanum zirconate based solid electrolyte material Pending CN105428706A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019162314A1 (en) * 2018-02-26 2019-08-29 Volkswagen Aktiengesellschaft Coating for a tool for handling lithium metal, tool and method for producing such a tool

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2159867A1 (en) * 2008-08-21 2010-03-03 Ngk Insulator, Ltd. Aluminium-doped Li7La3Zr2O12 solid electrolyte and process for producing the same
CN102280659A (en) * 2011-06-30 2011-12-14 清华大学 Lithium-lanthanum-zirconium (Li-La-Zr) oxide solid electrolyte material as well as manufacturing method and application thereof
CN103594725A (en) * 2012-08-17 2014-02-19 万向电动汽车有限公司 Preparation method of lithium ion battery solid electrolyte material Li7La3Zr2O12

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2159867A1 (en) * 2008-08-21 2010-03-03 Ngk Insulator, Ltd. Aluminium-doped Li7La3Zr2O12 solid electrolyte and process for producing the same
CN102280659A (en) * 2011-06-30 2011-12-14 清华大学 Lithium-lanthanum-zirconium (Li-La-Zr) oxide solid electrolyte material as well as manufacturing method and application thereof
CN103594725A (en) * 2012-08-17 2014-02-19 万向电动汽车有限公司 Preparation method of lithium ion battery solid electrolyte material Li7La3Zr2O12

Non-Patent Citations (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019162314A1 (en) * 2018-02-26 2019-08-29 Volkswagen Aktiengesellschaft Coating for a tool for handling lithium metal, tool and method for producing such a tool
CN111770907A (en) * 2018-02-26 2020-10-13 大众汽车股份公司 Coating for a tool for manipulating lithium metal, tool and method for producing such a tool

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Application publication date: 20160323