CN104051782A - Lithium lanthanum titanate (LLTO) composite solid-state lithium ion electrolyte material, preparation method and application thereof - Google Patents

Lithium lanthanum titanate (LLTO) composite solid-state lithium ion electrolyte material, preparation method and application thereof Download PDF

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CN104051782A
CN104051782A CN201310076874.0A CN201310076874A CN104051782A CN 104051782 A CN104051782 A CN 104051782A CN 201310076874 A CN201310076874 A CN 201310076874A CN 104051782 A CN104051782 A CN 104051782A
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lithium
composite solid
electrolyte material
ion electrolyte
titanium oxide
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陈凯
沈洋
南策文
裴佳宁
刘振国
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Tsinghua University
Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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    • H01—ELECTRIC ELEMENTS
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • 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
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Abstract

An embodiment of the invention provides a lithium lanthanum titanate (LLTO) composite solid-state lithium ion electrolyte material which is composed of Li<3x>La<2/3-x>TiO3 and zirconium which is enriched in a crystal boundary layer of the Li<3x>La<2/3-x>TiO3, wherein 0<x<0.16. The material is of excellent crystal boundary conductivity and total conductivity and is simple in a preparation technology. The embodiment of the invention also provides a preparation method of the LLTO composite solid-state lithium ion electrolyte material. A precursor powder of the composite solid-state lithium ion electrolyte material is prepared in a manner of coating LLTO by a lithium-lanthanum-zirconium-oxygen sol and then performing a sintering process to obtain the LLTO composite solid-state lithium ion electrolyte material. The LLTO is increased in crystal boundary conductivity and total conductivity. The preparation method is simple. In addition, the embodiment of the invention provides an application of the LLTO composite solid-state lithium ion electrolyte material in a lithium ion battery.

Description

A kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material and its preparation method and application
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material and its preparation method and application.
Background technology
Commercial lithium ion battery is used liquid electrolyte at present, has the potential safety hazards such as burning, blast, has seriously limited the application of lithium ion battery in new forms of energy energy-accumulating power station and electric automobile field.Use all solid state lithium ion battery that inorganic solid electrolyte makes to substitute the commercial li-ion battery that uses liquid electrolyte to make, fundamentally solve the safety problem of lithium ion battery, further improved serviceability temperature scope and the storage life of lithium ion battery.
Inorganic solid electrolyte is the core of all solid state lithium ion battery.First require solid electrolyte material to there is higher ionic conductivity, it is generally acknowledged and will reach 10 -4s/cm just can meet practical application request.Next requires solid electrolyte material preparation technology simple, and synthesis condition is variable, strong operability, for use in meeting high-performance all solid state lithium ion battery combined electrode structure, three-dimensional electrolysis matter structure and the isostructural assembling requirement of membrane structure.
In a large amount of inorganic solid electrolyte materials, lithium lanthanum titanium oxide (LLTO, Lithium Lanthanum Titanate) is close to meeting above-mentioned requirements.The chemical formula of LLTO is Li 3xla 2/3-xtiO 3(0<x<0.16), synthesis technique is simple, and room temperature crystal grain conductivity reaches 10 -3s/cm, but crystal boundary conductivity only has 10 -5s/cm.Lower crystal boundary conductivity has had a strong impact on the total conductivity of LLTO material, so improve the crystal boundary conductivity of LLTO material, seems particularly important.
At present less about the research of LLTO material crystal boundary conductivity.Publication number is that the Chinese patent application of CN101325094 has proposed the composite ceramics that the grain boundaries between LLTO material grains contains amorphous nano-silicon oxide skin(coating), and adopts wet chemical method to realize compound in Li-La-Ti oxygen solid electrolyte material of this amorphous nano-silicon oxide.In the method, utilize amorphous silicon oxide to improve LLTO crystal boundary conductivity, but the nano-silicon oxide skin(coating) adding is lithium ion insulator, limited to the raising effect of crystal boundary conductivity and total conductivity.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, and in order to solve, the crystal boundary conductivity of lithium lanthanum titanium oxide solid lithium ion electrolyte in prior art is low causes the problem that its total conductivity is low.Embodiment of the present invention second aspect provides a kind of preparation method of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.The embodiment of the present invention third aspect provides the application of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material in lithium ion battery.
First aspect, the embodiment of the present invention provides a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.
Wherein, Li 3xla 2/3-xtiO 3(0<x<0.16) be that a class has high-lithium ion conductivity ceramic material, its crystal structure belongs to perovskite structure.The embodiment of the present invention provides a kind of composite solid lithium-ion electrolyte material, and zr element is enriched in Li 3xla 2/3-xtiO 3(0<x<0.16) grain boundary layer of intergranule.The existence form of zr element is the complex compound of Li, La, Zr, Ti, O.
Preferably, described Li 3xla 2/3-xtiO 3(0<x<0.16) be Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
Preferably, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 0.217%～2.17% to zr element.
More preferably, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 1.083% to zr element.
Embodiment of the present invention first aspect provides a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, and this material has good crystal boundary conductivity and total conductivity, and preparation technology is simple.
Second aspect, the embodiment of the present invention provides a kind of preparation method of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: use solid phase method or sol-gal process to make Li 3xla 2/3-xtiO 3, 0<x<0.16;
(2) Li-La-Zr-O colloidal sol preparation: with LiNO 3, La (NO 3) 36H 2o, ZrO (NO 3) 22H 2o and acetylacetone,2,4-pentanedione are raw material, according to Li 7la 3zr 2o 12in the metering ratio of each element carry out proportioning, add at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether, make Li-La-Zr-O colloidal sol;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in step (1) 3xla 2/3-xtiO 3add at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether, add subsequently the Li-La-Zr-O colloidal sol making in step (2), stir 0.5～10 hour, make mixed solution, then described mixed solution is placed in to baking oven and is dried 2～12 hours at 20～130 ℃ of temperature, in 150～1000 ℃ of heat treatments 0.5～10 hour, make composite solid lithium-ion electrolyte material presoma powder subsequently;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1000 ℃～1450 ℃ sintering 1～10 hour, obtain lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
Wherein, by adopting Li-La-Zr-O Sol-gel Coated lithium lanthanum titanium oxide to prepare composite solid lithium-ion electrolyte material presoma powder, by sintering, make lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material subsequently.Described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material is by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.The existence form of zr element is the complex compound of Li, La, Zr, Ti, O.
Preferably, described Li 3xla 2/3-xtiO 3(0<x<0.16) be Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
Preferably, in described step (3), press Li 3xla 2/3-xtiO 3with Li corresponding in Li-La-Zr-O colloidal sol 7la 3zr 2o 12the mass ratio of Theoretical Mass is that 9:1～99:1 adds Li-La-Zr-O colloidal sol.
Preferably, in described step (3), press Li 3xla 2/3-xtiO 3with Li corresponding in Li-La-Zr-O colloidal sol 7la 3zr 2o 12the mass ratio of Theoretical Mass is that 19:1 adds Li-La-Zr-O colloidal sol.
Preferably, Li in described step (3) 3xla 2/3-xtiO 3add at least one latter ultrasonic 0.5～4 hour in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether.
Preferably, described baking temperature is 50～80 ℃.
Preferably, described heat treated temperature is 250～450 ℃.
Preferably, described sintering temperature is 1250～1350 ℃.
The preparation method of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material that embodiment of the present invention second aspect provides, adopt Li-La-Zr-O Sol-gel Coated, can make zr element be evenly distributed in the grain boundary layer of lithium lanthanum titanium oxide, in Li-La-Zr-O colloidal sol colloidal sol, also contain Li, La, the elements such as O, make in coating layer zr element with Li, La, Zr, Ti, the form of O complex compound exists, formed grain boundary layer is lithium ion conductor, than general lithium ion insulator coating layer, raising effect to crystal boundary conductivity and total conductivity is more obvious.
The third aspect, the embodiment of the present invention provides the application of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material in lithium ion battery, and described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material is by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.
Wherein, the existence form of zr element is the complex compound of Li, La, Zr, Ti, O.
Preferably, described Li 3xla 2/3-xtiO 3(0<x<0.16) be Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
Preferably, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 0.217%～2.17% to zr element.
More preferably, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 1.083% to zr element.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can know by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the ESEM picture of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material surface of making in the embodiment of the present invention one;
Fig. 2 be a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material of making in the embodiment of the present invention two across the elementary analysis of crystal boundary x ray energy spectrum line sweep;
Fig. 3 is the lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material room-temperature conductivity situation of change under different zr element content theoretical value conditions making in the embodiment of the present invention one, embodiment bis-and embodiment tri-.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, and in order to solve, the crystal boundary conductivity of lithium lanthanum titanium oxide solid lithium ion electrolyte in prior art is low causes the problem that its total conductivity is low.Embodiment of the present invention second aspect provides a kind of preparation method of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.The embodiment of the present invention third aspect provides the application of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material in lithium ion battery.
First aspect, the embodiment of the present invention provides a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.
Wherein, Li 3xla 2/3-xtiO 3(0<x<0.16) be that a class has high-lithium ion conductivity ceramic material, its crystal structure belongs to perovskite structure.The embodiment of the present invention provides a kind of composite solid lithium-ion electrolyte material, and zr element is enriched in Li 3xla 2/3-xtiO 3(0<x<0.16) grain boundary layer of intergranule.The existence form of zr element is the complex compound of Li, La, Zr, Ti, O.
Described Li 3xla 2/3-xtiO 3(0<x<0.16) be Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
Zr element in described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material shared mass percent can be according to preparation method in the difference of zr element consumption rationally regulate.In the embodiment of the present invention, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 0.217%～2.17% to zr element.Particularly, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 1.083% to zr element.
Embodiment of the present invention first aspect provides a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, and this material has good crystal boundary conductivity and total conductivity, and preparation technology is simple.
Second aspect, the embodiment of the present invention provides a kind of preparation method of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: use solid phase method or sol-gal process to make Li 3xla 2/3-xtiO 3, 0<x<0.16;
(2) Li-La-Zr-O colloidal sol preparation: with LiNO 3, La (NO 3) 36H 2o, ZrO (NO 3) 22H 2o and acetylacetone,2,4-pentanedione are raw material, according to Li 7la 3zr 2o 12in the metering ratio of each element carry out proportioning, add at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether, make Li-La-Zr-O colloidal sol;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in step (1) 3xla 2/3-xtiO 3add at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether, add subsequently the Li-La-Zr-O colloidal sol making in step (2), stir 0.5～10 hour, make mixed solution, then described mixed solution is placed in to baking oven and is dried 2～12 hours at 20～130 ℃ of temperature, in 150～1000 ℃ of heat treatments 0.5～10 hour, make composite solid lithium-ion electrolyte material presoma powder subsequently;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1000 ℃～1450 ℃ sintering 1～10 hour, obtain lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
Wherein, by adopting Li-La-Zr-O Sol-gel Coated lithium lanthanum titanium oxide to prepare composite solid lithium-ion electrolyte material presoma powder, by sintering, make lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material subsequently.Described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material is by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.The existence form of zr element is the complex compound of Li, La, Zr, Ti, O.
In described step (1), solid phase method and sol-gal process are conventional method in industry.Described Li 3xla 2/3-xtiO 3(0<x<0.16) be Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
In described step (2), acetylacetone,2,4-pentanedione is chelating agent, and at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether is organic solvent, and the quality of the Li-La-Zr-O colloidal sol making comprises LiNO 3, La (NO 3) 36H 2o, ZrO (NO 3) 22H 2the quality of O and acetylacetone,2,4-pentanedione, and the quality that comprises organic solvent.Wherein, Li element, La element and Zr element be take mol ratio and are existed as 7:3:2, and the existence of O element can be understood as a part and meets Li with Li element, La element and Zr element proportioning 7la 3zr 2o 12in the mol ratio of each element, another part exists with other forms.
Described step is pressed Li in (3) 3xla 2/3-xtiO 3mix with certain mass ratio with Li-La-Zr-O colloidal sol, this ratio depends on Li in Li-La-Zr-O colloidal sol 7la 3zr 2o 12theoretical Mass.In Li-La-Zr-O colloidal sol, directly do not generate Li 7la 3zr 2o 12, but this does not affect by conversion calculations and goes out Li wherein 7la 3zr 2o 12theoretical Mass, i.e. wherein Li element, La element, Zr element and meet Li with Li element, La element and Zr element proportioning 7la 3zr 2o 12in the quality sum of O element of mol ratio of each element.
Described step is pressed Li in (3) 3xla 2/3-xtiO 3with Li corresponding in Li-La-Zr-O colloidal sol 7la 3zr 2o 12the mass ratio of Theoretical Mass is that 9:1～99:1 adds Li-La-Zr-O colloidal sol.Particularly, in described step (3), press Li 3xla 2/3-xtiO 3with Li corresponding in Li-La-Zr-O colloidal sol 7la 3zr 2o 12the mass ratio of Theoretical Mass is that 19:1 adds Li-La-Zr-O colloidal sol.
Li in described step (3) 3xla 2/3-xtiO 3add at least one latter ultrasonic 0.5～4 hour in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether.
Described baking temperature is 50～80 ℃.
Described heat treated temperature is 250～450 ℃.
Described sintering temperature is 1250～1350 ℃.
The preparation method of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material that embodiment of the present invention second aspect provides, adopt Li-La-Zr-O Sol-gel Coated, can make zr element be evenly distributed in the grain boundary layer of lithium lanthanum titanium oxide, in Li-La-Zr-O colloidal sol colloidal sol, also contain Li, La, the elements such as O, make in coating layer zr element with Li, La, Zr, Ti, the form of O complex compound exists, formed grain boundary layer is lithium ion conductor, than general lithium ion insulator coating layer, raising effect to crystal boundary conductivity and total conductivity is more obvious.
The third aspect, the embodiment of the present invention provides the application of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material in lithium ion battery, and described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material is by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.
Wherein, the existence form of zr element is the complex compound of Li, La, Zr, Ti, O.
Described Li 3xla 2/3-xtiO 3(0<x<0.16) be Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
It is 0.217%～2.17% that zr element accounts for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage.Particularly, to account for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage be 1.083% to zr element.
Embodiment mono-
A preparation method for lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: with 0.7962g LiNO 3(lithium excessive 10%), 7.145gLa (NO 3) 36H 2o, 10.211g butyl titanate and 6.007g acetylacetone,2,4-pentanedione are raw material, take ethylene glycol monoemethyl ether as solvent, utilize sol-gal process, at 70 ℃, are dried, and 900 ℃ of calcinings make Li 0.35la 0.55tiO 3;
(2) Li-La-Zr-O colloidal sol preparation: with 2.896g LiNO 3, 7.794g La (NO 3) 36H 2o, 3.207gZrO (NO 3) 22H 2o and 3.604g acetylacetone,2,4-pentanedione are raw material, add in 40ml organic solvent ethylene glycol monoemethyl ether solution (density is 0.9647g/ml) and dissolve, make Li-La-Zr-O colloidal sol, wherein containing Li element 0.042mol, La element 0.018mol, Zr element 0.012mol, in O element, 0.072mol and Li element, La element and Zr element proportioning meet Li 7la 3zr 2o 12in the mol ratio of each element, O element in addition exists with other forms, like this, the gross mass that is calculated as Li-La-Zr-O colloidal sol is 56.089g, wherein correspondingly contains the Li that theoretical value is 0.006mol 7la 3zr 2o 12, correspondence contains the Li that Theoretical Mass is 5.04g 7la 3zr 2o 12;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in 1.98g step (1) 0.35la 0.55tiO 3add in 20ml organic solvent ethylene glycol monoemethyl ether solution, ultrasonic 1 hour, by Li 3xla 2/3-xtiO 3the Li corresponding with Li-La-Zr-O colloidal sol 7la 3zr 2o 12theoretical Mass than adding Li-La-Zr-O colloidal sol 0.226g for 99:1, stir 0.5 hour, make mixed solution, then described mixed solution is placed in to baking oven and is dried 2 hours at 50 ℃ of temperature, in 150 ℃ of heat treatments 1 hour, make composite solid lithium-ion electrolyte material presoma powder subsequently;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1250 ℃ of sintering 2 hours, obtains lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
A kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material making, by Li 0.35la 0.55tiO 3be enriched in Li 0.35la 0.55tiO 3the zr element of grain boundary layer form, wherein to account for the theoretical value of lithium lanthanum titanium oxide solid ionic electrolyte quality of materials percentage be 0.217% to zr element, according to inductive coupling plasma emission spectrograph (ICP), test, in the lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material that the present embodiment makes, zr element accounts for lithium lanthanum titanium oxide solid ionic electrolyte quality of materials percentage and approaches theoretical value, is 0.2%.
Embodiment bis-
A preparation method for lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: with 1.137g LiNO 3(lithium excessive 10%), 6.495gLa (NO 3) 36H 2o, 10.211g butyl titanate and 6.007g acetylacetone,2,4-pentanedione are raw material, take ethylene glycol monoemethyl ether as solvent, utilize sol-gal process, at 70 ℃, are dried, and 900 ℃ of calcinings make Li 0.5la 0.5tiO 3;
(2) Li-La-Zr-O colloidal sol preparation: with 2.896g LiNO 3, 7.794g La (NO 3) 36H 2o, 3.207gZrO (NO 3) 22H 2o and 3.604g acetylacetone,2,4-pentanedione are raw material, add in 40ml organic solvent ethylene glycol monoemethyl ether solution (density is 0.9647g/ml) and dissolve, make Li-La-Zr-O colloidal sol, wherein containing Li element 0.042mol, La element 0.018mol, Zr element 0.012mol, in O element, 0.072mol and Li element, La element and Zr element proportioning meet Li 7la 3zr 2o 12in the mol ratio of each element, O element in addition exists with other forms, like this, the gross mass that is calculated as Li-La-Zr-O colloidal sol is 56.089g, wherein correspondingly contains the Li that theoretical value is 0.006mol 7la 3zr 2o 12, correspondence contains the Li that Theoretical Mass is 5.04g 7la 3zr 2o 12;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in 1.9g step (1) 0.5la 0.5tiO 3add in 20ml organic solvent ethylene glycol monoemethyl ether solution, ultrasonic 1 hour, by Li 3xla 2/3-xtiO 3the Li corresponding with Li-La-Zr-O colloidal sol 7la 3zr 2o 12theoretical Mass than adding Li-La-Zr-O colloidal sol 1.13g for 19:1, stir 4 hours, make mixed solution, then described mixed solution is placed in to baking oven and is dried 6 hours at 70 ℃ of temperature, in 250 ℃ of heat treatments 2 hours, make composite solid lithium-ion electrolyte material presoma powder subsequently;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1300 ℃ of sintering 4 hours, obtains lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
A kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material making, by Li 0.5la 0.5tiO 3be enriched in Li 0.5la 0.5tiO 3the zr element of grain boundary layer form, wherein to account for the theoretical value of lithium lanthanum titanium oxide solid ionic electrolyte quality of materials percentage be 1.083% to zr element, according to inductive coupling plasma emission spectrograph (ICP), test, in the lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material that the present embodiment makes, zr element accounts for lithium lanthanum titanium oxide solid ionic electrolyte quality of materials percentage and approaches theoretical value, is 1.02%.
Embodiment tri-
A preparation method for lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: with 1.422g Li 2cO 3(lithium excessive 10%), 8.960g La 2o 3, 7.987g TiO 2for raw material, utilize solid phase method, first ball milling mixes, then through 1100 ℃ and 1150 ℃ of two step calcining, makes Li 0.35la 0.55tiO 3;
(2) Li-La-Zr-O colloidal sol preparation: with 2.896g LiNO 3, 7.794g La (NO 3) 36H 2o, 3.207gZrO (NO 3) 22H 2o and 3.604g acetylacetone,2,4-pentanedione are raw material, add in 40ml organic solvent ethylene glycol monoemethyl ether solution (density is 0.9647g/ml) and dissolve, make Li-La-Zr-O colloidal sol, wherein containing Li element 0.042mol, La element 0.018mol, Zr element 0.012mol, in O element, 0.072mol and Li element, La element and Zr element proportioning meet Li 7la 3zr 2o 12in the mol ratio of each element, O element in addition exists with other forms, like this, the gross mass that is calculated as Li-La-Zr-O colloidal sol is 56.089g, wherein correspondingly contains the Li that theoretical value is 0.006mol 7la 3zr 2o 12, correspondence contains the Li that Theoretical Mass is 5.04g 7la 3zr 2o 12;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in 1.8g step (1) 0.35la 0.55tiO 3add in 20ml organic solvent ethylene glycol monoemethyl ether solution, ultrasonic 1 hour, by Li 3xla 2/3-xtiO 3the Li corresponding with Li-La-Zr-O colloidal sol 7la 3zr 2o 12theoretical Mass than adding Li-La-Zr-O colloidal sol 2.26g for 9:1,, stir 2 hours, make mixed solution, then described mixed solution is placed in to baking oven and is dried 10 hours at 70 ℃ of temperature, subsequently in 350 ℃ of heat treatments 4 hours, make composite solid lithium-ion electrolyte material presoma powder;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1350 ℃ of sintering 8 hours, obtains lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
A kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material making, by Li 0.35la 0.55tiO 3be enriched in Li 0.35la 0.55tiO 3the zr element of grain boundary layer form.
Embodiment tetra-
A preparation method for lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: with 2.032g Li 2cO 3(lithium excessive 10%), 8.145g La 2o 3, 7.987g TiO 2for raw material, utilize solid phase method, first ball milling mixes, then through 1100 ℃ and 1150 ℃ of two step calcining, makes Li 0.5la 0.5tiO 3;
(2) Li-La-Zr-O colloidal sol preparation: with 2.896g LiNO 3, 7.794g La (NO 3) 36H 2o, 3.207gZrO (NO 3) 22H 2o and 3.604g acetylacetone,2,4-pentanedione are raw material, add in 40ml organic solvent ethylene glycol monoemethyl ether solution (density is 0.9647g/ml) and dissolve, make Li-La-Zr-O colloidal sol, wherein containing Li element 0.042mol, La element 0.018mol, Zr element 0.012mol, in O element, 0.072mol and Li element, La element and Zr element proportioning meet Li 7la 3zr 2o 12in the mol ratio of each element, O element in addition exists with other forms, like this, the gross mass that is calculated as Li-La-Zr-O colloidal sol is 56.089g, wherein correspondingly contains the Li that theoretical value is 0.006mol 7la 3zr 2o 12, correspondence contains the Li that Theoretical Mass is 5.04g 7la 3zr 2o 12;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in 1.8g step (1) 3xla 2/3-xtiO 3add in 20ml organic solvent ethylene glycol monoemethyl ether solution, ultrasonic 1 hour, by Li 3xla 2/3-xtiO 3the Li corresponding with Li-La-Zr-O colloidal sol 7la 3zr 2o 12theoretical Mass than adding Li-La-Zr-O colloidal sol 2.26g for 9:1, stir 4 hours, make mixed solution, then described mixed solution is placed in to baking oven and is dried 12 hours at 80 ℃ of temperature, in 450 ℃ of heat treatments 5 hours, make composite solid lithium-ion electrolyte material presoma powder subsequently;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1450 ℃ of sintering 6 hours, obtains lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
A kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material making, by Li 0.5la 0.5tiO 3be enriched in Li 0.5la 0.5tiO 3the zr element of grain boundary layer form.
Effect embodiment
For the beneficial effect of the embodiment of the present invention is made and being provided powerful support for, provide effect embodiment as follows.
One, material surface electron-microscope scanning
Lithium lanthanum titanium oxide composite solid electrolyte ceramic material is put into ESEM, regulate and focus on and except astigmatism, under suitable multiplication factor, obtain surface topography photo.
Fig. 1 is the ESEM picture of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material surface of making in the embodiment of the present invention one.As can be seen from Figure 1, the crystallite dimension of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material is in micron dimension, and closely, hole seldom, illustrates that compactness is good in intercrystalline contact.
Two, material is across the elementary analysis of crystal boundary x ray energy spectrum line sweep
Lithium lanthanum titanium oxide composite solid electrolyte ceramic material is put into ESEM, observe surface topography, select suitable crystal boundary position, set the scanning pattern on cross-border boundary, carry out the x ray energy spectrum line scanning of element.
Fig. 2 be a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material of making in the embodiment of the present invention one across the elementary analysis of crystal boundary x ray energy spectrum line sweep.As can be seen from Figure 2, the zr element content in crystal boundary, apparently higher than the zr element content in crystal grain, illustrates that zr element is at Li 3xla 2/3-xtiO 3grain boundary layer enrichment.
Three, the mensuration of material electric conductivity
By lithium lanthanum titanium oxide composite solid electrolyte ceramic material upper and lower surface metal spraying, put into ac impedance measurement instrument, test ac impedance spectroscopy, and utilize electrochemistry equivalent electric circuit and process software to carry out matching, obtain crystal grain conductivity, crystal boundary conductivity and total conductivity numerical value.
Fig. 3 is the lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material room-temperature conductivity situation of change under different zr element content theoretical value conditions making in the embodiment of the present invention one, embodiment bis-and embodiment tri-.As can be seen from Figure 3, the total conductivity of lithium lanthanum titanium oxide composite solid electrolyte material significantly increases with the introducing of zr element, and the content of zr element account for lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials mark 1.083% time reach maximum, illustrate that the introducing of zr element can significantly improve Li 3xla 2/3-xtiO 3grain boundary layer conductivity, improve total conductivity.

Claims (10)

1. a lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, is characterized in that, by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.
2. a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 1, is characterized in that described Li 3xla 2/3-xtiO 3for Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
3. a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 1, is characterized in that, it is 0.217%～2.17% that described zr element accounts for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage.
4. a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 1, is characterized in that, it is 1.083% that described zr element accounts for described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte quality of materials percentage.
5. a preparation method for lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material, is characterized in that, comprises the following steps:
(1) lithium lanthanum titanium oxide preparation: use solid phase method or sol-gal process to make Li 3xla 2/3-xtiO 3, 0<x<0.16;
(2) Li-La-Zr-O colloidal sol preparation: with LiNO 3, La (NO 3) 36H 2o, ZrO (NO 3) 22H 2o and acetylacetone,2,4-pentanedione are raw material, according to Li 7la 3zr 2o 12in the metering ratio of each element carry out proportioning, add at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether, make Li-La-Zr-O colloidal sol;
(3) composite solid lithium-ion electrolyte material precursor system is standby: get the Li making in step (1) 3xla 2/3-xtiO 3add at least one in ethanol, acetone, isopropyl alcohol, ethylene glycol, ethylene glycol monoemethyl ether, add subsequently the Li-La-Zr-O colloidal sol making in step (2), stir 0.5～10 hour, make mixed solution, then described mixed solution is placed in to baking oven and is dried 2～12 hours at 20～130 ℃ of temperature, in 150～1000 ℃ of heat treatments 0.5～10 hour, make composite solid lithium-ion electrolyte material presoma powder subsequently;
(4) composite solid lithium-ion electrolyte material preparation: get the composite solid lithium-ion electrolyte material presoma powder making in step (3), compressing tablet, 1000 ℃～1450 ℃ sintering 1～10 hour, obtain lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material.
6. the preparation method of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 5, is characterized in that described Li 3xla 2/3-xtiO 3for Li 0.35la 0.55tiO 3or Li 0.5la 0.5tiO 3.
7. the preparation method of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 5, is characterized in that, step is pressed Li in (3) 3xla 2/3-xtiO 3with Li corresponding in Li-La-Zr-O colloidal sol 7la 3zr 2o 12the mass ratio of Theoretical Mass is that 9:1～99:1 adds Li-La-Zr-O colloidal sol.
8. the preparation method of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 5, is characterized in that, described baking temperature is 50～80 ℃, and described heat treated temperature is 250～450 ℃.
9. the preparation method of a kind of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material as claimed in claim 5, is characterized in that, described sintering temperature is 1250～1350 ℃.
10. the application of lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material in lithium ion battery, described lithium lanthanum titanium oxide composite solid lithium-ion electrolyte material is by Li 3xla 2/3-xtiO 3be enriched in described Li 3xla 2/3-xtiO 3the zr element of grain boundary layer form, 0<x<0.16.
CN201310076874.0A 2013-03-12 2013-03-12 Lithium lanthanum titanate (LLTO) composite solid-state lithium ion electrolyte material, preparation method and application thereof Pending CN104051782A (en)

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