WO2011100778A1 - Procédé de fabrication de titanate de lithium - Google Patents

Procédé de fabrication de titanate de lithium Download PDF

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Publication number
WO2011100778A1
WO2011100778A1 PCT/AT2011/000086 AT2011000086W WO2011100778A1 WO 2011100778 A1 WO2011100778 A1 WO 2011100778A1 AT 2011000086 W AT2011000086 W AT 2011000086W WO 2011100778 A1 WO2011100778 A1 WO 2011100778A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
titanium
drying
alcohol
lithium titanate
Prior art date
Application number
PCT/AT2011/000086
Other languages
German (de)
English (en)
Inventor
Lukas Rubacek
Jiri Duchoslav
Original Assignee
Lukas Rubacek
Jiri Duchoslav
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 Lukas Rubacek, Jiri Duchoslav filed Critical Lukas Rubacek
Publication of WO2011100778A1 publication Critical patent/WO2011100778A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the invention relates to a process for producing lithium titanate, wherein a solution of lithium and titanium compounds is prepared before, after drying by separation of the solvent, calcining the obtained drying product to obtain lithium titanate.
  • Lithium titanates in crystal form having the stoichiometric formula Li 4 Ti 5 O 2 are particularly suitable for the production of the electrodes of lithium-ion batteries.
  • Various processes are known for the preparation of lithium titanates, which can be subdivided by dry and wet processes. While dry processes, which always use insoluble or only partially soluble starting materials, such as lithium hydroxide or lithium carbonate as the lithium compound and titanium dioxide as the titanium compound, are more economical, wet processes yield crystalline lithium titanates with better properties for the electrode production of lithium-ion batteries, not least because of the better mixing of the lithium used and titanium compounds in a liquid phase.
  • This substantially anhydrous drying product is then calcined at a temperature for a time sufficient to convert the mixture of titanium and lithium compounds to lithium titanate having the desired structure and particle size.
  • the reaction temperature is substantially between 700 and 900 ° C.
  • the disadvantage is the comparatively low yield.
  • the invention is therefore based on the object, a method of the type described in such a way that pure crystalline lithium titanate can be produced economically advantageous for the production of electrodes for lithium-ion batteries properties in particular in terms of particle size and specific surface area
  • the invention achieves the stated object by dissolving an alcohol-soluble lithium salt and a titanium alkoxide in a mixture of alcohol and a chelating agent for retarding the hydrolysis of the titanium alkoxide, before the drying product is calcined in the form of a viscous sludge.
  • the invention is based on the finding that water, which is present in the solution or in the air, a hydrolysis of the titanium compounds and as a result of a precipitation of amorphous titanium dioxide in the form of anatase and rutile with comparatively large particles because of the uncontrolled and rapid reaction which impairs the homogeneity of the mixture of lithium and titanium compounds obtained after drying, and leads to an undesired L ⁇ TiO ß phase in the final product. Therefore, when starting from insoluble in water lithium and titanium compounds and an alcohol used as a solvent, an essential prerequisite to avoid hydrolysis of titanium compounds is created.
  • This condition is not yet sufficient, because inhibition of the hydrolysis as a prerequisite for ensuring that after drying a homogeneous mixture of lithium and titanium compounds as drying product is obtained after drying of the alcohol which is only soluble in alcohol Requirements for subsequent calcination advantageously corresponds.
  • This drying product may be directly subjected to the heat treatment under protective gas in the form of a viscous slurry to obtain pure nanocrystalline lithium titanate having a comparatively high specific surface area.
  • an alcohol-soluble lithium salt from the group of lithium nitrates, lithium chlorides and lithium hydroxides can be selected. Preference is given to using a lithium acetate dihydrate which can be dissolved in an alcohol.
  • Particularly suitable solvents are lower-valent alcohols, such as methanol, ethanol, propanol, isopropanol or butanol. Preferably, ethanol is used.
  • the water-insoluble titanium compounds used as starting material for titanium are selected from the group of titanium (IV) alkoxides, for example from the group containing titanium (IV) methoxides, ethoxides, -propoxides, -isopropoxides and tert-butoxides, preferably titanium (IV).
  • IV) tetrabutoxide is used.
  • the molar ratio between titanium and lithium is selected in the range between 1: 0.8 to 1: 1, 2, preferably 1: 1.
  • Acetylacetone can advantageously be used as a chelating agent. Titanium alkoxides react very rapidly with the chelating agent acetylacetone to obtain a titanium acetylacetonate complex compound and alcohol. In the case of the use of titanium tetrabutoxide, the reaction gives butanol.
  • the molar ratio between the titanium alkoxide and the chelating agent can be chosen between 1: 0.2 to 1: 2, preferably 1: 1.
  • Particularly advantageous conditions for the further processing of the nanocrystalline final product can be ensured if the alcoholic solution of the lithium salt and the titanium alkoxide before drying a nanoscale carbon powder is added, which ensures the electrical conductivity of the electrodes produced and the otherwise necessary admixture of a carbon powder for Lithium titanate makes redundant.
  • the carbon powder acts as a template for calcining and inhibits the sintering of the resulting lithium titanate particles which are directly covered with the conductive carbon and together with the carbon yield particles having an average grain diameter of 1 to 10 ⁇ m, which markedly improves the processability of these powders , Carbon can be added to the solution in an amount of 1 to 2% by weight of the titanium compounds used.
  • the final product of lithium titanate and carbon obtained after calcining may contain small residual amounts of lithium salt, which is preferably dissolved in a superstoichiometric amount. For this reason, the final product can be washed from the calcination with water to remove residual lithium salt.
  • the washed product may be dried at a temperature between 100 and 120 ° C to evaporate the water and obtain a dry powder. Subsequently, the fired and washed powder can be ground to obtain a predetermined grain size of the crystalline lithium titanate.
  • the product obtained after this calcination consisted of crystalline lithium titanate Li 4 Ti 5 Oi 2 having a particle size of about 30 to 80 nm.
  • the calcined product was suspended in water and ground with zirconium as grinding medium for eight hours.
  • the specific surface area of the product was about 53 m g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Geology (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de fabrication de titanate de lithium, une solution de composés de lithium et de titane étant fabriquée, avant que le produit de séchage obtenu ne soit calciné après un séchage par séparation du solvant pour obtenir du titanate de lithium. Pour réaliser des conditions de fabrication avantageuses, l'invention propose qu'un sel de lithium soluble dans l'alcool et un alcoxyde de titane soient dissous dans un mélange d'alcool et d'un agent chélatant pour le ralentissement de l'hydrolyse de l'alcoxyde de titane, avant que le produit de séchage sous forme d'une boue visqueuse ne soit calciné.
PCT/AT2011/000086 2010-02-19 2011-02-21 Procédé de fabrication de titanate de lithium WO2011100778A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA254/2010 2010-02-19
AT2542010A AT509504A1 (de) 2010-02-19 2010-02-19 Verfahren zum herstellen von lithiumtitanat

Publications (1)

Publication Number Publication Date
WO2011100778A1 true WO2011100778A1 (fr) 2011-08-25

Family

ID=44170509

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2011/000086 WO2011100778A1 (fr) 2010-02-19 2011-02-21 Procédé de fabrication de titanate de lithium

Country Status (2)

Country Link
AT (1) AT509504A1 (fr)
WO (1) WO2011100778A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2746220A3 (fr) * 2012-12-21 2014-07-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Particules de grande surface revêtues d'un matériau d'intercalation, leur procédé de fabrication et utilisation des particules dans des électrodes hybrides et des condensateurs à double couche à haute capacité et des batteries rapides
CN113921806A (zh) * 2020-07-10 2022-01-11 精工爱普生株式会社 负极活性物质的前体溶液、粉末及负极活性物质制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003008334A1 (fr) 2001-07-20 2003-01-30 Altair Nanomaterials Inc. Procede destine a fabriquer du titanate de lithium
US20080285211A1 (en) * 2000-12-05 2008-11-20 Hydro-Quebec Li4Ti5O12,Li(4-alpha)ZalphaTi5O12 or Li4ZbetaTi(5-beta)O12 particles processes for obtaining same and use as electrochemical generators
WO2009135448A2 (fr) * 2008-05-06 2009-11-12 Elmarco S.R.O. Procédé de production de nanofibres inorganiques par filage électrostatique
CN101609883A (zh) * 2009-07-13 2009-12-23 北京安华联合能源科技有限责任公司 一种纳米银颗粒分散Li4Ti5O12薄膜锂离子电池负极制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080285211A1 (en) * 2000-12-05 2008-11-20 Hydro-Quebec Li4Ti5O12,Li(4-alpha)ZalphaTi5O12 or Li4ZbetaTi(5-beta)O12 particles processes for obtaining same and use as electrochemical generators
WO2003008334A1 (fr) 2001-07-20 2003-01-30 Altair Nanomaterials Inc. Procede destine a fabriquer du titanate de lithium
WO2009135448A2 (fr) * 2008-05-06 2009-11-12 Elmarco S.R.O. Procédé de production de nanofibres inorganiques par filage électrostatique
CN101609883A (zh) * 2009-07-13 2009-12-23 北京安华联合能源科技有限责任公司 一种纳米银颗粒分散Li4Ti5O12薄膜锂离子电池负极制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2746220A3 (fr) * 2012-12-21 2014-07-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Particules de grande surface revêtues d'un matériau d'intercalation, leur procédé de fabrication et utilisation des particules dans des électrodes hybrides et des condensateurs à double couche à haute capacité et des batteries rapides
CN113921806A (zh) * 2020-07-10 2022-01-11 精工爱普生株式会社 负极活性物质的前体溶液、粉末及负极活性物质制造方法

Also Published As

Publication number Publication date
AT509504A1 (de) 2011-09-15

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