WO2012140035A1 - Procédé de fabrication de spinelles de titanate de lithium - Google Patents

Procédé de fabrication de spinelles de titanate de lithium Download PDF

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Publication number
WO2012140035A1
WO2012140035A1 PCT/EP2012/056510 EP2012056510W WO2012140035A1 WO 2012140035 A1 WO2012140035 A1 WO 2012140035A1 EP 2012056510 W EP2012056510 W EP 2012056510W WO 2012140035 A1 WO2012140035 A1 WO 2012140035A1
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WO
WIPO (PCT)
Prior art keywords
lithium titanate
carbon
lithium
coated
doped
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.)
Ceased
Application number
PCT/EP2012/056510
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German (de)
English (en)
Inventor
Michael Holzapfel
Nicolas Tran
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Sued Chemie AG
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Sued Chemie AG
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Filing date
Publication date
Application filed by Sued Chemie AG filed Critical Sued Chemie AG
Publication of WO2012140035A1 publication Critical patent/WO2012140035A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/40—Electric properties
    • 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
    • C01P2006/80—Compositional purity
    • 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

Definitions

  • the present invention relates to a method for
  • Lithium titanate Li 4 Ti 5 0i 2, or lithium titan spinel for short has recently been proposed as a substitute for graphite as an anode material in rechargeable lithium ion batteries, also known as a so-called secondary lithium ion battery.
  • Li 4 Ti 5 0i2 has a relatively constant potential difference of 1.55 V to lithium and reaches several 1000 charge and Entladezyklen with a capacity loss of ⁇ 20%.
  • lithium titanium spinel shows a significantly more positive potential than graphite, which, as already stated, has traditionally been used as an anode in rechargeable lithium-ion batteries.
  • Li 4 Ti 5 0i 2 has a long life and is non-toxic and therefore not harmful to the environment
  • LiFeP0 4 or its doped derivatives is used as a cathode material in lithium-ion batteries, so that in a combination of Li 4 Ti 5 0i 2 and (doped or undoped) LiFeP0 4, a voltage difference of 2 V can be achieved.
  • Lithium titanate Li 4 Ti 5 O 2 is described in detail in many respects. Usually, Li 4 Ti 5 0i 2 by means of a
  • Organotitanium compounds such as Titantetraisopropoxide or titanium tetrabutoxide in anhydrous media with, for example, lithium acetate or lithium ethoxide to Li 4 Ti 5 0i 2 reacted.
  • the sol-gel methods require the use of titanium starting compounds which are far more expensive than T 1O 2 and their titanium content is lower than in T 1O 2 , so that a production of lithium titanium spinel by the sol-gel method is usually uneconomical, especially the Product still has to be calcined after the sol-gel reaction in order to obtain crystallinity.
  • Solid-state reaction such as Li 2 Ti0 3 etc.
  • Carbon-coated spinel advantageously has small primary particle sizes and almost no undesirable secondary agglomerates, such as non-carbon-coated lithium titanium spinel, for example.
  • the efficiency of carbon coating is increasingly called into question because finely divided lithium titanium spinel without secondary agglomerates is similar during cycling electronic properties such as carbon coated
  • Lithium titanium spinel should have.
  • Lithium ititanate still increased. This may be related to the fact that due to the reduced agglomeration of the
  • Lithium t itanatpart ikel the electrolyte can diffuse significantly better inside the agglomerates, which especially the lithiation, that is, the charging process is accelerated. A reduction of the electronic conductivity by the Elimination of the carbon layer was surprisingly not found.
  • the material obtained according to the invention also has in embodiments of the present invention
  • lithium titanate carbon-coated lithium titanate (about 165 mAh / g).
  • lithium titanate lithium titanium spinel
  • lithium titanate according to the invention refers to both the non-doped and the doped forms.
  • phase-pure lithium titanate means that no rutile phase can be detected in the end product by means of XRD measurements within the usual measurement accuracy.
  • the carbon layer is preferably removed by oxidation
  • a method according to the invention in embodiments of the present invention, is a lithium titanate having a
  • the heating is typically carried out for a period of 2 to 16 hours to ensure complete removal of the carbon coating of the lithium titanate employed.
  • the object of the present invention is further achieved by a carbon-free, finely particulate lithium titanate obtainable by the process according to the invention described above.
  • Lithium titanate obtained according to the invention doped with at least one further metal, which further increased to a
  • doped lithium titanate leads as an anode.
  • additional metal ions Preferably Al, Mg, Ga, Fe, Co, Sc, Y, Mn, Ni, Cr, V or more of these ions achieved in the lattice structure.
  • aluminum Preferably aluminum.
  • the dopant metal ions which can either sit on lattice sites of titanium or lithium, are usually present in an amount of 0.05 to 3 at.%, Preferably 1-3 at.%, Based on the total spinel.
  • Lithium titanium spinel is described in detail below.
  • the non-doped and doped lithium titanate obtainable according to the invention has a particle size d 9 o 5 pm, in other embodiments ⁇ 4 pm for a non-milled sample, ie directly after conversion and separation (see below) and in SEM images of the product no sintering phenomena are observed.
  • the lithium titanate according to the invention further has a
  • carbon-free lithium titanate also has a monomodal particle size distribution.
  • a small, in particular monomodal distributed particle size leads as already said to a higher current density and also to a better cycle stability, so that the
  • Lithium titanate according to the invention also without further mechanical grinding steps as part of an anode in
  • rechargeable lithium ion batteries can be used.
  • the product obtained can be further finely ground, if that is for a specific Application should be necessary.
  • the milling process can be carried out using methods known per se to those skilled in the art, for example by means of a jet mill. Surprisingly, it was also found that the
  • Lithium titanate has a relatively high BET surface area in the range of 2 - 15 m 2 / g, in developments of the invention of 10 - 15 m 2 / g and 13 - 14 m 2 / g.
  • the doped or non-doped lithium titanate according to the invention is preferably used as the active material in an anode in rechargeable lithium-ion batteries.
  • the invention therefore also relates to an anode comprising the lithium titanate obtainable according to the invention as active material.
  • the present invention relates to a
  • a rechargeable lithium-ion battery comprising an anode and a cathode and an electrolyte, wherein the anode
  • the invention contains doped or undoped lithium titanate.
  • the anode according to the invention has a
  • FIG. 1 shows the particle size distribution of the lithium titanate obtainable by means of the method according to the invention ("Inventive
  • Lithium titanate of the prior art obtainable by solid-state synthesis
  • Lithium titanate of the prior art according to DE 10 2008 026 580,
  • Fig. 4 shows the specific capacity of an electrode containing the inventive
  • FIGS. 5A and 5B show the discharge (5a) and charge (5b) capacities of a lithium titanate according to the invention
  • FIG. 6 shows the specific capacity of an electrode containing carbon-coated lithium titanate of the prior art according to DE 10 2008 026 580
  • FIGS. 7A and 7B the discharge (7a) and charge (7b) capacity of carbon-coated lithium titanate of the prior art according to DE 10 2008
  • Fig. IIA and IIB the discharge (11A) - and charging (11B) capaci ity of an electrode containing carbon-free lithium titanate of the prior art.
  • the synthesis of the lithium titanate and carbon coating preferably takes place in one step "in situ.” Alternatively, a two-stage process can also be used
  • Process management are selected, i. first synthesis of
  • Lithium titanate and then carbon coating of the material thus obtained The carbon content was 0.9 wt%.
  • the carbon-coated lithium titanate was placed in a reactor and heated at 370 ° C (Sample 1) or at 400 ° C (Sample 2) in air for 12 hours.
  • the resulting sample was white after heating with a slight gray cast.
  • the residual carbon content (including the carbonate content) was ⁇ 0.07%.
  • the determination of the carbon content was carried out with a CS-2000 from ELTRA, wherein the sample is oxidized at high temperature (up to 1550 ° C) and the CO 2 is then quantitatively determined by IR spectroscopy.
  • the electrode formulation consisted of 85% by weight of lithium titanate, 10% Super P, and 5% Kynar (PVdF).
  • Active mass content of the electrode was 2.54 ⁇ 0.20 mg / cm 2
  • the electrode was compacted for 20 sec. With 5 tons of pressing pressure.
  • FIG. 1 shows the particle size distribution of the lithium titanate obtainable according to the invention and corresponds approximately to that of the carbon-coated (starting) material (FIG. 3), which, however, has even larger secondary agglomerates in the region of> 10 ⁇ m.
  • the D 90 value of the lithium titanate obtainable according to the invention was 3 3.76 ⁇ m, the D 50 value 1,1 1.17 ⁇ m.
  • the particle size distribution of the material according to the invention is clearly different from the monomodal particle size distribution of the conventional carbon-free uncoated lithium titanate (FIG. 2) obtainable by one of the two abovementioned methods.
  • Fig. 4 shows the specific capacity of an electrode containing the carbon released at 370 ° C
  • Lithium titanate (sample 1) as the active composition.
  • the mass of the anode was 3.56 mg at 2.38 mg / cm 2 active mass.
  • FIG. 8 shows the specific capacity of an anode whose active composition is material according to the invention produced at 400 ° C. (sample 2)
  • FIG. 5a shows a similar characteristic here as carbon-coated material (FIG. 7A) and FIG. 7A.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de fabrication de titanate de lithium exempt de carbone, à fines particules, à partir de particules de titanate de lithium revêtues de carbone, dont la couche de carbone est ensuite retirée. La présente invention a en outre pour objet une électrode pour une batterie au lithium-ion secondaire contenant le titanate de lithium obtenu au moyen du procédé selon l'invention en tant que matériau actif ainsi qu'une batterie contenant une électrode de ce type.
PCT/EP2012/056510 2011-04-12 2012-04-11 Procédé de fabrication de spinelles de titanate de lithium Ceased WO2012140035A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011016836A DE102011016836A1 (de) 2011-04-12 2011-04-12 Verfahren zur Herstellung von Lithiumtitan-Spinell
DE102011016836.2 2011-04-12

Publications (1)

Publication Number Publication Date
WO2012140035A1 true WO2012140035A1 (fr) 2012-10-18

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PCT/EP2012/056510 Ceased WO2012140035A1 (fr) 2011-04-12 2012-04-11 Procédé de fabrication de spinelles de titanate de lithium

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DE (1) DE102011016836A1 (fr)
TW (1) TWI460131B (fr)
WO (1) WO2012140035A1 (fr)

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
JP6743513B2 (ja) 2016-06-22 2020-08-19 日本ケミコン株式会社 ハイブリッドキャパシタ及びその製造方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5545468A (en) 1993-03-17 1996-08-13 Matsushita Electric Industrial Co., Ltd. Rechargeable lithium cell and process for making an anode for use in the cell
US6645673B2 (en) 1999-02-16 2003-11-11 Toho Titanium Co., Ltd. Process for producing lithium titanate and lithium ion battery and negative electrode therein
DE10319464A1 (de) 2003-04-29 2004-11-18 Basf Ag Verfahren zur Herstellung von nanokristallinen Lithiumtitanat-Spinellen
EP1722439A1 (fr) 2005-05-13 2006-11-15 Kabushiki Kaisha Toshiba Batterie à électolyte non-aqueux, composite d'oxyde lithium-titanium, block de batterie et véhicule
US20070202036A1 (en) 2004-04-07 2007-08-30 Nathalie Jongen Production Of Barium Titanate Compounds
EP1049182B1 (fr) 1999-04-30 2008-01-02 Hydro-Quebec Matériaux d'électrode présentant une conductivité de surface élevée
US20090136415A1 (en) * 2006-08-04 2009-05-28 Enerdel, Inc. Lithium titanate and method of forming the same
DE102008026580A1 (de) 2008-06-03 2009-12-10 Süd-Chemie AG Verfahren zur Herstellung von Lithiumtitan-Spinell und dessen Verwendung
DE102008050692A1 (de) 2008-10-07 2010-04-08 Süd-Chemie AG Kohlenstoffbeschichteter Lithiumtitan-Spinell
WO2010052362A1 (fr) * 2008-11-04 2010-05-14 Sachtleben Pigments Oy Processus de préparation de titanates de métaux alcalins

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CA2327370A1 (fr) * 2000-12-05 2002-06-05 Hydro-Quebec Nouvelle methode de fabrication de li4ti5o12 pur a partir du compose ternaire tix-liy-carbone: effet du carbone sur la synthese et la conductivite de l'electrode
DE102009020832A1 (de) * 2009-05-11 2010-11-25 Süd-Chemie AG Verbundmaterial enthaltend ein gemischtes Lithium-Metalloxid
US9431649B2 (en) * 2009-11-23 2016-08-30 Uchicago Argonne, Llc Coated electroactive materials

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5545468A (en) 1993-03-17 1996-08-13 Matsushita Electric Industrial Co., Ltd. Rechargeable lithium cell and process for making an anode for use in the cell
US6645673B2 (en) 1999-02-16 2003-11-11 Toho Titanium Co., Ltd. Process for producing lithium titanate and lithium ion battery and negative electrode therein
EP1049182B1 (fr) 1999-04-30 2008-01-02 Hydro-Quebec Matériaux d'électrode présentant une conductivité de surface élevée
DE10319464A1 (de) 2003-04-29 2004-11-18 Basf Ag Verfahren zur Herstellung von nanokristallinen Lithiumtitanat-Spinellen
US20070202036A1 (en) 2004-04-07 2007-08-30 Nathalie Jongen Production Of Barium Titanate Compounds
EP1722439A1 (fr) 2005-05-13 2006-11-15 Kabushiki Kaisha Toshiba Batterie à électolyte non-aqueux, composite d'oxyde lithium-titanium, block de batterie et véhicule
US20090136415A1 (en) * 2006-08-04 2009-05-28 Enerdel, Inc. Lithium titanate and method of forming the same
DE102008026580A1 (de) 2008-06-03 2009-12-10 Süd-Chemie AG Verfahren zur Herstellung von Lithiumtitan-Spinell und dessen Verwendung
DE102008050692A1 (de) 2008-10-07 2010-04-08 Süd-Chemie AG Kohlenstoffbeschichteter Lithiumtitan-Spinell
WO2010052362A1 (fr) * 2008-11-04 2010-05-14 Sachtleben Pigments Oy Processus de préparation de titanates de métaux alcalins

Non-Patent Citations (3)

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Title
NAKAHARA K ET AL: "Preparation of particulate Li4Ti5O12 having excellent characteristics as an electrode active material for power storage cells", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 117, no. 1-2, 15 May 2003 (2003-05-15), pages 131 - 136, XP004423377, ISSN: 0378-7753, DOI: 10.1016/S0378-7753(03)00169-1 *
S. HUANG ET AL., J. POWER SOURCES, vol. 165, 2007, pages 408 - 412
TAO YUAN, XING YU, RUI CAI, YINGKE ZHOU, ZONGPING SHAO: "Synthesis of pristine and carbon-coated Li4Ti5O12 and their low-temperature electrochemical performance", JOURNAL OF POWER SOURCES, vol. 195, 17 February 2010 (2010-02-17), pages 4997 - 5004, XP026991272, DOI: 10.1016/j.jpowsour.2010.02.020 *

Also Published As

Publication number Publication date
TWI460131B (zh) 2014-11-11
DE102011016836A1 (de) 2012-10-18
TW201245048A (en) 2012-11-16

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