WO2012007123A1 - Procédé de production de lithium dihydrogène phosphate - Google Patents

Procédé de production de lithium dihydrogène phosphate Download PDF

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Publication number
WO2012007123A1
WO2012007123A1 PCT/EP2011/003357 EP2011003357W WO2012007123A1 WO 2012007123 A1 WO2012007123 A1 WO 2012007123A1 EP 2011003357 W EP2011003357 W EP 2011003357W WO 2012007123 A1 WO2012007123 A1 WO 2012007123A1
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WO
WIPO (PCT)
Prior art keywords
lithium
dihydrogen phosphate
production
phosphoric acid
lithium dihydrogen
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/EP2011/003357
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German (de)
English (en)
Inventor
Henrike Thauern
Thomas Staffel
Günther RAAB
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BK Giulini GmbH
Original Assignee
BK Giulini GmbH
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Filing date
Publication date
Application filed by BK Giulini GmbH filed Critical BK Giulini GmbH
Publication of WO2012007123A1 publication Critical patent/WO2012007123A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • 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 lithium dihydrogen phosphate, its preparation and its use in the production of LiMeP0 4 -hodenmaterial for Li-ion accumulators.
  • Rechargeable Li-ion batteries are widely used as energy storage devices in the field of mobile electronics. Nominal voltages of up to 3.7 volts can be reached today. Without going into detail on these modern Li batteries technically, the so-called cathode materials used there are all compounds or variations of LiMePO 4 where Me means different metals such as iron, manganese, nickel, cobalt.
  • iron (III) phosphate of iron sulfate, iron chloride, iron carbonate is e.g. B. from Gmelin's Handbook of Inorganic Chemistry, Part B, pages 773 ff. Described and known.
  • WO 02/30815 also describes a process for the production of LiFePO 4 , starting from iron phosphate and lithium. However, this method has not prevailed due to the uneconomic approach.
  • lithium iron phosphate for example starting, preferably from lithium dihydrogen phosphate, is described in WO2007049871.
  • Lithium dihydrogen phosphate as a precursor compound has already been described in the literature.
  • the preparation of lithium dihydrogen phosphate is e.g. in CN 101269806 (1).
  • This method involves a double reaction of phosphoric acid and lithium hydroxide according to the reaction equation:
  • Both starting compounds must be prepurified before the reaction. Both compounds are reacted as solutions with each other in a reactor. The crude solution thus obtained is treated with ⁇ - ⁇ 1 2 0 3 as a chromatographic filter to remove the remaining impurities. After filtration, the resulting solution is concentrated and then crystallized. The product is kept vacuum packed. It contains less than 30 ppm Na, Ca, Mg and sulfate anions.
  • CN 10131 1 108 (2) describes a crystallization method in the cold, after which very pure LiH 2 P0 4 is obtained. In particular, the particle size of the crystals thus obtained is uniform and small.
  • the lithium component should be crystalline, with relatively small regular crystals. Impurities, which may be mainly calcium, magnesium and sodium are to be reduced to a minimum, as far as possible below 30 ppm.
  • the inventors of the present invention have therefore set themselves the task of finding a method by which the production of LiH 2 P0 4 is industrially and economically possible.
  • the inventive method is characterized in that the reaction of the lithium compound with the phosphoric acid takes place without the addition of water.
  • the heat of neutralization which is formed during the reaction of the two components LiOH and H3PO4, is also used. Subsequently, only a small amount of water has to be evaporated at low temperatures.
  • the combination of these two types of drying leads to a crystalline product with the required properties.
  • the process can be carried out in one stage, while saving the process steps grinding, filtration and drying.
  • both LiOH and Li 2 C0 3 can be used.
  • the production takes place in a heatable mixing unit, whereby all common mixers can be used. Particularly preferred is a Lödige mixer or plowshare mixer. LiOH or Li 2 CO_? can be presented in solid form. The concentrated phosphoric acid is added slowly and the mixture is stirred. The temperature in the reaction does not exceed 80 ° C, so that the reaction can be carried out in an open manner.
  • the product after crystallization is a white, fine, but not nanoparticulate powder which is readily soluble in water and has a pH of 4.5.
  • the physical characterization of the crystalline LiH 2 P0 4 was performed by XRD images, IR spectrum, and by scanning electron micrographs (SEM).
  • Figure 1 shows a typical XRD spectrum of LiH 2 P0 4 , with the 2Theta value of about 23 0 as the site with the highest absolute intensity.
  • the spectrum shows an almost 100% agreement with the standard spectrum. This is a proof of the almost 100% conversion of the two starting compounds to the process product according to the invention.
  • Lithium can not be detected with this method. If unreacted Li 2 C0 3 vorläge, then you would find at a measuring point only oxygen and carbon.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un lithium dihydrogène phosphate qui est utilisé lors de la production d'un matériau cathodique LiMePO4 pour des accumulateurs Li-ions, et qui est produit par la mise en réaction du composé lithium avec de l'acide phosphorique sans apport d'eau supplémentaire. Pour supprimer l'eau introduite par l'acide phosphorique, on utilise la chaleur de neutralisation générée lors de la mise en réaction des deux constituants. Le lithium dihydrogène phosphate ainsi produit est particulièrement pur et convient donc particulièrement à la production d'un matériau cathodique LiMePCU.
PCT/EP2011/003357 2010-07-12 2011-07-06 Procédé de production de lithium dihydrogène phosphate Ceased WO2012007123A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010026828.4 2010-07-12
DE102010026828A DE102010026828A1 (de) 2010-07-12 2010-07-12 Verfahren zur Herstellung von Lithiumdihydrogenphosphat

Publications (1)

Publication Number Publication Date
WO2012007123A1 true WO2012007123A1 (fr) 2012-01-19

Family

ID=44543141

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/003357 Ceased WO2012007123A1 (fr) 2010-07-12 2011-07-06 Procédé de production de lithium dihydrogène phosphate

Country Status (2)

Country Link
DE (1) DE102010026828A1 (fr)
WO (1) WO2012007123A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116986562A (zh) * 2023-07-10 2023-11-03 四川省绵竹市汉旺无机盐化工有限公司 一种电池级磷酸二氢锂生产工艺
CN120943225A (zh) * 2025-08-18 2025-11-14 湖南智电谷能源科技有限公司 一种电池级磷酸二氢锂的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104445128B (zh) * 2014-12-23 2016-08-24 中国地质科学院郑州矿产综合利用研究所 电池级磷酸二氢锂的制备方法
CN108147384B (zh) * 2017-12-28 2021-03-19 江西赣锋循环科技有限公司 一种利用磷酸亚铁锂废料制备电池级磷酸二氢锂的方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002030815A1 (fr) 2000-10-11 2002-04-18 Rhodia Chimie Procede de preparation d'un phosphate de fer et d'un alcalin
US20040018135A1 (en) * 2002-07-26 2004-01-29 Adamson George W. Alkali metal hydrogen phosphates as precursors for phosphate-containing electrochemical active materials
EP0904607B1 (fr) 1996-04-23 2004-10-27 The Board Of Regents, The University Of Texas System Materiaux cathodiques pour batterie d'accumulateurs au lithium (rechargeable)
JP2004359538A (ja) * 2003-05-09 2004-12-24 Nippon Chem Ind Co Ltd リン酸リチウム凝集体、その製造方法及びリチウム鉄リン系複合酸化物の製造方法
WO2007049871A1 (fr) 2005-10-26 2007-05-03 Lg Chem, Ltd. Accumulateur possedant des caracteristiques de longevite ameliorees
CN101269806A (zh) 2008-05-06 2008-09-24 四川天齐锂业股份有限公司 电池级磷酸二氢锂的制备方法
CN101311108A (zh) 2007-05-22 2008-11-26 上海比亚迪有限公司 一种磷酸二氢锂的分离方法及其制备方法
DE102007049757A1 (de) 2007-10-16 2009-04-23 Chemische Fabrik Budenheim Kg Eisen(III)orthophosphat für Li-Ionen-Akkumulatoren
CN101638225A (zh) * 2009-09-04 2010-02-03 江西赣锋锂业股份有限公司 制备电池级磷酸二氢锂的方法及由此制得的电池级磷酸二氢锂
CN101767782A (zh) * 2010-03-05 2010-07-07 四川国理锂材料有限公司 磷酸二氢锂的生产方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0904607B1 (fr) 1996-04-23 2004-10-27 The Board Of Regents, The University Of Texas System Materiaux cathodiques pour batterie d'accumulateurs au lithium (rechargeable)
WO2002030815A1 (fr) 2000-10-11 2002-04-18 Rhodia Chimie Procede de preparation d'un phosphate de fer et d'un alcalin
US20040018135A1 (en) * 2002-07-26 2004-01-29 Adamson George W. Alkali metal hydrogen phosphates as precursors for phosphate-containing electrochemical active materials
JP2004359538A (ja) * 2003-05-09 2004-12-24 Nippon Chem Ind Co Ltd リン酸リチウム凝集体、その製造方法及びリチウム鉄リン系複合酸化物の製造方法
WO2007049871A1 (fr) 2005-10-26 2007-05-03 Lg Chem, Ltd. Accumulateur possedant des caracteristiques de longevite ameliorees
CN101311108A (zh) 2007-05-22 2008-11-26 上海比亚迪有限公司 一种磷酸二氢锂的分离方法及其制备方法
DE102007049757A1 (de) 2007-10-16 2009-04-23 Chemische Fabrik Budenheim Kg Eisen(III)orthophosphat für Li-Ionen-Akkumulatoren
CN101269806A (zh) 2008-05-06 2008-09-24 四川天齐锂业股份有限公司 电池级磷酸二氢锂的制备方法
CN101638225A (zh) * 2009-09-04 2010-02-03 江西赣锋锂业股份有限公司 制备电池级磷酸二氢锂的方法及由此制得的电池级磷酸二氢锂
CN101767782A (zh) * 2010-03-05 2010-07-07 四川国理锂材料有限公司 磷酸二氢锂的生产方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200506, Derwent World Patents Index; AN 2005-051258, XP002661023 *
DATABASE WPI Week 201059, Derwent World Patents Index; AN 2010-K16569, XP002661024 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116986562A (zh) * 2023-07-10 2023-11-03 四川省绵竹市汉旺无机盐化工有限公司 一种电池级磷酸二氢锂生产工艺
CN120943225A (zh) * 2025-08-18 2025-11-14 湖南智电谷能源科技有限公司 一种电池级磷酸二氢锂的制备方法

Also Published As

Publication number Publication date
DE102010026828A1 (de) 2012-01-12

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