WO2004043856A1 - フッ素含有リチウム化合物の製造方法 - Google Patents
フッ素含有リチウム化合物の製造方法 Download PDFInfo
- Publication number
- WO2004043856A1 WO2004043856A1 PCT/JP2003/014383 JP0314383W WO2004043856A1 WO 2004043856 A1 WO2004043856 A1 WO 2004043856A1 JP 0314383 W JP0314383 W JP 0314383W WO 2004043856 A1 WO2004043856 A1 WO 2004043856A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- reaction
- lithium compound
- containing lithium
- producing
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- 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
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/005—Lithium hexafluorophosphate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/006—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/02—Halides
-
- 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
Definitions
- the present invention provides an element represented by the general formula LiMFx (M is an element selected from the group consisting of B, P, As, Sb, Bi, V, Nb, and Ta, and X is 4 to 6
- the present invention relates to a method for producing a fluorine-containing lithium compound represented by the following formula, and in particular, to easily produce LiMFx that does not contain impurities such as HF and other by-products that adversely affect battery performance. On how to do it.
- a lithium ion secondary battery such as ethylene carbonate or propylene carbonate is used.
- the electrolyte for lithium ion batteries using such a non-aqueous solvent can be used at a high voltage because of the high electrochemical stability of the non-aqueous solvent and the electrolyte.
- the electrolyte contains impurities, almost all of these impurities are electrochemically stable compared to the non-aqueous solvent and the electrolyte because of the design to maximize the performance.
- the reaction is easy to occur inside the battery due to its low battery, which causes the battery performance to deteriorate.
- the non-aqueous solvent and the electrolyte constituting such an electrolytic solution do not contain impurities.
- Li PF 6 which is used exclusively as an electrolyte for lithium-ion batteries
- HP F 6 is also known a method for producing in the reaction, for in this way to be mixed as an impurity in the L i PF 6 hydrolysis products are obtained, the method usually prepared by the reaction of L i F and PF 5 is This is common (for example, see Patent Documents 1 to 4).
- PF 5 used in this reaction is generally allowed to react with other pentavalent phosphorus compound and HF of PC 1 5 etc.
- ligand exchange, or PC 1 3 monovalent phosphide compounds such as 3 the produced by ligand exchange with oxidized HF, and this and generate reaction PF 5, also often be employed to the reaction with the PF 5 which generated an i F implemented as a series of reactions ( For example, refer to Patent Documents 5 to 10).
- Non-Patent Document 1 Makoto Ue et al., “Development and Market of Lithium-ion Battery Materials”
- the present invention solves the above conventional problems, the general formula L i MF X (M is B, P, A s, S b, B i, V, Nb, and an element selected from the group consisting of T a X is a number from 4 to 6.)
- This is a method for producing a fluorine-containing lithium compound represented by the formula: Li MFx that does not contain impurities such as HF and its by-products that adversely affect battery performance. It is an object of the present invention to provide a method capable of easily producing the same.
- the method for producing a fluorine-containing lithium compound of the present invention is a method for producing a fluorine-containing lithium compound represented by the general formula LiMF x (M is B, P, As, Sb, Bi, V, Nb, and one selected from the group consisting of Ta or
- LiF and M element or LiF and M element fluoride, or a mixture of M element fluoride and M element in the presence of fluorine gas.
- contacting in a single reaction vessel at a temperature of 100 ° C.
- B, P, As, Sb, B i, V, Nb, and Ta and a fluoride selected from the group consisting of As F 3 , S b F 3 , S b F 5 , B i F 3 , VF 2 , VF 4, VF 5, N b F 4, Nb F 5, T a F 5 , and the like.
- a fluoride selected from the group consisting of As F 3 , S b F 3 , S b F 5 , B i F 3 , VF 2 , VF 4, VF 5, N b F 4, Nb F 5, T a F 5 , and the like.
- two or more M elements can be used in combination.
- the charged molar ratio of LiF to the element M and Z or its fluoride is usually 1.0 or more and 2.0 or less, preferably more than 1.0 and 1.5 or less.
- the fine particles are finer in terms of reactivity from the viewpoint of reactivity. Is preferably a fine powder of 10 / im or less. However, if the particle size is too small, there is a problem such as scattering of the powder. Therefore, the average particle size is preferably 0.11 ⁇ or more, and particularly preferably the average particle size is 0.1 to 1 ⁇ . Better. LiF and M element, or LiF and M element fluoride or a mixture of M element fluoride and M element may be used by mixing those having been adjusted to a predetermined particle size in advance. Alternatively, it may be pulverized while being mixed to adjust such an average particle size.
- the Li F and M elements may be separately charged into a reaction vessel to start the reaction, but it is preferable to start the reaction after mixing them in advance.
- the mixing method of L i F and M element, or the mixing method of L i F and M element fluoride or M element fluoride and M element mixture is to mix in a single device. Alternatively, mixing may be performed in multiple stages using a mixer suitable for each of the convection, shearing, and diffusion mixing zones.
- a mortar can be used in a small amount.
- Equipment suitable for the convection mixing area such as ribbon-type blender, V-plender, conical-type blender, etc., which can cover all mixing areas with one unit.
- Vertical axis rotation as a device suitable for the diffusion mixing zone Devices that have blades, rolls, etc. on each rotating shaft of the rotary type and the horizontal shaft type can be mentioned.
- Fluorine gas (F 2 ) used in the reaction is a gas at normal temperature and has extremely high reactivity. For this reason, the reaction is preferably used in undiluted, it may be used as diluted with an inert gas with respect to F 2.
- an inert gas a rare gas such as helium or argon, nitrogen, or a perfluoroalkane having 4 or less carbon atoms is used.
- the concentration of fluorine gas in these inert gases is usually 1% by volume or more, preferably 50% by volume or more. If this concentration is too low, the productivity will deteriorate.
- the charged amount of F 2 with respect to element M and / or fluorides needs to supply more than the theoretical amount required to form a L i MF X at least, preferably 2 times or more the stoichiometric amount is there. If the charged amount of F 2 is high, but no problem in the reaction surface, because of a problem of recovery such as pressure or unreacted F 2 in the device, 1 ⁇ 0 more than double of a theoretical amount, preferably 2 0 times The following is preferred.
- reaction between the fluoride and F 2 is preferably carried out under heating at 100 ° C. or higher. This reaction is carried out by supplying the raw materials and reacting the solid raw materials Li F and M element. , fluorides L i F and M element, or L i F and M element and the reaction vessel charged with the fluoride, after Hama the F 2 charge, may be carried out by heating, charged with solid material After heating the reaction vessel, F 2 may be charged or distributed. Also, within the reaction vessel, it may be supplied solid body material while circulating F 2.
- reaction efficiency can be increased by appropriately feeding the reaction raw material, for example, F 2 gas or the like in a divided manner.
- the inside of the reaction tank is evacuated or the inert gas is filled. It is preferable to keep the reaction atmosphere (gas phase) during the reaction. It is desirable that, besides the intermediate produced, substantially only F 2 gas' inert gas is used.
- the reactor may be either a batch type or a flow type.
- stirring in the reaction tank is not essential, but if a reaction tank provided with a vertical or horizontal rotating shaft having blades, rolls, etc. is used. This is preferable because the reaction can smoothly proceed.
- the product is in an inert gas environment at the time of extracting the product. If the substance is also reactive with compounds contaminating from the outside air such as water and oxygen, and if it is necessary to maintain its purity, it can be taken out of the device and stored in an inert gas environment. is necessary.
- a reaction raw material is supplied to a reaction system, a desired fluorine-containing lithium compound can be obtained without a removal operation as a reaction intermediate or the like, so-called One pot synthesis (One pot synthesis). It is industrially advantageous in that it can be taken.
- reaction tank Since the reaction tank is filled or circulated with the F 2 gas, it is necessary that the reaction tank has a high hermeticity and can withstand the pressure and temperature under the reaction conditions described later. However, it is not desirable from the viewpoint of facilities to design so that it can withstand much more severe conditions than those actually used for the reaction, and it is sufficient if the design is appropriate for the selected reaction conditions.
- the material of the reaction tank must be able to withstand F 2 gas at a predetermined reaction temperature and pressure under a condition where water, oxygen, and other substances other than raw materials are not present.
- stainless steel Ya Monel ⁇ generally special steel is said to withstand F 2 of Ah Ru such Inkoneru are mentioned in.
- the reaction pressure is preferably 0.1 to; L00 atm (0.01 to 10 MPa), and more preferably 5 to 10 atm (0.05 to IMPa).
- the reaction temperature is preferably from 100 to 1000 ° C, more preferably from 200 to 500 ° C.
- the reaction time is different temperatures, pressures, and feed charged amount or, F 2 concentration, the manipulation-back number in the case of F 2 filling method, the F 2 flow amount and the like per unit time in the case of F 2 flow method However, it is usually 1 to 500 hours.
- a fluorine-containing lithium compound produced by the present invention preferably, Li PF 6 , Li BF 4 and the like are mentioned.
- Example 1 the method of the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
- Example 1 the method of the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
- L i F 28.69 mg (1.106 mmo 1) and 34.23 mg of red phosphorus (1.105 mmo 1) were mixed in an agate mortar under a nitrogen atmosphere, and the mixture was mixed.
- the mixture was charged in a stainless steel pressure vessel having an internal volume of 2 lm 1, and the pressure was reduced to a high vacuum state. Then, the atmosphere was replaced with Ar, and oxygen was removed from the atmosphere by reducing the pressure again. Then, after the pressure was reduced again, the container was filled with F 2 gas until the pressure reached 4 atm (0.4 MPa), and the container was sealed. After that, the temperature was raised to 300 ° C and maintained for 10.5 hours.
- Li MFx free from impurities such as HF and its by-products that adversely affect battery performance can be easily manufactured.
- the method of the present invention per the production of L i PF e as an electrolyte used in the electrolytic solution for lithium ion batteries, adversely affects the battery performance, conveniently prepared an electrolyte that does not contain impurities of such HF and its by-products
- the industrial utility is extremely large.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003280748A AU2003280748A1 (en) | 2002-11-12 | 2003-11-12 | Method for producing fluorine-containing lithium compound |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002328548 | 2002-11-12 | ||
JP2002-328548 | 2002-11-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004043856A1 true WO2004043856A1 (ja) | 2004-05-27 |
Family
ID=32310546
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/014383 WO2004043856A1 (ja) | 2002-11-12 | 2003-11-12 | フッ素含有リチウム化合物の製造方法 |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR101068065B1 (ja) |
CN (1) | CN1304279C (ja) |
AU (1) | AU2003280748A1 (ja) |
WO (1) | WO2004043856A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101068065B1 (ko) | 2002-11-12 | 2011-09-28 | 가부시키가이샤 산도쿠 | 불소 함유 리튬 화합물의 제조 방법 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5609283B2 (ja) * | 2010-06-08 | 2014-10-22 | セントラル硝子株式会社 | リチウムイオン電池用電解液の製造方法およびそれを用いたリチウムイオン電池 |
CN110970604A (zh) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | 一种包覆型三元正极材料、其制备方法及其用途 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61151024A (ja) * | 1984-12-25 | 1986-07-09 | Hashimoto Kasei Kogyo Kk | 高純度フツ化リチウム錯塩の製造法 |
JP2001122605A (ja) * | 1999-10-22 | 2001-05-08 | Kanto Denka Kogyo Co Ltd | 高純度六フッ化リン酸リチウムの製造方法 |
JP2001122604A (ja) * | 1999-10-22 | 2001-05-08 | Kanto Denka Kogyo Co Ltd | 高純度六フッ化リン酸リチウムの製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6472901A (en) * | 1987-09-14 | 1989-03-17 | Central Glass Co Ltd | Production of lithium fluoride complex salt |
KR101068065B1 (ko) | 2002-11-12 | 2011-09-28 | 가부시키가이샤 산도쿠 | 불소 함유 리튬 화합물의 제조 방법 |
-
2003
- 2003-11-12 KR KR1020057008441A patent/KR101068065B1/ko active IP Right Grant
- 2003-11-12 AU AU2003280748A patent/AU2003280748A1/en not_active Abandoned
- 2003-11-12 WO PCT/JP2003/014383 patent/WO2004043856A1/ja active Application Filing
- 2003-11-12 CN CNB2003801029929A patent/CN1304279C/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61151024A (ja) * | 1984-12-25 | 1986-07-09 | Hashimoto Kasei Kogyo Kk | 高純度フツ化リチウム錯塩の製造法 |
JP2001122605A (ja) * | 1999-10-22 | 2001-05-08 | Kanto Denka Kogyo Co Ltd | 高純度六フッ化リン酸リチウムの製造方法 |
JP2001122604A (ja) * | 1999-10-22 | 2001-05-08 | Kanto Denka Kogyo Co Ltd | 高純度六フッ化リン酸リチウムの製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101068065B1 (ko) | 2002-11-12 | 2011-09-28 | 가부시키가이샤 산도쿠 | 불소 함유 리튬 화합물의 제조 방법 |
Also Published As
Publication number | Publication date |
---|---|
KR101068065B1 (ko) | 2011-09-28 |
CN1304279C (zh) | 2007-03-14 |
CN1711214A (zh) | 2005-12-21 |
KR20050067436A (ko) | 2005-07-01 |
AU2003280748A8 (en) | 2004-06-03 |
AU2003280748A1 (en) | 2004-06-03 |
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