JP4008671B2 - Method for producing LiBF4 - Google Patents
Method for producing LiBF4 Download PDFInfo
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- JP4008671B2 JP4008671B2 JP2001101747A JP2001101747A JP4008671B2 JP 4008671 B2 JP4008671 B2 JP 4008671B2 JP 2001101747 A JP2001101747 A JP 2001101747A JP 2001101747 A JP2001101747 A JP 2001101747A JP 4008671 B2 JP4008671 B2 JP 4008671B2
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- libo
- libf
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- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 title 1
- 229910013184 LiBO Inorganic materials 0.000 claims description 26
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- 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
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- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明はＬｉＢＦ4 の製造方法に関する。
【０００２】
【従来の技術】
ＬｉＢＦ4 は高起電力のＬｉ一次／二次電池に非常に有用な用途を有する。ＬｉＢＦ4 は電池電解質として周知である。この化合物は、以前は面倒な方法で製造され、収率は、劣っていた。製造される生成物の純度は劣り、再結晶を必要とした。
【０００３】
米国特許第５，０７９，１０９号明細書はリチウム電池のための非水性電解質としてＬｉＢＦ4 の使用を開示する。
いくつかの方法が従来技術においてＬｉＢＦ4 の製造について知られているが、このような方法は、次のような不利益を受ける。
１．生成物の純度は低い。
【０００４】
２．生成物の収率は低い。
３．生成物産生のための外気温反応。
４．副反応が生じる。
５．多数の工程が必要とされる。
【０００５】
【発明が解決しようとする課題】
本発明の主たる目的は、簡易な化学反応によりＬｉＢＦ4 を得ることである。
本発明のもう１つの目的は、高収率でＬｉＢＦ4 を得ることである。
本発明のさらなる目的は、効率的な方法でＬｉＢＦ4 を得ることである。
本発明の方法は、上に列挙された従来技術の不利益を克服することである。
【０００６】
【課題を解決するための手段】
したがって、本発明は、ＬｉＢＯ2 化合物を１０〜４８％のＨＦ水性溶液と外気温で反応させること、生成物を濃縮すること、ならびに再結晶させて高純度ＬｉＢＦ4 を得る、ことを含むＬｉＢＦ4 の製造法に関する。
本発明の１つの態様において、ＬｉＢＯ2 は水性媒体／非水性媒体中に懸濁され、ＨＦと反応する。
【０００７】
本発明のさらなる態様において、ＬｉＢＯ2 のペースト状物がＨＦに添加される。
本発明のもう１つの態様において、ＬｉＢＯ2 は水でペースト状にされ、ＨＦと反応する。
【０００８】
【発明の実施の形態】
本発明において、ＬｉＢＦ4 は、水性溶液中の ＬｉＢＯ2／Ｌｉ2 Ｎ2 Ｏ4 の懸濁粒子または水中のＬｉＢＯ2 ペースト状物をＨＦで処理することにより製造される。ＬｉＢＯ2 およびＨＦの量は、別々に反応について計算される。反応の停止後に、生成物は濃縮され、そして結晶化された。形成された生成物は試験され、Ｘ線で同定され、そして生成物の純度が測定された。
【０００９】
計算量のＨＦは、既知質量のＬｉＢＯ2 水性溶液中に注意深く添加された。反応は続行された。反応が停止すると、生成物は濃縮され、再結晶化され、非常に高純度の生成物を得た。生成物はその純度を試験され、Ｘ線で同定された。図１は利用しうる文献（表１）と一致するＸ線分析を示す。
【００１０】
【表１】
ＬｉＢＯ2 の合成は出願人の係属中の出願に開示されている。
【００１２】
【実施例】
実施例１：ＬｉＢＯ2 の製造
Ｌｉ2 ＣＯ3(２．９６ｇ）およびＢ2 Ｏ3(２．８ｇ）が混合され、６００℃まで加熱され、ＬｉＢＯ2 を９８％より大きい収率で得た。生成物の色は白であり、単１相で得られた。プロピレンカーボネート中の１Ｍ ＬｉＣｌＯ4 のＬｉに関してＬｉＢＯ2 の単極電位（ｓｉｎｇｌｅ ｅｌｅｃｔｒｏｄｅ ｐｏｔｅｎｔｉａｌ）は２．９９Ｖであった。
実施例２：ＬｉＢＯ2 の製造
Ｌｉ2 ＯＨ（１．６８ｇ）およびＢ2 Ｏ3(２．８ｇ）が混合され、６００℃まで加熱され、ＬｉＢＯ2 を９８％より大きい収率で得た。生成物の色は白であり、単１相で得られた。プロピレンカーボネート中の１Ｍ ＬｉＣｌＯ4 のＬｉに関してＬｉＢＯ2 の単極電位は２．９９Ｖであった。
【００１３】
実施例１および２の双方の工程で得られたＬｉＢＯ2 は高純度で、副反応は生じなかった。
実施例３：ＬｉＢＦ4 の製造
ＬｉＢＯ2 およびＨＦが、「テフロン」容器中の水にＨＦを導入し、温度を−４℃に保持し、ゆっくりＬｉＢＯ2 を添加することにより、１：４のモル比で混合された。反応が停止すると、混合物は約１００℃までゆっくり加熱して乾燥され、約９５％の収率で乾燥ＬｉＢＦ4 が得られる。生成物の色は白であり、生成物は単１相で得られた。プロピレンカーボネート中の１Ｍ ＬｉＣｌＯ4 のＬｉに関してＬｉＢＯ2 の単極電位は２．９９Ｖであった。
実施例４：ＬｉＢＦ4 の製造
ＬｉＢＯ2 およびＨＦが、「テフロン」容器中のアルコール溶媒にＨＦを導入し、温度を−４℃に保持し、ゆっくりＬｉＢＯ2 を添加することにより１：４のモル比で混合された。反応が停止すると、混合物は約１００℃までゆっくり加熱して乾燥され、約９５％の収率で乾燥ＬｉＢＦ4 が得られる。生成物の色は白であり、生成物は単１相で得られた。１Ｍプロピレンカーボネート中のＬｉＢＦ4 の３０℃における当量コンダクタンスは３４．０ohm-1cm2mole-1であった。
【００１４】
【発明の効果】
本発明においては、次の利点がＬｉＢＦ4 の合成について得られる。
１．副反応が生じない。
２．一工程の方法がこの化合物を製造するのに十分である。
３．所要量の生成物は計算量の反応物を反応させることにより製造されうる。
【００１５】
４．得られる生成物は高純度である。
５．生成物の収率は、もし温度が−４℃に保持されると１００％となる。
６．ＬｉＢＯ2 のぬれは反応の間、生成されるＢＦ4 の蒸発を妨げる。
【図面の簡単な説明】
【図１】本発明で得られるＬｉＢＦ4 のＸ線回折図形を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing LiBF 4 .
[0002]
[Prior art]
LiBF 4 has very useful applications for high electromotive force Li primary / secondary batteries. LiBF 4 is well known as a battery electrolyte. This compound was previously produced in a cumbersome manner and the yield was poor. The purity of the product produced was poor and required recrystallization.
[0003]
US Pat. No. 5,079,109 discloses the use of LiBF 4 as a non-aqueous electrolyte for lithium batteries.
Several methods are known in the prior art for the production of LiBF 4 , but such methods suffer from the following disadvantages.
1. The purity of the product is low.
[0004]
2. The product yield is low.
3. Ambient temperature response for product production.
4). Side reactions occur.
5). A number of steps are required.
[0005]
[Problems to be solved by the invention]
The main object of the present invention is to obtain LiBF 4 by a simple chemical reaction.
Another object of the present invention is to obtain LiBF 4 in high yield.
A further object of the present invention is to obtain LiBF 4 in an efficient manner.
The method of the present invention is to overcome the disadvantages of the prior art listed above.
[0006]
[Means for Solving the Problems]
Accordingly, the present invention is, LiBF 4 comprising reacting in an HF aqueous solution and the outside air temperature of LiBO 2 compound 10-48%, concentrating the product, and recrystallized to obtain high purity LiBF 4 and, that Relates to the manufacturing method.
In one embodiment of the invention, LiBO 2 is suspended in an aqueous / non-aqueous medium and reacts with HF.
[0007]
In a further embodiment of the invention, a LiBO 2 paste is added to HF.
In another embodiment of the invention, LiBO 2 is pasted with water and reacted with HF.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, LiBF 4 is produced by treating suspended particles of LiBO 2 / Li 2 N 2 O 4 in an aqueous solution or LiBO 2 paste in water with HF. The amounts of LiBO 2 and HF are calculated for the reaction separately. After stopping the reaction, the product was concentrated and crystallized. The product formed was examined, identified by X-ray and the purity of the product was measured.
[0009]
The calculated amount of HF was carefully added into a known mass of LiBO 2 aqueous solution. The reaction continued. When the reaction stopped, the product was concentrated and recrystallized to give a very pure product. The product was tested for purity and identified by X-ray. FIG. 1 shows an X-ray analysis consistent with the available literature (Table 1).
[0010]
[Table 1]
The synthesis of LiBO 2 is disclosed in Applicants' pending application.
[0012]
【Example】
Example 1: Preparation of LiBO 2 Li 2 CO 3 (2.96 g) and B 2 O 3 (2.8 g) were mixed and heated to 600 ° C. to give LiBO 2 in a yield greater than 98%. The product color was white and was obtained in a single phase. The LiBO 2 single electrode potential was 2.99 V with respect to 1 M LiClO 4 Li in propylene carbonate.
Example 2: Preparation of LiBO 2 Li 2 OH (1.68 g) and B 2 O 3 (2.8 g) were mixed and heated to 600 ° C. to give LiBO 2 in a yield greater than 98%. The product color was white and was obtained in a single phase. The LiBO 2 monopolar potential was 2.99 V with respect to 1 M LiClO 4 Li in propylene carbonate.
[0013]
LiBO 2 obtained in both steps of Examples 1 and 2 was highly pure and no side reaction occurred.
Example 3: Preparation of LiBF 4 LiBO 2 and HF were introduced at a 1: 4 mole by introducing HF into the water in the “Teflon” vessel, keeping the temperature at −4 ° C., and slowly adding LiBO 2. Mixed in ratio. When the reaction is stopped, the mixture is dried by slowly heating to about 100 ° C. to obtain dry LiBF 4 in a yield of about 95%. The product color was white and the product was obtained in a single phase. The LiBO 2 monopolar potential was 2.99 V with respect to 1 M LiClO 4 Li in propylene carbonate.
Example 4: Preparation of LiBF 4 LiBO 2 and HF were introduced at a molar ratio of 1: 4 by introducing HF into an alcohol solvent in a “Teflon” vessel, keeping the temperature at −4 ° C., and slowly adding LiBO 2. Mixed in ratio. When the reaction is stopped, the mixture is dried by slowly heating to about 100 ° C. to obtain dry LiBF 4 in a yield of about 95%. The product color was white and the product was obtained in a single phase. The equivalent conductance at 30 ° C. of LiBF 4 in 1M propylene carbonate was 34.0 ohm −1 cm 2 mole −1 .
[0014]
【The invention's effect】
In the present invention, the following advantages are obtained for the synthesis of LiBF 4 .
1. There is no side reaction.
2. A one-step process is sufficient to produce this compound.
3. The required amount of product can be produced by reacting the calculated amount of reactants.
[0015]
4). The resulting product is highly pure.
5). The product yield is 100% if the temperature is kept at -4 ° C.
6). LiBO 2 wetting prevents evaporation of the BF 4 produced during the reaction.
[Brief description of the drawings]
FIG. 1 shows an X-ray diffraction pattern of LiBF 4 obtained by the present invention.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001101747A JP4008671B2 (en) | 2001-03-30 | 2001-03-30 | Method for producing LiBF4 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001101747A JP4008671B2 (en) | 2001-03-30 | 2001-03-30 | Method for producing LiBF4 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002293533A JP2002293533A (en) | 2002-10-09 |
| JP4008671B2 true JP4008671B2 (en) | 2007-11-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001101747A Expired - Lifetime JP4008671B2 (en) | 2001-03-30 | 2001-03-30 | Method for producing LiBF4 |
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| Country | Link |
|---|---|
| JP (1) | JP4008671B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102028B (en) * | 2022-12-12 | 2023-12-12 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium tetrafluoroborate |
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- 2001-03-30 JP JP2001101747A patent/JP4008671B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| JP2002293533A (en) | 2002-10-09 |
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