JPH11157830A - Production of lithium tetrafluoroborate - Google Patents
Production of lithium tetrafluoroborateInfo
- Publication number
- JPH11157830A JPH11157830A JP9318343A JP31834397A JPH11157830A JP H11157830 A JPH11157830 A JP H11157830A JP 9318343 A JP9318343 A JP 9318343A JP 31834397 A JP31834397 A JP 31834397A JP H11157830 A JPH11157830 A JP H11157830A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- solvent
- lithium tetrafluoroborate
- carbonate
- solution
- 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.)
- Granted
Links
- -1 lithium tetrafluoroborate Chemical compound 0.000 title claims abstract description 46
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 38
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 22
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims description 35
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 150000005678 chain carbonates Chemical class 0.000 claims description 7
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000000926 separation method Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム電池用電
解質として有用なテトラフルオロホウ酸リチウムの製造
法に関する。The present invention relates to a method for producing lithium tetrafluoroborate useful as an electrolyte for a lithium battery.
【０００２】[0002]
【従来の技術および発明が解決しようとする問題点】テ
トラフルオロホウ酸リチウム（ＬｉＢＦ4）の公知の合
成方法としては、湿式法とエーテル法の二種類が報告さ
れている。湿式法では、ホウ弗酸と炭酸リチウムとの反
応により、含水塩（ＬｉＢＦ4・Ｈ2Ｏ）が生成する。こ
の含水塩を脱水するために２００℃程度の加熱が必要で
あるため、テトラフルオロホウ酸リチウムの分解（Ｌｉ
ＢＦ4→ＬｉＦ＋ＢＦ3）が起こり純度が低下するばかり
でなく、水分が残留するためリチウム電池用には使用で
きない。エーテル法では、三フッ化ホウ素とメチルエー
テルあるいはエチルエーテルとの錯化合物とフッ化リチ
ウムの反応により無水塩が得られるが、エーテルに対し
てテトラフルオロホウ酸リチウムが難溶性であるため、
リチウム電池用の品質を満足するものが得にくいこと、
また危険なエーテルを使用することなどの欠点がある。2. Description of the Related Art Two known methods for synthesizing lithium tetrafluoroborate (LiBF 4 ), a wet method and an ether method, have been reported. In the wet method, a hydrous salt (LiBF 4 .H 2 O) is generated by a reaction between borofluoric acid and lithium carbonate. Since heating at about 200 ° C. is required to dehydrate the hydrated salt, decomposition of lithium tetrafluoroborate (Li
BF 4 → LiF + BF 3 ) occurs, not only lowering the purity, but also leaving residual moisture, which cannot be used for lithium batteries. In the ether method, an anhydrous salt is obtained by the reaction of lithium fluoride with a complex compound of boron trifluoride and methyl ether or ethyl ether.Since lithium tetrafluoroborate is hardly soluble in ether,
It is difficult to obtain products that satisfy the quality for lithium batteries,
It also has disadvantages such as the use of dangerous ethers.
【０００３】このように従来の方法においては、得られ
るテトラフルオロホウ酸リチウム及びこれを用いた電解
液は、必ずしも満足できるものではなかった。As described above, in the conventional method, the obtained lithium tetrafluoroborate and the electrolytic solution using the same have not always been satisfactory.
【０００４】[0004]
【問題点を解決するための具体的手段】本発明者らは、
かかる従来技術の問題点に鑑み鋭意検討の結果、特定溶
媒中でテトラフルオロホウ酸リチウムを得ることにより
不純物の少ない電解液等を得る方法を見出し本発明に到
達したものである。[Specific means for solving the problem]
As a result of intensive studies in view of the problems of the prior art, the present inventors have found a method for obtaining an electrolyte solution with less impurities by obtaining lithium tetrafluoroborate in a specific solvent, and have reached the present invention.
【０００５】すなわち本発明は、溶媒である鎖状の炭酸
エステル中で、フッ化リチウムと三フッ化ホウ素とを反
応させてテトラフルオロホウ酸リチウムを生成させて溶
媒中に溶解させること、また該溶液からテトラフルオロ
ホウ酸リチウムを析出分離することを特徴とするテトラ
フルオロホウ酸リチウムの製造方法で、さらに、該溶液
をリチウム電池用電解液または該溶液に環状の炭酸エス
テルを添加して、鎖状の炭酸エステルを蒸留除去した溶
液をリチウム電池用電解液とするテトラフルオロホウ酸
リチウムの製造方法を提供するものである。That is, the present invention provides a method of reacting lithium fluoride and boron trifluoride in a chain carbonate ester as a solvent to produce lithium tetrafluoroborate and dissolving the same in a solvent. A method for producing lithium tetrafluoroborate, comprising separating lithium tetrafluoroborate from a solution, further comprising adding a cyclic carbonate to the lithium battery electrolyte or the solution to form a chain. An object of the present invention is to provide a method for producing lithium tetrafluoroborate using a solution obtained by distilling and removing a carbonate in a form of an electrolyte as an electrolyte for a lithium battery.
【０００６】本発明の製造方法は、反応収率が高く、反
応の制御も容易で、製品の純度の点でも十分満足できる
ものであり、しかも、テトラフルオロホウ酸リチウムを
結晶として、取り出しても良く、また溶媒にリチウム電
池用のものを使用しているため、反応後の溶液を直接電
解液として使用することも可能である。The production method of the present invention has a high reaction yield, is easy to control the reaction, is sufficiently satisfactory in terms of the purity of the product, and even when lithium tetrafluoroborate is taken out as crystals. Also, since a solvent for lithium batteries is used as the solvent, the solution after the reaction can be used directly as an electrolyte.
【０００７】以下、本発明を詳細に説明する。本発明の
製造方法において、テトラフルオロホウ酸リチウムの生
成反応は、鎖状の炭酸エステル中で実施される。これら
の溶媒に対して、原料であるフッ化リチウムの溶解度は
非常に小さいため、溶媒に分散した状態で三フッ化ホウ
素のガスを吹き込み反応を行う。ここで、生成したテト
ラフルオロホウ酸リチウムは非常に溶解度が大きいの
で、溶媒中に溶解して、フッ化リチウムの表面に被膜と
して残ることがないために反応は完全に進行する。Hereinafter, the present invention will be described in detail. In the production method of the present invention, the reaction for producing lithium tetrafluoroborate is carried out in a chain carbonate. Since the solubility of the raw material lithium fluoride in these solvents is very small, boron trifluoride gas is blown in a state of being dispersed in the solvent to carry out the reaction. Here, since the produced lithium tetrafluoroborate has a very high solubility, it is dissolved in a solvent and does not remain as a film on the surface of lithium fluoride, so that the reaction proceeds completely.
【０００８】テトラフルオロホウ酸リチウムの生成反応
で使用される鎖状の炭酸エステルは、化学的な安定性が
高く、しかもテトラフルオロホウ酸リチウムの溶解度が
高い、ジメチルカーボネート、ジエチルカーボネート、
エチルメチルカーボネートが好ましい。The chain carbonate used in the reaction for producing lithium tetrafluoroborate has high chemical stability and high solubility of lithium tetrafluoroborate, such as dimethyl carbonate, diethyl carbonate, and the like.
Ethyl methyl carbonate is preferred.
【０００９】この反応を行う際の温度は、−４０〜１０
０℃の範囲が好ましく、さらに０〜６０℃の範囲が最適
である。反応温度が−４０℃未満では、溶媒が凝固する
ため反応が進行せず、また、１００℃を超える場合は、
溶媒と三フッ化ホウ素との反応が起こり、着色や粘度増
加の原因となるため好ましくない。The temperature for carrying out this reaction is -40 to 10
A range of 0 ° C. is preferred, and a range of 0 to 60 ° C. is optimal. When the reaction temperature is lower than −40 ° C., the reaction does not proceed because the solvent coagulates.
A reaction between the solvent and boron trifluoride occurs, which is not preferable because it causes coloring and an increase in viscosity.
【００１０】フッ化リチウムの量は、溶媒１リットルに
対して、２００ｇ以下、好ましくは１００ｇ以下であ
る。フッ化リチウムの量が溶媒に対して、２００ｇより
多い場合は生成物が飽和になり、フッ化リチウム表面に
被膜が生成し、未反応のフッ化リチウムが残存する上、
さらに溶媒の粘度が上昇するため、濾過等の分離操作が
困難になる。The amount of lithium fluoride is 200 g or less, preferably 100 g or less, per liter of the solvent. If the amount of lithium fluoride is more than 200 g with respect to the solvent, the product becomes saturated, a film is formed on the surface of lithium fluoride, and unreacted lithium fluoride remains,
Further, since the viscosity of the solvent increases, separation operations such as filtration become difficult.
【００１１】三フッ化ホウ素の量は、フッ化リチウムに
対して当量以上あれば良いが、過剰に系内に導入した場
合、溶媒中に吸収されるため、反応後に加熱、減圧等の
操作により除去する必要がある。The amount of boron trifluoride may be at least equivalent to lithium fluoride. However, if introduced into the system excessively, it will be absorbed into the solvent. Need to be removed.
【００１２】この反応において、原料の三フッ化ホウ
素、および生成物のテトラフルオロホウ酸リチウムは、
水分により容易に加水分解を受けるので、水分を含まな
い雰囲気で反応を実施する必要がある。すなわち、真空
に近い状態や窒素等の不活性ガス雰囲気中で反応を行う
ことが好ましい。In this reaction, boron trifluoride as a raw material and lithium tetrafluoroborate as a product are:
Since the reaction is easily hydrolyzed by water, it is necessary to carry out the reaction in an atmosphere containing no water. That is, the reaction is preferably performed in a state close to vacuum or in an atmosphere of an inert gas such as nitrogen.
【００１３】このようにして得られた溶媒溶液から、冷
却や濃縮という操作により、析出分離することにより高
純度のテトラフルオロホウ酸リチウムが得られる。テト
ラフルオロホウ酸リチウムは、高純度の結晶として得ら
れるが、反応により得られた溶媒溶液は、そのまま、ま
たは、エチレンカーボネート、プロピレンカーボネー
ト、γ−ブチロラクトン等を混合してリチウム電池用電
解液として使用できる。ただし、リチウム電池用非水溶
媒として、エチレンカーボネート、プロピレンカーボネ
ート、γ−ブチロラクトンを単独で使用する場合もあ
り、その場合上記のような反応をこれらの環状の炭酸エ
ステル中で行うと、三フッ化ホウ素により分解、重合等
が発生するため、好ましくない。そこで本発明では、上
記のように安定な鎖状の炭酸エステル中で反応により得
られた溶媒中に、リチウム電池用有機非水溶媒である環
状の炭酸エステルを添加して、先の鎖状の炭酸エステル
を蒸留除去することにより、リチウム電池用電解液を製
造する。本発明において、添加する環状の炭酸エステル
は、エチレンカーボネート、プロピレンカーボネート、
γ−ブチロラクトン等が挙げられる。From the solvent solution thus obtained, a high purity lithium tetrafluoroborate can be obtained by precipitation and separation by an operation of cooling or concentration. Lithium tetrafluoroborate is obtained as high-purity crystals, and the solvent solution obtained by the reaction is used as it is or as an electrolyte for lithium batteries by mixing ethylene carbonate, propylene carbonate, γ-butyrolactone, etc. it can. However, ethylene carbonate, propylene carbonate, and γ-butyrolactone may be used alone as a nonaqueous solvent for a lithium battery. In such a case, if the above reaction is performed in these cyclic carbonates, trifluoride Decomposition, polymerization and the like are caused by boron, which is not preferable. Therefore, in the present invention, a cyclic carbonate which is an organic non-aqueous solvent for a lithium battery is added to the solvent obtained by the reaction in the stable chain carbonate as described above, and the above-mentioned chain chain is added. By distilling and removing the carbonate, an electrolyte for a lithium battery is produced. In the present invention, the cyclic carbonate to be added is ethylene carbonate, propylene carbonate,
γ-butyrolactone and the like.
【００１４】鎖状の炭酸エステルを除去し、環状の炭酸
エステルに置換する方法としては蒸留法を用いるため、
反応に使用する鎖状の炭酸エステルの沸点は、添加する
環状の炭酸エステルの沸点よりも低いものを選択する必
要がある。また、溶媒の劣化等の問題を考慮すると、置
換の際の蒸留は減圧蒸留を行い、蒸留温度を低くするほ
うが好ましい。このようにして、鎖状の炭酸エステルを
除去し、環状の炭酸エステルに置換した後、所定の濃度
に調整することにより、テトラフルオロホウ酸リチウム
を含有したリチウム電池用電解液が得られる。As a method for removing a chain carbonate and replacing it with a cyclic carbonate, a distillation method is used.
The boiling point of the chain carbonate used in the reaction must be lower than the boiling point of the cyclic carbonate to be added. Further, in consideration of problems such as deterioration of the solvent, it is preferable to perform distillation at the time of substitution under reduced pressure to lower the distillation temperature. In this way, the chain carbonate is removed, replaced with a cyclic carbonate, and then adjusted to a predetermined concentration to obtain a lithium battery electrolyte containing lithium tetrafluoroborate.
【００１５】以上のような操作により、従来の方法に比
べて、極めて純度の高いテトラフルオロホウ酸リチウム
が得られる。また、本発明では溶媒としてリチウム電池
用溶媒を使用しているため、反応により得られた溶液を
直接リチウム電池用電解液として使用するが可能であ
る。By the above operation, lithium tetrafluoroborate having extremely high purity can be obtained as compared with the conventional method. In the present invention, since a solvent for a lithium battery is used as a solvent, a solution obtained by the reaction can be directly used as an electrolyte for a lithium battery.
【００１６】[0016]
【実施例】以下実施例により本発明を具体的に説明する
が、本発明はかかる実施例により限定されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００１７】実施例１ フッ素樹脂製反応器中で２００ｍｌのジメチルカーボネ
ートに５．２ｇのフッ化リチウムを添加して、混合分散
した。この分散液を冷却して５℃を維持しながら、ガス
導入管を通して窒素ガスにより１７ｖｏｌ％に希釈した
三フッ化ホウ素ガスをバブリングした。ジメチルカーボ
ネート中に分散されたフッ化リチウムが消失した時点
で、反応を終了した。このときの三フッ化ホウ素の消費
量は１４ｇであった。 得られた溶媒溶液からジメチル
カーボネートを減圧で留出させることにより、テトラフ
ルオロホウ酸リチウム１８．５ｇ（収率：９８．７％）
を得た。また、リチウム電池に応用する場合に問題とな
る酸性不純物濃度は１００ｐｐｍであった。Example 1 In a fluororesin reactor, 5.2 g of lithium fluoride was added to 200 ml of dimethyl carbonate and mixed and dispersed. While the dispersion was cooled and maintained at 5 ° C., a boron trifluoride gas diluted to 17 vol% with nitrogen gas was bubbled through a gas inlet tube. The reaction was terminated when lithium fluoride dispersed in dimethyl carbonate disappeared. At this time, the consumption of boron trifluoride was 14 g. Dimethyl carbonate was distilled off from the obtained solvent solution under reduced pressure, whereby 18.5 g of lithium tetrafluoroborate (yield: 98.7%) was obtained.
I got In addition, the concentration of acidic impurities that became a problem when applied to a lithium battery was 100 ppm.
【００１８】実施例２ フッ素樹脂製反応器中で２００ｍｌのジエチルカーボネ
ートに５．２ｇのフッ化リチウムを添加して、混合分散
した。この分散液を冷却して２０℃を維持しながら、ガ
ス導入管を通して窒素ガスにより１７ｖｏｌ％に希釈し
た三フッ化ホウ素ガスをバブリングした。ジエチルカー
ボネート中に分散されたフッ化リチウムが消失した時点
で、反応を終了した。このときの三フッ化ホウ素の消費
量は１４ｇであった。Example 2 In a fluororesin reactor, 5.2 g of lithium fluoride was added to 200 ml of diethyl carbonate and mixed and dispersed. While the dispersion was cooled and maintained at 20 ° C., a boron trifluoride gas diluted to 17 vol% with nitrogen gas was bubbled through a gas inlet tube. The reaction was terminated when lithium fluoride dispersed in diethyl carbonate disappeared. At this time, the consumption of boron trifluoride was 14 g.
【００１９】得られた溶媒溶液を５０℃に昇温して、真
空ポンプで脱気することにより過剰の三フッ化ホウ素を
除外した。Ｆ19−ＮＭＲとイオンクロマトグラムによ
り、テトラフルオロホウ酸リチウムの生成が確認され
た。溶媒溶液中の酸性不純物濃度は１０ｐｐｍで、テト
ラフルオロホウ酸リチウムベースに換算すると７０ｐｐ
ｍとなる。The resulting solvent solution was heated to 50 ° C. and degassed with a vacuum pump to remove excess boron trifluoride. The formation of lithium tetrafluoroborate was confirmed by F 19 -NMR and ion chromatogram. The acidic impurity concentration in the solvent solution is 10 ppm, which is 70 pp in terms of lithium tetrafluoroborate base.
m.
【００２０】実施例３ フッ素樹脂製反応器中で２００ｍｌのジエチルカーボネ
ートに５．２ｇのフッ化リチウムを添加して、混合分散
した。この分散液を冷却して２０℃を維持しながら、ガ
ス導入管を通して窒素ガスにより１７ｖｏｌ％に希釈し
た三フッ化ホウ素ガスをバブリングした。ジエチルカー
ボネート中に分散されたフッ化リチウムが消失した時点
で、反応を終了した。このときの三フッ化ホウ素の消費
量は１４ｇであった。Example 3 In a fluororesin reactor, 5.2 g of lithium fluoride was added to 200 ml of diethyl carbonate and mixed and dispersed. While the dispersion was cooled and maintained at 20 ° C., a boron trifluoride gas diluted to 17 vol% with nitrogen gas was bubbled through a gas inlet tube. The reaction was terminated when lithium fluoride dispersed in diethyl carbonate disappeared. At this time, the consumption of boron trifluoride was 14 g.
【００２１】得られた溶媒溶液を４０℃に加熱し、減圧
することにより、未反応の五フッ化リンを除去した。次
に、この溶媒溶液中に２００ｍｌのプロピレンカーボネ
ートを添加して、十分混合した後、１ｔｏｒｒ程度の圧
力で減圧蒸留を行ったところ、３６℃でジエチルカーボ
ネートが留出した。ジエチルカーボネートの留出が停止
した時点で蒸留を終了した。The unreacted phosphorus pentafluoride was removed by heating the obtained solvent solution to 40 ° C. and reducing the pressure. Next, 200 ml of propylene carbonate was added to the solvent solution, mixed well, and then distilled under reduced pressure at a pressure of about 1 torr. As a result, diethyl carbonate was distilled at 36 ° C. The distillation was stopped when the distillation of diethyl carbonate stopped.
【００２２】このようにして得られたテトラフルオロホ
ウ酸リチウムのプロピレンカーボネート溶媒溶液は、外
観的には全く着色もなく、ＩＲ、ＮＭＲ、ガスクロマト
グラフィー等の分析を行った結果からも、溶媒の分解生
成物等は存在していなかった。また、テトラフルオロホ
ウ酸リチウムの生成は、Ｆ19−ＮＭＲとイオンクロマト
グラフィーにより確認した。The thus obtained solution of lithium tetrafluoroborate in propylene carbonate has no color at all in appearance, and the results of analysis by IR, NMR, gas chromatography and the like show that the solvent is No decomposition products or the like were present. Further, generation of lithium tetrafluoroborate were confirmed by F 19 -NMR and ion chromatography.
【００２３】テトラフルオロホウ酸リチウムの生成量
は、溶媒を蒸発させることにより確認したところ、１８
ｇ（収率：９６．０％）であった。また、リチウム電池
に応用する場合に問題となる酸性不純物濃度は１０ｐｐ
ｍであった。The amount of lithium tetrafluoroborate produced was confirmed by evaporating the solvent.
g (yield: 96.0%). In addition, the concentration of an acidic impurity which causes a problem when applied to a lithium battery is 10 pp.
m.
【００２４】比較例１ フッ素樹脂製反応器中で２００ｍｌのプロピレンカーボ
ネートに５．２ｇのフッ化リチウムを添加して、混合分
散した。この分散液を冷却して０℃を維持しながら、ガ
ス導入管を通して窒素ガスにより１７ｖｏｌ％に希釈し
た三フッ化ホウ素ガスをバブリングを開始したところ、
テトラフルオロホウ酸リチウムの生成反応は進行するも
のの、徐々に溶液が褐色に着色し、粘度も上昇した。Comparative Example 1 In a fluororesin reactor, 5.2 g of lithium fluoride was added to 200 ml of propylene carbonate and mixed and dispersed. When the dispersion was cooled and maintained at 0 ° C., bubbling of boron trifluoride gas diluted to 17 vol% with nitrogen gas through a gas inlet tube was started.
Although the formation reaction of lithium tetrafluoroborate proceeded, the solution gradually turned brown and the viscosity increased.
【００２５】実施例４ 実施例２で得られたテトラフルオロホウ酸リチウムのジ
エチルカーボネート溶液に１００ｍｌのエチレンカーボ
ネートを添加し、十分混合した後、１ｔｏｒｒ程度の圧
力で減圧蒸留を行ったところ、３６℃でジエチルカーボ
ネートが留出した。ジエチルカーボネートが１００ｍｌ
留出した時点で蒸留を終了した。この操作により濃度１
ｍｏｌ／ｌのテトラフルオロホウ酸リチウム／（ジエチ
ルカーボネート：エチレンカーボネート＝１：１）溶液
が得られた。Example 4 100 ml of ethylene carbonate was added to the diethyl carbonate solution of lithium tetrafluoroborate obtained in Example 2 and mixed well, and then vacuum distillation was performed at a pressure of about 1 torr. Distilled out diethyl carbonate. 100 ml of diethyl carbonate
Distillation was completed at the time of distillation. By this operation, the density 1
A mol / l solution of lithium tetrafluoroborate / (diethyl carbonate: ethylene carbonate = 1: 1) was obtained.
【００２６】次に、この溶液を用いてテストセルを作製
し、充放電試験により電解液としての性能を評価した。
具体的には、天然黒鉛粉末９５重量部に、バインダーと
して５重量部のポリフッ化ビニリデン（ＰＶＤＦ）を混
合し、さらにＮ，Ｎ−ジメチルホルムアミドを添加し、
スラリー状にした。このスラリーをニッケルメッシュ上
に塗布して、１５０℃で１２時間乾燥させることによ
り、試験用負極体とした。また、コバルト酸リチウム８
５重量部に、黒鉛粉末１０重量部およびＰＶＤＦ５重量
部を混合し、さらに、Ｎ，Ｎ−ジメチルホルムアミドを
添加し、スラリー状にした。このスラリーをアルミニウ
ム箔上に塗布して、１５０℃で１２時間乾燥させること
により、試験用正極体とした。ポリプロピレン不織布を
セパレーターとして、上記のテトラフルオロホウ酸リチ
ウム／（ジエチルカーボネート：エチレンカーボネート
＝１：１）溶液を電解液とし、上記負極体および正極体
とを用いてテストセルを組み立てた。続いて、次のよう
な条件で、定電流充放電試験を実施した。充電、放電と
もに電流密度０．３５ｍＡ／ｃｍ2で行い、充電は４．
２Ｖ、放電は２．５Ｖまで行い、この充放電サイクルを
繰り返して放電容量の変化を観察した。その結果、充放
電効率はほぼ１００％で、充放電を１００サイクル繰り
返したところ、放電容量は全く変化しなかった。Next, a test cell was prepared using this solution, and the performance as an electrolyte was evaluated by a charge / discharge test.
Specifically, 5 parts by weight of polyvinylidene fluoride (PVDF) is mixed as a binder with 95 parts by weight of natural graphite powder, and N, N-dimethylformamide is further added.
A slurry was formed. This slurry was applied on a nickel mesh and dried at 150 ° C. for 12 hours to obtain a test negative electrode body. In addition, lithium cobaltate 8
10 parts by weight of graphite powder and 5 parts by weight of PVDF were mixed with 5 parts by weight, and N, N-dimethylformamide was further added to form a slurry. This slurry was applied on an aluminum foil and dried at 150 ° C. for 12 hours to obtain a positive electrode for testing. Using a polypropylene nonwoven fabric as a separator, a test cell was assembled using the above-described negative electrode body and positive electrode body with the above-mentioned lithium tetrafluoroborate / (diethyl carbonate: ethylene carbonate = 1: 1) solution as an electrolytic solution. Subsequently, a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 .
The discharge was performed at 2 V and up to 2.5 V, and the charge / discharge cycle was repeated to observe the change in the discharge capacity. As a result, the charge / discharge efficiency was almost 100%. When charge / discharge was repeated 100 cycles, the discharge capacity did not change at all.
【００２７】[0027]
【発明の効果】本発明の製造方法によれば、反応の制御
が容易で、製品の純度の点でも十分満足でき、しかも、
テトラフルオロホウ酸リチウムを結晶として、取り出し
ても良く、また、溶媒にリチウム電池用のものを使用し
ているため、反応後の溶液を直接電解液として使用する
ことができる。According to the production method of the present invention, the control of the reaction is easy, and the purity of the product can be sufficiently satisfied.
Lithium tetrafluoroborate may be taken out as a crystal, and since a solvent for a lithium battery is used as a solvent, the solution after the reaction can be used directly as an electrolyte.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 徳永 敦之 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社化学研究所内 (72)発明者 高畑 満夫 山口県宇部市大字沖宇部5253番地 セント ラル硝子株式会社化学研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Atsuyuki Tokunaga 5253 Oki Ube, Oji, Ube City, Yamaguchi Prefecture Inside the Chemical Research Laboratory of Central Glass Co., Ltd. (72) Mitsuo Takahata 5253 Oki Ube Odai, Ube City, Yamaguchi Prefecture, Central Glass Inside the Chemical Laboratory Co., Ltd.
Claims (4)
ッ化リチウムと三フッ化ホウ素とを反応させてテトラフ
ルオロホウ酸リチウムを生成させて溶媒中に溶解させる
ことを特徴とするテトラフルオロホウ酸リチウムの製造
方法。1. A method for producing lithium tetrafluoroborate by reacting lithium fluoride and boron trifluoride in a chain carbonate ester as a solvent and dissolving the same in a solvent. A method for producing lithium borate.
を溶解させた溶液からテトラフルオロホウ酸リチウムを
析出分離することを特徴とする請求項１記載のテトラフ
ルオロホウ酸リチウムの製造方法。2. The method for producing lithium tetrafluoroborate according to claim 1, wherein lithium tetrafluoroborate is precipitated and separated from a solution in which lithium tetrafluoroborate is dissolved in a solvent.
を溶解させたままの溶液がリチウム電池用電解液である
請求項１記載のテトラフルオロホウ酸リチウムの製造方
法。3. The method for producing lithium tetrafluoroborate according to claim 1, wherein the solution in which lithium tetrafluoroborate is dissolved in the solvent is an electrolyte for a lithium battery.
を溶解させた溶液に環状の炭酸エステルを添加して、鎖
状の炭酸エステルを蒸留除去したままの溶液がリチウム
電池用電解液である請求項１記載のテトラフルオロホウ
酸リチウムの製造方法。4. A solution in which a cyclic carbonate is added to a solution in which lithium tetrafluoroborate is dissolved in a solvent, and the chain carbonate is removed by distillation, which is an electrolyte for a lithium battery. 2. The method for producing lithium tetrafluoroborate according to 1 above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31834397A JP3375049B2 (en) | 1997-11-19 | 1997-11-19 | Method for producing lithium tetrafluoroborate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31834397A JP3375049B2 (en) | 1997-11-19 | 1997-11-19 | Method for producing lithium tetrafluoroborate |
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| Publication Number | Publication Date |
|---|---|
| JPH11157830A true JPH11157830A (en) | 1999-06-15 |
| JP3375049B2 JP3375049B2 (en) | 2003-02-10 |
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ID=18098110
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31834397A Expired - Fee Related JP3375049B2 (en) | 1997-11-19 | 1997-11-19 | Method for producing lithium tetrafluoroborate |
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| Country | Link |
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| JP (1) | JP3375049B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007937A3 (en) * | 1998-08-06 | 2001-08-16 | Basf Ag | Method for producing highly pure libf¿4? |
| WO2006090657A1 (en) * | 2005-02-23 | 2006-08-31 | Mitsubishi Gas Chemical Company, Inc. | Process for producing boron tetrafluoride, boron tetrafluoride produced by said process, electrolysis solution for electric double layer capacitor using said boron tetrafluoride, and process for producing said electrolysis solution |
| JP2009155130A (en) * | 2007-12-25 | 2009-07-16 | Stella Chemifa Corp | Method for producing tetrafluoroborate |
| WO2010146710A1 (en) | 2009-06-19 | 2010-12-23 | ステラケミファ株式会社 | Method for producing tetrafluoroborate |
| WO2013018784A1 (en) * | 2011-08-03 | 2013-02-07 | セントラル硝子株式会社 | Method for producing lithium tetrafluoroborate solution |
| CN111204776A (en) * | 2020-02-26 | 2020-05-29 | 东莞东阳光科研发有限公司 | Purification method of lithium tetrafluoroborate |
| CN115196646A (en) * | 2022-08-23 | 2022-10-18 | 江苏瀚康电子材料有限公司 | Method for synthesizing lithium tetrafluoroborate |
| CN116102028A (en) * | 2022-12-12 | 2023-05-12 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium tetrafluoroborate |
| CN116715214A (en) * | 2023-07-06 | 2023-09-08 | 中国科学院兰州化学物理研究所 | An ultrasonic-promoted method for preparing lithium difluorophosphate to co-produce lithium tetrafluoroborate |
| CN116730352A (en) * | 2023-06-28 | 2023-09-12 | 广州天赐高新材料股份有限公司 | Synthesis method of lithium tetrafluoroborate and electrolyte |
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|---|---|---|---|---|
| JPS56145113A (en) * | 1980-04-09 | 1981-11-11 | Morita Kagaku Kogyo Kk | Synthesis of anhydrous lithium borofluoride |
| JPH09165210A (en) * | 1995-12-14 | 1997-06-24 | Central Glass Co Ltd | Production of lithium hexafluorophosphate |
| JPH09245807A (en) * | 1996-03-11 | 1997-09-19 | Central Glass Co Ltd | Manufacture of electrolyte for lithium battery and lithium battery |
-
1997
- 1997-11-19 JP JP31834397A patent/JP3375049B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56145113A (en) * | 1980-04-09 | 1981-11-11 | Morita Kagaku Kogyo Kk | Synthesis of anhydrous lithium borofluoride |
| JPH09165210A (en) * | 1995-12-14 | 1997-06-24 | Central Glass Co Ltd | Production of lithium hexafluorophosphate |
| JPH09245807A (en) * | 1996-03-11 | 1997-09-19 | Central Glass Co Ltd | Manufacture of electrolyte for lithium battery and lithium battery |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000007937A3 (en) * | 1998-08-06 | 2001-08-16 | Basf Ag | Method for producing highly pure libf¿4? |
| US6537512B1 (en) | 1998-08-06 | 2003-03-25 | Basf Aktiengesellschaft | Method for producing highly pure LiBF4 |
| WO2006090657A1 (en) * | 2005-02-23 | 2006-08-31 | Mitsubishi Gas Chemical Company, Inc. | Process for producing boron tetrafluoride, boron tetrafluoride produced by said process, electrolysis solution for electric double layer capacitor using said boron tetrafluoride, and process for producing said electrolysis solution |
| JP5029353B2 (en) * | 2005-02-23 | 2012-09-19 | 三菱瓦斯化学株式会社 | Method for producing boron tetrafluoride salt, boron tetrafluoride salt obtained by the method, electrolytic solution for electric double layer capacitor using the same, and method for producing the same |
| JP2009155130A (en) * | 2007-12-25 | 2009-07-16 | Stella Chemifa Corp | Method for producing tetrafluoroborate |
| WO2010146710A1 (en) | 2009-06-19 | 2010-12-23 | ステラケミファ株式会社 | Method for producing tetrafluoroborate |
| KR20120039648A (en) | 2009-06-19 | 2012-04-25 | 스텔라 케미파 가부시키가이샤 | Method for producing tetrafluoroborate |
| US9376323B2 (en) | 2009-06-19 | 2016-06-28 | Stella Chemifa Corporation | Method for producing tetrafluoroborate |
| US9356319B2 (en) | 2011-08-03 | 2016-05-31 | Central Glass Company, Limited | Method for producing lithium tetrafluoroborate solution |
| WO2013018784A1 (en) * | 2011-08-03 | 2013-02-07 | セントラル硝子株式会社 | Method for producing lithium tetrafluoroborate solution |
| CN111204776A (en) * | 2020-02-26 | 2020-05-29 | 东莞东阳光科研发有限公司 | Purification method of lithium tetrafluoroborate |
| CN115196646A (en) * | 2022-08-23 | 2022-10-18 | 江苏瀚康电子材料有限公司 | Method for synthesizing lithium tetrafluoroborate |
| CN116102028A (en) * | 2022-12-12 | 2023-05-12 | 湖南法恩莱特新能源科技有限公司 | Preparation method of lithium tetrafluoroborate |
| 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 |
| CN116730352A (en) * | 2023-06-28 | 2023-09-12 | 广州天赐高新材料股份有限公司 | Synthesis method of lithium tetrafluoroborate and electrolyte |
| CN116715214A (en) * | 2023-07-06 | 2023-09-08 | 中国科学院兰州化学物理研究所 | An ultrasonic-promoted method for preparing lithium difluorophosphate to co-produce lithium tetrafluoroborate |
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