JP4047817B2 - Synthesis of lithium hexafluorophosphate by solid-state heating reaction - Google Patents
Synthesis of lithium hexafluorophosphate by solid-state heating reaction Download PDFInfo
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- JP4047817B2 JP4047817B2 JP2003578279A JP2003578279A JP4047817B2 JP 4047817 B2 JP4047817 B2 JP 4047817B2 JP 2003578279 A JP2003578279 A JP 2003578279A JP 2003578279 A JP2003578279 A JP 2003578279A JP 4047817 B2 JP4047817 B2 JP 4047817B2
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- 238000010438 heat treatment Methods 0.000 title claims description 31
- 238000006243 chemical reaction Methods 0.000 title claims description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 title claims description 13
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 238000001308 synthesis method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 17
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 15
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 10
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 5
- 238000001816 cooling Methods 0.000 claims 1
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 13
- 229910013870 LiPF 6 Inorganic materials 0.000 description 13
- 229910013553 LiNO Inorganic materials 0.000 description 12
- 229910012258 LiPO Inorganic materials 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005696 Diammonium phosphate Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical class O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】
【産業上の利用分野】
本発明はヘキサフルオロ燐酸リチウム（ＬｉＰＦ6）を合成する新規な方法に関する。特に、本発明は電池の電解質、特にロッキングチェア電池、非水溶液リチウムイオン電池、リチウムポリマー電池の電解質として有用なヘキサフルオロ燐酸リチウムを製造する新規な方法に関する。
【０００２】
【従来の技術】
ＬｉＰＦ6はリチウムイオン二次電池の電解質としてよく知られており、Ｐ2Ｏ5、Ｌｉ2Ｏ、やＰＦ5またはフッ素ガスなど、原料が非常に活性であるため製造が困難であった。文献には幾つかの化学的方法が知られているが、それらは慎重な取扱いと精製とが必要である。
【０００３】
更にこれらの方法による生成物は、電池電解質用の基本的化合物とするまでに種々の処理を行う装置を必要とする。
【０００４】
金属成分がＣａ、Ｋ、またはＬｉであるフッ化燐酸の金属塩は、フッ化金属（ＭＦ）をＰＦ3と反応させて合成する[Paul et. al., Fluorine Chemistry, 56, 1995]。反応式は下記の通りである。
【０００５】
３ＭＦ＋５ＰＦ3 →３ＭＰＦ6＋２Ｐ
【０００６】
金属成分がＣａ、Ｋ、またはＣｓの場合、ＭＰＦ6はＨＰＦ6を適当な塩基で中和することにより製造される。
【０００７】
２ＨＰＦ6 ＋Ｃａ（ＯＨ）2 → Ｃａ（ＰＦ 6 ） 2 ＋２Ｈ2Ｏ
【０００８】
同様に幾つかのヘキサフルオロ燐酸の金属塩はＮＨ4ＰＦ6やＫＰＦ6の二重分解により製造される[Paul et. al., Fluorine Chemistry, 56, (1995)][L.H. Simons, Fluorine Chemistry, Vol.5, 131(1819)(1964)][H.J. Emelson, Fluorine Chemistry, Vol.1 76(219)(1995)]。従来のＬｉＰＦ6の製造方法には幾つかの不都合がある。有毒な化学薬品を反応原料として使用するため、それら薬品の取り扱いが困難であり、部分的反応が生ずるため反応生成物が未反応の不純物を含み精製のため更なる処理が必要となる。
【０００９】
【発明が解決しようとする課題】
本発明の主たる目的はバッテリの電解質として用いられるヘキサフルオロ燐酸リチウム（ＬｉＰＦ6）を合成する新規な方法を提供するにある。本発明の他の目的は完全な固相反応による合成方法を提供するにある。更に本発明の他の目的は取扱いの困難な活性化学薬品を使用せずに、更には不快なガスを使用せずに、合成する方法を提供するにある。更に本発明の他の目的は未反応成分を含まない生成物を得る合成方法を提供するにある。本発明の上記及び他の目的及び従来方法に伴う不都合の克服は以下に記す本発明による方法により達成される。
【００１０】
【課題を解決する手段】
ヘキサフルオロ燐酸リチウム（ＬｉＰＦ6）を合成する新規な方法によれば、Ｌｉ2Ｏ、Ｌｉ2ＣＯ3又はＬｉＮＯ3などの乾燥精製したリチウム原料を、等モル量の乾燥精製した燐酸水素二アンモニウムと混合し、この混合物を電気炉内で２００〜６００℃で連続的に６時間加熱した。生成物を冷却して乾燥容器に移した。生成物は透明な物質で、Ｘ線解析により、ＬｉＰＦ 6 であることが確認された。
【００１１】
従って、本発明はヘキサフルオロ燐酸リチウムを合成する新規な固相加熱反応による合成方法を提供し、当該合成方法は下記のステップからなる。
【００１２】
（ａ）酸化リチウム、リチウム塩またはその混合物からなる群より選択されたリチウム原料と燐酸二アンモニウムと等モル比で混合する、
（ｂ）混合物を炉内で１５０〜６００℃で連続的に加熱し、ＬｉＰＯ3を得る、
（ｃ）ＬｉＰＯ3を冷却して粉末化する、
（ｄ）上記粉末化した生成物を６〜９倍量のフッ化アンモニウムと混合し、テフロン（登録商標）容器内に密閉して炉を用いて１５０〜２００℃の温度範囲で４〜６時間連続的に加熱する、
（ｅ）生成品を乾燥容器に移す。
【００１３】
本発明の一実施形態においては、上記ステップ（ｂ）の加熱は４〜６時間の範囲で行う。本発明の他の実施形態においては、ＬｉＰＯ3はＮＨ4Ｆと１：６〜９の比で混合され、ＬｉＰＦ6を得る。本発明の他の実施形態においては、メタ燐酸リチウム（ＬｉＰＯ3）はフッ化アンモニウムと１：７の比で混合され、電気炉中で２００℃で６時間連続的に加熱しヘキサフルオロ燐酸リチウムを得る。
【００１４】
更に本発明の他の実施形態においては、Ｌｉ2ＯまたはＬｉ2ＣＯ3またはＬｉＮＯ3は燐酸水素二アンモニウム及びフッ化アンモニウムとモル比１：２：６〜９の割合で混合される。本発明の他の実施形態においては、Ｌｉ2ＯまたはＬｉ2ＣＯ3またはＬｉＮＯ3は燐酸水素二アンモニウム及びフッ化アンモニウムと１：１：７の割合で混合される。本発明の更なる他の実施形態においては、Ｌｉ2ＯまたはＬｉＮＯ3は燐酸水素二アンモニウム及びフッ化アンモニウムと１：１：７の割合で混合され、混合物は電気炉内で２００℃で１２時間連続的に加熱されてＬｉＰＦ6を得る。本発明の実施形態においては、Ｌｉ2ＯまたはＬｉ2ＣＯ3またはＬｉＮＯ3は燐酸二アンモニウムと１：１の比で混合され、この混合物の生成物はＮＨ4Ｆと１：７で混合し加熱する。
【００１５】
本発明の更なる他の実施形態においては、Ｌｉ2ＯまたはＬｉＮＯ3が出発原料の場合は、ＬｉＰＦ6を合成する温度は１５０〜３５０℃の間に維持される。本発明の他の実施形態においては、Ｌｉ2ＣＯ3と（ＮＨ4）2ＨＰＯ4を混合して６００℃近傍で加熱し、続いてＮＨ4Ｆと混合して１５０〜３５０℃間の温度で加熱する。本発明の実施の形態においては反応は固体状態で行われる。本発明の他の実施形態においては、合成方法は下記の２ステップの反応からなる。
【００１６】
第１ステップ
【００１７】
２（ＮＨ4）2ＨＰＯ4＋Ｌｉ2Ｏ → ２ＬｉＰＯ3＋４ＮＨ3＋３Ｈ2Ｏ
２（ＮＨ4）2ＨＰＯ4＋Ｌｉ2ＣＯ3→ ２ＬｉＰＯ3＋４ＮＨ3＋ＣＯ2 ＋３Ｈ2Ｏ
２（ＮＨ4）2ＨＰＯ4＋ＬｉＮＯ3→ ２ＬｉＰＯ3＋４ＮＨ3＋２ＮＯ2 ＋２Ｈ2Ｏ＋Ｏ2
【００１８】
第２ステップ
【００１９】
ＬｉＰＯ3＋６ＮＨ4Ｆ → ＬｉＰＦ6＋６ＮＨ3＋３Ｈ2Ｏ
【００２０】
本発明の更なる他の実施形態においては、１５０〜３００℃の温度範囲で下記反応式による単一ステップの反応を行う。
【００２１】
Ｌｉ2Ｏ＋２（ＮＨ4）2ＨＰＯ4＋１２ＮＨ4Ｆ→２ＬｉＰＦ6＋１６ＮＨ3＋９Ｈ2Ｏ
Ｌｉ2ＣＯ3＋２（ＮＨ4）2ＨＰＯ4＋１２ＮＨ4Ｆ→２ＬｉＰＦ6＋１６ＮＨ3＋ＣＯ2 ＋９Ｈ2Ｏ
ＬｉＮＯ3＋２（ＮＨ4）2ＨＰＯ4＋１２ＮＨ4Ｆ→２ＬｉＰＦ6＋１６ＮＨ3＋ＮＯ2 ＋９Ｈ2Ｏ
【００２２】
本発明の他の実施形態においては、乾燥精製Ｌｉ2ＯまたはＬｉ2ＣＯ3またはＬｉＮＯ3はモル比１：２の燐酸二アンモニウムと混合し、該混合物を間接加熱炉または電気炉でＬｉ2ＣＯ３の場合は６００℃で、Ｌｉ2ＯまたはＬｉＮＯ3の場合は３００℃で６時間連続的に加熱する。生成物を８０℃で乾燥し、続いてモル比１：６〜８のＮＨ4Ｆと共に電気炉で１５０〜３５０℃で４時間連続的に加熱し反応させる。本発明の特徴は総ての原料が固体状態であること、反応のため電気炉または間接加熱炉を使用すること、下記反応式による単一ステップ反応処理が可能であること、である。
【００２３】
（ａ） ＬｉＰＯ3＋６ＮＨ4Ｆ → ＬｉＰＦ6＋６ＮＨ3＋３Ｈ2Ｏ
【００２４】
【発明の実施の形態】
ヘキサフルオロ燐酸リチウムはロッキングチェア電池やリチウムイオン電池に用いる基本的化学製品であるが、この化合物を製造する従来の方法は困難なものであり、多くの欠点を有していた。本発明は従来の困難性を克服することのできる新規な固相加熱反応によるＬｉＰＦ6の合成方法を提供する。この方法は酸化リチウムまたはリチウム塩またはその混合物を等モル比の燐酸二アンモニウムと混合して得られる二つの化合物の混合物を得ることからなる。この混合物を炉中で６００℃で加熱し、得られた生成物を冷却後粉末化する。続いて、反応で得られたこの粉末ＬｉＰＯ3を６倍量のフッ化アンモニウムと混合し、密閉したテフロン（登録商標）容器に入れて炉を用いて２００℃で４〜６時間連続的に加熱する。
【００２５】
本発明による方法の有利な点は、第１に副反応を生じない点、第２に方法を選択することにより単一ステップまたは二段のステップによる反応が可能である点、第３に純度の高いＬｉＰＦ6が得られる点、第４に加熱制御のもとに行う完全に固体状態の反応であり初期の反応においてもガスや液体を使用しない点、第５に製品の純度が反応材料の純度に依存する点、最後に方法が簡単で複雑でなく高効率である点である。
【００２６】
以下に実施例を参照して本発明を詳細に説明するが、実施例は本発明を説明するためのものであって、いかなる方法によっても本発明の技術範囲を限定するものと解釈してはならない。
【００２７】
実施例１
【００２８】
Ｌｉ2ＣＯ3と（ＮＨ4）2ＨＰＯ4の等モル比の混合物をよく摩砕して、電気炉または間接加熱炉を用いて６００℃で６時間連続的に加熱した。生成物をよく摩砕してＮＨ4Ｆと混合し電気炉または間接加熱炉を用いて２００℃で４時間加熱した。
【００３０】
実施例２
【００３１】
Ｌｉ2Ｏと（ＮＨ4）2ＨＰＯ4の等モル比の混合物をよく摩砕して、電気炉または間接加熱炉を用いて４００℃で６時間連続的に加熱した。生成物をよく摩砕してＮＨ4Ｆと混合し電気炉または間接加熱炉を用いて２００℃で４時間加熱した。
【００３２】
実施例３
【００３４】
ＬｉＮＯ3と（ＮＨ4）2ＨＰＯ4の等モル比の混合物をよく摩砕して、電気炉または間接加熱炉を用いて４００℃で６時間連続的に加熱した。生成物をよく摩砕してＮＨ4Ｆと混合し電気炉または間接加熱炉を用いて２００℃で４時間加熱した。
【００３５】
実施例４
【００３７】
メタ燐酸リチウム（ＬｉＰＯ3）とフッ化アンモニウム１：６〜８の混合物をよく摩砕して、電気炉または間接加熱炉を用いて２００℃で４時間最終生成物が形成するまで加熱した。
【００３８】
実施例５
【００４０】
Ｌｉ2Ｏと（ＮＨ4）2ＨＰＯ4及びＮＨ4Ｆの１：２：７の混合物を電気炉または間接加熱炉を用いて３００℃で６時間連続的に加熱した。
【００４１】
実施例６
【００４３】
Ｌｉ2ＣＯ3と（ＮＨ4）2ＨＰＯ4及びＮＨ4Ｆの１：２：７の混合物を電気炉または間接加熱炉を用いて６００℃で６時間連続的に加熱した。
【００４４】
実施例７
【００４６】
ＬｉＮＯ3と（ＮＨ4）2ＨＰＯ4及びＮＨ4Ｆの１：２：７の混合物を電気炉または間接加熱炉を用いて３００℃で４時間連続的に加熱した。
【００４７】
[Industrial application fields]
The present invention relates to a novel method for synthesizing lithium hexafluorophosphate (LiPF 6 ). In particular, the present invention relates to a novel process for producing lithium hexafluorophosphate useful as battery electrolytes, particularly as rocking chair batteries, non-aqueous lithium ion batteries, and lithium polymer battery electrolytes.
[0002]
[Prior art]
LiPF 6 is well known as an electrolyte for lithium ion secondary batteries, and its production is difficult because the raw materials such as P 2 O 5 , Li 2 O, PF 5 , and fluorine gas are very active. Several chemical methods are known in the literature, but they require careful handling and purification.
[0003]
Furthermore, the products produced by these methods require equipment for various treatments before becoming a basic compound for battery electrolytes.
[0004]
A metal salt of fluorophosphoric acid whose metal component is Ca, K, or Li is synthesized by reacting metal fluoride (MF) with PF 3 [Paul et. Al., Fluorine Chemistry, 56, 1995]. The reaction formula is as follows.
[0005]
3MF + 5PF 3 → 3MPF 6 + 2P
[0006]
When the metal component is Ca, K, or Cs, MPF 6 is produced by neutralizing HPF 6 with a suitable base.
[0007]
2HPF 6 + Ca (OH) 2 → Ca (PF 6 ) 2 + 2H 2 O
[0008]
Similarly, some metal salts of hexafluorophosphoric acid are produced by double decomposition of NH 4 PF 6 and KPF 6 [Paul et. Al., Fluorine Chemistry, 56, (1995)] [LH Simons, Fluorine Chemistry, Vol. 5, 131 (1819) (1964)] [HJ Emelson, Fluorine Chemistry, Vol. 1 76 (219) (1995)]. The conventional LiPF 6 production method has several disadvantages. Since toxic chemicals are used as reaction raw materials, handling of these chemicals is difficult, and partial reactions occur, so that the reaction product contains unreacted impurities and requires further processing for purification.
[0009]
[Problems to be solved by the invention]
The main object of the present invention is to provide a novel method for synthesizing lithium hexafluorophosphate (LiPF 6 ) used as an electrolyte of a battery. Another object of the present invention is to provide a synthesis method by a complete solid phase reaction. Yet another object of the present invention is to provide a method of synthesis without the use of active chemicals that are difficult to handle and without the use of unpleasant gases. Still another object of the present invention is to provide a synthesis method for obtaining a product containing no unreacted components. The above and other objects of the present invention and the disadvantages associated with conventional methods are overcome by the method according to the present invention described below.
[0010]
[Means for solving the problems]
According to a novel method of synthesizing the lithium hexafluorophosphate (LiPF 6), Li 2 O , and dried purified lithium source, hydrogen phosphate diammonium dried purified equimolar amounts, such as Li 2 CO 3 or LiNO 3 After mixing , the mixture was continuously heated in an electric furnace at 200 to 600 ° C. for 6 hours. The product was cooled and transferred to a drying vessel. The product was a transparent substance and was confirmed to be LiPF 6 by X-ray analysis.
[0011]
Therefore, the present invention provides a novel synthesis method by solid phase heating reaction for synthesizing lithium hexafluorophosphate, and the synthesis method comprises the following steps.
[0012]
(A) mixing a lithium raw material selected from the group consisting of lithium oxide, a lithium salt or a mixture thereof and diammonium phosphate in an equimolar ratio;
(B) The mixture is continuously heated in a furnace at 150 to 600 ° C. to obtain LiPO 3 .
(C) LiPO 3 is cooled and pulverized.
(D) The powdered product is mixed with 6 to 9 times the amount of ammonium fluoride, sealed in a Teflon (registered trademark) container, and used in a furnace at a temperature range of 150 to 200 ° C. for 4 to 6 hours. Heating continuously,
(E) Transfer the product to a dry container.
[0013]
In one embodiment of the present invention, the heating in step (b) is performed in a range of 4 to 6 hours. In another embodiment of the present invention, LiPO 3 is NH 4 F and 1: is mixed at a ratio of 6-9 to obtain LiPF 6. In another embodiment of the present invention, lithium metaphosphate (LiPO 3 ) is mixed with ammonium fluoride in a ratio of 1: 7 and heated continuously in an electric furnace at 200 ° C. for 6 hours to give lithium hexafluorophosphate. obtain.
[0014]
In still another embodiment of the present invention, Li 2 O or Li 2 CO 3 or LiNO 3 is mixed with diammonium hydrogen phosphate and ammonium fluoride in a molar ratio of 1: 2: 6-9. In another embodiment of the invention, Li 2 O or Li 2 CO 3 or LiNO 3 is mixed with diammonium hydrogen phosphate and ammonium fluoride in a ratio of 1: 1: 7. In yet another embodiment of the invention, Li 2 O or LiNO 3 is mixed with diammonium hydrogen phosphate and ammonium fluoride in a ratio of 1: 1: 7 and the mixture is placed in an electric furnace at 200 ° C. for 12 hours. Heat continuously to obtain LiPF 6 . In an embodiment of the invention, Li 2 O or Li 2 CO 3 or LiNO 3 is mixed with diammonium phosphate in a 1: 1 ratio, and the product of this mixture is mixed with NH 4 F at 1: 7 and heated. To do.
[0015]
In yet another embodiment of the present invention, when Li 2 O or LiNO 3 is the starting material, the temperature for synthesizing LiPF 6 is maintained between 150-350 ° C. In another embodiment of the present invention, Li 2 CO 3 and (NH 4 ) 2 HPO 4 are mixed and heated at around 600 ° C. and subsequently mixed with NH 4 F at a temperature between 150 and 350 ° C. Heat. In the embodiment of the present invention, the reaction is performed in a solid state. In another embodiment of the present invention, the synthesis method comprises the following two-step reaction.
[0016]
First step [0017]
2 (NH 4 ) 2 HPO 4 + Li 2 O → 2LiPO 3 + 4NH 3 + 3H 2 O
2 (NH 4 ) 2 HPO 4 + Li 2 CO 3 → 2LiPO 3 + 4NH 3 + CO 2 + 3H 2 O
2 (NH 4 ) 2 HPO 4 + LiNO 3 → 2LiPO 3 + 4NH 3 + 2NO 2 + 2H 2 O + O 2
[0018]
Second step [0019]
LiPO 3 + 6NH 4 F → LiPF 6 + 6NH 3 + 3H 2 O
[0020]
In still another embodiment of the present invention, a single-step reaction is performed according to the following reaction formula in a temperature range of 150 to 300 ° C.
[0021]
Li 2 O + 2 (NH 4 ) 2 HPO 4 + 12NH 4 F → 2LiPF 6 + 16NH 3 + 9H 2 O
Li 2 CO 3 +2 (NH 4 ) 2 HPO 4 + 12NH 4 F → 2LiPF 6 + 16NH 3 + CO 2 + 9H 2 O
LiNO 3 +2 (NH 4 ) 2 HPO 4 + 12NH 4 F → 2LiPF 6 + 16NH 3 + NO 2 + 9H 2 O
[0022]
In another embodiment of the present invention, dried and purified Li 2 O or Li 2 CO 3 or LiNO 3 molar ratio of 1: 2 was mixed with diammonium phosphate, Li 2 the mixture with indirect heating furnace or electric furnace CO3 Is heated at 600 ° C., and Li 2 O or LiNO 3 is continuously heated at 300 ° C. for 6 hours. The product is dried at 80 ° C. and subsequently heated and reacted in an electric furnace at 150-350 ° C. for 4 hours with NH 4 F in a molar ratio of 1: 6-8. The features of the present invention are that all raw materials are in a solid state, an electric furnace or an indirect heating furnace is used for the reaction, and a single-step reaction process according to the following reaction formula is possible.
[0023]
(A) LiPO 3 + 6NH 4 F → LiPF 6 + 6NH 3 + 3H 2 O
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Lithium hexafluorophosphate is a basic chemical product used in rocking chair batteries and lithium ion batteries, but the conventional method for producing this compound is difficult and has many drawbacks. The present invention provides a novel method of synthesizing LiPF 6 by a solid phase heating reaction that can overcome the conventional difficulties. This process consists of obtaining a mixture of two compounds obtained by mixing lithium oxide or a lithium salt or a mixture thereof with an equimolar ratio of diammonium phosphate. The mixture is heated in a furnace at 600 ° C. and the resulting product is cooled and pulverized. Subsequently, this powder LiPO 3 obtained by the reaction was mixed with 6 times the amount of ammonium fluoride, placed in a sealed Teflon (registered trademark) container, and continuously heated at 200 ° C. for 4 to 6 hours using a furnace. To do.
[0025]
The advantages of the method according to the present invention are that first, no side reactions occur, secondly, the reaction can be performed in a single step or two steps by selecting the method, and thirdly, the purity High LiPF 6 is obtained, fourth is a completely solid state reaction under heating control, and no gas or liquid is used in the initial reaction, and fifth, the purity of the product is the purity of the reaction material Finally, the method is simple, uncomplicated and highly efficient.
[0026]
The present invention will be described in detail below with reference to examples. However, the examples are for explaining the present invention, and should not be construed as limiting the technical scope of the present invention in any way. Don't be.
[0027]
Example 1
[0028]
A mixture of equimolar ratios of Li 2 CO 3 and (NH 4 ) 2 HPO 4 was thoroughly ground and continuously heated at 600 ° C. for 6 hours using an electric furnace or an indirect heating furnace. The product was well ground and mixed with NH 4 F and heated at 200 ° C. for 4 hours using an electric furnace or an indirect heating furnace.
[0030]
Example 2
[0031]
A mixture of equimolar ratio of Li 2 O and (NH 4 ) 2 HPO 4 was thoroughly ground and continuously heated at 400 ° C. for 6 hours using an electric furnace or an indirect heating furnace. The product was well ground and mixed with NH 4 F and heated at 200 ° C. for 4 hours using an electric furnace or an indirect heating furnace.
[0032]
Example 3
[0034]
An equimolar ratio mixture of LiNO 3 and (NH 4 ) 2 HPO 4 was well ground and continuously heated at 400 ° C. for 6 hours using an electric furnace or an indirect heating furnace. The product was well ground and mixed with NH 4 F and heated at 200 ° C. for 4 hours using an electric furnace or an indirect heating furnace.
[0035]
Example 4
[0037]
A mixture of lithium metaphosphate (LiPO 3 ) and ammonium fluoride 1: 6-8 was well ground and heated using an electric furnace or indirect heating furnace at 200 ° C. for 4 hours until the final product formed.
[0038]
Example 5
[0040]
A 1: 2: 7 mixture of Li 2 O, (NH 4 ) 2 HPO 4 and NH 4 F was continuously heated at 300 ° C. for 6 hours using an electric furnace or an indirect heating furnace.
[0041]
Example 6
[0043]
A 1: 2: 7 mixture of Li 2 CO 3 and (NH 4 ) 2 HPO 4 and NH 4 F was continuously heated at 600 ° C. for 6 hours using an electric furnace or an indirect heating furnace.
[0044]
Example 7
[0046]
A 1: 2: 7 mixture of LiNO 3 and (NH 4 ) 2 HPO 4 and NH 4 F was continuously heated at 300 ° C. for 4 hours using an electric furnace or an indirect heating furnace.
[0047]
Claims (17)
（ａ）酸化リチウム、リチウム塩又はそれらの混合物からなる群より選択されたリチウム原料と燐酸水素二アンモニウムとを混合すること、
（ｂ）前記混合物を１５０〜６００℃の温度範囲で連続的に加熱し、生成物としてメタ燐酸リチウムを得ること、
（ｃ）前記生成物を冷却し粉末化すること、
（ｄ）前記粉末化したメタ燐酸リチウムをフッ化アンモニウムと混合し、密閉した容器に入れ１５０〜３５０℃の温度範囲で４〜６時間連続的に加熱すること、
（ｅ）最終生成物を乾燥容器に移すこと、
以上のステップ（ａ）〜（ｅ）からなることを特徴とする合成方法。In the method of synthesizing lithium hexafluorophosphate,
(A) lithium oxide, mixing the lithium salt or lithium material and hydrogen phosphate diammonium selected from the group consisting of a mixture thereof,
(B) continuously heating the mixture in a temperature range of 150 to 600 ° C. to obtain lithium metaphosphate as a product ;
(C) cooling and pulverizing the product;
And (d) wherein the powdered meth lithium phosphate is mixed with ammonium fluoride, to 4-6 hours continuously heated at a temperature range of 150 to 350 ° C. was placed in a sealed container,
(E) transferring the final product in the drying vessel,
A synthesis method comprising the above steps (a) to (e) .
前記ステップ（ｄ）において、粉末化したメタ燐酸リチウムとフッ化アンモニウムとの混合比をモル比１：７とすることを特徴とする請求項１記載の合成方法。In the step (a), lithium carbonate, lithium oxide or lithium nitrate is mixed as a lithium raw material with diammonium hydrogen phosphate at a molar ratio of 1: 1,
The synthesis method according to claim 1, wherein in the step (d), a mixing ratio of powdered lithium metaphosphate and ammonium fluoride is set to 1: 7.
前記ステップ（ｂ）において、電気炉又は間接加熱炉を用いて３５０℃で連続的に加熱し、生成物であるメタ燐酸リチウムを８０℃で乾燥した後、
前記ステップ（ｄ）においてモル比１：６〜８でフッ化アンモニウムと混合し、電気炉内で１５０〜３５０℃の温度範囲で連続的に４時間加熱することを特徴とする請求項１記載の合成方法。In the step (a), dry purified lithium oxide or purified lithium nitrate and diammonium hydrogen phosphate are mixed at a molar ratio of 1: 2.
In the step (b), after continuously heating at 350 ° C. using an electric furnace or an indirect heating furnace and drying the product lithium metaphosphate at 80 ° C.,
The step (d) comprises mixing with ammonium fluoride in a molar ratio of 1: 6 to 8 and continuously heating in an electric furnace at a temperature range of 150 to 350 ° C for 4 hours. Synthesis method.
（ａ）酸化リチウム、リチウム塩又はそれらの混合物からなる群より選択されたリチウム原料と、燐酸水素二アンモニウムと、フッ化アンモニウムとを混合し、
（ｂ）前記混合物を１５０〜３００℃の温度範囲で加熱することを特徴とする合成方法。In the synthesis method of lithium hexafluorophosphate,
(A) mixing a lithium raw material selected from the group consisting of lithium oxide, a lithium salt or a mixture thereof, diammonium hydrogen phosphate, and ammonium fluoride;
(B) The synthesis method, wherein the mixture is heated in a temperature range of 150 to 300 ° C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/IN2002/000056 WO2003080511A1 (en) | 2002-03-13 | 2002-03-21 | Solid state thermal method for the synthesis of lithium hexafluro phosphate |
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| Publication Number | Publication Date |
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| JP2005519839A JP2005519839A (en) | 2005-07-07 |
| JP2005519839A5 JP2005519839A5 (en) | 2005-09-22 |
| JP4047817B2 true JP4047817B2 (en) | 2008-02-13 |
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| JP5540281B2 (en) * | 2009-05-01 | 2014-07-02 | 国立大学法人九州大学 | Method for producing positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same |
| JP5862015B2 (en) * | 2011-02-17 | 2016-02-16 | 宇部興産株式会社 | Method for producing lithium hexafluorophosphate-carbonate complex and precursor thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378445A (en) * | 1993-12-23 | 1995-01-03 | Fmc Corporation | Preparation of lithium hexafluorophosphate solutions |
| DE19614503A1 (en) * | 1995-04-12 | 1996-10-17 | Basf Ag | Anhydrous lithium hexa:fluoro:phosphate with low chloride content |
| DE19712988A1 (en) * | 1996-06-26 | 1998-01-02 | Solvay Fluor & Derivate | Manufacture of lithium hexafluorometalates |
| DE19625448A1 (en) * | 1996-06-26 | 1998-01-02 | Solvay Fluor & Derivate | Process for the preparation of LiPF¶¶¶ |
| DE19632543C1 (en) * | 1996-08-13 | 1998-04-02 | Metallgesellschaft Ag | Process for the production of LiPF¶6¶ |
| DE19805356C1 (en) * | 1998-02-12 | 1999-06-17 | Metallgesellschaft Ag | Lithium hexafluorophosphate is produced by reacting phosphorus pentachloride with an acidified lithium fluoride-diethylether suspension |
| DE19816691A1 (en) * | 1998-04-15 | 1999-10-21 | Riedel De Haen Gmbh | Process for the production of LiPF¶6¶ and electrolyte solutions containing it |
| KR100288825B1 (en) * | 1998-12-31 | 2001-05-02 | 박대치 | Method for producing lithium hexafluorophosphate |
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| AU2002242941A1 (en) | 2003-10-08 |
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