JP6150233B2 - 硫化リチウム−鉄−炭素複合体 - Google Patents
硫化リチウム−鉄−炭素複合体 Download PDFInfo
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- JP6150233B2 JP6150233B2 JP2015536591A JP2015536591A JP6150233B2 JP 6150233 B2 JP6150233 B2 JP 6150233B2 JP 2015536591 A JP2015536591 A JP 2015536591A JP 2015536591 A JP2015536591 A JP 2015536591A JP 6150233 B2 JP6150233 B2 JP 6150233B2
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- Prior art keywords
- iron
- lithium
- capacity
- lithium sulfide
- positive electrode
- Prior art date
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- 239000002131 composite material Substances 0.000 title claims description 89
- RHHFOWJQTQOEEU-UHFFFAOYSA-N [C+4].[Fe+2].[S-2].[Li+] Chemical compound [C+4].[Fe+2].[S-2].[Li+] RHHFOWJQTQOEEU-UHFFFAOYSA-N 0.000 title claims description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 89
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 61
- 229910052744 lithium Inorganic materials 0.000 claims description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 46
- 229910052717 sulfur Inorganic materials 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 45
- 229910052742 iron Inorganic materials 0.000 claims description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 40
- 229910001416 lithium ion Inorganic materials 0.000 claims description 40
- 239000007774 positive electrode material Substances 0.000 claims description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 35
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- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims 1
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- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 6
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
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- KNQQOSPYVAFZSX-UHFFFAOYSA-N [Fe]=S.[S-2].[Li+].[Li+] Chemical compound [Fe]=S.[S-2].[Li+].[Li+] KNQQOSPYVAFZSX-UHFFFAOYSA-N 0.000 description 3
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910003000 Li(Ni,Mn,Co)O2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
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Description
項1.リチウム、鉄、硫黄及び炭素を構成元素として含む複合体であって、
硫化リチウム(Li2S)を主相として含み、粉末X線回折によって得られたLi2Sの(111)面に基づく回折ピークの半価幅から算出される結晶子サイズが50nm以下であり、
前記複合体を基準としてRietveld解析により見積もられたLi 2 Sの存在比が90モル%以上であり、前記鉄が前記Li 2 Sの結晶格子内に配置してFe−S結合を形成している、硫化リチウム−鉄−炭素複合体。
項2.Li含有量が40〜60原子%、Fe含有量が2〜10原子%、S含有量が20〜40原子%、C含有量が10〜20原子%である、項1に記載の硫化リチウム−鉄−炭素複合体。
項3.リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において、該混合物を加圧した状態で直流パルス電流を通電して該混合物を加熱反応させた後、得られた生成物を炭素含有化合物と共にメカニカルミリング処理することを特徴とする、項1に記載の硫化リチウム−鉄−炭素複合体の製造方法。
項4.項1又は2に記載の硫化リチウム−鉄−炭素複合体を含むリチウムイオン二次電池用正極活物質。
項5.項4に記載の正極活物質を構成要素とするリチウムイオン二次電池。
項6.項4に記載の正極活物質とリチウムイオン伝導性固体電解質を構成要素として含む全固体リチウムイオン二次電池。
項7.項1又は2に記載の硫化リチウム−鉄−炭素複合体を正極活物質として含むリチウムイオン二次電池を形成した後、正極活物質の理論容量より低い容量で充放電を行い、次いで、容量を段階的に増加して、充放電を繰り返すことを特徴とする、リチウムイオン二次電池の前処理方法。
項8.最初の充放電を正極活物質の理論容量の1/10〜1/15の容量で行い、容量を30〜100mAh/gずつ段階的に増加させて充放電を行うことを特徴とする、項7に記載のリチウムイオン二次電池の前処理方法。
項9.電位範囲が、下限電圧1.0〜1.3V、上限電圧2.8〜3.0Vの範囲内で行うことを特徴とする、項7又は8に記載のリチウムイオン二次電池の前処理方法。
本発明の硫化リチウム−鉄−炭素複合体は、リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において該混合物を加圧した状態で直流パルス電流を通電して該混合物を加熱反応させた後、生成物を炭素含有化合物と共にメカニカルミリング処理することによって得ることができる。この方法によれば、加熱反応によって原子レベルでの反応が適度に進行した硫化リチウムと硫化鉄の混合物を得ることができ、これを炭素と共にメカニカルミリング処理することによって、粒子が微細化されて、鉄原子が硫化リチウム相内に取り込まれた準安定相が安定化され、更に、炭素が均一に分散した状態の複合体を得ることができる。以下、この方法について具体的に説明する。
本発明では、原料として、リチウム含有化合物、鉄含有化合物、硫黄含有化合物、及び炭素含有化合物を用いる。
(i)通電焼結工程
本発明では、まず、通電焼結工程として、リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において該混合物を加圧した状態で、放電プラズマ焼結法、パルス通電焼結法、プラズマ活性化焼結法等と呼ばれる直流パルス電流を通電する方法で各化合物を加熱反応させる。原料として用いる炭素含有化合物は、この段階で添加してもよく、後述するメカニカルミリング処理の際に添加してもよい。この方法によれば、通電焼結工程における熱処理により、各元素が拡散移動し、原子レベルで相互に混合した状態の中間体を作製することが出来る。
上記した通電焼結工程で得られた生成物を炭素含有化合物と共にメカニカルミリング処理して、混合、粉砕及び反応させることによって、本発明の目的とする硫化リチウム−鉄−炭素複合体を得ることができる。通電焼結工程で用いた原料に、所定量の炭素含有化合物が含まれていない場合には、メカニカルミリング工程の前に、炭素含有化合物を加えればよい。
上記した方法で得られる硫化リチウム−鉄−炭素複合体は、粉末X線回折測定において、主相が硫化リチウムからなるものである。硫化リチウム相の存在量は特に限定的ではないが、該複合体全体を基準として90モル%程度以上であることが好ましい。
本発明の硫化リチウム−鉄−炭素複合体を、非水電解質リチウムイオン二次電池、全固体型リチウムイオン二次電池等のリチウム二次電池の正極活物質として用いる場合には、目的とする構造の電池を作成した後、予備的に、理論容量より低い容量で充放電を行い、段階的に容量を増加させて充放電を繰り返し行うことが好ましい。この方法によれば、本発明の硫化リチウム−鉄−炭素複合体は、Liの脱離・挿入を少量ずつ段階的に行われ、それに伴う構造的な変化、すなわち各構成原子の再配列が段階的に大きくなることで、Liの脱離・挿入がスムーズになり、メカニカルミリング法によって得られた直後の複合体よりも良好な充放電特性を示す。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が3:1となるよう、アルゴンガス雰囲気のグローブボックス内(露点−80℃)で秤量し、乳鉢で充分に混合後、内径15mmの黒鉛型材に充填した。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が3:1となるよう混合後、実施例1と同じ条件で通電焼結法で600℃処理した。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が3:1となるよう秤量後、更にアセチレンブラック(AB)粉末を、硫化リチウム+硫化鉄の混合粉:AB=9:1の重量比となるよう混合し、実施例1と同様の条件でメカニカルミリング法により8時間処理して複合体を作製した。原料に用いた各元素の比率(原子%)は、実施例1と全く同様、Li41.7%、Fe7.0%、S34.8%、C16.5%であった。
硫化リチウム(Li2S)と硫化鉄(FeS2)の混合比を、モル比で4:1とすること以外は実施例1と全く同様にして硫化リチウム−鉄−炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li44.9%、Fe5.6%、S33.7%、C15.8%であった。
硫化リチウム(Li2S)と硫化鉄(FeS2)の混合比を、モル比で5:1とすること以外は実施例1と全く同様にして硫化リチウム−鉄−炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li47.1%、Fe4.7%、S33.0%、C15.2%であった。
市販の硫化リチウム(Li2S)(平均粒径約16μm)と硫化鉄(FeS2)(平均粒径約6μm)を、モル比が5:1となるよう混合後、実施例3と同じ条件で600℃で通電焼結を行った。
原料として用いた鉄含有化合物を硫化鉄(FeS)(平均粒径約8μm)とする以外は実施例1と全く同様にして硫化リチウム−鉄−炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li45.8%、Fe7.6%、S30.6%、C16.0%であった。
硫化リチウム(Li2S)と硫化鉄(FeS)の混合比を、モル比で4:1とすること以外は実施例4と全く同様にして硫化リチウム−鉄−炭素複合体を作製した。原料に用いた各元素の比率(原子%)は、Li48.4%、Fe6.1%、S30.3%、C15.2%であった。
実施例5で得られた硫化リチウム−鉄−炭素複合体を正極材料に用い、負極にインジウム金属、電解質に75Li2S−25P2S5を用いて全固体電池を組み上げ、充放電試験を行った。
実施例3で得られた硫化リチウム−鉄−炭素複合体を正極材料に用い、電位範囲を下限電圧1.8V、上限電圧2.6Vにすること以外は、予備的充放電処理を含めて実施例3と全く同様にして充放電試験を行った。充放電特性は図8に示す通りであり、初期充電容量は約620mAh/g、初期放電容量は約600mAh/gとなり、実施例3で測定した試料の場合の値(初期充電容量約560mAh/g、初期放電容量約600mA/g)と同程度の高い充放電容量を示した。また、5サイクル後の放電容量は約490mAh/g(容量維持率約81%)となり、実施例3での値(約450mAh/g、約75%)よりも高い値を示した。
2 試料
3 ダイ(導電性容器)
4、5 通電用パンチ
6,7 パンチ電極
8 水冷真空チャンバー
9 冷却水路
10、16 水冷却機構
11 焼結用電源
12 制御装置
13 加圧機構
14 位置計測機構
15 雰囲気制御機構
17 温度計測装置
Claims (9)
- リチウム、鉄、硫黄及び炭素を構成元素として含む複合体であって、
硫化リチウム(Li2S)を主相として含み、粉末X線回折によって得られたLi2Sの(111)面に基づく回折ピークの半価幅から算出される結晶子サイズが50nm以下であり、
前記複合体を基準としてRietveld解析により見積もられたLi 2 Sの存在比が90モル%以上であり、前記鉄が前記Li 2 Sの結晶格子内に配置してFe−S結合を形成している、硫化リチウム−鉄−炭素複合体。 - Li含有量が40〜60原子%、Fe含有量が2〜10原子%、S含有量が20〜40原子%、C含有量が10〜20原子%である、請求項1に記載の硫化リチウム−鉄−炭素複合体。
- リチウム含有化合物、鉄含有化合物、及び硫黄含有化合物を含む混合物を、導電性を有する型に充填し、非酸化性雰囲気下において、該混合物を加圧した状態で直流パルス電流を通電して該混合物を加熱反応させた後、得られた生成物を炭素含有化合物と共にメカニカルミリング処理することを特徴とする、請求項1に記載の硫化リチウム−鉄−炭素複合体の製造方法。
- 請求項1又は2に記載の硫化リチウム−鉄−炭素複合体を含むリチウムイオン二次電池用正極活物質。
- 請求項4に記載の正極活物質を構成要素とするリチウムイオン二次電池。
- 請求項4に記載の正極活物質とリチウムイオン伝導性固体電解質を構成要素として含む全固体リチウムイオン二次電池。
- 請求項1又は2に記載の硫化リチウム−鉄−炭素複合体を正極活物質として含むリチウムイオン二次電池を形成した後、正極活物質の理論容量より低い容量で充放電を行い、次いで、容量を段階的に増加して、充放電を繰り返すことを特徴とする、リチウムイオン二次電池の前処理方法。
- 最初の充放電を正極活物質の理論容量の1/10〜1/15の容量で行い、容量を30〜100mAh/gずつ段階的に増加させて充放電を行うことを特徴とする、請求項7に記載のリチウムイオン二次電池の前処理方法。
- 電位範囲が、下限電圧1.0〜1.3V、上限電圧2.8〜3.0Vの範囲内で行うことを特徴とする、請求項7又は8に記載のリチウムイオン二次電池の前処理方法。
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EP3046169B1 (en) | 2018-08-29 |
KR20160055213A (ko) | 2016-05-17 |
JPWO2015037598A1 (ja) | 2017-03-02 |
CN105518913A (zh) | 2016-04-20 |
EP3046169A1 (en) | 2016-07-20 |
EP3046169A8 (en) | 2016-09-14 |
US10290870B2 (en) | 2019-05-14 |
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