JP6669345B2 - リチウム二次電池用正極活物質、その製造方法およびこれを含むリチウム二次電池 - Google Patents
リチウム二次電池用正極活物質、その製造方法およびこれを含むリチウム二次電池 Download PDFInfo
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- JP6669345B2 JP6669345B2 JP2015148346A JP2015148346A JP6669345B2 JP 6669345 B2 JP6669345 B2 JP 6669345B2 JP 2015148346 A JP2015148346 A JP 2015148346A JP 2015148346 A JP2015148346 A JP 2015148346A JP 6669345 B2 JP6669345 B2 JP 6669345B2
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- Prior art keywords
- lithium
- positive electrode
- active material
- electrode active
- secondary battery
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- 229910052744 lithium Inorganic materials 0.000 title claims description 124
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 84
- 239000007774 positive electrode material Substances 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229910019142 PO4 Inorganic materials 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 29
- 239000010452 phosphate Substances 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
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- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 claims description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 3
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 33
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- -1 LiCoO 2 Chemical class 0.000 description 19
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
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- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- KEQHHFKPFQFWAJ-UHFFFAOYSA-M lithium;acetate;hydrate Chemical compound [Li+].O.CC([O-])=O KEQHHFKPFQFWAJ-UHFFFAOYSA-M 0.000 description 1
- XWFDVMYCFYYTTG-UHFFFAOYSA-N lithium;nitrate;hydrate Chemical compound [Li+].O.[O-][N+]([O-])=O XWFDVMYCFYYTTG-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229940057061 mevalonolactone Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- GHZRKQCHJFHJPX-UHFFFAOYSA-N oxacycloundecan-2-one Chemical compound O=C1CCCCCCCCCO1 GHZRKQCHJFHJPX-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910021435 silicon-carbon complex Inorganic materials 0.000 description 1
- 239000011867 silicon-carbon complex material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H01M4/139—Processes of manufacture
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
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Description
これにより、上記した正極活物質による電気化学的性能と安定性の問題によって、代替物質の開発に対する研究が活発に行われている。
本発明の他の目的は、上記リチウム二次電池用正極活物質の製造方法を提供することである。
本発明のさらに他の目的は、上記リチウム二次電池用正極活物質を含むリチウム二次電池を提供することである。
[化学式1]
Li1+(x+y)AxByTi2−(x+y)(PO4)3
(前記化学式1において、Aは4価元素であり、Bは2価元素であり、0<x≦1、0<y≦1である。)
前記化学式1において、0<x<1および0<y<1であってよい。
前記リチウム金属リン酸化物は、前記コアの表面に島状に付着していてもよい。
前記リチウム金属リン酸化物は、前記リチウムの挿入および脱離が可能な化合物100重量部に対して、0.01重量部〜20重量部で含まれてもよい。
前記リチウムの挿入および脱離が可能な化合物は、ニッケル系酸化物であってよく、前記ニッケル系酸化物は、リチウムニッケルコバルト酸化物、リチウムニッケルコバルトアルミニウム酸化物、リチウムニッケルコバルトマンガン酸化物、またはこれらの組み合わせを含むことができる。
さらに他の側面は、前記正極活物質を含むリチウム二次電池を提供する。
その他実施形態の具体的な事項は以下の詳細な説明に含まれている。
本実施形態に係る正極活物質は、リチウムの挿入および脱離が可能な化合物を含むコアと、コアの表面に位置するリチウム金属リン酸化物とを含むことができる。
[化学式1]
Li1+(x+y)AxByTi2−(x+y)(PO4)3
(化学式1において、Aは4価元素であり、Bは2価元素であり、0<x≦1、0<y≦1である。)
また、ここに記載されていない内容は、この技術分野における熟練した者であれば十分に技術的に類推できるので、その説明を省略する。
「製造例1:LZMTPの製造」
CH3COOLi・2H2O、Ti[OCH(CH3)2]4、NH4H2PO4、ジルコニウムアセチルアセトネート(C20H28O8Zr)、およびMg(CH3COO)2・4H2Oを最終物質のモル比どおりに混合した混合物と、水、エタノール、およびイソプロピルアルコールの混合溶媒(8:38:54の重量比)を混合して、Li1.5Zr0.2Mg0.3Ti1.5(PO4)3を含有する溶液を製造した。
CH3COOLi・2H2O、Al(NO3)3・9H2O、Ti[OCH(CH3)2]4、およびNH4H2PO4を最終物質のモル比どおりに混合した混合物と、水、エタノール、およびイソプロピルアルコールの混合溶媒(8:38:54の重量比)を混合して、Li1.3Al0.3Ti1.7(PO4)3を含有する溶液を製造した。
「実施例1」
製造例1で製造されたLZMTPを含有する溶液にLiNi1/3Co1/3Mn1/3O2(NCM)を添加して撹拌した後、上記混合物を撹拌しながら120℃で乾燥した後、不活性ガス雰囲気下、750℃で120分間焼結して、LZMTPでコーティングされたNCMを製造した。この時、上記LZMTPの含有量は、上記NCM100重量部に対して、1重量部で使用された。
LiNi1/3Co1/3Mn1/3O2(NCM)を正極活物質として使用した。
製造例1で製造されたLZMTPを含有する溶液にLiNi87.5Co11Al1.5O2(NCA)を添加して撹拌した後、この混合物を撹拌しながら120℃で乾燥した後、不活性ガス雰囲気下、750℃で120分間焼結して、LZMTPでコーティングされたNCAを製造した。この時、このLZMTPの含有量は、NCA100重量部に対して、1重量部で使用された。
LiNi87.5Co11Al1.5O2(NCA)を正極活物質として使用した。
製造例1で製造されたLZMTPの代わりに、比較製造例1で製造されたLATPを使用したことを除いては、実施例1と同様の方法によってLATPでコーティングされたNCAを製造した。
上記実施例1および2と比較例1〜3でそれぞれ製造された正極活物質94重量%、ポリビニリデンフルオライド(PVDF)3重量%、およびカーボンブラック3重量%を混合した後、N−メチル−2−ピロリドンに分散させて、スラリーを製造した。次に、15μmの厚さのアルミニウム箔上に上記スラリーを塗布および乾燥後、圧延して、正極を製造した。
図2Aおよび図2Bは、製造例1によるリチウム金属リン酸化物の走査電子顕微鏡(SEM)写真であって、それぞれ10,000倍率および30,000倍率で拡大した写真である。
図2Aおよび図2Bを参照すれば、製造例1の製造方法によれば、LZMTPのリチウム金属リン酸化物が製造されたことが分かる。
図3Aおよび図3Bは、実施例1による正極活物質の走査電子顕微鏡(SEM)写真であって、それぞれ10,000倍率および30,000倍率で拡大した写真である。また、図4Aおよび図4Bは、比較例1による正極活物質の走査電子顕微鏡(SEM)写真であって、それぞれ10,000倍率および30,000倍率で拡大した写真である。
図5は、実施例1による正極活物質のX線回折(XRD)分析グラフである。
図5を参照すれば、23.5°〜25.5°で現れる主ピークはLi1.5Zr0.2Mg0.3Ti1.5(PO4)3に関するもので、ナシコン構造であることを確認することができる。
実施例2および比較例2によるコインセルを4.5Vに完全充電した状態で、セルを解体して正極極板のみを取った後、ジメチルカーボネート(DMC)に浸してリチウム塩を除去した後、乾燥させて、極板を用意した。用意された極板からアルミニウム(Al)薄膜を除いた正極のみを取って、DSC用耐圧ファンに5mgを入れた後、コインセルに使用した電解液と同一の電解液を2μl挿入してよく閉じた後、DSC測定を進行させた。その結果は図6の通りである。
実施例2と比較例2および3による正極を3X5cmのサイズに切断し、リチウム金属を極板の前後面に分離膜を挟んで密着させてテフロン(登録商標)板で固定させた後、コインセルに使用した電解液と同一の電解液を用いてパウチ内に入れて、各面に熱を加えて密封する方法でパウチタイプの3電極セルをそれぞれ作製した。
実施例2および比較例2による正極活物質を用いたリチウム二次電池の効率を測定して、その結果を図8および図9に示した。
1.充電:0.1C、4.5V、0.05Cカットオフ/放電:0.1C、3Vカットオフ
2.充電:0.2C、4.5V、0.05Cカットオフ/放電:0.2C、3Vカットオフ
3.充電:0.5C、4.5V、0.05Cカットオフ/放電:0.5C、3Vカットオフ
4.充電:1C、4.5V、0.05Cカットオフ/放電:1C、3Vカットオフ
5.充電:2C、4.5V、0.05Cカットオフ/放電:2C、3Vカットオフ
6.充電:3C、4.5V、0.05Cカットオフ/放電:3C、3Vカットオフ
7.充電:5C、4.5V、0.05Cカットオフ/放電:5C、3Vカットオフ
8.充電:7C、4.5V、0.05Cカットオフ/放電:7C、3Vカットオフ
実施例1および比較例1による正極活物質を用いたリチウム二次電池の寿命特性を測定して、その結果を図10に示した。
実施例1および比較例1による正極活物質を用いたリチウム二次電池の効率特性を測定して、その結果を図11に示した。
112:負極
113:セパレータ
114:正極
120:電池容器
140:密封部材
Claims (8)
- リチウムの挿入および脱離が可能な化合物を含むコアと、
前記コアの表面に位置するリチウム金属リン酸化物とを含み、
前記リチウム金属リン酸化物は、前記リチウムの挿入および脱離が可能な化合物と相異なり、下記化学式1で表される、リチウム二次電池用正極活物質。
[化学式1]
Li1+(x+y)AxByTi2−(x+y)(PO4)3
(前記化学式1において、Aは4価元素であって、Zr、Nb、Mo、Ce、Cr、Ge、Ru、Se、Sn、Ta、Tb、V、W、またはこれらの組み合わせであり、Bは2価元素であって、Mg、Zn、Cu、Ca、Sr、Ba、Cd、Fe、Mn、Nd、Yb、またはこれらの組み合わせであり、0<x<1、0<y<1である。) - 前記化学式1において、Aは、Zrであり、Bは、Mgである、請求項1に記載のリチウム二次電池用正極活物質。
- 前記リチウム金属リン酸化物は、前記コアの表面に島状に付着する、請求項1または2に記載のリチウム二次電池用正極活物質。
- 前記リチウム金属リン酸化物は、前記リチウムの挿入および脱離が可能な化合物100重量部に対して、0.01重量部〜20重量部で含まれる、請求項1から3のいずれか1項に記載のリチウム二次電池用正極活物質。
- 前記リチウムの挿入および脱離が可能な化合物は、ニッケル系酸化物である、請求項1から4のいずれか1項に記載のリチウム二次電池用正極活物質。
- 前記ニッケル系酸化物は、リチウムニッケルコバルト酸化物、リチウムニッケルコバルトアルミニウム酸化物、リチウムニッケルコバルトマンガン酸化物、またはこれらの組み合わせを含む、請求項5に記載のリチウム二次電池用正極活物質。
- リチウム含有化合物、4価元素含有化合物、2価元素含有化合物、チタン含有化合物、リン酸塩、および溶媒を混合して、下記化学式1で表されるリチウム金属リン酸化物を含有する溶液を製造する段階と、
前記リチウム金属リン酸化物を含有する溶液にリチウムの挿入および脱離が可能な化合物を添加して混合物を得る段階と、
前記混合物を乾燥および焼結する段階とを含む、リチウム二次電池用正極活物質の製造方法。
[化学式1]
Li1+(x+y)AxByTi2−(x+y)(PO4)3
(前記化学式1において、Aは4価元素であって、Zr、Nb、Mo、Ce、Cr、Ge、Ru、Se、Sn、Ta、Tb、V、W、またはこれらの組み合わせであり、Bは2価元素であって、Mg、Zn、Cu、Ca、Sr、Ba、Cd、Fe、Mn、Nd、Yb、またはこれらの組み合わせであり、0<x<1、0<y<1である。) - 請求項1から6のいずれか1項に記載の正極活物質を含む、リチウム二次電池。
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