JP4344874B2 - Method for producing foil strip for negative electrode of lithium ion secondary battery by non-aqueous solvent plating method - Google Patents
Method for producing foil strip for negative electrode of lithium ion secondary battery by non-aqueous solvent plating method Download PDFInfo
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- JP4344874B2 JP4344874B2 JP2003347079A JP2003347079A JP4344874B2 JP 4344874 B2 JP4344874 B2 JP 4344874B2 JP 2003347079 A JP2003347079 A JP 2003347079A JP 2003347079 A JP2003347079 A JP 2003347079A JP 4344874 B2 JP4344874 B2 JP 4344874B2
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- foil strip
- lithium ion
- negative electrode
- secondary battery
- ion secondary
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- 238000007747 plating Methods 0.000 title claims description 101
- 239000011888 foil Substances 0.000 title claims description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000003125 aqueous solvent Substances 0.000 title description 7
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 24
- 239000003115 supporting electrolyte Substances 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- -1 γ-butyl lactone Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 42
- 239000011889 copper foil Substances 0.000 description 16
- 239000011255 nonaqueous electrolyte Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 239000007773 negative electrode material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
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- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
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- 239000000243 solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 229940070337 ammonium silicofluoride Drugs 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
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- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
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- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
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- 239000002759 woven fabric Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VFRGATWKSPNXLT-UHFFFAOYSA-N 1,2-dimethoxybutane Chemical compound CCC(OC)COC VFRGATWKSPNXLT-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- LJEHUBMFBQDJIP-UHFFFAOYSA-N 1,3-dioxolan-2-one;methylsulfinylmethane Chemical compound CS(C)=O.O=C1OCCO1 LJEHUBMFBQDJIP-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018598 Si-Co Inorganic materials 0.000 description 1
- 229910018594 Si-Cu Inorganic materials 0.000 description 1
- 229910008071 Si-Ni Inorganic materials 0.000 description 1
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- 229910008453 Si—Co Inorganic materials 0.000 description 1
- 229910008465 Si—Cu Inorganic materials 0.000 description 1
- 229910006300 Si—Ni Inorganic materials 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-NJFSPNSNSA-N lithium-9 Chemical compound [9Li] WHXSMMKQMYFTQS-NJFSPNSNSA-N 0.000 description 1
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Images
Classifications
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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
Description
本発明は、非水電解質リチウムイオン二次電池に関し、より詳しくはLiを多量かつ可逆的に吸蔵・放出することができるリチウムイオン二次電池負極用のSi系メッキ層付箔帯とその製造方法、得られたSi系メッキ層付箔帯を負極として用いる非水電解質リチウムイオン二次電池に関する。 TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte lithium ion secondary battery, and more specifically, a foil strip with a Si-based plating layer for a negative electrode of a lithium ion secondary battery capable of reversibly occluding and releasing Li in a large amount and reversibly. The present invention also relates to a non-aqueous electrolyte lithium ion secondary battery using the obtained foil strip with a Si plating layer as a negative electrode.
なお、本発明において、「非水電解質リチウムイオン二次電池」とは、Ｌｉ塩を溶解した非水溶媒を用いたリチウムイオン二次電池と高分子電解質或いはゲル電解質を用いたリチウムイオン二次電池とを包含する。 In the present invention, the “non-aqueous electrolyte lithium ion secondary battery” means a lithium ion secondary battery using a non-aqueous solvent in which a Li salt is dissolved and a lithium ion secondary battery using a polymer electrolyte or a gel electrolyte. Including.
近年、パーソナルコンピューター、携帯電話、PDAなどの携帯機器類の急速な普及に伴って、高容量の非水電解液二次電池の需要が高まるとともに、そのより一層の高容量化が求められている。 In recent years, with the rapid spread of portable devices such as personal computers, mobile phones, and PDAs, the demand for high-capacity non-aqueous electrolyte secondary batteries has increased, and there has been a demand for higher capacities. .
現在実用化されている非水電解液二次電池は、炭素材料を負極に用いたリチウムイオン二次電池である。炭素材料を負極として用いるリチウムイオン二次電池においては、炭素材料として黒鉛を使用する場合でも、理論容量最大値が372mAh/gと低いので、高容量化には限界がある。 The non-aqueous electrolyte secondary battery currently in practical use is a lithium ion secondary battery using a carbon material as a negative electrode. In a lithium ion secondary battery using a carbon material as a negative electrode, even when graphite is used as the carbon material, the maximum theoretical capacity is as low as 372 mAh / g, so there is a limit to increasing the capacity.
Li系金属(金属Li或いはLi合金)により負極を構成する場合には、炭素材料を負極とする場合に比して、10倍以上の高容量化が可能となる。しかしながら、Li系金属を負極とするリチウムイオン二次電池では、充電時に負極に金属Liがデンドライト状に析出し、セパレータを突き破って正極と接触して、短絡する危険性がある。従って、電池の安全性を考慮すると、Li系金属を負極として用いるリチウムイオン二次電池は、実用化されるには至っていない。 When the negative electrode is made of Li-based metal (metal Li or Li alloy), the capacity can be increased by 10 times or more compared with the case where the carbon material is used as the negative electrode. However, in a lithium ion secondary battery using a Li-based metal as a negative electrode, there is a danger that metal Li is deposited in a dendrite state on the negative electrode during charging, breaks through the separator, contacts the positive electrode, and is short-circuited. Therefore, considering the safety of the battery, a lithium ion secondary battery using a Li-based metal as a negative electrode has not been put into practical use.
金属Liに代わる新たな高容量負極材料として、理論容量がLiに匹敵するAl、Si、Snおよびそれらの金属間化合物を使用することが提案されている(特許文献１、非特許文献１)。 As a new high-capacity negative electrode material that replaces metallic Li, it has been proposed to use Al, Si, Sn, and their intermetallic compounds whose theoretical capacity is comparable to Li (Patent Document 1, Non-Patent Document 1).
しかしながら、これらの材料は、高容量を達成することができるものの、充電放電に伴う膨張収縮が大きいため、充電放電を繰り返すと割れが生じ、微粉化する。そのため、これらの材料を負極に用いたリチウムイオン二次電池は、充電放電に伴う容量低下が大きく、サイクル寿命が著しく短いものとなる。 However, although these materials can achieve a high capacity, since expansion and contraction associated with charge / discharge are large, cracks are generated and pulverized when charge / discharge is repeated. Therefore, a lithium ion secondary battery using these materials for the negative electrode has a large capacity reduction due to charge and discharge, and has a significantly short cycle life.
現在の負極極板は、バインダーを用いて黒鉛負極粉末を集電箔の上に塗布して結着させる構成を備えている。上記の高容量Al系負極活物質を使用する場合に、集電箔との密着性を高めることにより、長期の充電放電サイクル後も安定して集電できるようにするために、集電箔にメッキ層を形成した負極が提案されている（特許文献２）。 The current negative electrode plate has a configuration in which a graphite negative electrode powder is applied onto a current collector foil and bound using a binder. When using the above high-capacity Al-based negative electrode active material, to improve the adhesion with the current collector foil, in order to be able to collect current stably after a long charge-discharge cycle, A negative electrode formed with a plating layer has been proposed (Patent Document 2).
また、上記のSn系負極材料においては、充電放電時の粉化（クラック）を防止し、充放電サイクル寿命を改善する手法として、微細結晶粒化メッキ法(結晶粒1μm未満)が提案されている（特許文献３）。 In addition, in the above Sn-based negative electrode materials, a fine grain plating method (with crystal grains of less than 1 μm) has been proposed as a technique for preventing powdering (cracking) during charge / discharge and improving the charge / discharge cycle life. (Patent Document 3).
さらに、特許文献２には、Al系負極材料活物質のクラック発生防止方法として、溶融塩電解Alメッキ組成を、Liを吸蔵する相と吸蔵しないで膨張時の骨となり支える相（粉化防止相）とを分散させる多相組織で構成させることにより、良好なサイクル特性が得る事例が示されている。 Furthermore, Patent Document 2 describes a method for preventing cracking of an Al-based negative electrode material active material, in which a molten salt electrolytic Al plating composition is supported by a phase that supports and becomes a bone during expansion without occlusion of Li. ) Is dispersed in a multiphase structure, and an example of obtaining good cycle characteristics is shown.
理論容量が最も高いSi(約4200mAh/g)については、溶媒を用いるメッキ方法が実施困難であるため、あまり研究が進んでいないというのが実状である。例えば、太陽電池用負極に関して、ケイフッ化アンモニウムのホルムアルデヒド溶液を用いて集電箔へのSiメッキ層形成を試みた例がある(非特許文献２)。しかしながら、この方法には、シリカ(SiO2)が析出するなどの問題があり、実用化には至らなかった。 As for Si (about 4200 mAh / g), which has the highest theoretical capacity, it is difficult to carry out a plating method using a solvent. For example, with respect to a negative electrode for a solar cell, there is an example of trying to form a Si plating layer on a current collector foil using a formaldehyde solution of ammonium silicofluoride (Non-patent Document 2). However, this method has problems such as precipitation of silica (SiO 2 ) and has not been put into practical use.
また、密着性を高めるため、化学気相蒸着による集電箔へのSiメッキ層形成が試みられているが（非特許文献３）、プロセスが非常に高コストであること、生産性が低いこと、サイクル特性改善のための多相組織が実現困難であることなどの問題点がある。
本発明は、理論容量が最も高いSi(約4200mAh/g)を用いて、サイクル特性に優れた負極箔帯を高い生産効率で安価に製造する技術を提供することを主な目的とする。 The main object of the present invention is to provide a technique for manufacturing a negative electrode foil strip excellent in cycle characteristics at high production efficiency at low cost using Si (about 4200 mAh / g) having the highest theoretical capacity.
本発明者は、従来実用化が困難であった溶媒系メッキ法によるリチウムイオン二次電池用負極箔帯へのSiメッキ層の形成について研究を重ねた結果、微細結晶相と膨張時の骨となり支える相（粉化防止相）とを分散させる多相組織を生成させて、サイクル特性に優れた負極箔帯を製造する新規な技術を確立することに成功した。 As a result of repeated research on the formation of a Si plating layer on a negative electrode foil strip for a lithium ion secondary battery by a solvent-based plating method, which has been difficult to put into practical use, the present inventor has become a fine crystal phase and a bone at the time of expansion. We succeeded in establishing a new technology for producing a negative electrode foil strip with excellent cycle characteristics by generating a multiphase structure in which the supporting phase (anti-powdering phase) is dispersed.
本発明は、下記の負極箔帯製造技術とそれに基づくリチウムイオン二次電池を提供する。
１．支持電解質と四塩化珪素および／またはSiHCl3の珪素塩とを含む有機溶媒をメッキ浴とし、カソード側に被メッキ材である箔帯を配置して、箔帯上にSiを析出させるか或いはLiと反応しない金属元素とSiとを共析させることを特徴とするリチウムイオン二次電池負極用箔帯の製造方法。
２．有機溶媒が、プロピレンカーボネート、エチレンカーボネート、ジメチルスルホキシド、γ-ブチルラクトン、スルホラン、1,2-ジメトキシエタン、テトラヒドロフラン、ジオキソラン、シエチルカーボネート、メチルエチルカーボネート、ジメチルカーボネートおよびアセトンからなる群から選ばれる少なくとも1種である上記項１に記載のリチウムイオン二次電池負極用箔帯の製造方法。
３．支持電解質が、テトラブチルアンモニウム過塩素酸塩、テトラメチルアンモニウム過塩素酸塩、無水塩化カリウムおよび無水塩化ナトリウムからなる群から選ばれた少なくとも１種である上記項１または２に記載のリチウムイオン二次電池負極用箔帯の製造方法。
４．Liと反応しない金属イオンを金属塩化物の形態でメッキ浴に供給する上記項１〜３のいずれかに記載のリチウムイオン二次電池負極用箔帯の製造方法。
５．アノード電極をLiと反応しない金属により構成して、その溶解により生成する金属イオンをメッキ浴中に供給する上記項１〜４のいずれかに記載のリチウムイオン二次電池負極用箔帯の製造方法。
６．支持電解質が、リチウムイオン源となるLiCF3SO3、LiAsF6、LiClO4、LiBF4およびLiPF6からなる群から選ばれる少なくとも１種を含む上記項１〜５のいずれかに記載のリチウムイオン二次電池負極用箔帯の製造方法。
７．被メッキ材である箔帯が、銅、鉄、チタンおよびニッケルならびにこれらを含む合金から選ばれた１種である上記項１〜６のいずれかに記載のリチウムイオン二次電池負極用箔帯の製造方法。
８．上記項１〜７のいずれかに記載の方法により得られたメッキ層付箔帯からなるリチウムイオン二次電池用負極。
９．上記項１〜７のいずれかに記載の方法により得られたメッキ層付箔帯を負極として用いるリチウムイオン二次電池。
The present invention provides the following negative electrode foil strip manufacturing technique and a lithium ion secondary battery based thereon.
1. An organic solvent containing a supporting electrolyte and silicon tetrachloride and / or silicon salt of SiHCl 3 is used as a plating bath, and a foil strip as a material to be plated is disposed on the cathode side, and Si is deposited on the foil strip, or Li A method for producing a foil strip for a negative electrode of a lithium ion secondary battery, characterized by co-depositing a metal element that does not react with Si and Si.
2. The organic solvent is at least selected from the group consisting of propylene carbonate, ethylene carbonate, dimethyl sulfoxide, γ-butyl lactone, sulfolane, 1,2-dimethoxyethane, tetrahydrofuran, dioxolane, ciethyl carbonate, methyl ethyl carbonate, dimethyl carbonate and acetone. The manufacturing method of the foil strip for lithium ion secondary battery negative electrodes of said claim | item 1 which is 1 type.
3. 3. The lithium ion 2 according to item 1 or 2, wherein the supporting electrolyte is at least one selected from the group consisting of tetrabutylammonium perchlorate, tetramethylammonium perchlorate, anhydrous potassium chloride, and anhydrous sodium chloride. Manufacturing method of foil strip for secondary battery negative electrode.
4).
5.
6). Item 6. The lithium ion battery according to any one of Items 1 to 5, wherein the supporting electrolyte contains at least one selected from the group consisting of LiCF 3 SO 3 , LiAsF 6 , LiClO 4 , LiBF 4 and LiPF 6 serving as a lithium ion source. Manufacturing method of foil strip for secondary battery negative electrode.
7). The foil strip for a lithium ion secondary battery negative electrode according to any one of Items 1 to 6, wherein the foil strip as the material to be plated is one selected from copper, iron, titanium, nickel, and an alloy containing these. Production method.
8). The negative electrode for lithium ion secondary batteries which consists of a foil strip with a plating layer obtained by the method in any one of said item | term 1-7.
9. The lithium ion secondary battery which uses the foil strip with a plating layer obtained by the method in any one of said items 1-7 as a negative electrode.
有機溶媒系Siメッキ浴を使用する本発明によれば、以下の様な効果が達成される。
１．気相法と異なり、常温近傍でメッキ操作を行うことができる。
２．溶媒系のメッキ法によるので、連続メッキ操作を行うことができる。
３．上記１および２の結果として、Siメッキ層を備えた箔帯の製造コストを著しく低減することができる。
４．メッキ層として、Si単体のみならず、他の金属元素との共析層を形成することができる。
５．電析させる条件によっては、アモルファスのSiメッキ層或いはナノメーターオーダーの結晶性Siメッキ層を形成することができる。
６．得られたSi系箔帯は、リチウムイオン二次電池用の負極として、Si特有の高容量を発揮し、かつサイクル特性に優れている。
According to the present invention using an organic solvent-based Si plating bath, the following effects are achieved.
1. Unlike the vapor phase method, the plating operation can be performed near room temperature.
2. Since it is based on a solvent-based plating method, a continuous plating operation can be performed.
3. As a result of the above 1 and 2, the manufacturing cost of the foil strip provided with the Si plating layer can be significantly reduced.
4). As a plating layer, not only a simple substance of Si but also a eutectoid layer with other metal elements can be formed.
5. Depending on the conditions for electrodeposition, an amorphous Si plating layer or a nanometer order crystalline Si plating layer can be formed.
6). The obtained Si-based foil strip exhibits a high capacity peculiar to Si as a negative electrode for a lithium ion secondary battery and is excellent in cycle characteristics.
以下に、本発明による非水溶媒Siメッキ法の構成要件について、詳細に説明する。
I．溶媒
メッキ浴中に水分が存在する場合には、水の電気分解が先に始まるので、メッキを円滑に行うことができない。従って、溶媒としては、無水の有機溶媒或いはメッキ操作を阻害しない程度まで水分含量を抑制した有機溶媒を使用する。有機溶媒としては、Siを電析させるために必要な高めの電圧(Siが析出しないで安定に存在する溶媒。例えば対Ｌｉ金属で５Ｖ程度)においても分解しない溶媒、例えば、プロピレンカーボネート、エチレンカーボネート、ジメチルスルホキシド、γ-ブチルラクトン、スルホラン、1,2-ジメトキシエタン、テトラヒドロフラン、ジオキソラン、ジエチルカーボネート、メチルエチルカーボネート、ジメチルカーボネート、アセトンなどを使用する。これらの溶媒は、必要に応じて、単独で使用しても良く、或いは２種以上を併用しても良い。これらの溶媒中では、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート、メチルエチルカーボネート、ジメチルカーボネート、アセトンなどが好ましく、さらにプロピレンカーボネートおよびエチレンカーボネートならびに両者の混合物がより好ましい。
II．支持電解質
上記の有機溶媒は、伝導度が低いので、伝導度を高めるために支持電解質を用いる。支持電解質としては、テトラブチルアンモニウム過塩素酸塩、テトラメチルアンモニウム過塩素酸塩、無水塩化カリウム、無水塩化ナトリウムなどを用いる。これらの支持電解質は、単独で使用しても良く、或いは２種以上を併用しても良い。これらの中では、テトラブチルアンモニウム過塩素酸塩およびテトラメチルアンモニウム過塩素酸塩が、伝導度を大きく向上させるので、より好ましい。
Hereinafter, the constituent requirements of the nonaqueous solvent Si plating method according to the present invention will be described in detail.
I. Solvent When water is present in the plating bath, electrolysis of water starts first, so plating cannot be performed smoothly. Therefore, as the solvent, an anhydrous organic solvent or an organic solvent whose moisture content is suppressed to such an extent that does not hinder the plating operation is used. As the organic solvent, a solvent that does not decompose even at a high voltage necessary for electrodeposition of Si (a solvent that does not precipitate Si and exists stably, for example, about 5 V with respect to Li metal), such as propylene carbonate, ethylene carbonate Dimethyl sulfoxide, γ-butyl lactone, sulfolane, 1,2-dimethoxyethane, tetrahydrofuran, dioxolane, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, acetone and the like are used. These solvents may be used alone or in combination of two or more as required. Among these solvents, propylene carbonate, ethylene carbonate, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, acetone and the like are preferable, and propylene carbonate and ethylene carbonate and a mixture of both are more preferable.
II. Supporting electrolyte Since the above organic solvent has low conductivity, a supporting electrolyte is used to increase the conductivity. As the supporting electrolyte, tetrabutylammonium perchlorate, tetramethylammonium perchlorate, anhydrous potassium chloride, anhydrous sodium chloride and the like are used. These supporting electrolytes may be used alone or in combination of two or more. Among these, tetrabutylammonium perchlorate and tetramethylammonium perchlorate are more preferable because they greatly improve conductivity.
有機溶媒に対する支持電解質の配合量は、有機溶媒の種類、支持電解質の種類などにより異なるが、通常メッキ浴の伝導度が3mScm-1以上となる量以上であり、より好ましくは5 mScm-1以上である。 The amount of the supporting electrolyte in an organic solvent, the kind of organic solvent, such as by different but the kind of the supporting electrolyte is at an amount more than the conductivity of the normal plating bath is 3MScm -1 or more, more preferably 5 MSCM -1 or It is.
また、上記の支持電解質とともに、補助的な支持電解質として、Li化合物を配合することができる。この様なLi化合物としては、LiCF3SO3、LiAsF6、LiClO4、LiBF4、LiPF6などが例示される。この様な化合物を配合する場合には、箔帯表面に析出形成されるSiメッキ層にLiイオンが吸蔵されることになる。 In addition to the above supporting electrolyte, a Li compound can be blended as an auxiliary supporting electrolyte. Examples of such Li compounds include LiCF 3 SO 3 , LiAsF 6 , LiClO 4 , LiBF 4 , and LiPF 6 . When such a compound is blended, Li ions are occluded in the Si plating layer deposited on the surface of the foil strip.
一般に、リチウムイオン電池用の負極材には、初回充電時に充電は出来るものの放電が出来ない容量が発生する。本発明方法によりSiメッキ層を設けた箔帯をカソードとして使用するリチウムイオン電池では、メッキ時に電析Si中に吸蔵されるLiイオンが、この放電できない容量の一部を担うこととなる。従って、実際に電池を構成した場合に、メッキ操作時に吸蔵されたLiの効果として、放電出来ない容量が少なくなるため、高い効率が得られる。 In general, a negative electrode material for a lithium ion battery generates a capacity that can be charged at the first charge but cannot be discharged. In a lithium ion battery using a foil strip provided with a Si plating layer by the method of the present invention as a cathode, Li ions occluded in electrodeposited Si during plating bear a part of the capacity that cannot be discharged. Therefore, when the battery is actually configured, the capacity that cannot be discharged is reduced as an effect of the Li occluded during the plating operation, so that high efficiency can be obtained.
吸蔵Liイオン源となるLi化合物の配合量は、主たる支持電解質の1/2以下であることが望ましい。過剰量のLi化合物が存在する条件下にメッキ操作を行う場合には、電析時にSiメッキ層中に多量のLiが吸蔵されるので、電析したSiメッキ層の活性が著しく高くなり、メッキ層形成後に大気と接触した際に急速な酸化が進行する。従って、Siメッキ層中のLi量は、Si重量またはSi+共析金属(後述のCu、Ni、Ti、Co、Feなど)の合計重量の50％程度以下とすることが好ましく、10％程度とすることがより好ましい。
III．Si源
Si源としては、SiCl4および／またはSiHCl3を用いることができる。安全を考慮すれば、取り扱いが容易なSiCl4を使用することが好ましい。
The blending amount of the Li compound serving as the occlusion Li ion source is desirably 1/2 or less of the main supporting electrolyte. When plating is performed under conditions where an excessive amount of Li compound is present, a large amount of Li is occluded in the Si plating layer during electrodeposition, so that the activity of the electrodeposited Si plating layer is significantly increased. Rapid oxidation proceeds upon contact with the atmosphere after layer formation. Therefore, the amount of Li in the Si plating layer is preferably about 50% or less of the total weight of Si weight or Si + eutectoid metal (Cu, Ni, Ti, Co, Fe, etc. described later), and about 10%. More preferably.
III. Si source
As the Si source, SiCl 4 and / or SiHCl 3 can be used. In consideration of safety, it is preferable to use SiCl 4 which is easy to handle.
有機溶媒に対するSi源化合物の配合量は、所定の有機溶媒に対するその溶解度などを考慮して、定めることができる。一般に、この配合量は、0.01mol/l以上であれば、メッキが可能となるが、実用的には、通常0.05〜0.5mol/l程度の範囲内にあり、より好ましくは0.1〜0.3mol/l程度の範囲内にある。Si源化合物の配合量が過剰となる場合には、メッキ浴中に伝導度が低いSi源化合物が分離して存在することになるので、メッキ浴が不均質となり、不均一なメッキ層が生じる危険性がある。
IV．アノート゛
一般に、メッキ操作時にアノード側からの塩素発生を抑制するためには、珪素からなる電極を用いることが望ましい。しかしながら、珪素は電気抵抗が高いので、高電流量条件下でメッキをおこなう場合には、炭素などの不溶性の電極を用いることもできる。不溶性の電極を用いる場合には、メッキ浴組成が常に変動するので、メッキ操作時にSi源化合物などを適宜補給して、組成変動を抑制する必要がある。
The compounding amount of the Si source compound in the organic solvent can be determined in consideration of its solubility in a predetermined organic solvent. Generally, if the blending amount is 0.01 mol / l or more, plating is possible, but practically it is usually in the range of about 0.05 to 0.5 mol / l, more preferably 0.1 to 0.3 mol / l. Within the range of l. When the compounding amount of the Si source compound is excessive, the Si source compound having low conductivity is present separately in the plating bath, so that the plating bath becomes inhomogeneous and an uneven plating layer is generated. There is a risk.
IV. In general, it is desirable to use an electrode made of silicon in order to suppress generation of chlorine from the anode side during the plating operation. However, since silicon has a high electric resistance, an insoluble electrode such as carbon can also be used when plating is performed under a high current amount condition. When an insoluble electrode is used, the composition of the plating bath constantly changes, so it is necessary to appropriately replenish the Si source compound during the plating operation to suppress the composition fluctuation.
また、箔帯表面にSiと他の金属元素とを共析させる場合には、Cu、Ni、Ti、Co、Feなどを消耗電極として用いることにより、共析金属の供給源とすることができる。 When Si and other metal elements are co-deposited on the foil strip surface, the source of eutectoid metal can be obtained by using Cu, Ni, Ti, Co, Fe, etc. as a consumable electrode. .
さらに、箔帯表面にSiと他の金属元素とを共析させるためには、Liと反応しない金属(Cu、Ni、Co、Feなど)を金属塩化物の形態でメッキ浴中に供給しても良い。 Furthermore, in order to eutect Si and other metal elements on the foil strip surface, a metal that does not react with Li (Cu, Ni, Co, Fe, etc.) is supplied into the plating bath in the form of metal chloride. Also good.
箔帯表面に形成される共析メッキ層においては、Siの割合を少なくとも50 重量％以上とすることが好ましく、さらに90重量％程度とすることがより好ましい。共析メッキ層の組成は、常法に従って、メッキ浴組成、メッキ条件などを適宜選択することにより、調整可能である。
Ｖ．カソード
本発明方法においては、被メッキ材である箔帯をカソードとして用いる。具体的には、銅箔帯ならびにLiと合金を形成しない金属(Fe、Ti、Ni、ステンレス鋼など)からなる箔帯を用いることができる。これらの中では、銅箔が最も好ましい。
VI．メッキ操作時の雰囲気
上記の箔帯にメッキ層を形成するに際し、有機溶媒中に酸素が存在すると、メッキ層として析出したSiが酸化してSiO或いはSiO2に転化する可能性がある。従って、メッキ操作開始に先立って、雰囲気を予めN2、Ar、Heなどの不活性ガスにより置換しておき、かつメッキ操作中に空気が混入しない様に留意することが必要である。
VII．その他のメッキ条件
本発明によるメッキ方法において、通電は、平滑直流、リップル直流或いはパルス直流のいずれでおこなっても良い。
In the eutectoid plating layer formed on the surface of the foil strip, the proportion of Si is at least 50 It is preferable to set it as weight% or more, and it is more preferable to set it as about 90 weight%. The composition of the eutectoid plating layer can be adjusted by appropriately selecting a plating bath composition, plating conditions and the like according to a conventional method.
V. Cathode In the method of the present invention, a foil strip as a material to be plated is used as a cathode. Specifically, a copper foil strip and a foil strip made of a metal that does not form an alloy with Li (Fe, Ti, Ni, stainless steel, etc.) can be used. Of these, copper foil is most preferred.
VI. Atmosphere at the time of plating When oxygen is present in the organic solvent when the plating layer is formed on the foil strip, Si deposited as the plating layer may be oxidized and converted to SiO or SiO 2 . Therefore, prior to the start of the plating operation, it is necessary to replace the atmosphere with an inert gas such as N 2 , Ar, or He in advance and take care not to mix air during the plating operation.
VII. Other Plating Conditions In the plating method according to the present invention, energization may be performed by any of smooth DC, ripple DC, or pulse DC.
メッキ浴は、攪拌などにより、被メッキ材（箔帯）に対して0.5m/sec以上の相対速度で流動させることが望ましい。或いは、被メッキ材を回転または走行させることにより、メッキ浴を相対的に流動させても良い。特に、長尺の箔帯上にメッキ層形成を行う場合には、箔帯を連続走行させながらメッキ処理を実施することが望ましい。
VIII．メッキ層を有する箔帯
本発明方法により箔帯表面に形成されるメッキ層は、Si単独層、SiとLiと合金を形成しない金属との合金層、Liを吸蔵するSi層、或いはSiとLiと合金を形成しない金属との合金からなる。メッキ層の厚さは、特に限定されないが、通常50μm程度であり、より好ましくは20μm程度である。
The plating bath is preferably flowed at a relative speed of 0.5 m / sec or more with respect to the material to be plated (foil strip) by stirring or the like. Alternatively, the plating bath may be relatively fluidized by rotating or running the material to be plated. In particular, when a plating layer is formed on a long foil strip, it is desirable to perform the plating process while continuously running the foil strip.
VIII. Foil strip having a plating layer The plating layer formed on the surface of the foil strip by the method of the present invention is a single layer of Si, an alloy layer of a metal that does not form an alloy with Si and Li, a Si layer that occludes Li, or Si and Li And an alloy of a metal that does not form an alloy. The thickness of the plating layer is not particularly limited, but is usually about 50 μm, more preferably about 20 μm.
本発明方法により得られたSi系メッキ層を有する箔帯は、公知の構造を有する非水電解質リチウムイオン二次電池において、公知の負極材に代替する新規な負極材として使用することができる。 The foil strip having a Si-based plating layer obtained by the method of the present invention can be used as a novel negative electrode material that replaces a known negative electrode material in a non-aqueous electrolyte lithium ion secondary battery having a known structure.
以下に、非水電解質リチウムイオン二次電池の一例とその各構成要素について、説明する。負極材以外の構成要素は、従来の非水系リチウムイオン二次電池におけると同様のものを使用することができる。
１．電池の構造
この様なリチウムイオン電池の一例の断面図を図１に示す。このR2016タイプのコイン型試験セル(直径20mm、高さ1.6mm)において、ステンレス鋼板製のセルケース５およびカバー６間は、ポリプロピレン製ガスケット１１を介して電解液が蒸発しない様に、気密性が保持されている。負極箔帯９は、セルケース５の内面に溶接されたNiメッシュからなる集電体７と一体に成型されている。カバー６内面には、円板状金属Li極８が圧着されている。
Below, an example of a nonaqueous electrolyte lithium ion secondary battery and each component are demonstrated. As the constituent elements other than the negative electrode material, the same components as in the conventional non-aqueous lithium ion secondary battery can be used.
1. Battery Structure FIG. 1 shows a cross-sectional view of an example of such a lithium ion battery. In this R2016 type coin-type test cell (diameter 20 mm, height 1.6 mm), the
負極箔帯成型極９と金属極８とは、微多孔性ポリプロピレン膜からなるセパレータ１０により隔離されており、極間、負極箔帯５およびセパレータ１０内には、有機電解液（非水電解液：下記参照）が注液含浸されている。
２．非水電解液
非水電解液は、電気絶縁性およびリチウムイオン伝導性を有するものであれば、特に限定されない。例えば、非水溶媒とその溶媒に溶解するリチウム塩とからなる非水電解液を用いることができる。
The negative electrode foil
2. Nonaqueous Electrolytic Solution The nonaqueous electrolytic solution is not particularly limited as long as it has electrical insulation and lithium ion conductivity. For example, a nonaqueous electrolytic solution composed of a nonaqueous solvent and a lithium salt dissolved in the solvent can be used.
非水溶媒としては、例えば、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)、ビニレンカーボネート(VC)などの環状カーボネート類；ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)、ジプロピルカーボネート(DPC)などの鎖状カーボネート類；ギ酸メチル、酢酸メチル、プロピオン酸メチル、プロピオン酸エチルなどの脂肪族カルボン酸エステル類、γ-ブチロラクトンなどのγ-ラクトン類；1,2-ジメトキシエタン(DME)、1,2-ジエトキシエタン(DEE)、エトキシメトキシエタン(EME)などの鎖状エーテル類；テトラヒドロフラン、2-メチルテトラヒドロフランなどの環状エーテル類；ジメチルスルホキシド、1,3-ジオキソラン、ホルムアミド、アセトアミド、ジメチルホルムアミド、ジオキソラン、アセトニトリル、プロピルニトリル、ニトロメタン、エチルモノグライム、リン酸トリエステル、トリメトキシメタン、ジオキソラン誘導体、スルホラン、メチルスルホラン、1,3-ジメチル-2-イミダゾリジノン、3-メチル-2-オキサゾリジノン、プロピレンカーボネート誘導体、テトラヒドロフラン誘導体、エチルエーテル、1,3-プロパンサルトン、アニソール、ジメチルスルホキシド、N-メチルピロリドンなどの非プロトン性有機溶媒などを用いることができる。これらの非水溶媒は単独で使用しても良く、或いは２種以上を混合して使用しても良い。２種以上を併用する場合には、例えば、環状カーボネートと鎖状カーボネートとの混合溶媒（例えば、エチレンカーボネートとジメチルカーボネートとの混合溶媒、エチレンカーボネートとエチルメチルカーボネートとの混合溶媒）、環状カーボネートと鎖状カ−ボネートと脂肪族カルボン酸エステルとの混合溶媒などが好ましい。 Non-aqueous solvents include, for example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl Chain carbonates such as methyl carbonate (EMC) and dipropyl carbonate (DPC); aliphatic carboxylic acid esters such as methyl formate, methyl acetate, methyl propionate and ethyl propionate, and γ-lactones such as γ-butyrolactone Chain ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE) and ethoxymethoxyethane (EME); cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran; dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, Oxolane, acetonitrile, propyl nitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, Aprotic organic solvents such as propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, 1,3-propane sultone, anisole, dimethyl sulfoxide, and N-methylpyrrolidone can be used. These nonaqueous solvents may be used alone or in combination of two or more. When using 2 or more types in combination, for example, a mixed solvent of cyclic carbonate and chain carbonate (for example, a mixed solvent of ethylene carbonate and dimethyl carbonate, a mixed solvent of ethylene carbonate and ethyl methyl carbonate), cyclic carbonate, A mixed solvent of a chain carbonate and an aliphatic carboxylic acid ester is preferred.
上記の非水溶媒に溶解させるリチウム塩としては、例えば、LiClO4、LiBF4、LiPF6、LiAIC14、LiSbF6、LiSCN、LiCl、LiCF3SO3、LiCF3CO2、Li(CF3SO2)2、LiAsF6、LiN(CF3SO2)2、LiB10Cl10、低級脂肪族カルボン酸リチウム、LiCl、LiBr、LiI、クロロボランリチウム、四フェニルホウ酸リチウム、イミド類などを用いることができる。上記リチウム塩は、単独で使用しても良く、或いは２種以上を混合して使用しても良い。リチウム塩としては、LiPF6を用いることがより好ましい。 Examples of the lithium salt dissolved in the non-aqueous solvent include LiClO 4 , LiBF 4 , LiPF 6 , LiAIC1 4 , LiSbF 6 , LiSCN, LiCl, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (CF 3 SO 2 ) 2 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiB 10 Cl 10 , lower aliphatic lithium carboxylate, LiCl, LiBr, LiI, lithium chloroborane, lithium tetraphenylborate, imides, etc. can be used . The lithium salt may be used alone or in combination of two or more. More preferably, LiPF 6 is used as the lithium salt.
リチウム塩の非水溶媒に対する溶解量は、特に限定されないが、通常0.2〜2mol/l程度の範囲であり、0.5〜1.5mol/l程度がより好ましい。 The amount of lithium salt dissolved in the non-aqueous solvent is not particularly limited, but is usually in the range of about 0.2 to 2 mol / l, more preferably about 0.5 to 1.5 mol / l.
上記非水電解液の電池への添加量は、正極材料の量、負極材料の量および電池のサイズによって調整すればよい。
３．セパレータ
セパレータとしては、リチウムイオン透過度が大きく、電池内部で腐食などを受けず、一定の機械的強度を有する電気絶縁性の薄膜であれば、特に限定されない。具体的には、公知の非水電解液二次電池においてに用いられている、上記特性を備えた微多孔性薄膜を用いればよい。さらに、短絡などにより電池が一定の温度以上に達した場合に、孔が閉塞するなどで、電気抵抗が増大する機能を有するセパレータを用いてもよい。
The amount of the nonaqueous electrolyte added to the battery may be adjusted according to the amount of the positive electrode material, the amount of the negative electrode material, and the size of the battery.
3. Separator The separator is not particularly limited as long as it is an electrically insulating thin film having a large lithium ion permeability, no corrosion inside the battery, and a certain mechanical strength. Specifically, a microporous thin film having the above characteristics, which is used in known nonaqueous electrolyte secondary batteries, may be used. Furthermore, when the battery reaches a certain temperature or more due to a short circuit or the like, a separator having a function of increasing electrical resistance by closing a hole may be used.
例えば、ポリプロピレンおよびポリエチレンから選ばれる少なくとも1種の樹脂を含むオレフイン系ポリマーからなるシート、不織布または織布；ガラス繊維からなるシート、不織布または織布などを用いることができる。また、セパレータの厚さは、例えば、10μm〜300μmである。セパレータの平均孔径は、電極シートより脱離した正負極材料、結着剤、導電剤などが透過しない範囲であることが好ましく、例えば、0.01μｍ〜1μｍの範囲である。また、セパレータの平均空孔率は、セパレータを構成する材料の電気絶縁性、リチウムイオン透過性、セパレータの膜厚などにより決定されるが、例えば、30vol％〜80vol％の範囲である。 For example, a sheet made of an olefin polymer containing at least one resin selected from polypropylene and polyethylene, a nonwoven fabric or a woven fabric; a sheet made of glass fiber, a nonwoven fabric or a woven fabric can be used. Moreover, the thickness of a separator is 10 micrometers-300 micrometers, for example. The average pore diameter of the separator is preferably in a range in which the positive and negative electrode materials, the binder, the conductive agent and the like detached from the electrode sheet do not permeate, for example, in the range of 0.01 μm to 1 μm. Moreover, although the average porosity of a separator is determined by the electrical insulation of the material which comprises a separator, lithium ion permeability, the film thickness of a separator, etc., it is the range of 30 vol%-80 vol%, for example.
本発明の非水電解液二次電池は、図示しないが、非水溶媒とリチウム塩とからなる非水電解液をポリマー材料に吸収保持させたものを正極合剤および負極合剤に含ませ、さらに、上記の多孔性セパレータと上記正極および上記負極とを一体化した構造の円筒型電池とすることもできる。上記ポリマー材料としては、電気絶縁性を有し、かつ非水電解液を吸収保持できるものであれば良く、例えば、フッ化ビニリデンとへキサフルオロプロピレンとの共重合体などを用いることができる。 Although the non-aqueous electrolyte secondary battery of the present invention is not shown, the non-aqueous electrolyte composed of a non-aqueous solvent and a lithium salt is absorbed and held in the polymer material in the positive electrode mixture and the negative electrode mixture, Furthermore, a cylindrical battery having a structure in which the porous separator, the positive electrode, and the negative electrode are integrated can be provided. The polymer material may be any material as long as it has electrical insulation and can absorb and hold a non-aqueous electrolyte. For example, a copolymer of vinylidene fluoride and hexafluoropropylene can be used.
なお、本発明における非水電解質二次電池の形状は、上記で説明したコイン型および円筒型に限定されることはなく、例えば、シート型、積層型、偏平型、角形、電気自動車に用いる大型のものなど、任意の形状とすることができる。 In addition, the shape of the nonaqueous electrolyte secondary battery in the present invention is not limited to the coin type and the cylindrical type described above, and for example, a sheet type, a laminated type, a flat type, a square type, a large size used for an electric vehicle. Any shape can be used.
以下に実施例および比較例を示し、本発明の特徴とするところをより一層明らかにする。本発明は、以下の実施例により限定されるものではない。
［実施例１］〜［実施例８］および［比較例１］
メッキ浴専用のフローセル(SUS316L)を作製し、フローチャンネル内にアノードとして黒鉛板を設置し、被メッキ材(カソード)として20μｍ厚の電解銅箔を陰極に設置した。次いで、表１に示す組成の非水溶媒系のメッキ液を調製した後、表２に示す条件でそれぞれメッキ処理を行った。
Examples and Comparative Examples are shown below to further clarify the features of the present invention. The present invention is not limited by the following examples.
[Example 1] to [Example 8] and [Comparative Example 1]
A flow cell (SUS316L) dedicated to the plating bath was prepared, a graphite plate was installed as an anode in the flow channel, and an electrolytic copper foil having a thickness of 20 μm was installed at the cathode as a material to be plated (cathode). Next, after preparing a nonaqueous solvent-based plating solution having the composition shown in Table 1, plating treatment was performed under the conditions shown in Table 2.
＊有機電解質
(1)プロピレンカーボネート
(2)エチレンカーボネート
(3)ジメチルスルホキシド
(4)γ-ブチルラクトン
＊支持電解質
(1)テトラブチルアンモニウム過塩素酸塩
(2)テトラメチルアンモニウム過塩素酸塩
(3)KCl
(4)NaCl
(5)ホルムアミド溶液+ケイフッ化アンモニウム
また、比較例１は、前記非特許文献２に記載された方法を追試したものである。すなわち、メッキは、同報告の表１に示された条件下に行い、カソードのみを非特許文献２に記載の方法により得られた厚さ20μｍのSiメッキ銅箔とした。
* Organic electrolyte
(1) Propylene carbonate
(2) Ethylene carbonate
(3) Dimethyl sulfoxide
(4) γ-Butyllactone * Supporting electrolyte
(1) Tetrabutylammonium perchlorate
(2) Tetramethylammonium perchlorate
(3) KCl
(4) NaCl
(5) Formamide solution + ammonium silicofluoride In Comparative Example 1, the method described in Non-Patent Document 2 was added. That is, the plating was performed under the conditions shown in Table 1 of the same report, and only the cathode was a Si-plated copper foil having a thickness of 20 μm obtained by the method described in Non-Patent Document 2.
付着Si量=負極の重量-同径の無メッキ箔帯の重量
得られたSi重量(活物質重量)は、メッキ条件によって異なるが、数十mg程度であった。
Adhering Si amount = weight of negative electrode−weight of unplated foil strip of the same diameter The obtained Si weight (active material weight) was about several tens mg, although it varied depending on the plating conditions.
次いで、打ち抜いた円形の負極を用いて、上述の図１に示す構造の試験セル（コイン型電池）を組み立てて、下記の電池特性試験に供した。非水電解液としては、エチレンカーボネートとジメチルカーボネートとの等体積混合溶媒にLiPF6を1mol/lの割合で溶解させたものを用いた。
＜電池特性評価試験＞
試験コイン型電池の充電・放電は、20℃の恒温室において、“電流密度0.05mA/cm2の定電流量で0Vになるまで充電し、その後1.5Vになるまで放電をおこなう”という条件で、繰り返し行った。なお、充電・放電は、300サイクルまで繰り返して行い、初期の最大放電容量に対する300サイクル目の放電容量の比を容量維持率（％）とした。
＜結果＞
表３は、電池特性評価試験の結果を示す。本発明による非水溶媒Siメッキ法で得られた負極箔は、いずれも2400mAh/g以上の高い放電容量を有し、かつ300サイクル容量維持率は、80％以上という高い値を示している。
Next, using the punched circular negative electrode, a test cell (coin-type battery) having the structure shown in FIG. 1 was assembled and subjected to the following battery characteristic test. As the non-aqueous electrolyte, a solution obtained by dissolving LiPF 6 in an equal volume mixed solvent of ethylene carbonate and dimethyl carbonate at a rate of 1 mol / l was used.
<Battery characteristics evaluation test>
The test coin type battery is charged / discharged in a constant temperature room of 20 ° C under the condition of “charging to 0 V at a constant current amount of 0.05 mA / cm 2 and then discharging to 1.5 V”. , Repeated. Charging / discharging was repeated up to 300 cycles, and the ratio of the discharge capacity at the 300th cycle to the initial maximum discharge capacity was defined as the capacity retention rate (%).
<Result>
Table 3 shows the results of the battery characteristic evaluation test. The negative electrode foils obtained by the non-aqueous solvent Si plating method according to the present invention all have a high discharge capacity of 2400 mAh / g or more, and the 300 cycle capacity retention rate shows a high value of 80% or more.
これに対し、表３に示す結果から明らかな様に、非特許文献１に記載された公知のメッキ法により得られたSiメッキ負極では、容量および維持率が低く、本発明に比してサイクル特性が劣ることが明らかである。この低い電池特性は、メッキ操作時のSiO2の生成に起因するものと推測される。 On the other hand, as is apparent from the results shown in Table 3, the capacity and maintenance rate of the Si-plated negative electrode obtained by the known plating method described in Non-Patent Document 1 is low, and the cycle is lower than that of the present invention. It is clear that the characteristics are inferior. This low battery characteristic is presumed to be caused by the generation of SiO 2 during the plating operation.
なお、本発明による全ての実施例においては、コイン型電池を用いて本発明の顕著な効果を明らかにしたが、それ以外の構造を有する電池、例えば、円筒型電池、角形電池、ポリマー電解質を用いた積層型電池などを用いた同様の試験においても、同様な顕著な結果が得られた。
［実施例９］〜［実施例１６］
メッキ浴の有機溶媒を変えた以外は実施例１の手法に準じて銅箔にSiメッキ層を形成し、Siメッキ銅箔を負極として電池を作成し、その電池特性を評価した。メッキ浴の組成、メッキ条件および電池特性をそれぞれ表４、表５および表６に示す。
In all of the examples according to the present invention, the remarkable effect of the present invention was clarified using a coin-type battery. However, batteries having other structures such as a cylindrical battery, a prismatic battery, and a polymer electrolyte are used. Similar remarkable results were obtained in the same test using the stacked battery used.
[Example 9] to [Example 16]
Except for changing the organic solvent of the plating bath, a Si plating layer was formed on the copper foil according to the method of Example 1, a battery was prepared using the Si plating copper foil as a negative electrode, and the battery characteristics were evaluated. The composition of the plating bath, the plating conditions, and the battery characteristics are shown in Table 4, Table 5, and Table 6, respectively.
［実施例１７］〜［実施例２７］
Siと共析させるための金属源として、Cu、NiまたはCoの無水塩化物をメッキ浴に添加する以外は実施例１の手法に準じて、銅箔にSi系メッキ層を形成し、得られたSi系メッキ銅箔を負極として電池を作成し、その電池特性を評価した。共析メッキ浴の組成、メッキ条件および電池特性をそれぞれ表７、表８および表９に示す。なお、表７〜９には、参考のため、実施例２についてのメッキ浴組成、メッキ条件および電池特性を併せて示す。
[Example 17] to [Example 27]
According to the method of Example 1, except that Cu, Ni or Co anhydrous chloride is added to the plating bath as a metal source for eutecting with Si, it is obtained by forming a Si-based plating layer on the copper foil. A battery was prepared using the Si-based plated copper foil as a negative electrode, and the battery characteristics were evaluated. Tables 7, 8 and 9 show the composition of eutectoid plating bath, plating conditions and battery characteristics, respectively. Tables 7 to 9 also show the plating bath composition, plating conditions and battery characteristics for Example 2 for reference.
実施例１７〜２９においては、膨張時の骨となり支える相（粉化防止相＝Liと反応しない金属の相）が分散析出したSiと共析金属との多相組織が実現できたため、良好なサイクル特性が得られたものと推測される。 In Examples 17 to 29, since a multiphase structure of Si and a eutectoid metal in which a phase that becomes a bone at the time of expansion and a supporting phase (phase of metal that does not react with Li) was precipitated was realized, it was favorable. It is presumed that cycle characteristics were obtained.
また、この粉化防止相である共析金属は、Siと比較して、電子伝導性に優れているため、合金中に電気が流れやすく、結果として高率放電特性が改善されるという効果が発現されたものと推測される。 In addition, the eutectoid metal, which is the anti-powder phase, is superior in electronic conductivity to Si, so that electricity can easily flow in the alloy, resulting in improved high-rate discharge characteristics. Presumed to have been expressed.
さらに、実施例２８で得られた箔帯表面のSi系メッキ層は、電子線回折においてリング状を呈することから、アモルファス状態であることが確認された。また、このメッキ層は、Cuを約9.4重量％共析したSi-Cu複合体であった。
［実施例２８］〜［実施例２９］
Siと共析させるための金属源として、Ni またはCuをアノード(消耗電極)として用いる以外は実施例１の手法に準じて、銅箔にSi系メッキ層を形成し、Si系メッキ銅箔を負極として電池を作成し、その電池特性を評価した。共析メッキ浴の組成、メッキ条件および電池特性をそれぞれ表１０、表１１および表１２に示す。
Furthermore, the Si-based plating layer on the surface of the foil strip obtained in Example 28 was confirmed to be in an amorphous state because it exhibited a ring shape in electron beam diffraction. The plated layer was a Si-Cu composite in which Cu was co-deposited with about 9.4% by weight.
[Example 28] to [Example 29]
According to the method of Example 1 except that Ni or Cu is used as an anode (consumable electrode) as a metal source for eutecting with Si, a Si-based plating layer is formed on the copper foil, and the Si-based plated copper foil is used. A battery was prepared as a negative electrode, and its battery characteristics were evaluated. Tables 10, 11, and 12 show the composition of the eutectoid plating bath, plating conditions, and battery characteristics, respectively.
［実施例３０］〜［実施例３５］
メッキ浴に対し、Liを含む支持電解質をさらに添加した以外は実施例６の手法に準じて銅箔にSiメッキ層を形成し、得られたSiメッキ銅箔を負極として電池を作成し、その電池特性を評価した。メッキ浴の組成、メッキ条件および電池特性をそれぞれ表１３、表１４および表１５に示す。
[Example 30] to [Example 35]
A Si plating layer was formed on the copper foil according to the method of Example 6 except that a supporting electrolyte containing Li was further added to the plating bath, and a battery was prepared using the obtained Si plated copper foil as a negative electrode. Battery characteristics were evaluated. The composition of the plating bath, the plating conditions and the battery characteristics are shown in Table 13, Table 14 and Table 15, respectively.
なお、初回クーロン効率(A)は、下式により算出した。 The initial coulomb efficiency (A) was calculated by the following formula.
A=初回放電容量(mAh/g)／初回充電容量(mAh/g)×100(%) A = Initial discharge capacity (mAh / g) / Initial charge capacity (mAh / g) x 100 (%)
５…電池ケース
６…カバー
７…集電体
８…金属リチウム
９…メッキ層を備えた負極箔帯
１０…セパレータ
１１…ガスケット
5 ...
Claims (9)
The lithium ion secondary battery which uses the foil strip with a plating layer obtained by the method in any one of Claims 1-7 as a negative electrode.
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| JP2012204195A (en) * | 2011-03-25 | 2012-10-22 | Waseda Univ | Active material for lithium secondary battery, negative electrode for lithium secondary battery, and lithium secondary battery |
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| JP6057208B2 (en) * | 2012-11-12 | 2017-01-11 | 学校法人早稲田大学 | Electroplating solution, method for producing active material for lithium secondary battery, and lithium secondary battery |
| JP6090778B2 (en) * | 2013-01-11 | 2017-03-08 | 学校法人早稲田大学 | Method for producing electrode of lithium secondary battery and method for producing lithium secondary battery |
| US11827993B1 (en) | 2020-09-18 | 2023-11-28 | GRU Energy Lab Inc. | Methods of forming active materials for electrochemical cells using low-temperature electrochemical deposition |
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