JP5192703B2 - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary battery Download PDFInfo
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- JP5192703B2 JP5192703B2 JP2007026617A JP2007026617A JP5192703B2 JP 5192703 B2 JP5192703 B2 JP 5192703B2 JP 2007026617 A JP2007026617 A JP 2007026617A JP 2007026617 A JP2007026617 A JP 2007026617A JP 5192703 B2 JP5192703 B2 JP 5192703B2
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 28
- 239000011149 active material Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- RYIRMSRYCSMGJA-UHFFFAOYSA-N 1,5,2,4-dioxadithiepane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCCO1 RYIRMSRYCSMGJA-UHFFFAOYSA-N 0.000 claims description 5
- JCOYWFCMMHGFSY-UHFFFAOYSA-N 6-methyl-1,5,2,4-dioxadithiepane 2,2,4,4-tetraoxide Chemical compound CC1COS(=O)(=O)CS(=O)(=O)O1 JCOYWFCMMHGFSY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 150000005678 chain carbonates Chemical class 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- -1 sulfonate ester Chemical class 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- 150000003459 sulfonic acid esters Chemical class 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 210000001787 dendrite Anatomy 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 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
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- WHBMWHKJXUBZFV-UHFFFAOYSA-N dimethyl methanedisulfonate Chemical compound COS(=O)(=O)CS(=O)(=O)OC WHBMWHKJXUBZFV-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
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- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- RJCRUVXAWQRZKQ-UHFFFAOYSA-N oxosilicon;silicon Chemical compound [Si].[Si]=O RJCRUVXAWQRZKQ-UHFFFAOYSA-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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、非水電解質二次電池に関し、特に高容量で充放電サイクル寿命を改善した非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery having a high capacity and an improved charge / discharge cycle life.
携帯電話やノートパソコン等のモバイル機器の普及により、その電力源となる二次電池の役割が重要視されている。これらの二次電池には小型・軽量でかつ高容量であり、充放電を繰り返しても、劣化しにくい性能が求められることから、現在はリチウムイオン二次電池が最も多く使用されている。 With the widespread use of mobile devices such as mobile phones and laptop computers, the role of secondary batteries as power sources is gaining importance. Since these secondary batteries are small, light and have a high capacity and are required to have a performance that does not easily deteriorate even after repeated charge and discharge, lithium ion secondary batteries are most frequently used.
リチウムイオン二次電池の負極には、主として黒鉛やハードカーボン等の炭素を用いている。炭素は、充放電サイクルを良好に繰り返すことができるものの、理論容量付近まで容量向上を実現していることから、今後大幅な容量の増加は期待出来ない。その一方で、リチウムイオン二次電池の容量向上の要求は強いことから、炭素よりも高容量すなわち高エネルギー密度を有する負極材料の検討が行われている。 Carbon such as graphite and hard carbon is mainly used for the negative electrode of the lithium ion secondary battery. Although carbon can repeat charge / discharge cycles satisfactorily, the capacity has been improved to near the theoretical capacity, so a significant increase in capacity cannot be expected in the future. On the other hand, since there is a strong demand for improving the capacity of lithium ion secondary batteries, negative electrode materials having a higher capacity, that is, a higher energy density than carbon, have been studied.
リチウムイオン二次電池の負極には、高エネルギー密度でかつ軽量という観点から金属リチウムの検討もされているが、充放電サイクルの進行にともない、充電時に金属リチウム表面にデンドライト(樹枝状晶)が析出し、この結晶がセパレータを貫通し、内部短絡を起こし、寿命が短いという問題点があった。 In the negative electrode of lithium ion secondary batteries, metal lithium has been studied from the viewpoint of high energy density and light weight, but as the charge / discharge cycle progresses, dendrites (dendrites) are formed on the surface of the metal lithium during charging. There is a problem that the crystals are deposited and the crystal penetrates the separator, causing an internal short circuit and a short life.
エネルギー密度を高める材料として、組成式がLixA(Aはアルミニウムなどの元素からなる)で表されるリチウムと合金を形成するLi吸蔵物質を負極活物質として用いることが検討されている。この負極は単位体積当りのリチウムイオンの吸蔵放出量が多く、高容量である。最近では、特にケイ素を負極活物質として用いることが非特許文献1に記載されている。このような負極材料を用いることによって、高容量の負極が得られるとされている。 As a material for increasing the energy density, it has been studied to use, as a negative electrode active material, a Li storage material that forms an alloy with lithium represented by the composition formula Li x A (A is made of an element such as aluminum). This negative electrode has a large amount of occlusion and release of lithium ions per unit volume, and has a high capacity. Recently, the use of silicon as a negative electrode active material has been described in Non-Patent Document 1. It is said that a high capacity negative electrode can be obtained by using such a negative electrode material.
この種のケイ素を用いた負極は、単位体積当りのリチウムイオンの吸蔵放出量が多く、高容量であるものの、リチウムイオンが吸蔵放出される際に電極活物質自体が膨脹収縮するために微粉化が進行し、初回充放電における不可逆容量が大きく、また充放電サイクル寿命が短いという問題点があった。 Although this type of silicon-based negative electrode has a large amount of lithium ion storage and release per unit volume and high capacity, the electrode active material itself expands and contracts when lithium ion is stored and released. Progressed, the irreversible capacity in the first charge / discharge was large, and the charge / discharge cycle life was short.
ケイ素を用いた不可逆容量の低減及び充放電サイクル寿命の改善対策として、ケイ素酸化物を活物質として用いる方法が特許文献1で提案されている。特許文献1においては、ケイ素酸化物を活物質として用いることにより活物質単位重量あたりの体積膨張収縮を減らすことができるためサイクル特性の向上が確認されている。一方、酸化物の導電性が低いため、集電性が低下し、不可逆容量が大きいという問題点を有していた。また、ケイ素酸化物を活物質として用いた際の集電性を向上させるために、ケイ素酸化物に鉄やチタンを添加することが特許文献2で提案されている。しかし、これらの金属は電解液に対する耐食性や、耐酸化性が弱いために、金属を添加しただけではサイクルを繰り返すと導電性が低下してしまうという問題点を有していた。さらに不可逆容量の低減及び充放電サイクル寿命の改善対策として、ケイ素、ケイ素酸化物に炭素材料を複合化させた粒子を活物質として用いる方法が特許文献3で提案されている。これによりサイクル特性の向上が確認されたものの、まだ不十分であった。 Patent Document 1 proposes a method of using silicon oxide as an active material as a measure for reducing irreversible capacity using silicon and improving charge / discharge cycle life. In Patent Document 1, since the volume expansion / shrinkage per unit weight of the active material can be reduced by using silicon oxide as the active material, improvement in cycle characteristics has been confirmed. On the other hand, since the conductivity of the oxide is low, there is a problem that the current collecting property is lowered and the irreversible capacity is large. In addition, Patent Document 2 proposes that iron or titanium is added to silicon oxide in order to improve current collecting performance when silicon oxide is used as an active material. However, since these metals are weak in corrosion resistance and oxidation resistance to the electrolytic solution, there is a problem that the conductivity decreases when the cycle is repeated only by adding the metal. Further, Patent Document 3 proposes a method of using, as an active material, particles obtained by combining a carbon material with silicon or silicon oxide as a measure for reducing irreversible capacity and improving the charge / discharge cycle life. Although this improved the cycle characteristics, it was still insufficient.
その一方で、従来から、サイクル特性改善を目的として、バインダ(結着材)として熱硬化性を有する樹脂材料を用いることが報告されている。具体的には、酸化スズと酸化ケイ素と炭素をポリイミドバインダと混合して焼結させる方法が特許文献4で提案され、ケイ素及び/またはケイ素合金を含む活物質粒子と導電性金属粉末の混合物をポリイミドバインダと混合させたものを前記集電体の表面上で非酸化性雰囲気下に焼結させる方法が特許文献5で提案されている。しかしこれらは、実使用上での判断となる炭素負極並のサイクル特性を実現するには至らなかった。 On the other hand, it has been conventionally reported that a resin material having thermosetting properties is used as a binder (binder) for the purpose of improving cycle characteristics. Specifically, a method of mixing and sintering tin oxide, silicon oxide, and carbon with a polyimide binder is proposed in Patent Document 4, and a mixture of active material particles containing silicon and / or silicon alloy and conductive metal powder is prepared. Patent Document 5 proposes a method of sintering a mixture with a polyimide binder in a non-oxidizing atmosphere on the surface of the current collector. However, these have not led to the realization of cycle characteristics comparable to those of a carbon negative electrode, which is a judgment in actual use.
本発明は、ケイ素もしくはケイ素酸化物系負極は高容量であるものの、充放電サイクル寿命が不十分であり、初回充放電での充放電効率が低いという問題を解決するものである。本発明の課題は、集電性を向上させ、初回充放電での充放電効率が高く、かつ、エネルギー密度の高い、高温においても良好なサイクル特性を持つ非水電解質二次電池を提供することにある。 The present invention solves the problem that although the silicon or silicon oxide negative electrode has a high capacity, the charge / discharge cycle life is insufficient and the charge / discharge efficiency in the first charge / discharge is low. An object of the present invention is to provide a non-aqueous electrolyte secondary battery that improves current collecting performance, has high charge / discharge efficiency at the first charge / discharge, has high energy density, and has good cycle characteristics even at high temperatures. It is in.
上記課題を解決するため本発明による非水電解質二次電池は、負極と正極とリチウムイオン導電性の非水電解質とを有する非水電解質二次電池において、前記負極は、単体ケイ素とケイ素酸化物の混合物の周辺をアモルファス系炭素及び黒鉛系炭素の混合組成からなる炭素で被覆した活物質粒子と、加熱により脱水縮合反応を生じる熱硬化性樹脂の混合物を含み、前記熱硬化性樹脂により前記活物質粒子間、及び前記活物質粒子と集電体とが結着され、前記非水電解質が非水溶媒とスルホン酸エステルとを含むことを特徴とする。また、前記非水溶媒が少なくとも鎖状カーボネート又は環状カーボネートを含有することが好ましく、前記スルホン酸エステルが環状スルホン酸エステル、環状ジスルホン酸エステル又は鎖状ジスルホン酸エステルの少なくとも一種で構成されることが好ましく、前記環状スルホン酸エステルが、1,3−プロパンスルトン又は1,4−ブタンスルトンの少なくとも一種で構成されることが好ましく、さらに、前記環状ジスルホン酸エステルが、メチレンメタンジスルホネート、エチレンメタンジスルホネート及びプロピレンメタンジスルホネートから選ばれる少なくとも一種で構成されることが好ましい。 In order to solve the above problems, a non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte secondary battery having a negative electrode, a positive electrode, and a lithium ion conductive non-aqueous electrolyte. A mixture of active material particles coated with carbon having a mixed composition of amorphous carbon and graphite carbon, and a thermosetting resin that causes a dehydration condensation reaction by heating, and the active resin is heated by the thermosetting resin. The active material particles and the current collector are bound between the material particles, and the non-aqueous electrolyte includes a non-aqueous solvent and a sulfonate ester. The non-aqueous solvent preferably contains at least a chain carbonate or a cyclic carbonate, and the sulfonate ester is composed of at least one of a cyclic sulfonate ester, a cyclic disulfonate ester, or a chain disulfonate ester. Preferably, the cyclic sulfonic acid ester is preferably composed of at least one of 1,3-propane sultone or 1,4-butane sultone, and the cyclic disulfonic acid ester is methylene methane disulfonate, ethylene methane disulfonate. And at least one selected from propylene methane disulfonate.
非水電解質にスルホン酸エステルを含有させることにより、初期充電時のガス発生を抑制し、初回充放電での充放電効率が高くかつ、良好なサイクル特性を持つ非水電解質二次電池を提供することができる。初期の充電により有機硫黄化合物が反応し、負極表面に一般的にSEI(Solid Electrolyte Interface)膜と呼ばれる皮膜が形成される。皮膜が形成されることにより、負極活物質と電子との受け渡しがスムーズになる。 Providing a non-aqueous electrolyte secondary battery that suppresses gas generation during initial charge, has high charge / discharge efficiency in the first charge / discharge, and has good cycle characteristics by containing a sulfonate ester in the non-aqueous electrolyte. be able to. The organic sulfur compound reacts by the initial charge, and a film generally called a SEI (Solid Electrolyte Interface) film is formed on the negative electrode surface. By forming the film, the transfer between the negative electrode active material and the electrons becomes smooth.
本発明によれば、高容量を示す半面、充電による体積膨張の大きい単体ケイ素にケイ素酸化物を混合し、さらにその周辺にアモルファス系炭素を被覆することにより、電極活物質自体の膨脹収縮を緩和するため、充放電サイクル寿命が改善される。一方、単体ケイ素とケイ素酸化物の混合物に黒鉛系炭素を被覆し、導電性を向上させて、初回充放電容量の向上につながるだけでなく、活物質であるケイ素の電解液に対する耐食性や耐酸化性を保つことが出来る。さらに電解質成分としてスルホン酸エステルを含むことにより、初回充放電容量且つサイクル寿命を向上させることができる。特に環状ジエステルスルホン酸を用いた場合、高温でのサイクル寿命が改善できる。またバインダとして機能する熱硬化性樹脂は、加熱により脱水縮合反応を生じるため、活物質粒子間、及び活物質粒子−集電体間を強固に結着させる作用を示すため、接触抵抗の低減ひいては集電性の向上により初回充放電容量を向上させることが出来る。 According to the present invention, the expansion and contraction of the electrode active material itself is alleviated by mixing silicon oxide with simple silicon that exhibits high capacity and large volume expansion due to charging, and further coating the surrounding area with amorphous carbon. Therefore, the charge / discharge cycle life is improved. On the other hand, a mixture of simple silicon and silicon oxide is coated with graphite-based carbon to improve conductivity and lead to an improvement in initial charge / discharge capacity, as well as corrosion resistance and oxidation resistance to silicon electrolyte as an active material. You can keep the sex. Furthermore, by including a sulfonic acid ester as an electrolyte component, the initial charge / discharge capacity and the cycle life can be improved. In particular, when a cyclic diester sulfonic acid is used, cycle life at a high temperature can be improved. In addition, since the thermosetting resin that functions as a binder causes a dehydration condensation reaction by heating, it exhibits an action of firmly binding between the active material particles and between the active material particles and the current collector. The initial charge / discharge capacity can be improved by improving the current collecting property.
本発明の実施の形態について図面を参照して説明する。図1に本発明の非水電解質二次電池の負極の活物質粒子の模式断面図を示す。 Embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows a schematic cross-sectional view of the active material particles of the negative electrode of the nonaqueous electrolyte secondary battery of the present invention.
図1に示すように、負極の活物質粒子5は、単体ケイ素1、ケイ素酸化物2を核とし、その周辺にアモルファス系炭素3、黒鉛系炭素4の混合物である炭素で被覆した粒径D95が50μm以下、望ましくは20μm以下の粒子である。なおD95はある粒径以下の体積割合の合計が95%となるときの粒径を示す。 As shown in FIG. 1, the active material particle 5 of the negative electrode has a particle size D in which the elemental silicon 1 and the silicon oxide 2 are used as nuclei and the periphery thereof is coated with carbon which is a mixture of amorphous carbon 3 and graphite carbon 4. 95 is a particle of 50 μm or less, desirably 20 μm or less. D 95 indicates the particle size when the sum of the volume ratios below a certain particle size is 95%.
単体ケイ素1は、充放電の際Liを吸蔵あるいは放出する。ケイ素酸化物2は活物質自体の膨脹収縮を緩和する役目がある。外側にある炭素被覆層は、アモルファス系炭素3と黒鉛系炭素4の混合物である。上記負極活物質中に被覆される炭素が重量比で5%以上、望ましくは10%以上50%未満であることが好ましい。 The simple silicon 1 occludes or releases Li during charge / discharge. The silicon oxide 2 has a role of relaxing expansion and contraction of the active material itself. The carbon coating layer on the outside is a mixture of amorphous carbon 3 and graphite carbon 4. It is preferable that the carbon covered in the negative electrode active material is 5% or more by weight, desirably 10% or more and less than 50%.
負極活物質粒子の作製方法としては、最初に核となるケイ素とケイ素酸化物を混合し、高温減圧下にて焼結させる。次に高温非酸素雰囲気下で有機化合物の気体雰囲気中にケイ素とケイ素酸化物の混合焼結物を導入する、もしくは高温非酸素雰囲気下でケイ素とケイ素酸化物の混合焼結物と炭素の前駆体樹脂を混合させることで、ケイ素とケイ素酸化物の核の周辺に炭素被覆層が形成される。ここで炭素被覆層中の黒鉛系炭素の割合は被覆層形成時の温度によるため、望ましくは600℃以上1200℃未満であれば被覆層内にアモルファス系炭素と黒鉛系炭素の両方を担持させることが出来る。 As a method for producing the negative electrode active material particles, first, silicon and silicon oxide as nuclei are mixed and sintered under high temperature and reduced pressure. Next, a mixed sintered product of silicon and silicon oxide is introduced into a gaseous atmosphere of an organic compound in a high temperature non-oxygen atmosphere, or a mixed sintered product of silicon and silicon oxide and a precursor of carbon in a high temperature non-oxygen atmosphere. By mixing the body resin, a carbon coating layer is formed around the core of silicon and silicon oxide. Here, since the ratio of the graphite-based carbon in the carbon coating layer depends on the temperature at which the coating layer is formed, it is desirable that both amorphous carbon and graphite-based carbon be supported in the coating layer if it is 600 ° C. or higher and lower than 1200 ° C. I can do it.
図2に本発明の非水電解質二次電池の断面図を示す。図2に示すように、負極8は、活物質層6と集電体7からなる。また正極11は、活物質層9と集電体10からなる。負極の集電体7は通常は銅箔が、正極の集電体10は通常はアルミ箔が、それぞれ用いられる。負極8と正極11の間にセパレータ12を配置している。セパレータ12としては、ポリプロピレン、ポリエチレン等のポリオレフィン、フッ素樹脂等の多孔性フィルムを用いることができる。外装フィルム13はラミネートフィルムを使用することができ、フィルム同士を融着させる融着層と絶縁層からなる。また負極8と正極11から、それぞれ電気取り出しのための負極リードタブ14、正極リードタブ15が外装フィルムの融着部分により固定されている。
FIG. 2 shows a cross-sectional view of the nonaqueous electrolyte secondary battery of the present invention. As shown in FIG. 2, the
負極活物質層6は上記の方法で生成した負極活物質粒子と、ポリイミド、ポリアミド、ポリアミドイミド、ポリアクリル酸系樹脂、ポリメタクリル酸系樹脂に代表される熱硬化性を有する結着剤とをN−メチル−2−ピロリドン(NMP)等の溶剤に分散させ混練し、集電体7の上に塗布し、高温雰囲気で乾燥することにより形成される。負極の活物質層6中には、必要に応じて導電性を付与するため、カーボンブラックやアセチレンブラック等を混合してもよい。集電体7の厚みは、強度を保てるような厚みとすることが好ましいことから、4〜100μmであることが好ましく、エネルギー密度を高めるためには、5〜30μmであることがさらに好ましい。
The negative electrode
電解質に含まれる非水溶媒としては、プロピレンカーボネート(PC)、エチレンカーボネート(EC)、ブチレンカーボネート(BC)、ビニレンカーボネート(VC)等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)等の鎖状カーボネート類、ギ酸メチル、酢酸メチル、プロピオン酸エチル等の脂肪族カルボン酸エステル類、γ−ブチロラクトン等のγ−ラクトン類、1,2−エトキシエタン(DEE)、エトキシメトキシエタン(EME)等の鎖状エーテル類、テトラヒドロフラン、2−メチルテトラヒドロフラン等の環状エーテル類、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−プロパンスルトン、アニソール、N−メチルピロリドン、フッ素化カルボン酸エステルなどの非プロトン性有機溶媒を一種又は二種以上を混合して使用できるが、これらに限定されるものではない。 Nonaqueous solvents contained in the electrolyte include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC), dimethyl carbonate (DMC), and diethyl carbonate (DEC). Chain carbonates such as ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, and γ-lactones such as γ-butyrolactone, , 2-Ethoxyethane (DEE), chain ethers such as ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3 dioxolane, formamide, acetamide , Dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl- Mix one or more aprotic organic solvents such as 2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ethyl ether, 1,3-propane sultone, anisole, N-methylpyrrolidone, fluorinated carboxylic acid ester Although it can be used, it is not limited to these.
電解質に含まれるスルホン酸エステルとしては、環状モノスルホン酸エステル、環状ジスルホン酸エステル、鎖状スルホン酸エステルなどが適宜使用できる。環状モノスルホン酸エステルとしては1,3−プロパンスルトン(1,3−PS)、α−トリフルオロメチル−γ−スルトン、β−トリフルオロメチル−γ−スルトン、γ−トリフルオロメチル−γ−スルトン、α−メチル−γ−スルトン、α,β−ジ(トリフルオロメチル)−γ−スルトン、α,α−ジ(トリフルオロメチル)−γ−スルトン、α−ウンデカフルオロペンチル−γ−スルトン、α−ヘプタフルオロプロピル−γ−スルトン、1,4−ブタンスルトン(1,4−BS)などがあげられる。環状ジスルホン酸エステルとしてはメチレンメタンジスルホネート(MMDS)、エチレンメタンジスルホネート(EMDS)、プロピレンメタンジスルホネート(PMDS)等があげられる。鎖状スルホン酸エステルとしては、メタンスルホン酸メチルエステル、メタンスルホン酸エチルエステル、ブスルファン、ジメチル−メタンジスルホネートなどが挙げられる。 As the sulfonic acid ester contained in the electrolyte, a cyclic monosulfonic acid ester, a cyclic disulfonic acid ester, a chain sulfonic acid ester, and the like can be appropriately used. Examples of cyclic monosulfonic acid esters include 1,3-propane sultone (1,3-PS), α-trifluoromethyl-γ-sultone, β-trifluoromethyl-γ-sultone, and γ-trifluoromethyl-γ-sultone. , Α-methyl-γ-sultone, α, β-di (trifluoromethyl) -γ-sultone, α, α-di (trifluoromethyl) -γ-sultone, α-undecafluoropentyl-γ-sultone, Examples include α-heptafluoropropyl-γ-sultone and 1,4-butane sultone (1,4-BS). Examples of the cyclic disulfonate include methylene methane disulfonate (MMDS), ethylene methane disulfonate (EMDS), and propylene methane disulfonate (PMDS). Examples of chain sulfonic acid esters include methanesulfonic acid methyl ester, methanesulfonic acid ethyl ester, busulfan, and dimethyl-methane disulfonate.
これらスルホン酸エステルの中でも1,3−PSやMMDSを使用することが特に好ましい。1,3−PSやMMDSはリチウムイオン二次電池の電極上での分解皮膜を形成すると考えられている。例えば1,3−PSの最低空軌道エネルギー(LUMO)は0.07eVであり、1,3−PSが溶媒分子であるEC(LUMO:1.18eV)やDEC(LUMO:1.26eV)よりも先に分解し皮膜を形成することが考えられる。その結果溶媒分子の分解が抑制され、ガス発生による電池の膨れの抑制やレート特性改善が期待できる。また、例えば正極にマンガン酸リチウムを含む場合にはMMDSの添加によって高温で溶出したMnが負極表面に吸着することを防止し、結果として抵抗上昇抑制によるサイクル特性向上に有効であると考えられる。 Among these sulfonic acid esters, it is particularly preferable to use 1,3-PS or MMDS. 1,3-PS and MMDS are considered to form a decomposition film on the electrode of the lithium ion secondary battery. For example, the lowest unoccupied orbital energy (LUMO) of 1,3-PS is 0.07 eV, which is higher than EC (LUMO: 1.18 eV) or DEC (LUMO: 1.26 eV) where 1,3-PS is a solvent molecule. It is conceivable that the film is first decomposed to form a film. As a result, decomposition of solvent molecules is suppressed, and suppression of battery swelling due to gas generation and improvement of rate characteristics can be expected. Further, for example, when lithium manganate is included in the positive electrode, it is considered that Mn eluted at a high temperature by addition of MMDS is prevented from adsorbing on the negative electrode surface, and as a result, it is effective for improving cycle characteristics by suppressing resistance increase.
これらの電解質中に含まれるスルホン酸エステルの濃度は、特に限定されるものではないが、正極活物質層としてマンガン酸リチウムを含む正極を使用した二次電池の場合には、0.1質量%以上5.0質量%以下が好ましく、更に好ましくは0.5質量%以上3.0質量%以下が特に好ましい。0.1質量%未満では電極表面に十分な皮膜が形成されず、サイクル特性改善効果が小さい。5.0質量%を越えると、抵抗が高くなってサイクル特性が悪くなる。 The concentration of the sulfonate ester contained in these electrolytes is not particularly limited, but in the case of a secondary battery using a positive electrode containing lithium manganate as the positive electrode active material layer, 0.1% by mass The content is preferably 5.0% by mass or less, more preferably 0.5% by mass or more and 3.0% by mass or less. If it is less than 0.1% by mass, a sufficient film is not formed on the electrode surface, and the effect of improving the cycle characteristics is small. If it exceeds 5.0% by mass, the resistance increases and the cycle characteristics deteriorate.
電解質に含まれる支持塩としては、特に限定されないがLiPF6、LiBF4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2など一般的に非水電解質二次電池に用いられる電解質が使用できる。 The supporting salt contained in the electrolyte is not particularly limited, but electrolytes generally used for nonaqueous electrolyte secondary batteries such as LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 are used. Can be used.
また、正極活物質として、例えば、LiCoO2、LiNi1-xCoxO2、LiNixMn2−xO4 (0<x<1) 、LiFePO4、LiMn2O4複合酸化物正極材料が使用できるが、これらに限定されるものではない。 Examples of the positive electrode active material include LiCoO 2 , LiNi 1-x Co x O 2 , LiNi x Mn 2 -x O 4 (0 <x <1), LiFePO 4 , LiMn 2 O 4 composite oxide positive electrode material. Although it can be used, it is not limited to these.
セパレータとしては、ポリプロピレン、ポリエチレン等のポリオレフィン、フッ素樹脂等の多孔性フィルムがなどが使用できるが、これに限定されるものではない。 Examples of the separator include polyolefin such as polypropylene and polyethylene, and porous films such as fluororesin, but are not limited thereto.
本発明の実施例について以下に説明する。 Examples of the present invention will be described below.
(実施例1)
単体ケイ素とケイ素酸化物をモル比1:1にて混合し、1400℃、13.3Paにて溶融、急冷させてケイ素‐ケイ素酸化物混合粉末を形成した。混合物の粒径D95は20μm以下であった。エタノール溶液中ボールミルにて最大粒径50μm以下に粉砕した。上記粉末とフェノール樹脂を混合し、窒素雰囲気下、900℃にて焼成した後、最大粒径D95が30μm以下となるよう粉砕処理を行った。これにより活物質中の炭素比率が20%となる複合活物質粒子を作製した。
Example 1
Single silicon and silicon oxide were mixed at a molar ratio of 1: 1, melted at 1400 ° C. and 13.3 Pa, and rapidly cooled to form a silicon-silicon oxide mixed powder. The particle size D 95 of the mixture was 20 μm or less. The maximum particle size was pulverized to 50 μm or less with a ball mill in an ethanol solution. The powder and the phenol resin were mixed and baked at 900 ° C. in a nitrogen atmosphere, and then pulverized so that the maximum particle size D 95 was 30 μm or less. Thus, composite active material particles having a carbon ratio in the active material of 20% were produced.
このようにして生成した複合活物質粒子を用いて、以下のようにして活物質層を作製した。負極活物質層は上記活物質粒子、ポリイミド、及びNMPを混合した電極材を10μmの銅箔の上に塗布し、125℃、5分間乾燥した後、ロールプレスにて圧縮成型を行い、再度乾燥炉にて300℃、10分間乾燥処理を行った。この活物質層/銅箔シートを30×28mmに打ち抜き、電荷取り出しのためのニッケルタブを超音波により融着し正極活物質については、マンガン酸リチウムからなる活物質粒子、バインダとしてポリフッ化ビニリデン、溶剤としてNMPを混合した電極材を20μmのアルミ箔の上に塗布し、125℃、5分間乾燥処理を行い、活物質層/アルミ箔シートを30×28mmに打ち抜き、電荷取り出しのためのアルミタブを超音波により融着した。負極活物質層/銅箔シート、セパレータ、正極活物質層/アルミ箔シートの順に、活物質層がセパレータと対面するように積層した後、ラミネートフィルムではさみ、電解液を注液し、真空下にて封止することによりラミネート型電池を作製した。なお電解液は、エチレンカーボネート(EC)30質量%とジエチルカーボネート(DEC)58質量%に、リチウム塩としてLiPF612質量%からなる電解液に対して、1,3−PSを1質量%を加えたものを使用した。 Using the composite active material particles thus produced, an active material layer was produced as follows. For the negative electrode active material layer, the electrode material mixed with the above active material particles, polyimide, and NMP was applied onto a 10 μm copper foil, dried at 125 ° C. for 5 minutes, then subjected to compression molding with a roll press and dried again. Drying was performed in an oven at 300 ° C. for 10 minutes. This active material layer / copper foil sheet is punched out to 30 × 28 mm, a nickel tab for taking out electric charges is fused by ultrasonic waves, and for the positive electrode active material, active material particles made of lithium manganate, polyvinylidene fluoride as a binder, An electrode material mixed with NMP as a solvent is applied onto an aluminum foil of 20 μm, dried at 125 ° C. for 5 minutes, the active material layer / aluminum foil sheet is punched out to 30 × 28 mm, and an aluminum tab for taking out electric charges is used. Fusion was performed by ultrasonic waves. After laminating the negative electrode active material layer / copper foil sheet, the separator, and the positive electrode active material layer / aluminum foil sheet in this order so that the active material layer faces the separator, the laminate film is sandwiched, and the electrolyte solution is injected under vacuum. The laminate type battery was produced by sealing with. The electrolytic solution is 30% by mass of ethylene carbonate (EC) and 58% by mass of diethyl carbonate (DEC), and 1% by mass of 1,3-PS with respect to the electrolytic solution consisting of 12% by mass of LiPF 6 as a lithium salt. What was added was used.
(実施例2)
1,3−PSの濃度が0.5質量%になるように電解液を調整する以外、実施例1と同様に電池を作製した。
(Example 2)
A battery was fabricated in the same manner as in Example 1 except that the electrolyte was adjusted so that the concentration of 1,3-PS was 0.5% by mass.
(実施例3)
1,3−PSの濃度が0.1質量%になるように電解質を調整する以外、実施例1と同様に電池を作製した。
(Example 3)
A battery was produced in the same manner as in Example 1 except that the electrolyte was adjusted so that the concentration of 1,3-PS was 0.1% by mass.
(実施例4)
1,3−PSの濃度が3.0質量%になるように電解質を調整する以外、実施例1と同様に電池を作製した。
Example 4
A battery was produced in the same manner as in Example 1 except that the electrolyte was adjusted so that the concentration of 1,3-PS was 3.0% by mass.
(実施例5)
1,3−PSの濃度が5.0質量%になるように電解質を調整する以外、実施例1と同様に電池を作製した。
(Example 5)
A battery was fabricated in the same manner as in Example 1 except that the electrolyte was adjusted so that the concentration of 1,3-PS was 5.0% by mass.
(比較例1)
1,3−PS含有量が0質量%である以外は実施例1と同様にして非水電解質電池を作製した。
(Comparative Example 1)
A nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the 1,3-PS content was 0% by mass.
実施例1〜5、比較例1により得られた非水電解質二次電池を、電池電圧4.2Vまで充電し(充電条件:電流:0.2C、時間:6.5時間、温度20℃)、0.2Cで電池電圧2.5Vまで放電しそのときの充電に対する放電容量を充放電効率とした。得られた非水電解質二次電池の容量維持率は、1サイクル目の放電容量(1.0C)に対する300サイクル目の放電容量(1.0C)の割合で示した。なお、サイクルの条件は、充電:上限電圧4.2 V、電流1.0C、時間2.5時間、放電:下限電圧2.5V、電流1.0Cとし、いずれも20℃、60℃で実施した。表1に充放電効率と容量維持率を示した。 The nonaqueous electrolyte secondary batteries obtained in Examples 1 to 5 and Comparative Example 1 were charged to a battery voltage of 4.2 V (charging conditions: current: 0.2 C, time: 6.5 hours, temperature 20 ° C.). The battery was discharged at 0.2 C to a battery voltage of 2.5 V, and the discharge capacity for charging at that time was defined as the charge / discharge efficiency. The capacity retention rate of the obtained nonaqueous electrolyte secondary battery was shown as the ratio of the discharge capacity (1.0 C) at the 300th cycle to the discharge capacity (1.0 C) at the first cycle. The cycle conditions were as follows: charge: upper limit voltage 4.2 V, current 1.0 C, time 2.5 hours, discharge: lower limit voltage 2.5 V, current 1.0 C, both at 20 ° C. and 60 ° C. did. Table 1 shows the charge / discharge efficiency and capacity retention rate.
本発明の非水電解質二次電池において、表1の実施例1〜5に示すように、スルホン酸エステルの濃度が0.1以上5.0質量%以下の場合、サイクル特性等においてスルホン酸エステルを添加しなかった比較例1よりも明らかに特性が良好であることがわかった。 In the nonaqueous electrolyte secondary battery of the present invention, as shown in Examples 1 to 5 of Table 1, when the concentration of the sulfonic acid ester is 0.1 or more and 5.0% by mass or less, the sulfonic acid ester in the cycle characteristics and the like It was found that the characteristics were clearly better than Comparative Example 1 in which no was added.
(実施例6)
1,3−PSの代わりにMMDSを用いる以外、実施例1と同様に電池を作製し、評価を行った。
(Example 6)
A battery was prepared and evaluated in the same manner as in Example 1 except that MMDS was used instead of 1,3-PS.
(実施例7)
1,3−PSの代わりにMMDSを用いる以外、実施例2と同様に電池を作製し、評価を行った。
(Example 7)
A battery was prepared and evaluated in the same manner as in Example 2 except that MMDS was used instead of 1,3-PS.
(実施例8)
1,3−PSの代わりにMMDSを用いる以外、実施例3と同様に電池を作製し、評価を行った。
(Example 8)
A battery was prepared and evaluated in the same manner as in Example 3 except that MMDS was used instead of 1,3-PS.
(実施例9)
1,3−PSの代わりにMMDSを用いる以外、実施例4と同様に電池を作製し、評価を行った。
Example 9
A battery was prepared and evaluated in the same manner as in Example 4 except that MMDS was used instead of 1,3-PS.
(実施例10)
1,3−PSの代わりにMMDSを用いる以外、実施例5と同様に電池を作製し、評価を行った。
(Example 10)
A battery was prepared and evaluated in the same manner as in Example 5 except that MMDS was used instead of 1,3-PS.
(比較例2)
1,3−PSの代わりにMMDSを用いる以外、比較例1と同様に電池を作製し、評価を行った。
(Comparative Example 2)
A battery was prepared and evaluated in the same manner as in Comparative Example 1 except that MMDS was used instead of 1,3-PS.
実施例6〜10および比較例2についての初回充放電効率、容量維持率について表2に示した。 Table 2 shows the initial charge / discharge efficiency and capacity retention rate for Examples 6 to 10 and Comparative Example 2.
本発明の非水電解質二次電池において、表2の実施例6〜10に示すように、スルホン酸エステルの濃度が0.1以上5.0質量%以下の場合、サイクル特性等においてスルホン酸エステルを添加しなかった比較例2よりも明らかに特性が良好であることがわかった。また、60度の高温サイクルにおいてもスルホン酸エステルの濃度が0.1以上5.0質量%以下の場合、サイクル特性が良好である。 In the nonaqueous electrolyte secondary battery of the present invention, as shown in Examples 6 to 10 in Table 2, when the concentration of the sulfonic acid ester is 0.1 or more and 5.0% by mass or less, the sulfonic acid ester in cycle characteristics and the like It was found that the characteristics were clearly better than those of Comparative Example 2 in which no was added. Even in a high-temperature cycle of 60 degrees, the cycle characteristics are good when the concentration of the sulfonic acid ester is 0.1 to 5.0% by mass.
1 単体ケイ素
2 ケイ素酸化物
3 アモルファス系炭素
4 黒鉛系炭素
5 (負極の)活物質粒子
6 (負極の)活物質層
7 (負極の)集電体
8 負極
9 (正極の)活物質層
10 (正極の)集電体
11 正極
12 セパレータ
13 外装フィルム
14 負極リードタブ
15 正極リードタブ
1 elemental silicon 2 silicon oxide 3 amorphous carbon 4 graphite carbon 5 (negative electrode) active material particles
6 Active material layer 7 (for negative electrode) Current collector 8 (for negative electrode)
13 Exterior film
14 Negative lead tab
15 Positive lead tab
Claims (3)
前記負極は、単体ケイ素とケイ素酸化物の混合焼結物の周辺をアモルファス系炭素及び黒鉛系炭素の混合組成からなる炭素で被覆した活物質粒子と、加熱により脱水縮合反応を生じる熱硬化性樹脂の混合物を含み、
前記熱硬化性樹脂により前記活物質粒子間、及び前記活物質粒子と集電体とが結着され、
前記非水電解質が、非水溶媒と、メチレンメタンジスルホネート、エチレンメタンジスルホネート及びプロピレンメタンジスルホネートから選ばれる少なくとも一種と、を含むことを特徴とする非水電解質二次電池。 In a non-aqueous electrolyte secondary battery having a negative electrode, a positive electrode, and a lithium ion conductive non-aqueous electrolyte,
The negative electrode is a thermosetting resin that generates a dehydration-condensation reaction by heating with active material particles in which the periphery of a mixed sintered product of simple silicon and silicon oxide is coated with carbon having a mixed composition of amorphous carbon and graphite carbon A mixture of
Between the active material particles and the active material particles and the current collector are bound by the thermosetting resin,
The non-aqueous electrolyte includes a non-aqueous solvent and at least one selected from methylene methane disulfonate, ethylene methane disulfonate, and propylene methane disulfonate .
前記負極は、単体ケイ素とケイ素酸化物の混合物の周辺をアモルファス系炭素及び黒鉛系炭素の混合組成からなる炭素で被覆した活物質粒子と、加熱により脱水縮合反応を生じる熱硬化性樹脂の混合物を含み、
前記熱硬化性樹脂により前記活物質粒子間、及び前記活物質粒子と集電体とが結着され、
前記非水電解質が非水溶媒と、さらに、メチレンメタンジスルホネート、エチレンメタンジスルホネート及びプロピレンメタンジスルホネートから選ばれる少なくとも一種とを含むことを特徴とする非水電解質二次電池。
In a non-aqueous electrolyte secondary battery having a negative electrode, a positive electrode, and a lithium ion conductive non-aqueous electrolyte,
The negative electrode comprises a mixture of active material particles in which the periphery of a mixture of simple silicon and silicon oxide is coated with carbon having a mixed composition of amorphous carbon and graphite carbon, and a thermosetting resin that causes a dehydration condensation reaction by heating. Including
Between the active material particles and the active material particles and the current collector are bound by the thermosetting resin,
A nonaqueous electrolyte secondary battery, wherein the nonaqueous electrolyte includes a nonaqueous solvent and at least one selected from methylenemethane disulfonate, ethylenemethane disulfonate, and propylene methane disulfonate.
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JP2008112722A (en) * | 2006-10-02 | 2008-05-15 | Nec Tokin Corp | Lithium polymer battery |
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