JP5277045B2 - Non-aqueous electrolyte and lithium ion secondary battery using the same - Google Patents
Non-aqueous electrolyte and lithium ion secondary battery using the same Download PDFInfo
- Publication number
- JP5277045B2 JP5277045B2 JP2009084795A JP2009084795A JP5277045B2 JP 5277045 B2 JP5277045 B2 JP 5277045B2 JP 2009084795 A JP2009084795 A JP 2009084795A JP 2009084795 A JP2009084795 A JP 2009084795A JP 5277045 B2 JP5277045 B2 JP 5277045B2
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- group
- lithium
- ion secondary
- lithium ion
- carbonate
- Prior art date
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 50
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- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 239000008151 electrolyte solution Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 15
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
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- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- JHMHRYYXUWUDGH-UHFFFAOYSA-N fluoro-[2-[fluoro(dimethyl)silyl]ethenyl]-dimethylsilane Chemical group C[Si](C)(F)C=C[Si](C)(C)F JHMHRYYXUWUDGH-UHFFFAOYSA-N 0.000 description 1
- WLXDJYZDTGKMSI-UHFFFAOYSA-N fluoro-[2-[fluoro(dimethyl)silyl]ethynyl]-dimethylsilane Chemical group C[Si](C)(F)C#C[Si](C)(C)F WLXDJYZDTGKMSI-UHFFFAOYSA-N 0.000 description 1
- GRSZDIOLMSYKOI-UHFFFAOYSA-N fluoro-[2-[fluoro(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C[Si](C)(F)C1=CC=CC=C1[Si](C)(C)F GRSZDIOLMSYKOI-UHFFFAOYSA-N 0.000 description 1
- BQEOIZLEQLETQT-UHFFFAOYSA-N fluoro-[3-[fluoro(dimethyl)silyl]propyl]-dimethylsilane Chemical compound C[Si](C)(F)CCC[Si](C)(C)F BQEOIZLEQLETQT-UHFFFAOYSA-N 0.000 description 1
- GWYYWNKVCNKIMF-UHFFFAOYSA-N fluoro-[4-[fluoro(dimethyl)silyl]butyl]-dimethylsilane Chemical compound C[Si](C)(F)CCCC[Si](C)(C)F GWYYWNKVCNKIMF-UHFFFAOYSA-N 0.000 description 1
- XEQXHROSXZWVRU-UHFFFAOYSA-N fluoro-[4-[fluoro(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C[Si](C)(F)C1=CC=C([Si](C)(C)F)C=C1 XEQXHROSXZWVRU-UHFFFAOYSA-N 0.000 description 1
- IZNPDMQYOJQYQI-UHFFFAOYSA-N fluoro-[[fluoro(dimethyl)silyl]methyl]-dimethylsilane Chemical compound C[Si](C)(F)C[Si](C)(C)F IZNPDMQYOJQYQI-UHFFFAOYSA-N 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- ROCSCYHXUBXLGH-UHFFFAOYSA-N hexan-3-yl hydrogen carbonate Chemical compound CCCC(CC)OC(O)=O ROCSCYHXUBXLGH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- XDLVYYYGCNMREZ-UHFFFAOYSA-N propane-1,2-diol;sulfuric acid Chemical compound CC(O)CO.OS(O)(=O)=O XDLVYYYGCNMREZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
Abstract
Description
本発明は、非水電解液及びそれを用いたリチウムイオン二次電池に係り、更には、そのようなリチウムイオン二次電池を電源として備えた電子機器や輸送機器等に関するものである。 The present invention relates to a non-aqueous electrolyte and a lithium ion secondary battery using the same, and further relates to an electronic device, a transport device, and the like equipped with such a lithium ion secondary battery as a power source.
近年、二次電池としてのリチウムイオン電池が、高出力や高エネルギー密度を実現し得る電池として注目され、既に、パソコン、携帯電話、携帯音楽プレイヤー等の小型民生機器用の領域では、その電源として実用化されており、また自動車産業においても、電気自動車やハイブリッド車等の車載用エネルギー源として、小型・軽量であるリチウムイオン二次電池の実用化が期待されている。 In recent years, lithium-ion batteries as secondary batteries have attracted attention as batteries that can achieve high output and high energy density, and have already been used as power sources in the area of small consumer devices such as personal computers, mobile phones, and portable music players. The lithium ion secondary battery, which is small and light, is expected to be put into practical use as an in-vehicle energy source for electric vehicles and hybrid vehicles in the automobile industry.
また、それらの用途の中で、小型民生機器に用いられる電池では、常温近傍で用いられることが多く、その寿命にあっても、車載用に求められるような長期に亘る信頼性は、必ずしも必要とはされていないのであるが、電気自動車或いはハイブリッド自動車用電池では、−４０℃に近い極低温から６０℃以上の高温に至る領域において、正常に作動することが求められ、民生用に比べると、非常に幅広い温度領域での使用が可能であることが要請され、更に、その寿命においても、民生用に比べて、遥かに長期に亘って機能するものであることが要請されている。例えば、米国先進バッテリー・コンソーシアム（ＵＳＡＢＣ）の目標においては、１５年、２４万ｋｍ走行相当において、車載用リチウムイオン電池として機能することが求められているのである。 In addition, among these applications, batteries used in small consumer devices are often used near room temperature, and even in their lifetime, long-term reliability required for in-vehicle use is always necessary. However, batteries for electric vehicles or hybrid vehicles are required to operate normally in the region from extremely low temperatures close to −40 ° C. to high temperatures of 60 ° C. or more, compared to consumer use. Therefore, it is required that it can be used in a very wide temperature range, and further, its life is required to function much longer than that for consumer use. For example, the goal of the US Advanced Battery Consortium (USABC) is to function as an in-vehicle lithium-ion battery for 15 years, equivalent to 240,000 km travel.
このため、従来から、かかるリチウムイオン二次電池については、活発な研究が行なわれてきており、それに用いられる非水電解液、即ち、リチウムを含む電解質塩を非水溶媒に溶解せしめてなる電解液についても、各種の提案が為されているのであって、例えば、特許文献１においては、オキサラト錯体をアニオンとするリチウム塩と、ビニレンカーボネート等の被膜形成剤とを添加せしめることにより、高温での保存特性の向上や、サイクル特性を改善する方法が、提案されている。 For this reason, active research has been conducted on such lithium ion secondary batteries, and the non-aqueous electrolyte used in the lithium-ion secondary battery, that is, an electrolytic solution obtained by dissolving an electrolyte salt containing lithium in a non-aqueous solvent. Various proposals have also been made for liquids. For example, in Patent Document 1, a lithium salt having an oxalato complex as an anion and a film forming agent such as vinylene carbonate are added at a high temperature. A method for improving the storage characteristics and improving the cycle characteristics has been proposed.
しかしながら、かかる特許文献１に明らかにされた非水電解液にあっては、そこで規定されるオキサラト錯体をアニオンとするリチウム塩を、ビニレンカーボネート等の被膜形成剤と共に、添加することによって、二次電池としての劣化が提示されているように少なく、改善されてはいるが、その効果は緩やかな条件下での使用に限られており、より厳しい条件下での使用では大きな劣化を示すという課題があるため、今後の高度なニーズに充分応え得るリチウムイオン二次電池を得るには至っていないのである。 However, in the non-aqueous electrolyte disclosed in Patent Document 1, a secondary salt is added by adding a lithium salt having an oxalato complex as an anion together with a film forming agent such as vinylene carbonate. Although the deterioration as a battery is small and improved as suggested, the effect is limited to use under mild conditions, and the problem is that it shows great deterioration when used under more severe conditions Therefore, a lithium-ion secondary battery that can sufficiently meet future advanced needs has not been obtained.
また、特許文献２においては、リチウムイオン二次電池の非水電解液に、ビス（トリフルオロメタンスルホニル）イミドリチウムと、ヘキサメチルシクロトリシロキサンのような環状のシロキサン等のＳｉ化合物とを組み合わせて使用し、被膜形成を行なうことにより、電極と非水系電解液との余分な副反応を抑制せしめて、出力特性を向上させながら、高温保存特性やサイクル特性を改善する手法が、提案されている。しかしながら、それらの手法にあっても、それなりの効果は認められるものの、より高い電池特性を発揮し得るものが、望まれている。 In Patent Document 2, a non-aqueous electrolyte of a lithium ion secondary battery is used in combination with bis (trifluoromethanesulfonyl) imide lithium and a Si compound such as cyclic siloxane such as hexamethylcyclotrisiloxane. In addition, there has been proposed a technique for improving the high-temperature storage characteristics and the cycle characteristics while suppressing the excessive side reaction between the electrode and the non-aqueous electrolyte by improving the output characteristics. However, even if these methods are used, a certain effect is recognized, but a device that can exhibit higher battery characteristics is desired.
ここにおいて、本発明は、かかる事情を背景にして為されたものであって、その解決課題とするところは、リチウムイオン二次電池における電池特性をより一層改善せしめ得る非水電解液を提供することにあり、また、そのような非水電解液を用いて、優れた電池特性を有するリチウムイオン二次電池を実現し、更には、かかるリチウムイオン二次電池を備えた電子機器や輸送機器等を提供することにある。 Here, the present invention has been made in the background of such circumstances, and the problem to be solved is to provide a non-aqueous electrolyte that can further improve the battery characteristics of the lithium ion secondary battery. In particular, by using such a non-aqueous electrolyte, a lithium ion secondary battery having excellent battery characteristics is realized, and further, an electronic device, a transportation device, etc. provided with such a lithium ion secondary battery Is to provide.
そして、本発明は、上記した課題又は明細書全体の記載から把握される課題を解決するために、以下に列挙せる如き各種の態様において、好適に実施され得るものであるが、また、以下に記載の各態様は、任意の組合せにおいても採用可能である。なお、本発明の態様乃至は技術的特徴は、以下に記載のものに何等限定されることなく、明細書全体の記載乃至はそこに開示の発明思想に基づいて、認識され得るものであることが、理解されるべきである。 The present invention can be suitably implemented in various modes as listed below in order to solve the problems described above or the problems grasped from the description of the entire specification. Each described aspect can be employed in any combination. It should be noted that aspects or technical features of the present invention are not limited to those described below, and can be recognized based on the description of the entire specification or the inventive idea disclosed therein. Should be understood.
（１） リチウムを含む電解質塩を非水系溶媒に溶解せしめてなる、リチウムイオン二次電池に用いられる非水電解液にして、オキサラト錯体をアニオンとするリチウム塩と、下記一般式（Ｉ）で表されるフッ化ケイ素化合物とを含有していることを特徴とする非水電解液。
（２） ハロゲン原子を有する炭酸エステルを、更に含有していることを特徴とする上記態様（１）に記載の非水電解液。 (2) The nonaqueous electrolytic solution according to the above aspect (1), further comprising a carbonic acid ester having a halogen atom.
（３） 前記ハロゲン原子を有する炭酸エステルが、非水電解液中に、０．０１重量％以上の割合において含有せしめられている上記態様（２）に記載の非水電解液。 (3) The nonaqueous electrolytic solution according to the above aspect (2), wherein the carbonic acid ester having a halogen atom is contained in the nonaqueous electrolytic solution in a proportion of 0.01% by weight or more.
（４） 前記ハロゲン原子を有する炭酸エステルが、フルオロエチレンカーボネート、ジフルオロエチレンカーボネート、フルオロメチルエチレンカーボネート並びにこれらの誘導体よりなる群から選ばれる１種以上のフッ素原子含有炭酸エステルである上記態様（２）又は（３）に記載の非水電解液。 (4) The above aspect (2), wherein the carbonic acid ester having a halogen atom is at least one fluorine atom-containing carbonic acid ester selected from the group consisting of fluoroethylene carbonate, difluoroethylene carbonate, fluoromethylethylene carbonate, and derivatives thereof. Or the nonaqueous electrolyte solution as described in (3).
（５） 前記オキサラト錯体をアニオンとするリチウム塩が、リチウムビス（オキサラト）ボレートである上記態様（１）乃至（４）の何れか一つに記載の非水電解液。 (5) The nonaqueous electrolytic solution according to any one of the above aspects (1) to (4), wherein the lithium salt having the oxalato complex as an anion is lithium bis (oxalato) borate.
（６） 前記オキサラト錯体をアニオンとするリチウム塩が、非水電解液中に、０．０１重量％以上の割合において含有せしめられている上記態様（１）乃至（５）の何れか一つに記載の非水電解液。 (6) In any one of the above embodiments (1) to (5), a lithium salt having the oxalato complex as an anion is contained in a non-aqueous electrolyte at a ratio of 0.01% by weight or more. The non-aqueous electrolyte described.
（７） 前記一般式（Ｉ）で表されるフッ化ケイ素化合物が、非水電解液中に、０．０１重量％以上の割合において含有せしめられている上記態様（１）乃至（６）の何れか一つに記載の非水電解液。 (7) The said aspect (1) thru | or (6) in which the silicon fluoride compound represented by the said general formula (I) is contained in the ratio of 0.01 weight% or more in the non-aqueous electrolyte. The nonaqueous electrolytic solution according to any one of the above.
（８） 正極活物質を有する正極と、負極活物質を有する負極と、それら正極及び負極の間に介在せしめられて、リチウムイオンを伝導する電解液とを備えたリチウムイオン二次電池において、該電解液として、上記態様（１）乃至（７）の何れか一つに記載の非水電解液が用いられていることを特徴とするリチウムイオン二次電池。 (8) In a lithium ion secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and an electrolytic solution that is interposed between the positive electrode and the negative electrode and conducts lithium ions, A lithium ion secondary battery, wherein the non-aqueous electrolyte according to any one of the above aspects (1) to (7) is used as the electrolyte.
このように、本発明に従う、リチウムイオン二次電池に用いられる非水電解液にあっては、オキサラト錯体をアニオンとするリチウム塩と、前記一般式（Ｉ）で表されるフッ化ケイ素化合物とが含有せしめられていることによって、そのようなリチウムイオン二次電池の充放電の繰り返しにおけるサイクル特性が、より一層向上せしめられ得ると共に、内部抵抗の上昇を効果的に抑制することが出来るのである。また、そのような特性の向上は、更に、ハロゲン原子を有する炭酸エステルが含有せしめられることによって、より一層有利に実現されることとなるのである。 Thus, in the non-aqueous electrolyte used for the lithium ion secondary battery according to the present invention, a lithium salt having an oxalato complex as an anion, and a silicon fluoride compound represented by the general formula (I) In this case, the cycle characteristics in the repeated charge / discharge of such a lithium ion secondary battery can be further improved, and the increase in internal resistance can be effectively suppressed. . Further, such an improvement in characteristics can be realized even more advantageously by containing a carbonic acid ester having a halogen atom.
なお、本発明において、そのような効果が得られる理由については、未だ充分に解明されてはいないが、現在までのところ、以下のように推測されている。即ち、オキサラト錯体をアニオンとするリチウム塩と前記特定のフッ化ケイ素化合物とが、或いはそれら二つの成分とハロゲン原子を有する炭酸エステルとが、負極及び正極で適度に反応して、リチウムイオン透過性に優れる安定な複合被膜を形成し、そして、この複合被膜により、活性の高い電極と非水系電解液との余分な副反応が抑制され、またリチウムイオンの脱挿入に係わる反応抵抗を低下させて、結果として抵抗上昇を抑制し、出力特性を向上させながら、高温保存特性やサイクル特性が改善されることとなるものと、推定されている。 The reason why such an effect can be obtained in the present invention has not yet been fully elucidated, but has been estimated as follows so far. That is, the lithium salt having an oxalate complex as an anion and the specific silicon fluoride compound, or these two components and a carbonic acid ester having a halogen atom react appropriately at the negative electrode and the positive electrode, and the lithium ion permeability This composite coating suppresses excessive side reactions between the highly active electrode and the non-aqueous electrolyte, and reduces the reaction resistance related to lithium ion desorption. As a result, it is estimated that the high-temperature storage characteristics and the cycle characteristics are improved while suppressing the increase in resistance and improving the output characteristics.
ところで、リチウムイオン二次電池に用いられる非水電解液は、一般に、リチウムを含む電解質塩を所定の非水系溶媒に溶解せしめて、調製され得るものであって、そこで用いられる電解質塩としては、よく知られているように、例えばＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3 、ＬｉＳｂＦ6、ＬｉＳｉＦ6、ＬｉＡｌＦ4、ＬｉＳＣＮ、ＬｉＣｌＯ4等の無機塩や有機塩を挙げることが出来る。また、それらリチウム塩の２種以上を組み合わせて、用いることも可能である。なお、この電解質塩は、非水電解液中の濃度において、一般に、０．１ｍｏｌ／Ｌ〜３．０ｍｏｌ／Ｌ程度において、好ましくは０．５ｍｏｌ／Ｌ〜２．０ｍｏｌ／Ｌ程度、更に好ましくは０．８ｍｏｌ／Ｌ〜１．６ｍｏｌ／Ｌ程度において、含有せしめられることとなる。なお、この電解質塩の濃度が低くなり過ぎると、非水電解液のイオン伝導度が低くなり、また、その濃度が高くなり過ぎると、逆に粘度が上昇するようになり、電池性能が低下することとなる。 By the way, the non-aqueous electrolyte used in the lithium ion secondary battery is generally one that can be prepared by dissolving an electrolyte salt containing lithium in a predetermined non-aqueous solvent. As is well known, for example, LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , Inorganic salts and organic salts such as LiSbF 6 , LiSiF 6 , LiAlF 4 , LiSCN, and LiClO 4 can be mentioned. In addition, two or more of these lithium salts can be used in combination. The electrolyte salt generally has a concentration in the non-aqueous electrolyte of about 0.1 mol / L to 3.0 mol / L, preferably about 0.5 mol / L to 2.0 mol / L, more preferably It is contained at about 0.8 mol / L to 1.6 mol / L. If the concentration of the electrolyte salt is too low, the ionic conductivity of the non-aqueous electrolyte is lowered, and if the concentration is too high, the viscosity increases and the battery performance is lowered. It will be.
また、かかるリチウムを含む電解質塩を溶解せしめる非水系溶媒としては、公知の各種の有機溶媒が用いられ得、例えば、カーボネート類、ラクトン類、エーテル類、スルホラン類、ジオキソラン類、イオン液体等を用いることが出来る。具体的には、カーボネート類としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の環状カーボネート類や、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネート、エチル−ｎ−ブチルカーボネート、メチル−ｔ−ブチルカーボネート、ジ−ｉ−プロピルカーボネート、ｔ−ブチル−ｉ−プロピルカーボネート等の鎖状カーボネート類を挙げることが出来、また、ラクトン類としては、γ−ブチルラクトン、γ−バレロラクトン等を、そして、エーテル類としては、テトラヒドロフラン、２−メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテルや、ジメトキシエタン、ジメトキシメタン等の鎖状エーテルを挙げることが出来、また、スルホラン類としては、スルホラン、テトラメチルスルホラン等を、更に、ジオキソラン類としては、１，３−ジオキソラン等を挙げることが出来る。 As the non-aqueous solvent for dissolving the electrolyte salt containing lithium, various known organic solvents can be used, for example, carbonates, lactones, ethers, sulfolanes, dioxolanes, ionic liquids, etc. I can do it. Specifically, as carbonates, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl-n-butyl carbonate, methyl-t-butyl carbonate, di-carbonate, Examples include chain carbonates such as -i-propyl carbonate and t-butyl-i-propyl carbonate, and examples of lactones include γ-butyl lactone and γ-valerolactone, and ethers. Can include cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran, and chain ethers such as dimethoxyethane and dimethoxymethane. Examples of tramethylsulfolane and the like, and examples of dioxolanes include 1,3-dioxolane.
これらの中でも、高誘電率溶媒である環状カーボネート類の少なくとも１種と、低粘度溶媒である鎖状カーボネート類、エーテル類のうちの少なくとも１種との組合せが、有利に用いられることとなる。それは、非水電解液中にＬｉ含有電解質塩を共存させる場合は、かかるＬｉ含有電解質塩の電離を促進させないと、そのイオン伝導度が大きく変わってしまうものであるところ、電解質塩の電離と溶媒の誘電率とは強い関係があり、より電離を促進させるためには、高い誘電率を持った溶媒を用いることが望ましいからである。また、高誘電率溶媒は粘性が高く、そのままでは充分なイオンの移動度を得ることが困難であるため、リチウムイオン電池の電位窓において分解しない低粘度溶媒を、更に混合せしめることで、リチウムイオンが移動し易くなるからである。 Among these, a combination of at least one cyclic carbonate that is a high dielectric constant solvent and at least one chain carbonate or ether that is a low viscosity solvent is advantageously used. That is, when Li-containing electrolyte salt coexists in a non-aqueous electrolyte solution, unless ionization of the Li-containing electrolyte salt is promoted, its ionic conductivity changes greatly. This is because it is desirable to use a solvent having a high dielectric constant in order to further promote ionization. In addition, since the high dielectric constant solvent has a high viscosity and it is difficult to obtain sufficient ion mobility as it is, a low-viscosity solvent that does not decompose in the potential window of the lithium ion battery is further mixed with lithium ions. This is because it becomes easy to move.
そして、本発明にあっては、かくの如きリチウムを含む電解質塩を所定の非水系溶媒に溶解せしめてなる非水電解液に、更に、オキサラト錯体をアニオンとするリチウム塩と、前記一般式（Ｉ）で表されるフッ化ケイ素化合物とを含有せしめるか、或いは、それら２成分と共に、ハロゲン原子を有する炭酸エステルを含有せしめることによって、リチウムイオン二次電池における電池特性をより一層向上せしめ得たのである。 In the present invention, a non-aqueous electrolyte obtained by dissolving an electrolyte salt containing lithium as described above in a predetermined non-aqueous solvent, a lithium salt having an oxalato complex as an anion, and the general formula ( The battery characteristics in the lithium ion secondary battery could be further improved by containing the silicon fluoride compound represented by I) or by containing a carbonate ester having a halogen atom together with these two components. It is.
ここで、本発明において用いられる、上記のオキサラト錯体をアニオンとするリチウム塩は、よく知られているように、中心原子にＣ2Ｏ4 2-が配位したアニオンを有するリチウム塩であって、例えば、リチウムビス（オキサラト）ボレート、リチウムジフルオロオキサラトボレート、リチウムジフルオロビス（オキサラト）ホスフェート、リチウムトリス（オキサラト）ホスフェート等を挙げることが出来るが、特に、本発明にあっては、リチウムビス（オキサラト）ボレート（ＬｉＢＯＢ）が有利に用いられることとなる。また、それらリチウム塩の２種以上を組み合わせて、用いることも可能である。 Here, as is well known, the lithium salt used in the present invention having the above oxalate complex as an anion is a lithium salt having an anion in which C 2 O 4 2− is coordinated to the central atom. Examples thereof include lithium bis (oxalato) borate, lithium difluorooxalatoborate, lithium difluorobis (oxalato) phosphate, lithium tris (oxalato) phosphate, etc. In particular, in the present invention, lithium bis ( Oxalato) borate (LiBOB) will be used advantageously. In addition, two or more of these lithium salts can be used in combination.
このようなオキサラト錯体をアニオンとするリチウム塩は、非水電解液中に、一般に、０．０１重量％以上の割合において含有せしめられ、中でも０．０５重量％以上１０重量％以下であることが好ましく、特に、０．１重量％以上５重量％以下であることが、より一層好ましい。その含有量が０．０１重量％以上であれば、充放電を繰り返した際の電池容量の低下を充分に抑制することが出来ることとなるのであり、更に、１０重量％以下の含有量として、オキサラト錯体をアニオンとするリチウム塩の含有量を抑えることによって、電極に生成する被膜による抵抗の増加を有利に抑制することが出来ることとなる。特に、その含有量を０．１重量％以上５重量％以下とすることにより、上記の効果をより一層大きく得ることが出来るのである。 Such a lithium salt having an oxalato complex as an anion is generally contained in a non-aqueous electrolyte at a ratio of 0.01% by weight or more, and more preferably 0.05% by weight or more and 10% by weight or less. In particular, it is more preferably 0.1% by weight or more and 5% by weight or less. If the content is 0.01% by weight or more, it is possible to sufficiently suppress the decrease in battery capacity when repeated charging and discharging, and further, as a content of 10% by weight or less, By suppressing the content of the lithium salt having an oxalato complex as an anion, an increase in resistance due to the coating film formed on the electrode can be advantageously suppressed. In particular, when the content is 0.1% by weight or more and 5% by weight or less, the above effect can be further enhanced.
また、本発明に従って非水電解液に更に添加含有せしめられる、前記一般式（Ｉ）で表されるフッ化ケイ素化合物は、特に限定されるものではないが、Ｒ1 としては、メチレン、エチレン、トリメチレン、２，２−ジメチルトリメチレン、テトラメチレン、ペンタメチレン、ヘキサメチレン等のアルキレン基、又はこれらの基から誘導されるアルキレンジオキシ基；ビニレン、プロペニレン、イソプロペニレン、ブテニレン、ペンテニレン等のアルケニレン基、又はこれらの基から誘導されるアルケニレンジオキシ基；エチニレン、プロピニレン、ブチニレン、ペンチニレン、１，１，４，４−テトラメチルブチニレン等のアルキニレン基、又はこれらの基から誘導されるアルキニレンジオキシ基；フェニレン、メチルフェニレン、ジメチルフェニレン、ｔ−ブチルフェニレン等のアリーレン基、又はこれらの基から誘導されるアリーレンジオキシ基等が挙げられる。Ｒ2〜Ｒ5としては、各々独立して、メチル、エチル、プロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、２−エチル−ヘキシル、ノニル、デシル等のアルキル基；ビニル、アリル、１−プロペニル、イソプロペニル、２−ブテニル、１，３−ブタジエニル、２−ペンテニル、２−オクテニル、ノネニル、デセニル等のアルケニル基；エチニル、２−プロピニル、１，１−ジメチル−２−プロピニル等のアルキニル基；シクロペンチル、シクロヘキシル、シクロヘプチル等のシクロアルキル基；シクロペンテニル、シクロヘキセニル等のシクロアルケニル基；フェニル、メチルフェニル、ジメチルフェニル、ｔ−ブチルフェニル等のアリール基；又はフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を挙げることが出来る。 Further, the silicon fluoride compound represented by the general formula (I), which is further added to the non-aqueous electrolyte according to the present invention, is not particularly limited, but as R 1 , methylene, ethylene, Alkylene groups such as trimethylene, 2,2-dimethyltrimethylene, tetramethylene, pentamethylene, hexamethylene, or alkylenedioxy groups derived from these groups; alkenylene such as vinylene, propenylene, isopropenylene, butenylene, pentenylene, etc. Or alkenylene dioxy groups derived from these groups; alkynylene groups such as ethynylene, propynylene, butynylene, pentynylene, 1,1,4,4-tetramethylbutynylene, or alkynylenes derived from these groups Rangeoxy group; phenylene, methylphenylene, dimethyl Eniren, arylene groups such as t- butyl phenylene, or arylene dioxy group derived from these groups. R 2 to R 5 are each independently an alkyl group such as methyl, ethyl, propyl, butyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl-hexyl, nonyl, decyl, etc. Alkenyl groups such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, nonenyl, decenyl; ethynyl, 2-propynyl, 1,1-dimethyl- Alkynyl groups such as 2-propynyl; cycloalkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl; aryl groups such as phenyl, methylphenyl, dimethylphenyl and t-butylphenyl; or fluorine Atoms, chlorine atoms, bromine atoms, iodine atoms, etc. It can be mentioned androgenic atom.
さらに、前記した一般式（Ｉ）で表されるフッ化ケイ素化合物として、より具体的には、ビス（ジメチルフルオロシリル）メタン、１，２−ビス（ジメチルフルオロシリル）エタン、１，３−ビス（ジメチルフルオロシリル）プロパン、１，４−ビス（ジメチルフルオロシリル）ブタン、１，４−ビス（ジメチルフルオロシリル）メチルブタン、１，４−ビス（ジメチルフルオロシリル）ベンゼン、１，２−ビス（ジメチルフルオロシリル）エチレン、１，４−ビス（ジメチルフルオロシリル）−２−ブテン、１，２−ビス（ジメチルフルオロシリル）アセチレン、１，４−ビス（ジメチルフルオロシリル）−２−ブチン等を挙げることが出来る。また、それらを、２種以上組み合わせて、用いることも可能である。 Further, as the silicon fluoride compound represented by the general formula (I), more specifically, bis (dimethylfluorosilyl) methane, 1,2-bis (dimethylfluorosilyl) ethane, 1,3-bis (Dimethylfluorosilyl) propane, 1,4-bis (dimethylfluorosilyl) butane, 1,4-bis (dimethylfluorosilyl) methylbutane, 1,4-bis (dimethylfluorosilyl) benzene, 1,2-bis (dimethyl) Fluorosilyl) ethylene, 1,4-bis (dimethylfluorosilyl) -2-butene, 1,2-bis (dimethylfluorosilyl) acetylene, 1,4-bis (dimethylfluorosilyl) -2-butyne I can do it. Moreover, it is also possible to use them combining 2 or more types.
そして、一般式（Ｉ）で表されるフッ化ケイ素化合物は、非水電解液中において、一般に、０．０１重量％以上の割合において含有せしめられ、中でも０．０５重量％以上５重量％以下であることが好ましく、特に、０．１重量％以上２重量％以下であることが、より一層好ましい。その含有量が０．０１重量％以上であれば、充放電を繰り返した際の電池抵抗の増加を充分に抑制することが出来るのであり、また、５重量％以下の含有量として、その含有量を抑えることによって、電極に生成する被膜による抵抗の増加を、有利に抑制することが出来ることとなる。なお、かかる含有量を、０．１重量％以上２重量％以下とすることによって、より一層大きな上記の効果を得ることが出来るのである。 The silicon fluoride compound represented by the general formula (I) is generally contained in a ratio of 0.01% by weight or more in the nonaqueous electrolytic solution, and more preferably 0.05% by weight or more and 5% by weight or less. In particular, it is more preferably 0.1% by weight or more and 2% by weight or less. If the content is 0.01% by weight or more, an increase in battery resistance when charging and discharging is repeated can be sufficiently suppressed, and the content is 5% by weight or less. By suppressing the increase in resistance, an increase in resistance due to the coating formed on the electrode can be advantageously suppressed. In addition, the said effect can be acquired much larger by making this content into 0.1 to 2 weight%.
また、本発明に従って、非水電解液に更に添加含有せしめられる、ハロゲンを有する炭酸エステルとしては、４−フルオロエチレンカーボネート、４−クロロエチレンカーボネート、４−ブロモエチレンカーボネート、４，５−ジフルオロエチレンカーボネート、４−フルオロメチルエチレンカーボネート、４−トリフルオロメチルエチレンカーボネート等を挙げることが出来るが、特に、本発明にあっては、４−フルオロエチレンカーボネート（ＦＥＣ）が、有利に用いられることとなる。また、それらハロゲンを有する炭酸エステルを２種以上組み合わせて、用いることも可能である。 Further, according to the present invention, the halogenated carbonate ester further added to the non-aqueous electrolyte includes 4-fluoroethylene carbonate, 4-chloroethylene carbonate, 4-bromoethylene carbonate, 4,5-difluoroethylene carbonate. , 4-fluoromethylethylene carbonate, 4-trifluoromethylethylene carbonate, and the like can be mentioned. Particularly, in the present invention, 4-fluoroethylene carbonate (FEC) is advantageously used. Moreover, it is also possible to use in combination of two or more of these carbonates having halogen.
そして、このハロゲンを有する炭酸エステルは、非水電解液中において、一般に、０．０１重量％以上の割合において含有せしめられ、中でも０．０５重量％以上１０重量％以下であることが好ましく、特に、０．１重量％以上５重量％以下であることが、より一層好ましい。その含有量が０．０１重量％以上であれば、充放電を繰り返した際の電池抵抗の増加を充分に抑制することが出来るのであり、また、１０重量％以下の含有量として、その含有量を抑えることによって、電極に生成する被膜による抵抗の増加を有利に抑制することが出来ることとなる。なお、かかる含有量を０．１重量％以上５重量％以下とすることによって、より一層大きな上記の効果を得ることが出来るのである。 The halogenated carbonate ester is generally contained in the non-aqueous electrolyte at a ratio of 0.01% by weight or more, and preferably 0.05% by weight or more and 10% by weight or less. More preferably, the content is 0.1% by weight or more and 5% by weight or less. If the content is 0.01% by weight or more, an increase in battery resistance when charging and discharging is repeated can be sufficiently suppressed, and the content is 10% by weight or less. By suppressing this, an increase in resistance due to the coating formed on the electrode can be advantageously suppressed. It should be noted that by making the content 0.1% by weight or more and 5% by weight or less, it is possible to obtain a greater effect as described above.
このように、本発明にあっては、オキサラト錯体をアニオンとするリチウム塩と前記一般式（Ｉ）で表されるフッ化ケイ素化合物、更にはハロゲンを有する炭酸エステルは、それぞれ、上述の如き割合において含有せしめられることとなるのであるが、特に、それら２成分又は３成分は、その合計含有量において、非水電解液中において１０重量％以下となるように調整されることが望ましく、中でも、５重量％以下とすることが、より好ましく、更に３重量％以下とすることが、より一層好ましい。そして、それら三つの成分の含有量と、得られる効果の関係や、コスト面を考慮すると、それら２成分又は３成分の合計含有量を、０．１重量％以上２重量％以下の割合となるように調整することが、より一層好ましいということが出来る。 As described above, in the present invention, the lithium salt having an oxalato complex as an anion, the silicon fluoride compound represented by the general formula (I), and the carbonic acid ester having a halogen are each in the proportions described above. In particular, these two or three components are preferably adjusted so that the total content thereof is 10% by weight or less in the non-aqueous electrolyte. It is more preferably 5% by weight or less, and further more preferably 3% by weight or less. And considering the relationship between the contents of these three components and the effect obtained and the cost, the total content of these two or three components is a ratio of 0.1 wt% or more and 2 wt% or less. It can be said that such adjustment is even more preferable.
なお、本発明に従うリチウムイオン二次電池の非水電解液には、上記した必須の添加成分の他にも、更に必要に応じて、公知の各種の添加成分を、本発明の効果を損なわない範囲で、任意の量で含有させることが出来る。そのような任意の添加成分となる他の化合物としては、具体的には、例えば、
（１）ビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、ｔ−ブチルベンゼン、ｔ−アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物；２−フルオロビフェニル、ｏ−シクロヘキシルフルオロベンゼン、ｐ−シクロヘキシルフルオロベンゼン等の前記芳香族化合物の部分フッ素化物等の過充電防止剤；
（２）ビニレンカーボネート、ビニルエチレンカーボネート等の不飽和結合含有カーボネート；無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸等の酸無水物等の負極被膜形成剤；
（３）亜硫酸エチレン、亜硫酸プロピレン、亜硫酸ジメチル、プロパンスルトン、ブタンスルトン、プロペンスルトン、メタンスルホン酸メチル、ブスルファン、トルエンスルホン酸メチル、硫酸ジメチル、硫酸エチレン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、ジフェニルスルフィド、チオアニソール、ジフェニルジスルフィド、グリコールサルフェートやプロピレングリコールサルフェート等の硫酸エステル類；メタンスルホン酸トリメチルシリル、エタンスルホン酸トリメチルシリル、メタンスルホン酸トリエチルシリル、フルオロメタンスルホン酸トリメチルシリル、フルオロメタンスルホン酸メチル等のスルホン酸エステル類等の正極保護剤；
（４）トリメチルホスフェートやトリエチルホスフェート等のリン酸エステル類；ポリリン酸メラミン塩やポリリン酸アンモニウム塩、ポリリン酸エチレンジアミン塩、ポリリン酸ヘキサメチレンジアミン塩、ポリリン酸ピペラジン塩等のポリリン酸塩類等の難燃化剤；
等が挙げられる。
The non-aqueous electrolyte of the lithium ion secondary battery according to the present invention may contain various known additive components in addition to the above-described essential additive components without impairing the effects of the present invention. It can be contained in any amount within the range. Specific examples of such other compounds that are optional components include, for example,
(1) Aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran; 2-fluorobiphenyl, o-cyclohexylfluoro Overcharge inhibitors such as partially fluorinated compounds of the aromatic compounds such as benzene and p-cyclohexylfluorobenzene;
(2) Unsaturated bond-containing carbonates such as vinylene carbonate and vinyl ethylene carbonate; negative electrode film forming agents such as acid anhydrides such as succinic anhydride, glutaric anhydride, maleic anhydride, and citraconic anhydride;
(3) Ethylene sulfite, propylene sulfite, dimethyl sulfite, propane sultone, butane sultone, propene sultone, methyl methanesulfonate, busulfan, methyl toluenesulfonate, dimethyl sulfate, ethylene sulfate, sulfolane, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl Sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, thioanisole, diphenyl disulfide, sulfate esters such as glycol sulfate and propylene glycol sulfate; Cathode protection of sulfonic acid esters such as methyl methanesulfonate Agent;
(4) Phosphate esters such as trimethyl phosphate and triethyl phosphate; Flame retardants such as polyphosphates such as melamine polyphosphate, ammonium polyphosphate, ethylenediamine diamine phosphate, hexamethylenediamine polyphosphate, piperazine polyphosphate Agent;
Etc.
そして、上記した各種の任意の添加成分の中で、過充電防止剤としては、ビフェニル、ターフェニル（又はその部分水素化体）、シクロヘキシルベンゼン、ｔ−ブチルベンゼンが、好ましく用いられる。それらは、２種類以上組み合わせて用いられても、何等差し支えない。 Of the various optional additives described above, biphenyl, terphenyl (or a partially hydrogenated product thereof), cyclohexylbenzene, and t-butylbenzene are preferably used as the overcharge inhibitor. They may be used in combination of two or more types.
また、負極被膜形成剤としては、上記の中でも、ビニレンカーボネート、ビニルエチレンカーボネート、無水コハク酸、無水マレイン酸が、好ましく用いられる。これらは、２種類以上併用して、用いられてもよい。更に、正極保護剤としては、亜硫酸エチレン、亜硫酸プロピレン、プロパンスルトン、ブタンスルトン、メタンスルホン酸メチルが、好ましく用いられる。これらは、２種類以上併用して、用いられてもよい。そして、負極被膜形成剤と正極保護剤との併用や、過充電防止剤と負極被膜形成剤と正極保護剤との併用が、特に好ましく採用される。 Of the above, vinylene carbonate, vinyl ethylene carbonate, succinic anhydride, and maleic anhydride are preferably used as the negative electrode film forming agent. Two or more of these may be used in combination. Furthermore, as the positive electrode protective agent, ethylene sulfite, propylene sulfite, propane sultone, butane sultone, or methyl methanesulfonate is preferably used. Two or more of these may be used in combination. And combined use with a negative electrode film formation agent and a positive electrode protective agent, and combined use with an overcharge inhibitor, a negative electrode film formation agent, and a positive electrode protective agent are employ | adopted especially preferably.
さらに、非水電解液中における、これら他の化合物の含有割合は、特に限定されるものではないが、非水系電解液全体に対し、それぞれ、０．０１重量％以上１０重量％以下が望ましく、より好ましくは０．１重量％以上５重量％以下、特に好ましくは０．２重量％以上２重量％以下である。これらの化合物を添加することにより、過充電による異常時に電池の破裂・発火を抑制したり、高温保存後の容量維持率やサイクル特性を向上させたりすることが出来る。 Furthermore, the content ratio of these other compounds in the non-aqueous electrolyte solution is not particularly limited, but is preferably 0.01% by weight or more and 10% by weight or less, respectively, with respect to the entire non-aqueous electrolyte solution. More preferably, they are 0.1 weight% or more and 5 weight% or less, Most preferably, they are 0.2 weight% or more and 2 weight% or less. By adding these compounds, it is possible to suppress rupture / ignition of the battery at the time of abnormality due to overcharge, and to improve the capacity retention rate and cycle characteristics after high temperature storage.
ところで、かくの如き本発明に従う非水電解液を用いたリチウムイオン二次電池は、よく知られているように、正極活物質を有する正極と、負極活物質を有する負極と、それら正極及び負極の間に介在せしめられた、本発明に従う非水電解液とを含んでなる構造において、基本的に構成されることとなる。 By the way, as is well known, a lithium ion secondary battery using a non-aqueous electrolyte according to the present invention as described above includes a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and these positive and negative electrodes. In the structure containing the nonaqueous electrolyte solution according to the present invention interposed between the two, it is basically configured.
そこにおいて、正極は、一般に、正極活物質と導電材と結着材とを含んで構成されている。具体的には、それら正極活物質と導電材と結着材とを適当な溶媒にて混合して得られた正極スラリーを用い、それを、適当な塗工装置にて所定の正極集電箔上に塗工することにより、正極シートを形成して、目的とする正極として用いられるのである。 In this regard, the positive electrode is generally configured to include a positive electrode active material, a conductive material, and a binder. Specifically, a positive electrode slurry obtained by mixing the positive electrode active material, the conductive material, and the binder with an appropriate solvent is used, and this is applied to a predetermined positive electrode current collector foil with an appropriate coating device. By coating on top, a positive electrode sheet is formed and used as a target positive electrode.
そして、そのような正極を与える構成成分の一つたる正極活物質は、リチウムイオンを吸蔵・放出可能なリチウム含有遷移金属複合酸化物、リチウム含有遷移金属リン酸化物が挙げられる。リチウム含有遷移金属酸化物としては、例えば、リチウムコバルト系複合酸化物（典型的にはＬｉＣｏＯ2 ）、リチウムニッケル系複合酸化物（典型的にはＬｉＮｉＯ2 ）、リチウムマンガン系複合酸化物（典型的にはＬｉＭｎ2Ｏ4）、リチウムバナジウム系複合酸化物（典型的にはＬｉＶ2Ｏ3）や、更に、遷移金属を２種以上含む複合酸化物等が挙げられる。リチウム含有遷移金属リン酸化物としては、例えば、鉄リン酸化物（典型的にはＬｉＦｅＰＯ4）、コバルトリン酸化物（典型的にはＬｉＣｏＰＯ4）や、遷移金属を２種以上含む複合リン酸化物等が挙げられる。 Examples of the positive electrode active material that is one of the components that provide such a positive electrode include lithium-containing transition metal composite oxides and lithium-containing transition metal phosphorous oxides that can occlude and release lithium ions. Examples of the lithium-containing transition metal oxide include lithium cobalt-based composite oxide (typically LiCoO 2 ), lithium nickel-based composite oxide (typically LiNiO 2 ), lithium manganese-based composite oxide (typical Include LiMn 2 O 4 ), lithium vanadium-based composite oxides (typically LiV 2 O 3 ), and composite oxides containing two or more transition metals. Examples of the lithium-containing transition metal phosphorous oxide include iron phosphorous oxide (typically LiFePO 4 ), cobalt phosphorous oxide (typically LiCoPO 4 ), and composite phosphorous oxide containing two or more transition metals. Etc.
また、導電材は、正極の電気伝導性を確保するためのものであり、一般に、公知の各種の炭素粉末材料が用いられ、例えば、非水電解液との反応がなく且つ良好な体積固有抵抗（１００Ω・ｃｍ未満）を有しているために、アセチレンブラック等のカーボンブラックや炭素繊維等の炭素微粉が用いられることとなる。更に、結着材は、活物質粒子及び導電材粒子を繋ぎ止める役割を果たすものであり、一般に、リチウムイオン二次電池の電位において分解反応がなく且つ非水電解液に対して不溶であるポリマー、例えば、ポリフッ化ビニリデン、ポリエチレンオキサイド、ポリプロピレンオキサイド等が、好適に用いられる。なお、正極活物質、導電材及び結着材を分散させる溶媒としては、例えば、Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、メチルエチルケトン、シクロヘキサノン、酢酸メチル、アクリル酸メチル、ジエチルトリアミン、Ｎ，Ｎ−ジメチルアミノプロピルアミン、エチレンオキシド、テトラヒドロフラン等が用いられ、更に、集電体となる集電箔の材質としては、アルミニウム、ステンレス、ニッケルメッキ鋼等が採用されることとなる。 In addition, the conductive material is for ensuring the electrical conductivity of the positive electrode, and generally, various known carbon powder materials are used. For example, there is no reaction with a non-aqueous electrolyte and a good volume resistivity. Therefore, carbon black such as acetylene black or carbon fine powder such as carbon fiber is used. Furthermore, the binder serves to bind the active material particles and the conductive material particles, and is generally a polymer that has no decomposition reaction at the potential of the lithium ion secondary battery and is insoluble in the non-aqueous electrolyte. For example, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide and the like are preferably used. Examples of the solvent in which the positive electrode active material, the conductive material, and the binder are dispersed include, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N , N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, and the like are used, and aluminum, stainless steel, nickel-plated steel, and the like are employed as the material of the current collector foil that becomes the current collector.
さらに、リチウムイオン二次電池における負極は、一般に、負極活物質と結着材とを含んで構成され、そして、その電気抵抗を下げるために、適宜に導電材が配合されて用いられることとなる。なお、それら負極活物質と結着材と更に必要に応じて配合される導電材には、上記した正極の場合と同様にして、適当な溶媒が加えられて、ペースト状の負極材として、所定の集電体の表面に塗工することにより、負極シートとして用いられるのである。 Furthermore, the negative electrode in the lithium ion secondary battery is generally configured to include a negative electrode active material and a binder, and a conductive material is appropriately mixed and used in order to reduce the electric resistance. . In addition, an appropriate solvent is added to the conductive material blended as necessary with the negative electrode active material and the binder, as in the case of the positive electrode described above, and a predetermined negative paste material is obtained as a paste-like negative electrode material. It is used as a negative electrode sheet by coating on the surface of the current collector.
なお、そのような負極を構成する成分の一つである負極活物質は、電気化学的にリチウムイオンを吸蔵・放出可能なものであれば、特に制限はなく、天然黒鉛や人造炭素物質、コークス等の炭素質材料、酸化錫や酸化ケイ素等の金属酸化物、金属複合酸化物、リチウム単体やリチウムアルミニウム合金等のリチウム合金、ＳｎやＳｉ等のリチウムと合金形成可能な金属等が挙げられる。これらは、１種類を単独で用いても、２種以上を任意の組み合わせ及び比率で併用してもよい。中でも、炭素質材料又はリチウム複合酸化物が安全性の点から好適に用いられることとなる。また、結着材としては、上記した正極の場合と同様に、ポリフッ化ビニリデン、ポリエチレンオキサイド、ポリプロピレンオキサイド等が好適に用いられ、更に導電材としては、非水電解液との反応がなく且つ良好な体積固有抵抗（１００Ω・ｃｍ未満）を有しているところから、アセチレンブラック等のカーボンブラックや、気相成長させた炭素繊維等の微粉体が、有利に用いられることとなる。更に、負極の集電体には、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等の箔を用いることが出来る。 The negative electrode active material, which is one of the components constituting such a negative electrode, is not particularly limited as long as it can electrochemically occlude and release lithium ions. Natural graphite, artificial carbon materials, coke Examples thereof include carbonaceous materials such as tin oxide, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium alloys such as lithium alone and lithium aluminum alloys, and metals that can form alloys with lithium such as Sn and Si. These may be used alone or in combination of two or more in any combination and ratio. Among these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of safety. As the binder, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, and the like are preferably used as in the case of the positive electrode described above, and the conductive material has no reaction with the non-aqueous electrolyte and is good. Therefore, carbon black such as acetylene black and fine powder such as vapor grown carbon fiber are advantageously used because of having a large volume resistivity (less than 100 Ω · cm). Furthermore, foils of copper, nickel, stainless steel, nickel-plated steel, etc. can be used for the negative electrode current collector.
また、本発明に従って構成されるリチウムイオン二次電池においても、従来と同様に、負極と正極との間に、適当なセパレータを配設することが可能である。このセパレータとしては、小型民生機器用リチウムイオン電池で従来から用いられているもので良く、特に限定されるものではない。尤も、正極と負極とを隔てることが可能であり且つ電解液を保持することが出来るものであることが望ましく、そのために、不織布や、ポリエチレン、ポリプロピレン等のポリオレフィン系微多孔膜（フィルム）が、好適に用いられることとなる。 Also in the lithium ion secondary battery constructed according to the present invention, an appropriate separator can be disposed between the negative electrode and the positive electrode, as in the prior art. As this separator, what is conventionally used with the lithium ion battery for small consumer devices may be used, and it is not specifically limited. However, it is desirable that the positive electrode and the negative electrode can be separated and the electrolyte solution can be held. For that purpose, a non-woven fabric, a polyolefin microporous film (film) such as polyethylene, polypropylene, etc. It will be used suitably.
加えて、本発明が適用されるリチウムイオン二次電池の形状としては、特に限定されるものではなく、従来から公知の各種の形状乃至は構造において、本発明が適用され得るものであって、例えば、コイン型、ボタン型、シート型、積層型、円筒型、扁平型、角型等の形状を採用することが可能である。また、電気自動車等の輸送機器に用いる大型のもの等にも、有利に適用することが可能である。 In addition, the shape of the lithium ion secondary battery to which the present invention is applied is not particularly limited, and the present invention can be applied to various conventionally known shapes or structures, For example, a coin shape, a button shape, a sheet shape, a stacked shape, a cylindrical shape, a flat shape, a square shape, or the like can be employed. In addition, the present invention can be advantageously applied to large-sized ones used for transportation equipment such as electric vehicles.
以上、本発明の実施形態について詳述してきたが、それは、あくまでも、例示に過ぎないものであって、本発明は、そのような実施形態に係る具体的な記述によって、何等限定的に解釈されるものではないことが、理解されるべきである。本発明は、当業者の知識に基づいて、種々なる変更、修正、改良等を加えた態様において実施され得るものであり、そしてそのような実施態様が、本発明の趣旨を逸脱しない限りにおいて、何れも、本発明の範疇に属するものであることは、言うまでもないところである。 The embodiment of the present invention has been described in detail above, but it is merely an example, and the present invention is interpreted in a limited manner by a specific description according to such an embodiment. It should be understood that it is not. The present invention can be implemented in variously modified, modified, improved, and other forms based on the knowledge of those skilled in the art, and such embodiments do not depart from the spirit of the present invention. It goes without saying that both belong to the category of the present invention.
以下に、本発明の代表的な実施例を示し、本発明を更に具体的に明らかにすることとするが、本発明が、そのような実施例の記載によって、何等の制約をも受けるものでないことも、また、理解されるべきである。 Hereinafter, representative examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited by the description of such examples. That should also be understood.
−非水電解液の調製−
エチレンカーボネート、ジメチルカーボネート、エチルメチルカーボネート及びジメチルカーボネートを、体積比で、１：１：１：１となるように混合してなる混合溶媒に対して、ＬｉＰＦ6 を、１ｍｏｌ／Ｌの濃度となるように溶解せしめ、更に、オキサラト錯体をアニオンとするリチウム塩として、リチウムビス（オキサラト）ボレート（ＬｉＢＯＢ）を、０．２重量％の割合において配合し、また、一般式（Ｉ）で表されるフッ化ケイ素化合物として、１，２−ビス（ジメチルフルオロシリル）エタンを０．３５重量％の割合となるように配合して、それぞれ溶解・含有せしめ、実験例１に係る非水電解液を調製した。
-Preparation of non-aqueous electrolyte-
LiPF 6 has a concentration of 1 mol / L with respect to a mixed solvent obtained by mixing ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and dimethyl carbonate in a volume ratio of 1: 1: 1: 1. Furthermore, lithium bis (oxalato) borate (LiBOB) is blended in a proportion of 0.2% by weight as a lithium salt having an oxalato complex as an anion, and is represented by the general formula (I) As a silicon fluoride compound, 1,2-bis (dimethylfluorosilyl) ethane was blended at a ratio of 0.35% by weight, dissolved and contained, respectively, to prepare a non-aqueous electrolyte according to Experimental Example 1 did.
また、実験例１における１，２−ビス（ジメチルフルオロシリル）エタンの配合量を、０．１重量％、１．０重量％又は２．０重量％とすること以外は、上記した実験例１の場合と同様にして、実験例２，３又は４に係る非水電解液を調製した。 In addition, Experimental Example 1 described above except that the blending amount of 1,2-bis (dimethylfluorosilyl) ethane in Experimental Example 1 is 0.1% by weight, 1.0% by weight, or 2.0% by weight. In the same manner as in the above, a nonaqueous electrolytic solution according to Experimental Example 2, 3 or 4 was prepared.
さらに、実験例１におけるＬｉＢＯＢの配合量を１．０重量％とすること以外は、上記した実験例１の場合と同様にして、実験例５に係る非水電解液を調製した。 Furthermore, a nonaqueous electrolytic solution according to Experimental Example 5 was prepared in the same manner as in Experimental Example 1 except that the blending amount of LiBOB in Experimental Example 1 was 1.0% by weight.
更にまた、実験例１における１，２−ビス（ジメチルフルオロシリル）エタンに代えて、１，４−ビス（ジメチルフルオロシリル）メチルブタン、１，２−ビス（ジメチルフルオロシリル）エチレン又は１，４−ビス（ジメチルフルオロシリル）ベンゼンを用いたこと以外は、上記した実験例１の場合と同様にして、実験例６，７又は８に係る非水電解液を調製した。 Furthermore, instead of 1,2-bis (dimethylfluorosilyl) ethane in Experimental Example 1, 1,4-bis (dimethylfluorosilyl) methylbutane, 1,2-bis (dimethylfluorosilyl) ethylene, or 1,4- A nonaqueous electrolytic solution according to Experimental Example 6, 7 or 8 was prepared in the same manner as in Experimental Example 1 except that bis (dimethylfluorosilyl) benzene was used.
一方、比較のために、実験例１におけるＬｉＢＯＢ及び１，２−ビス（ジメチルフルオロシリル）エタンを添加含有せしめないこと以外は、実験例１の場合と同様にして、非水電解液を調製し、比較例１に係る非水電解液とした。 On the other hand, for comparison, a nonaqueous electrolytic solution was prepared in the same manner as in Experimental Example 1 except that LiBOB and 1,2-bis (dimethylfluorosilyl) ethane in Experimental Example 1 were not added. The nonaqueous electrolytic solution according to Comparative Example 1 was obtained.
また、実験例１において、１，２−ビス（ジメチルフルオロシリル）エタンのみを添加せしめないこと、又はＬｉＢＯＢのみを添加含有せしめないこと以外は、実験例１の場合と同様にして、非水電解液を調製し、それぞれ、比較例２又は比較例３に係る非水電解液とした。 Further, in Experimental Example 1, non-aqueous electrolysis was carried out in the same manner as in Experimental Example 1, except that only 1,2-bis (dimethylfluorosilyl) ethane was not added or only LiBOB was not added. A liquid was prepared and used as a non-aqueous electrolyte according to Comparative Example 2 or Comparative Example 3, respectively.
さらに、実験例１におけるＬｉＢＯＢの電解液中の含有濃度を０．４重量％とし、１，２−ビス（ジメチルフルオロシリル）エタンは配合しないようにしたこと以外は、実験例１の場合と同様にして、比較例４に係る非水電解液を調製した。 Further, the content concentration of LiBOB in the electrolytic solution in Experimental Example 1 was set to 0.4% by weight, and 1,2-bis (dimethylfluorosilyl) ethane was not blended. Thus, a nonaqueous electrolytic solution according to Comparative Example 4 was prepared.
−リチウムイオン二次電池の作製−
［正極の作製］
正極活物質としてのＬｉＮｉ1/3Ｍｎ1/3Ｃｏ1/3Ｏ2の９０質量％と、導電剤としてのアセチレンブラックの５質量％と、結着材としてのポリフッ化ビニリデン（ＰＶｄＦ）の５質量％とを、Ｎ−メチルピロリドン溶媒中で混合して、スラリー化した。次いで、その得られたスラリーを厚さ２０μｍのアルミ箔の両面に塗布して乾燥し、そしてそれをプレス機で厚さ６４μｍに圧延したものを、活物質層として幅：８０ｍｍ、長さ：１２０ｍｍのサイズを有し且つ幅：１５ｍｍの未塗工部を有する形状に切り出し、正極とした。
-Fabrication of lithium ion secondary battery-
[Production of positive electrode]
90% by mass of LiNi 1/3 Mn 1/3 Co 1/3 O 2 as the positive electrode active material, 5% by mass of acetylene black as the conductive agent, and 5% of polyvinylidene fluoride (PVdF) as the binder % By mass was mixed in N-methylpyrrolidone solvent to make a slurry. Next, the obtained slurry was applied to both sides of an aluminum foil having a thickness of 20 μm, dried, and rolled into a thickness of 64 μm by a press machine, and the active material layer had a width of 80 mm and a length of 120 mm. And was cut out into a shape having an uncoated part with a width of 15 mm.
［負極の作製］
また、負極活物質としてのハードカーボンの９０質量％に、導電材としてのカーボンナノファイバ（昭和電工株式会社製ＶＧＣＦ）の５質量％と、結着材としてのポリフッ化ビニリデン（ＰＶｄＦ）の５質量％とを、Ｎ−メチルピロリドン溶媒中で混合して、スラリー化した。次いで、その得られたスラリーを厚さ１４μｍの銅箔の両面に塗布して乾燥し、そしてそれをプレス機で厚さ１０８μｍに圧延したものを、活物質層として幅：８３ｍｍ、長さ：１２４ｍｍのサイズを有し且つ幅：１３ｍｍの未塗工部を有する形状に切り出し、負極とした。
[Production of negative electrode]
Also, 90% by mass of hard carbon as the negative electrode active material, 5% by mass of carbon nanofiber (VGCF manufactured by Showa Denko KK) as the conductive material, and 5% by mass of polyvinylidene fluoride (PVdF) as the binder. % In an N-methylpyrrolidone solvent and slurried. Subsequently, the obtained slurry was applied to both sides of a copper foil having a thickness of 14 μm, dried, and rolled to a thickness of 108 μm with a press machine, and the active material layer had a width of 83 mm and a length of 124 mm. A negative electrode was cut into a shape having an uncoated part with a size of 13 mm and a width of 13 mm.
［電池の組立］
かくして得られた正極の２０枚と負極の２１枚とが交互となるように配置すると共に、各電極の間に、多孔性ポリプロピレンシートのセパレータ（厚さ２５μｍ）が挟まれるようにして、積層した。この際、正極活物質面が負極活物質面内から外れないよう対面させた。この正極と負極のそれぞれにおける未塗工部同士と金属集電体とを溶接して集電タブを作製し、電極群としたものを、ラミネート状の外装体（外寸：１６０×９０×６ｍｍ）に封入した。その後、かかる電極群を装填した電池に、先に調製した実験例１〜８及び比較例１〜４に係る非水系電解液を、それぞれ、１８ｍＬ注入して、電極に充分に浸透させ、そして密閉することにより、それぞれ、実験例１〜８及び比較例１〜４に係るリチウムイオン二次電池を作製した。この二次電池の１個の電池外装に収納される電池要素の持つ電気容量、即ち、かかる電池の定格放電容量は、約２アンペアーアワー（Ａｈ）であり、１０ｋＨｚ交流法で測定される直流抵抗成分は、約１ミリオーム（ｍΩ）であった。
[Battery assembly]
The 20 positive electrodes and 21 negative electrodes thus obtained were alternately arranged, and a porous polypropylene sheet separator (thickness 25 μm) was sandwiched between the electrodes, and the layers were laminated. . At this time, the positive electrode active material surface was faced so as not to deviate from the negative electrode active material surface. A current collector tab is prepared by welding uncoated portions of each of the positive electrode and the negative electrode to a metal current collector, and an electrode group is formed as a laminated outer package (outside dimension: 160 × 90 × 6 mm). ). Thereafter, 18 mL of each of the non-aqueous electrolytes according to Experimental Examples 1 to 8 and Comparative Examples 1 to 4 prepared above was injected into the battery loaded with such an electrode group, and the electrodes were sufficiently infiltrated and sealed. As a result, lithium ion secondary batteries according to Experimental Examples 1 to 8 and Comparative Examples 1 to 4 were produced. The electric capacity of the battery element housed in one battery exterior of the secondary battery, that is, the rated discharge capacity of the battery is about 2 ampere hours (Ah), and the DC resistance measured by the 10 kHz AC method. The component was about 1 milliohm (mΩ).
《電池の評価》
−容量測定−
上記で作製した実験例１〜８及び比較例１〜４のリチウムイオン二次電池を用いて、２５℃で、電圧範囲：４．２Ｖ〜２．７Ｖ、電流値：０．２Ｃ（１時間率の放電容量による定格容量を１時間で放電する電流値を１Ｃとする、以下同様）にて、６サイクル初期充放電を行なった。そして、この時の６サイクル目の１Ｃ放電容量を、初期容量とした。
<Battery evaluation>
-Capacity measurement-
Using the lithium ion secondary batteries of Experimental Examples 1 to 8 and Comparative Examples 1 to 4 prepared above, at 25 ° C., voltage range: 4.2 V to 2.7 V, current value: 0.2 C (1 hour rate 6 cycles initial charge / discharge was performed at a current value of 1 C for the rated capacity due to the discharge capacity of 1 C, and so on. And the 1C discharge capacity of the 6th cycle at this time was made into the initial stage capacity.
−サイクル試験−
上記で得られた実験例１〜８及び比較例１〜４のリチウムイオン二次電池を用いて、リチウム二次電池の実使用上限温度と目される６５℃の高温環境下にて、サイクル試験を行なった。このサイクル試験は、電池のＳＯＣ（state of charge ：充電率）を６０％まで定電流定電圧で充電した後、下記の充放電モードを３サイクル繰り返し、続いてＳＯＣを７０％まで定電流定電圧で充電した後、下記の充放電モードを３サイクル繰り返し、更に続いてＳＯＣを８０％まで定電流定電圧で充電した後、下記の充放電モードを３サイクル繰り返し、更に続いてＳＯＣ６０％まで定電流定電圧で放電してスタート時のＳＯＣ６０％に合わせる、という合計９サイクルの充放電モードの繰返しを１セットとして、繰り返すこととした。なお、充放電のモードの１サイクルは、放電が１００Ｃで６．７秒、回生は５０Ｃで１〜２秒を６回連続して実施し、そしてそれら放電・回生間の休止時間を５秒とすることにより、構成した。また、充電上限電圧を４．２Ｖ、放電下限電圧を２．７Ｖとし、万が一上下限電圧に達した場合は、当該電圧を保持する様に電流調整を行なった。そして、上記のセットを、４０００セットまで、繰り返した。
-Cycle test-
Using the lithium ion secondary batteries of Experimental Examples 1 to 8 and Comparative Examples 1 to 4 obtained above, a cycle test in a high temperature environment of 65 ° C. that is regarded as an actual use upper limit temperature of the lithium secondary battery Was done. In this cycle test, after charging the battery SOC (state of charge) to 60% at a constant current and constant voltage, the following charge / discharge mode was repeated for 3 cycles, and then the SOC was constant current and constant voltage to 70%. After charging the battery, the following charge / discharge mode is repeated for 3 cycles, and then the SOC is charged at a constant current / constant voltage up to 80%. Then, the following charge / discharge mode is repeated for 3 cycles, followed by a constant current until the SOC reaches 60%. It was decided to repeat the charge / discharge mode for a total of 9 cycles of discharging at a constant voltage and adjusting to SOC 60% at the start as one set. In one cycle of the charge / discharge mode, the discharge is 6.7 seconds at 100C, the regeneration is 6 times continuously at 1-2 seconds at 50C, and the rest time between the discharge and regeneration is 5 seconds. To make up. Moreover, the charge upper limit voltage was set to 4.2 V, the discharge lower limit voltage was set to 2.7 V, and in the event that the upper limit voltage was reached, current adjustment was performed so as to maintain the voltage. The above set was repeated up to 4000 sets.
−初期抵抗測定及びサイクル試験後の抵抗測定−
２５℃の環境下で、ＳＯＣ２０％から８０％まで各１０％毎に充電状態を調整して、各充電状態の下で、１０Ｃ、１５Ｃ、２０Ｃ、２５Ｃで１２秒間放電させ、その１０秒目の電圧を測定した。そして、電流−電圧直線と下限電圧（２．４Ｖ）とで囲まれる３角形の面積を放電出力（Ｗ）、電流−電圧直線と上限電圧（４．２Ｖ）とで囲まれる３角形の面積を回生出力（Ｗ）とした。なお、抵抗に関する比較には、ＳＯＣ５０％における放電出力を用いている。
-Initial resistance measurement and resistance measurement after cycle test-
Under the environment of 25 ° C, the state of charge is adjusted every 10% from SOC 20% to 80%, and discharged under 10C, 15C, 20C, 25C for 12 seconds under each state of charge. The voltage was measured. The area of the triangle surrounded by the current-voltage straight line and the lower limit voltage (2.4V) is the discharge output (W), and the area of the triangle surrounded by the current-voltage straight line and the upper limit voltage (4.2V) is Regenerative output (W). In addition, the discharge output in SOC50% is used for the comparison regarding resistance.
−容量維持率の測定−
上記４０００セットの繰返しからなるサイクル試験終了後の１Ｃ放電容量を、初期の１Ｃ放電容量で除した値を、容量維持率とした。
-Measurement of capacity retention rate-
The value obtained by dividing the 1C discharge capacity after the end of the cycle test consisting of the above 4000 sets by the initial 1C discharge capacity was defined as the capacity retention rate.
−抵抗増加率の測定−
上記４０００セットの繰返しからなるサイクル試験終了後のＳＯＣ５０％における放電出力を、初期のＳＯＣ５０％における放電出力で除した値を、抵抗増加率とした。
-Measurement of resistance increase rate-
The value obtained by dividing the discharge output at 50% SOC after the end of the cycle test consisting of the above 4000 sets by the discharge output at 50% of the initial SOC was defined as the resistance increase rate.
かくして得られた実験例１〜８及び比較例１〜４に係るリチウムイオン二次電池についての放電容量維持率、初期抵抗特性及び電池抵抗増加率に係る測定の結果を、下記表１に示した。 The results of measurement relating to the discharge capacity maintenance rate, initial resistance characteristics, and battery resistance increase rate for the lithium ion secondary batteries according to Experimental Examples 1 to 8 and Comparative Examples 1 to 4 thus obtained are shown in Table 1 below. .
かかる表１の結果から明らかなように、本発明に従って、非水系溶媒にリチウムを含む電解質塩を溶解させてなる非水電解液に対して、更に、オキサラト錯体をアニオンとするリチウム塩と、一般式（Ｉ）で表されるフッ化ケイ素化合物を添加配合せしめてなる非水電解液を用いたリチウムイオン二次電池（実験例１〜８）にあっては、その何れか一つを少なくとも含有していない比較例１〜比較例４に係るリチウムイオン電池に比べて、今回の実施した様な厳しい条件下での使用においても、初期抵抗及びサイクル試験後の容量維持率、抵抗増加率が有利に改善せしめられていることが、認められた。 As is clear from the results in Table 1, in accordance with the present invention, a lithium salt having an oxalato complex as an anion and a non-aqueous electrolyte obtained by dissolving an electrolyte salt containing lithium in a non-aqueous solvent, In the lithium ion secondary battery (Experimental Examples 1 to 8) using the non-aqueous electrolyte obtained by adding and blending the silicon fluoride compound represented by the formula (I), at least one of them is contained. Compared to the lithium ion batteries according to Comparative Examples 1 to 4, the initial resistance, the capacity retention rate after the cycle test, and the resistance increase rate are advantageous even when used under severe conditions such as those implemented this time. It has been confirmed that this has been improved.
また、実験例１において、更に、４−フルオロエチレンカーボネート（ＦＥＣ）を０．１重量％、１．０重量％又は２．０重量％の割合で添加含有せしめて、実験例９，１０又は１１の非水電解液を調製した。また、実験例１０において、１，２−ビス（ジメチルフルオロシリル）エタンに代えて、１，４−ビス（ジメチルフルオロシリル）メチルブタンを用いて、実験例１２に係る非水電解液を調製した。更に、実験例１０において、ＦＥＣに代えて、４−フルオロメチルエチレンカーボネートを用いて、実験例１３に係る非水電解液を調製した。それら非水電解液を用いて、実験例１と同様にしてリチウムイオン二次電池を作製した。 In Experimental Example 1, 4-fluoroethylene carbonate (FEC) was further added and contained at a ratio of 0.1% by weight, 1.0% by weight or 2.0% by weight, and Experimental Example 9, 10 or 11 was added. A non-aqueous electrolyte was prepared. In Experimental Example 10, 1,4-bis (dimethylfluorosilyl) methylbutane was used in place of 1,2-bis (dimethylfluorosilyl) ethane to prepare a nonaqueous electrolytic solution according to Experimental Example 12. Further, in Experimental Example 10, a nonaqueous electrolytic solution according to Experimental Example 13 was prepared using 4-fluoromethylethylene carbonate instead of FEC. Using these non-aqueous electrolytes, lithium ion secondary batteries were produced in the same manner as in Experimental Example 1.
かくして得られた実験例９〜１３に係るリチウムイオン二次電池について、先の実験例１〜８と同様の試験を行ない、初期抵抗、容量維持率、抵抗増加率を求めた。得られた結果を表２に示す。 About the lithium ion secondary battery which concerns on Experimental Examples 9-13 obtained in this way, the test similar to previous Experimental Examples 1-8 was done, and the initial stage resistance, the capacity | capacitance maintenance factor, and the resistance increase rate were calculated | required. The obtained results are shown in Table 2.
かかる表２の結果から分かるように、実験例９〜１３によれば、ハロゲンを含む炭酸エステルを含有していない実験例１よりも容量維持率が向上し、抵抗増加率を抑制する効果が見られた。即ち、本発明に従って、非水系溶媒にリチウムを含む電解質塩を溶解させてなる非水電解液に対して、更に、オキサラト錯体をアニオンとするリチウム塩と、一般式（Ｉ）で表されるフッ化ケイ素化合物と、ハロゲンを含む炭酸エステルとを添加配合せしめるようにすることで、より高い効果が得られることが分かった。 As can be seen from the results of Table 2, according to Experimental Examples 9 to 13, the capacity retention rate is improved and the effect of suppressing the resistance increase rate is seen as compared with Experimental Example 1 that does not contain a carbonate containing halogen. It was. That is, according to the present invention, a non-aqueous electrolyte obtained by dissolving an electrolyte salt containing lithium in a non-aqueous solvent is further mixed with a lithium salt having an oxalato complex as an anion and a fluorine represented by the general formula (I). It has been found that a higher effect can be obtained by adding and compounding a silicon fluoride compound and a carbonate containing halogen.
Claims (6)
In a lithium ion secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and an electrolyte solution that is interposed between the positive electrode and the negative electrode and conducts lithium ions, A lithium ion secondary battery using the nonaqueous electrolytic solution according to any one of claims 1 to 5 .
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| JP5781294B2 (en) * | 2010-11-16 | 2015-09-16 | 株式会社Adeka | Non-aqueous electrolyte secondary battery |
| JP5781293B2 (en) * | 2010-11-16 | 2015-09-16 | 株式会社Adeka | Non-aqueous electrolyte secondary battery |
| JP5915083B2 (en) * | 2011-10-31 | 2016-05-11 | トヨタ自動車株式会社 | Evaluation method of non-aqueous electrolyte secondary battery |
| JP5846040B2 (en) * | 2012-05-14 | 2016-01-20 | 株式会社豊田自動織機 | Electrolytic solution and lithium ion secondary battery including the same |
| JP6120068B2 (en) * | 2013-06-21 | 2017-04-26 | トヨタ自動車株式会社 | Method for producing non-aqueous electrolyte secondary battery |
| JP6120069B2 (en) * | 2013-06-21 | 2017-04-26 | トヨタ自動車株式会社 | Method for producing non-aqueous electrolyte secondary battery |
| JP6365082B2 (en) | 2014-08-01 | 2018-08-01 | セントラル硝子株式会社 | Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery using the same |
| JP6647211B2 (en) * | 2014-11-11 | 2020-02-14 | 株式会社Adeka | Non-aqueous electrolyte secondary battery |
| KR20180089244A (en) | 2017-01-31 | 2018-08-08 | 삼성전자주식회사 | Lithium secondary battery comprising the electrolyte containing monofluorosilane compound |
| CN112216867B (en) * | 2020-09-29 | 2023-02-07 | 中国科学院成都有机化学有限公司 | Electrolyte additive, lithium ion high-voltage electrolyte and lithium ion battery |
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| JP4070793B2 (en) * | 2005-05-30 | 2008-04-02 | 株式会社デンソー | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the electrolyte |
| US8197964B2 (en) * | 2007-07-09 | 2012-06-12 | Sony Corporation | Battery |
| JP5390131B2 (en) * | 2008-06-26 | 2014-01-15 | 株式会社デンソー | Non-aqueous electrolyte secondary battery electrode binder, non-aqueous electrolyte secondary battery electrode and non-aqueous electrolyte secondary battery using the binder |
| JP5230341B2 (en) * | 2008-10-09 | 2013-07-10 | 株式会社デンソー | Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery using the electrolyte |
| JP5270308B2 (en) * | 2008-11-12 | 2013-08-21 | 株式会社Ａｄｅｋａ | Novel polymer and non-aqueous electrolyte secondary battery using the polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109888387A (en) * | 2019-02-01 | 2019-06-14 | 无锡凯帕德瑞科技有限公司 | Capacitor batteries electrolyte and preparation method thereof |
| CN109888387B (en) * | 2019-02-01 | 2021-10-08 | 无锡凯帕德瑞科技有限公司 | Capacitor battery electrolyte and preparation method thereof |
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