JP4301923B2 - Non-aqueous electrolyte secondary battery - Google Patents
Non-aqueous electrolyte secondary battery Download PDFInfo
- Publication number
- JP4301923B2 JP4301923B2 JP2003384965A JP2003384965A JP4301923B2 JP 4301923 B2 JP4301923 B2 JP 4301923B2 JP 2003384965 A JP2003384965 A JP 2003384965A JP 2003384965 A JP2003384965 A JP 2003384965A JP 4301923 B2 JP4301923 B2 JP 4301923B2
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- electrolyte secondary
- group
- aqueous electrolyte
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 62
- -1 oxygen free radical Chemical class 0.000 claims description 60
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- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 7
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- 150000002170 ethers Chemical class 0.000 claims description 5
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- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
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- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、特定の構造を有する構成単位から構成されるピペリジル基含有共重合体を、正極、負極又はセパレータに添加したことを特徴とする非水電解液二次電池に関するものであり、さらに詳しくは、特に窒素原子に酸素原子が結合しているピペリジル基含有共重合体を、正極、負極又はセパレータに添加することにより、過充電や短絡等による発熱及び発火が抑制された、安全性の高い非水電解液二次電池に関するものである。本発明の非水電解液二次電池は、携帯用パソコン、ハンディビデオカメラ等の携帯電子機器、電池自動車、ハイブリッド車等の電源として用いることができる。 The present invention relates to a non-aqueous electrolyte secondary battery in which a piperidyl group-containing copolymer composed of a structural unit having a specific structure is added to a positive electrode, a negative electrode, or a separator. In particular, by adding a piperidyl group-containing copolymer in which an oxygen atom is bonded to a nitrogen atom to a positive electrode, a negative electrode, or a separator, heat generation and ignition due to overcharge, short circuit, etc. are suppressed, and high safety. The present invention relates to a non-aqueous electrolyte secondary battery. The nonaqueous electrolyte secondary battery of the present invention can be used as a power source for portable electronic devices such as portable personal computers and handy video cameras, battery cars, and hybrid cars.
近年の携帯用パソコン、ハンディビデオカメラ等の携帯電子機器の普及に伴い、高電圧、高エネルギー密度を有する非水電解液二次電池が電源として広く用いられるようになった。また、環境問題から電池自動車や電力を動力の一部に利用したハイブリッド車の実用化が行われている。 With the spread of portable electronic devices such as portable personal computers and handy video cameras in recent years, non-aqueous electrolyte secondary batteries having high voltage and high energy density have been widely used as power sources. In addition, due to environmental problems, battery cars and hybrid vehicles using electric power as a part of power have been put into practical use.
しかし、非水電解液二次電池は、高電圧や高エネルギー密度であるために、過充電や短絡等により発熱・発火する問題があり、安全性の向上が望まれている。 However, since the non-aqueous electrolyte secondary battery has a high voltage and high energy density, it has a problem of heat generation and ignition due to overcharge, short circuit, etc., and improvement in safety is desired.
非水電解液二次電池の安全性向上のために種々の添加剤を用いることが提案されている。例えば、特許文献1及び2には、特定の構造を有するヒンダードアミン化合物を用いることが提案されており、特許文献3には、特定の構造を有するフェノール系酸化防止剤、ホスファイト系酸化防止剤又はスルフィド系酸化防止剤を用いることが提案されている。しかし、これらの添加剤は、有機物の安定剤として公知の化合物から選択されたものであり、安定化効果は示すものの、非水電解液に溶出する等して電池性能を低下させるため、満足のいくものではなかった。
It has been proposed to use various additives for improving the safety of non-aqueous electrolyte secondary batteries. For example,
また、特許文献4には、ヒンダードアミン構造を(メタ)アクリル酸エステルに組み込んだポリマー型のヒンダードアミン化合物を、正極、負極又はセパレータに添加することが提案されている。しかし、該ヒンダードアミン化合物は、安全性の向上には効果があるものの、電解液との親和性が高く、電気特性が低下するため実用的ではなかった。 Patent Document 4 proposes that a polymer-type hindered amine compound in which a hindered amine structure is incorporated in a (meth) acrylic ester is added to a positive electrode, a negative electrode, or a separator. However, although the hindered amine compound is effective in improving safety, it has not been practical because it has high affinity with an electrolytic solution and electrical characteristics deteriorate.
本発明の目的は、電池性能を低下させることなく難燃性を向上させた、発熱及び発火の抑制された安全性の高い非水電解液二次電池を提供することにある。 An object of the present invention is to provide a highly safe non-aqueous electrolyte secondary battery in which flame retardancy is improved without deteriorating battery performance and heat generation and ignition are suppressed.
本発明者らは、検討の結果、非水電解液二次電池を製造するに際して、特定の構造を有するピペリジル基含有共重合体を添加した電極材料を用いることで、安全性に優れた非水電解液二次電池が得られることを知見した。 As a result of the study, the inventors of the present invention have made it possible to produce a nonaqueous electrolyte secondary battery by using an electrode material to which a piperidyl group-containing copolymer having a specific structure is added. It has been found that an electrolyte secondary battery can be obtained.
本発明は、上記知見に基づいてなされたものであり、正極、負極、セパレータ及び非水電解液を用いた二次電池において、上記正極、上記負極又は上記セパレータに、下記一般式(1)に示される構成単位及び下記一般式(2)に示される構成単位からなる群から選択される1種以上より構成され平均分子量が1000〜500000であるピペリジル基含有共重合体を添加してなる非水電解液二次電池を提供するものである。 The present invention has been made based on the above knowledge. In a secondary battery using a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, the positive electrode, the negative electrode, or the separator is represented by the following general formula (1). A non-aqueous solution comprising a piperidyl group-containing copolymer composed of one or more selected from the group consisting of the structural unit shown and the structural unit represented by the following general formula (2) and having an average molecular weight of 1000 to 500,000 An electrolyte secondary battery is provided.
本発明によれば、非水電解液二次電池において、正極、負極又はセパレータに特定のピペリジル基含有共重合体を添加することにより、電池性能を低下させることなく、高度の難燃性を有し安全性の高い非水電解液二次電池を提供することができる。 According to the present invention, in a non-aqueous electrolyte secondary battery, by adding a specific piperidyl group-containing copolymer to a positive electrode, a negative electrode, or a separator, it has high flame retardancy without deteriorating battery performance. In addition, a highly safe non-aqueous electrolyte secondary battery can be provided.
以下、上述した要旨をもってなる本発明の非水電解液二次電池について詳述する。 Hereinafter, the non-aqueous electrolyte secondary battery of the present invention having the above-described gist will be described in detail.
上記一般式(1)及び(3)において、R0で表される炭素原子数1〜10のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、ヘキシル、シクロヘキシル、ヘプチル、イソヘプチル、第三ヘプチル、n−オクチル、イソオクチル、第三オクチル、2−エチルヘキシル、ノニル、イソノニル、デシル等が挙げられ、アルコキシ基としてはこれらのアルキル基に対応する基が挙げられる。 In the general formulas (1) and (3), examples of the alkyl group having 1 to 10 carbon atoms represented by R 0 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, Amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, etc. Examples include groups corresponding to alkyl groups.
上記一般式(1)及び(2)において、R1、R2、R4、R6、R7、R8又はR9で表される炭素原子数1〜30のアルキル基としてはメチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、ヘキシル、シクロヘキシル、ヘプチル、イソヘプチル、第三ヘプチル、n−オクチル、イソオクチル、第三オクチル、2−エチルヘキシル、ノニル、イソノニル、デシル、ドデシル(ラウリル)、トリデシル、テトラデシル(ミリスチル)、ペンタデシル、ヘキサデシル(パルミチル)、ペプタデシル、オクタデシル(ステアリル)ノナデシル、エイコシル等が挙げられる。 In the above general formulas (1) and (2), the alkyl group having 1 to 30 carbon atoms represented by R 1 , R 2 , R 4 , R 6 , R 7 , R 8 or R 9 is methyl or ethyl. Propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl , Nonyl, isononyl, decyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl), pentadecyl, hexadecyl (palmityl), peptadecyl, octadecyl (stearyl) nonadecyl, eicosyl and the like.
上記一般式(1)及び(2)において、R1、R2、R4、R6、R7又はR8で表される炭素原子数6〜24のアリール基としては、フェニル、ナフチル、ビフェニル、4−第三ブチルフェニル等が挙げられる。 In the above general formulas (1) and (2), the aryl group having 6 to 24 carbon atoms represented by R 1 , R 2 , R 4 , R 6 , R 7 or R 8 includes phenyl, naphthyl, biphenyl. 4-tert-butylphenyl and the like.
上記一般式(1)及び(2)において、R1、R2、R7又はR8が−COOR’で表される基の場合のR’で表される炭素原子数1〜6のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、ヘキシル、シクロヘキシル等が挙げられる。 In the above general formulas (1) and (2), an alkyl group having 1 to 6 carbon atoms represented by R ′ when R 1 , R 2 , R 7 or R 8 is a group represented by —COOR ′. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl and the like.
上記一般式(1)及び(2)において、R1、R2、R7又はR8で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等が挙げられる。 In the general formulas (1) and (2), examples of the halogen atom represented by R 1 , R 2 , R 7, or R 8 include fluorine, chlorine, bromine, and iodine.
R4及びR6で表される金属としては、リチウム、ナトリウム、カリウム等のアルカリ金属、マグネシウム、カルシウム等のアルカリ土類金属、アルミニウム、亜鉛等が挙げられる。 Examples of the metal represented by R 4 and R 6 include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, aluminum and zinc.
上記一般式(1)に示される構成単位は、無水マレイン酸と、エチレン、プロピレン、ブテン、イソブチレン、ペンテン、メチルペンテン、スチレン、α−メチルスチレン、アクリル酸、(メタ)アクリル酸メチル等の(メタ)アクリル酸エステル等のα−オレフィンとから得られる無水マレイン酸−α−オレフィン共重合体にイミド化を行い、2,2,6,6−テトラメチル−4−アミノピペリジンを反応させて得ることができる。
また、上記一般式(2)に示される構成単位は、上記無水マレイン酸−α−オレフィン共重合体に無水炭酸ナトリウム等を反応させてナトリウム塩としたり、あるいは、上記無水マレイン酸−α−オレフィン共重合体に2,2,6,6−テトラメチル−4−アミノピペリジンを反応させてアミド化した後、一部をアルカリ金属塩にしてアニオン化することにより得ることができる。
また、これらの方法で得られる構成単位から構成されるピペリジル基含有共重合体中のピペリジル基を、過酸化水素等で酸化させてN−オキシルとすることも出来る。また、必要に応じて、ピペリジル基のN−OHとイソシアネート化合物とを反応させて末端をN置換カルバモイルオキシ基にすることも出来る。
The structural unit represented by the general formula (1) includes maleic anhydride, ethylene, propylene, butene, isobutylene, pentene, methylpentene, styrene, α-methylstyrene, acrylic acid, methyl (meth) acrylate, and the like ( It is obtained by imidizing a maleic anhydride-α-olefin copolymer obtained from an α-olefin such as a (meth) acrylate ester and reacting with 2,2,6,6-tetramethyl-4-aminopiperidine. be able to.
The structural unit represented by the general formula (2) is obtained by reacting the maleic anhydride-α-olefin copolymer with anhydrous sodium carbonate or the like to form a sodium salt, or the maleic anhydride-α-olefin. It can be obtained by reacting 2,2,6,6-tetramethyl-4-aminopiperidine with the copolymer to amidate, and then anionizing a part of it with an alkali metal salt.
Further, the piperidyl group in the piperidyl group-containing copolymer composed of the structural units obtained by these methods can be oxidized with hydrogen peroxide or the like to give N-oxyl. If necessary, the N-OH of the piperidyl group can be reacted with an isocyanate compound to make the terminal an N-substituted carbamoyloxy group.
上記一般式(4)で表される基中のRは任意の1価の有機基であるが、上記ピペリジル基のN−OHと上記イソシアネート化合物を反応させたときの上記イソシアネート化合物の残基である。 R in the group represented by the general formula (4) is an arbitrary monovalent organic group, but is a residue of the isocyanate compound when the N-OH of the piperidyl group is reacted with the isocyanate compound. is there.
上記イソシアネート化合物としては、特に制限はされないが、例えば脂肪族(モノ)ジイソシアネート、芳香族(モノ)ジイソシアネート、脂環族(モノ)ジイソシアネート等が挙げられる。 The isocyanate compound is not particularly limited, and examples thereof include aliphatic (mono) diisocyanate, aromatic (mono) diisocyanate, and alicyclic (mono) diisocyanate.
上記脂肪族モノイソシアネートとしては、例えば、メチルスルホニルイソシアネート、イソシアン酸−n−プロピルイソシアネート、ブチルイソシアネート、イソシアン酸ヘキサデシル、オクタデシルイソシアネート等が挙げられる。また、上記脂肪族ジイソシアネートとしては、例えば、メチレンジイソシアネート、ジメチレンジイソシアネート、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ペンタメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ジプロピルエーテルジイソシアネート、2,2−ジメチルペンタンジイソシアネート、3−メトキシヘキサンジイソシアネート、オクタメチレンジイソシアネート、2,2,4−トリメチルペンタンジイソシアネート、ノナメチレンジイソシアネート、デカメチレンジイソシアネート、3−ブトキシヘキサンジイソシアネート、1,4−ブチレングリコールジプロピルエーテルジイソシアネート、チオジヘキシルジイソシアネート、メタキシリレンジイソシアネート、パラキシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of the aliphatic monoisocyanate include methylsulfonyl isocyanate, isocyanic acid-n-propyl isocyanate, butyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and the like. Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, and 3-methoxy. Hexane diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate , Paraxylylene range Isocyanate, tetramethyl xylylene diisocyanate.
上記芳香族モノイソシアネートとしては、例えば、フェニルイソシアネート、トリルイソシアネート、イソシアン酸−3,4−ジクロロフェニル、m−ニトロフェニルイソシアネート、トルエンスルホニルイソシアネート等が挙げられる。また、上記芳香族ジイソシアネートとしては、例えば、メタフェニレンジイソシアネート、パラフェニレンジイソシアネート、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、ジメチルベンゼンジイソシアネート、エチルベンゼンジイソシアネート、イソプロピルベンゼンジイソシアネート、トリジンジイソシアネート、1,4−ナフタレンジイソシアネート、1,5−ナフタレンジイソシアネート、1,5−テトラヒドロナフタレンジイソシアネート、2,6−ナフタレンジイソシアネート、2,7−ナフタレンジイソシアネート等が挙げられる。 Examples of the aromatic monoisocyanate include phenyl isocyanate, tolyl isocyanate, isocyanic acid-3,4-dichlorophenyl, m-nitrophenyl isocyanate, and toluenesulfonyl isocyanate. Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1 , 4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, and the like.
上記脂環族モノイソシアネートとしては、例えばシクロヘキシルイソシアネートが挙げられる。 Examples of the alicyclic monoisocyanate include cyclohexyl isocyanate.
本発明の非水電解液二次電池で使用される上記ピペリジル基含有共重合体の具体例としては、下記化合物No.1〜10が挙げられる。尚、下記化合物No.5において、n’及びn''はそれぞれ1〜1000の数を示す。 Specific examples of the piperidyl group-containing copolymer used in the non-aqueous electrolyte secondary battery of the present invention include the following compound Nos. 1-10 are mentioned. In addition, the following compound No. 5, n ′ and n ″ each represent a number from 1 to 1000.
上記ピペリジル基含有共重合体としては、上記一般式(2)に示される構成単位より構成されているもの、特に、上記一般式(2)において、R4及びR6の一方が上記一般式(3)で表される基であり、上記一般式(3)におけるR0が酸素遊離基であり、R4及びR6の他方がリチウムである構成単位より構成されているものが好ましい。 Examples of the piperidyl group-containing copolymer include those composed of the structural unit represented by the general formula (2). In particular, in the general formula (2), one of R 4 and R 6 is the above general formula ( And a group represented by 3), wherein R 0 in the general formula (3) is an oxygen free radical and the other of R 4 and R 6 is lithium is preferred.
上記ピペリジル基含有共重合体の製造は、特に制限されるものではないが、水中、有機溶媒中又は無溶媒で、従来周知の重合触媒を用いて容易に行うことができ、各構成単位はブロック結合でもランダム結合でもブロック/ランダム結合でもよい。 The production of the above-mentioned piperidyl group-containing copolymer is not particularly limited, but can be easily carried out in water, in an organic solvent or in the absence of a solvent using a conventionally known polymerization catalyst. Bonds, random bonds, or block / random bonds may be used.
また、上記ピペリジル基含有共重合体は、非水電解液への溶解性をより低いものとするために、多価エポキシ化合物、多価イソシアネート化合物及び多価アミン化合物等の架橋剤による架橋構造を有することが好ましい。該架橋剤は、無水マレイン酸構造と直接反応させてもよく、また、無水マレイン酸をマレイン酸にしてから反応させてもよい。該架橋剤の使用量は、上記ピペリジル基含有共重合体100重量部に対して0.01〜5重量部が好ましい。尚、上記化合物No.3は、多価エポキシ化合物による架橋構造を有するピペリジル基含有共重合体の例である。 In addition, the piperidyl group-containing copolymer has a crosslinked structure with a crosslinking agent such as a polyvalent epoxy compound, a polyvalent isocyanate compound and a polyvalent amine compound in order to make the solubility in a non-aqueous electrolyte lower. It is preferable to have. The crosslinking agent may be reacted directly with the maleic anhydride structure, or may be reacted after the maleic anhydride is converted to maleic acid. The amount of the crosslinking agent used is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the piperidyl group-containing copolymer. In addition, said compound No. 3 is an example of a piperidyl group-containing copolymer having a crosslinked structure with a polyvalent epoxy compound.
上記多価エポキシ化合物としては、芳香族エポキシ化合物、脂環族エポキシ化合物、脂肪族エポキシ化合物等が用いられる。
上記芳香族エポキシ化合物としては、例えば、ハイドロキノン、レゾルシノール、ビスフェノールA、ビスフェノールF、4,4’−ジヒドロキシビフェニル、ノボラック、テトラブロモビスフェノールA、2,2−ビス(4−ヒドロキシフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン等の多価フェノールのグリシジルエーテル化合物が挙げられる。上記脂環族エポキシ化合物としては、少なくとも1個以上の脂環族環を有する多価アルコールのポリグリシジルエーテル又はシクロヘキセンやシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られるシクロヘキセンオキサイドやシクロペンテンオキサイド含有化合物が挙げられる。その具体例としては、水素添加ビスフェノールAジグリシジルエーテル、2,2−ビス(3,4−エポキシシクロヘキシル)プロパン、3,4−エポキシシクロヘキシルメチル−3,4−エポキシシクロヘキシルカルボキシレート、3,4−エポキシ−1−メチルシクロヘキシル−3,4−エポキシ−1−メチルヘキサンカルボキシレート、6−メチル−3,4−エポキシシクロヘキシメチル−6−メチル−3,4−エポキシシクロヘキサンカルボキシレート、3,4−エポキシ−3−メチルシクロヘキシルメチル−3,4−エポキシ−3−メチルシクロヘキサンカルボキシレート、3,4−エポキシ−5−メチルシクロヘキシルメチル−3,4−エポキシ−5−メチルシクロヘキサンカルボキシレート、ビス(3,4−エポキシシクロヘキシルメチル)アジペート、メチレンビス(3,4−エポキシシクロヘキサン)、2,2−ビス(3,4−エポキシシクロヘキシル)プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス(3,4−エポキシシクロヘキサンカルボキシレート)、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ−2−エチルへキシル等が挙げられる。上記脂肪族エポキシ化合物としては、脂肪族多価アルコール又はそのアルキレンオキサイド付加物のポリグリシジルエーテル、脂肪族長鎖多塩基酸のポリグリシジルエステル、グリシジルアクリレート又はグリシジルメタクリレートのビニル重合により合成したホモポリマー、グリシジルアクリレート又はグリシジルメタクリレートとその他のビニルモノマーとのビニル重合により合成したコポリマー等が挙げられる。代表的な化合物としては、1,4−ブタンジオールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル等の多価アルコールのグリシジルエーテル、またプロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに1種又は2種以上のアルキレンオキサイドを付加することにより得られるポリエーテルポリオールのポリグリシジルエーテル、脂肪族長鎖二塩基酸のジグリシジルエステルが挙げられる。さらに、脂肪族高級アルコールのモノグリシジルエーテルや、フェノール、クレゾール、ブチルフェノール、また、これらにアルキレンオキサイドを付加することによって得られるポリエーテルアルコールのモノグリシジルエーテル、高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル、エポキシ化ポリブタジエン等が挙げられる。
As the polyvalent epoxy compound, an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, or the like is used.
Examples of the aromatic epoxy compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, novolac, tetrabromobisphenol A, 2,2-bis (4-hydroxyphenyl) -1,1. , 1,3,3,3-hexafluoropropane and the like glycidyl ether compounds of polyhydric phenols. As the alicyclic epoxy compound, cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Containing compounds. Specific examples thereof include hydrogenated bisphenol A diglycidyl ether, 2,2-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4- Epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4- Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4 4-epoxycyclohex Rumethyl) adipate, methylenebis (3,4-epoxycyclohexane), 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxy hexa Examples include dioctyl hydrophthalate and di-2-ethylhexyl epoxyhexahydrophthalate. Examples of the aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, glycidyl Examples thereof include copolymers synthesized by vinyl polymerization of acrylate or glycidyl methacrylate and other vinyl monomers. Typical compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol. One or more of glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether of polyethylene glycol, diglycidyl ether of polyethylene glycol and diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin Polyglycidyl ethers of polyether polyols obtained by adding alkylene oxides of diglycidyl esters of aliphatic long-chain dibasic acids It is. Furthermore, monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butylphenol, polyether alcohol monoglycidyl ether obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acid, epoxidized soybean oil, Examples include octyl epoxy stearate, butyl epoxy stearate, and epoxidized polybutadiene.
上記多価イソシアネート化合物としては、脂肪族、脂環式及び芳香族ポリイソシアネートが挙げられ、具体的には2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、4,4−ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネートエステル、1,4−シクロヘキシレンジイソシアネート、4,4−ジシクロヘキシルメタンジイソシアネート、3,3’−ジメトキシ−4,4’−ビフェニレンジイソシアネート、1,5−ナフタレンジイソシアネート、イソホロンジイソシアネート等が挙げられる。 Examples of the polyvalent isocyanate compound include aliphatic, alicyclic and aromatic polyisocyanates. Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, Phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1,4-cyclohexylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 3,3'-dimethoxy-4, Examples include 4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, and isophorone diisocyanate.
上記多価アミン化合物としては、エチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、フェニレンジアミン、イソホロンジアミン等が挙げられる。 Examples of the polyvalent amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, phenylenediamine, and isophoronediamine.
本発明の非水電解液二次電池に用いられる上記ピペリジル基含有共重合体の分子量は、平均分子量が1000〜500000であり、5000〜500000がより好ましい。平均分子量が1000未満では保留性に劣るという問題がある。また、平均分子量が500000超では粘度が高すぎて作業性に問題がある。なお、平均分子量は、数平均分子量であり、ゲルパーミエーションクロマトグラフィーで標準ポリスチレン換算した分子量を示す。 As for the molecular weight of the piperidyl group-containing copolymer used in the non-aqueous electrolyte secondary battery of the present invention, the average molecular weight is 1000 to 500,000, and 5,000 to 500,000 is more preferable. If the average molecular weight is less than 1000, there is a problem that the retention is poor. On the other hand, if the average molecular weight exceeds 500,000, the viscosity is too high and there is a problem in workability. In addition, an average molecular weight is a number average molecular weight, and shows the molecular weight converted into standard polystyrene by gel permeation chromatography.
本発明の非水電解液二次電池において、上記ピペリジン基含有共重合体は、正極、負極又はセパレータに添加される。上記ピペリジン基含有共重合体の添加量は、正極、負極又はセパレータに用いられる上記ピペリジン基含有共重合体以外の成分の合計重量を基準として、好ましくは0.1重量%〜30重量%、さらに好ましくは1重量%〜20重量%である。上記ピペリジン基含有共重合体の添加量が0.1重量%より少ないと難燃化効果が少ない場合があり、30重量%を超えると非水電解液二次電池の充放電特性が不十分となる場合がある。 In the non-aqueous electrolyte secondary battery of the present invention, the piperidine group-containing copolymer is added to a positive electrode, a negative electrode, or a separator. The added amount of the piperidine group-containing copolymer is preferably 0.1% by weight to 30% by weight, based on the total weight of components other than the piperidine group-containing copolymer used for the positive electrode, the negative electrode or the separator. Preferably, it is 1 to 20% by weight. If the added amount of the piperidine group-containing copolymer is less than 0.1% by weight, the flame retarding effect may be small, and if it exceeds 30% by weight, the charge / discharge characteristics of the nonaqueous electrolyte secondary battery are insufficient. There is a case.
本発明の非水電解液二次電池に用いられる電極材料としては、正極及び負極がある。
上記正極としては、正極活物質と結着剤と導電材とをスラリー化したものを集電体に塗布し、乾燥してシート状にしたものが使用される。該正極活物質としては、リチウムを含有する遷移金属化合物、特に複合酸化物が好ましく、具体的には、LiCoO2 、LiNiO2 、LiMn2 O4 、LiMnO2 、LiV2 O3 等が挙げられる。正極活物質の結着剤としては、例えば、ポリフッ化ビニリデン(PVDF)、EPDM、SBR、NBR、フッ素ゴム等が挙げられるが、これらに制限されるものではない。
Examples of the electrode material used in the nonaqueous electrolyte secondary battery of the present invention include a positive electrode and a negative electrode.
As the positive electrode, a material obtained by applying a slurry of a positive electrode active material, a binder and a conductive material to a current collector and drying it into a sheet is used. The positive electrode active material is preferably a transition metal compound containing lithium, particularly a composite oxide. Specific examples include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , and LiV 2 O 3 . Examples of the binder for the positive electrode active material include, but are not limited to, polyvinylidene fluoride (PVDF), EPDM, SBR, NBR, fluororubber, and the like.
上記正極の導電材としては、黒鉛の微粒子、アセチレンブラック等のカーボンブラック、ニードルコークス等の無定形炭素の微粒子等が使用されるが、これらに制限されるものではない。スラリー化に用いられる溶媒としては、通常は上記結着剤を溶解する有機溶剤が使用され、例えば、N−メチルピロリドン、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挙げられるが、これらに制限されるものではない。また、水に分散剤、増粘剤等を加えてPTFE等で上記正極活物質をスラリー化する場合もある。 Examples of the conductive material for the positive electrode include graphite fine particles, carbon black such as acetylene black, and amorphous carbon fine particles such as needle coke, but are not limited thereto. As a solvent used for slurrying, an organic solvent that dissolves the above binder is usually used. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine , N-N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran and the like, but are not limited thereto. In some cases, the positive electrode active material is slurried with PTFE or the like by adding a dispersant, a thickener or the like to water.
上記負極としては、通常、負極活物質と結着剤とを溶媒でスラリー化したものを集電体に塗布し、乾燥してシート状にしたものが使用される。該負極活物質としては、リチウム又はリチウム合金を用いることもできるが、より安全性の高いリチウムイオンを吸蔵、放出できる炭素材料が好ましい。該炭素材料としては、特に制限されるものではないが、黒鉛、石油系コークス、石炭系コークス、石油系ピッチの炭化物、石炭系ピッチの炭化物、フェノール樹脂・結晶セルロース等樹脂の炭化物等及びこれらを一部炭化した炭素材、ファーネスブラック、アセチレンブラック、ピッチ系炭素繊維、PAN系炭素繊維等が挙げられる。上記結着剤としては、上記正極に用いられる結着剤として例示したものが挙げられる。スラリー化に用いられる上記溶媒としては、通常は上記結着剤を溶解する有機溶剤が使用され、例えば、N−メチルピロリドン、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挙げられるが、これらに制限されるものではない。また、水に分散剤、増粘剤等を加えてSBR等のラテックスで上記負極活物質をスラリー化する場合もある。 As the negative electrode, a negative electrode active material and a binder slurryed with a solvent is applied to a current collector and dried to form a sheet. As the negative electrode active material, lithium or a lithium alloy can be used, but a carbon material that can occlude and release lithium ions with higher safety is preferable. The carbon material is not particularly limited, and graphite, petroleum-based coke, coal-based coke, petroleum-based pitch carbide, coal-based pitch carbide, phenolic resin / crystalline cellulose resin carbide, and the like. Examples thereof include carbon materials partially carbonized, furnace black, acetylene black, pitch-based carbon fibers, and PAN-based carbon fibers. As said binder, what was illustrated as a binder used for the said positive electrode is mentioned. As the solvent used for slurrying, an organic solvent that dissolves the binder is usually used. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl Examples include, but are not limited to, triamine, N, N-dimethylaminopropylamine, ethylene oxide, and tetrahydrofuran. In some cases, the negative electrode active material is slurried with a latex such as SBR by adding a dispersant, a thickener or the like to water.
上記正極の集電体には、通常、アルミニウム、ステンレス鋼、ニッケルメッキ鋼等が使用され、上記負極の集電体には、通常、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等が使用される。 The positive electrode current collector is usually made of aluminum, stainless steel, nickel-plated steel or the like, and the negative electrode current collector is usually made of copper, nickel, stainless steel, nickel-plated steel or the like. .
本発明の非水電解液二次電池に用いられる上記セパレータとしては、非水電解液二次電池に通常用いられる高分子化合物からなる微多孔フィルムを特に制限なく使用することができ、例えば、ポリエチレン、ポリプロピレン、ポリフッ化ビニリデン、ポリ塩化ビニリデン、ポリアクリロニトリル、ポリアクリルアミド、ポリテトラフルオロエチレン、ポリスルホン、ポリエーテルスルホン、ポリカーボネート、ポリアミド、ポリイミド、ポリエチレンオキシドやポリプロピレンオキシド等のポリエーテル類、カルボキシメチルセルロースやヒドロキシプロピルセルロース等の種々のセルロース類、ポリ(メタ)アクリル酸及びその種々のエステル類等を主体とする高分子化合物やその誘導体、これらの共重合体や混合物等からなるフィルムが挙げられる。また、これらのフィルムは、単独で用いてもよいし、複数のフィルムを重ね合わせて複層フィルムとして用いてもよい。さらに、これらのフィルムには種々の添加剤を用いてもよく、その種類や含有量は特に制限されない。これらの微多孔フィルムの中でも、本発明の非水電解液二次電池には、ポリエチレン、ポリプロピレン、ポリフッ化ビニリデン及びポリスルホンからなる群から選択される1種以上からなるフィルムが好ましく用いられる。 As the separator used in the nonaqueous electrolyte secondary battery of the present invention, a microporous film made of a polymer compound usually used in a nonaqueous electrolyte secondary battery can be used without any particular limitation. For example, polyethylene , Polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethers such as polyethylene oxide and polypropylene oxide, carboxymethylcellulose and hydroxypropyl A film composed of various celluloses such as cellulose, polymer compounds mainly composed of poly (meth) acrylic acid and various esters thereof, derivatives thereof, copolymers and mixtures thereof, etc. It is below. In addition, these films may be used alone, or a plurality of films may be overlapped and used as a multilayer film. Furthermore, various additives may be used for these films, and the kind and content thereof are not particularly limited. Among these microporous films, a film made of at least one selected from the group consisting of polyethylene, polypropylene, polyvinylidene fluoride and polysulfone is preferably used for the nonaqueous electrolyte secondary battery of the present invention.
上記セパレータとして用いられるこれらのフィルムは、非水電解液がしみ込んでイオンが透過し易いように、微多孔化がなされている。この微多孔化の方法としては、上記高分子化合物と溶剤との溶液をミクロ相分離させながら製膜し、該溶剤を抽出除去して多孔化する「相分離法」、溶融した上記高分子化合物を高ドラフトで押し出し製膜した後に熱処理し、結晶を一方向に配列させ、さらに延伸によって該結晶間に間隙を形成して多孔化をはかる「延伸法」等が挙げられ、用いられる高分子化合物によって適宜選択される。特に、本発明の非水電解液二次電池に好ましく用いられるポリエチレンやポリフッ化ビニリデンに対しては、相分離法が好ましく用いられる。 These films used as the separator are microporous so that the non-aqueous electrolyte is soaked and ions are easily transmitted. As a method for microporosity, a “phase separation method” in which a film of the polymer compound and a solvent is formed while microphase separation is performed, and the solvent is extracted and removed to make a porous layer. High-draft extrusion film formation, followed by heat treatment, arranging the crystals in one direction, and further forming a gap between the crystals by stretching to form a porous film, etc. Is appropriately selected. In particular, the phase separation method is preferably used for polyethylene and polyvinylidene fluoride that are preferably used in the non-aqueous electrolyte secondary battery of the present invention.
本発明の非水電解液二次電池において、上記非水電解液には有機溶媒が用いられる。高誘電率溶媒としては、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、ビニレンカーボネート等の環状カーボネート、γ−ブチロラクトン、γ−バレロラクトン等の環状エステル、テトラメチルスルホラン、ジメチルスルフォキシド、N−メチルピロリドン、ジメチルフォルムアミドやこれらの誘導体等が挙げられるが、特に制限されるものではない。 In the non-aqueous electrolyte secondary battery of the present invention, an organic solvent is used for the non-aqueous electrolyte. Examples of the high dielectric constant solvent include cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate and vinylene carbonate, cyclic esters such as γ-butyrolactone and γ-valerolactone, tetramethylsulfolane, dimethyl sulfoxide, N-methylpyrrolidone, Examples thereof include dimethylformamide and derivatives thereof, but are not particularly limited.
低粘度溶媒としては、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等の鎖状カーボネート、ジメトキシエタン、エトキシメトキシエタン、ジエトキシエタン等の鎖状エーテル、テトラヒドロフラン、ジオキソラン、ジオキサン等の環状エーテル、蟻酸メチル、蟻酸エチル、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル等の鎖状エステル、アセトニトリル、プロピオニトリル、ニトロメタンやこれらの誘導体が挙げられるが、特に制限されるものではない。 Examples of the low-viscosity solvent include chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate, chain ethers such as dimethoxyethane, ethoxymethoxyethane, and diethoxyethane, cyclic ethers such as tetrahydrofuran, dioxolane, and dioxane, methyl formate, Examples include, but are not particularly limited to, chain esters such as ethyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate, acetonitrile, propionitrile, nitromethane, and derivatives thereof.
本発明の非水電解液二次電池においては、上記非水電解液が、これらの有機溶媒の中でも、カーボネート類、ラクトン類、エーテル類、スルホラン類及びジオキソラン類からなる非水溶媒の群から選択される一種以上を含有することが好ましく、特に、上記環状カーボネートの少なくとも1種及び上記鎖状カーボネートの少なくとも1種を含有することが好ましい。上記環状カーボネート及び上記鎖状カーボネートは、重量比10〜90:90〜10で用いるのが好ましい。また、上記環状カーボネートが、エチレンカーボネート及び1,2−ブチレンカーボネートからなる群から選択される1種以上であり、かつ、上記鎖状カーボネートが、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エチルカーボネートからなる群から選択される1種以上であることが最も好ましい。 In the non-aqueous electrolyte secondary battery of the present invention, the non-aqueous electrolyte is selected from the group of non-aqueous solvents consisting of carbonates, lactones, ethers, sulfolanes and dioxolanes among these organic solvents. It is preferable that at least one of the above cyclic carbonates and at least one of the above chain carbonates are contained. The cyclic carbonate and the chain carbonate are preferably used in a weight ratio of 10 to 90:90 to 10. Further, the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate and 1,2-butylene carbonate, and the chain carbonate is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate. Most preferably, it is at least one selected.
上記非水電解液に用いられる電解質としては、従来公知の電解質を用いることができ、例えば、LiPF6 、LiBF4 、LiAsF6 、LiCF3 SO3 、LiN(CF3 SO2 )2 、LiC(CF3 SO2 )3 、LiSbF6 、LiSiF5 、LiAlF4 、LiSCN、LiClO4 、LiCl、LiF、LiBr、LiAlF4 等が挙げられる。 As the electrolyte used for the non-aqueous electrolyte, a conventionally known electrolyte can be used. For example, LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiSbF 6 , LiSiF 5 , LiAlF 4 , LiSCN, LiClO 4 , LiCl, LiF, LiBr, LiAlF 4 and the like.
また、上記非水電解液に、下記一般式(5)で表される不飽和結合を有するケイ素化合物、下記一般式(6)で表されるケイ素化合物、下記一般式(7)で表される有機錫化合物及び下記一般式(8)で表される有機ゲルマニウム化合物の中から選ばれる少なくとも1種以上を含有させると、低温での出力を向上することができるので好ましい。 In addition, the non-aqueous electrolyte includes a silicon compound having an unsaturated bond represented by the following general formula (5), a silicon compound represented by the following general formula (6), and the following general formula (7). It is preferable to include at least one selected from an organic tin compound and an organic germanium compound represented by the following general formula (8), since the output at low temperature can be improved.
本発明の非水電解液二次電池における上記電極材料及び上記セパレータには、より安全性を向上させる目的で、フェノール系酸化防止剤、リン系酸化防止剤、チオエーテル系酸化防止剤、ヒンダードアミン系光安定剤等を添加してもよい。 In the non-aqueous electrolyte secondary battery of the present invention, the electrode material and the separator have a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, a hindered amine-based light for the purpose of improving safety. A stabilizer or the like may be added.
上記フェノール系酸化防止剤としては、例えば、1,6−ヘキサメチレンビス〔(3−第三ブチル−5−メチル−4−ヒドロキシフェニル)プロピオン酸アミド〕、4,4'−チオビス(6−第三ブチル−m−クレゾール)、4,4'−ブチリデンビス(6−第三ブチル−m−クレゾール)、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−第三ブチルフェニル)ブタン、1,3,5−トリス(2,6−ジメチル−3−ヒドロキシ−4−第三ブチルベンジル)イソシアヌレート、1,3,5−トリス(3,5−ジ第三ブチル−4−ヒドロキシベンジル)イソシアヌレート、1,3,5−トリス(3,5−ジ第三ブチル−4−ヒドロキシベンジル)−2,4,6−トリメチルベンゼン、テトラキス〔3−(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオン酸メチル〕メタン、チオジエチレングリコールビス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオネート〕、1,6−ヘキサメチレンビス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオネート〕、ビス〔3,3−ビス(4−ヒドロキシ−3−第三ブチルフェニル)ブチリックアシッド〕グリコールエステル、ビス〔2−第三ブチル−4−メチル−6−(2−ヒドロキシ−3−第三ブチル−5−メチルベンジル)フェニル〕テレフタレート、1,3,5−トリス〔(3,5−ジ第三ブチル−4−ヒドロキシフェニル)プロピオニルオキシエチル〕イソシアヌレート、3,9−ビス〔1,1−ジメチル−2−{(3−第三ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ}エチル〕−2,4,8,10−テトラオキサスピロ〔5,5〕ウンデカン、トリエチレングリコールビス〔(3−第三ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート〕等が挙げられ、上記電極材料又は上記セパレータ100重量部に対して、好ましくは0.01〜10重量部、より好ましくは、0.05〜5重量部が用いられる。 Examples of the phenol-based antioxidant include 1,6-hexamethylene bis [(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert. Tributyl-m-cresol), 4,4′-butylidenebis (6-tert-butyl-m-cresol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) ) Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [3- (3,5-ditert-butyl- 4-hi Roxyphenyl) methyl propionate] methane, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4 -Hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2- Hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9 -Bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propioni Ruoxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. Preferably, 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight is used with respect to 100 parts by weight of the electrode material or the separator.
上記リン系酸化防止剤としては、例えば、トリスノニルフェニルホスファイト、トリス〔2−第三ブチル−4−(3−第三ブチル−4−ヒドロキシ−5−メチルフェニルチオ)−5−メチルフェニル〕ホスファイト、トリデシルホスファイト、オクチルジフェニルホスファイト、ジ(デシル)モノフェニルホスファイト、ジ(トリデシル)ペンタエリスリトールジホスファイト、ジ(ノニルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4−ジ第三ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6−ジ第三ブチル−4−メチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4,6−トリ第三ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,4−ジクミルフェニル)ペンタエリスリトールジホスファイト、テトラ(トリデシル)イソプロピリデンジフェノールジホスファイト、テトラ(トリデシル)−4,4'−n−ブチリデンビス(2−第三ブチル−5−メチルフェノール)ジホスファイト、ヘキサ(トリデシル)−1,1,3−トリス(2−メチル−4−ヒドロキシ−5−第三ブチルフェニル)ブタントリホスファイト、テトラキス(2,4−ジ第三ブチルフェニル)ビフェニレンジホスホナイト、9,10−ジハイドロ−9−オキサ−10−ホスファフェナンスレン−10−オキサイド、2,2'−メチレンビス(4,6−第三ブチルフェニル)−2−エチルヘキシルホスファイト、2,2'−メチレンビス(4,6−第三ブチルフェニル)−オクタデシルホスファイト、2,2'−エチリデンビス(4,6−ジ第三ブチルフェニル)フルオロホスファイト、トリス(2−〔(2,4,8,10−テトラキス第三ブチルジベンゾ〔d,f〕〔1,3,2〕ジオキサホスフェピン−6−イル)オキシ〕エチル)アミン、2−エチル−2−ブチルプロピレングリコールと2,4,6−トリ第三ブチルフェノールのホスファイト等が挙げられる。 Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6- Tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) Oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like.
上記チオエーテル系酸化防止剤としては、例えば、チオジプロピオン酸ジラウリル、チオジプロピオン酸ジミリスチル、チオジプロピオン酸ジステアリル等のジアルキルチオジプロピオネート類及びペンタエリスリトールテトラ(β−アルキルメルカプトプロピオン酸エステル類が挙げられる。 Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate esters). Is mentioned.
上記ヒンダードアミン系光安定剤としては、例えば、2,2,6,6−テトラメチル−4−ピペリジルステアレート、1,2,2,6,6−ペンタメチル−4−ピペリジルステアレート、2,2,6,6−テトラメチル−4−ピペリジルベンゾエート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)セバケート、テトラキス(2,2,6,6−テトラメチル−4−ピペリジル)−1,2,3,4−ブタンテトラカルボキシレート、テトラキス(1,2,2,6,6−ペンタメチル−4−ピペリジル)−1,2,3,4−ブタンテトラカルボキシレート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)・ジ(トリデシル)−1,2,3,4−ブタンテトラカルボキシレート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)・ジ(トリデシル)−1,2,3,4−ブタンテトラカルボキシレート、ビス(1,2,2,4,4−ペンタメチル−4−ピペリジル)−2−ブチル−2−(3,5−ジ第三ブチル−4−ヒドロキシベンジル)マロネート、1−(2−ヒドロキシエチル)−2,2,6,6−テトラメチル−4−ピペリジノ−ル/コハク酸ジエチル重縮合物、1,6−ビス(2,2,6,6−テトラメチル−4−ピペリジルアミノ)ヘキサン/2,4−ジクロロ−6−モルホリノ−s−トリアジン重縮合物、1,6−ビス(2,2,6,6−テトラメチル−4−ピペリジルアミノ)ヘキサン/2,4−ジクロロ−6−第三オクチルアミノ−s−トリアジン重縮合物、1,5,8,12−テトラキス〔2,4−ビス(N−ブチル−N−(2,2,6,6−テトラメチル−4−ピペリジル)アミノ)−s−トリアジン−6−イル〕−1,5,8,12−テトラアザドデカン、1,5,8,12−テトラキス〔2,4−ビス(N−ブチル−N−(1,2,2,6,6−ペンタメチル−4−ピペリジル)アミノ)−s−トリアジン−6−イル〕−1,5,8−12−テトラアザドデカン、1,6,11−トリス〔2,4−ビス(N−ブチル−N−(2,2,6,6−テトラメチル−4−ピペリジル)アミノ)−s−トリアジン−6−イル〕アミノウンデカン、1,6,11−トリス〔2,4−ビス(N−ブチル−N−(1,2,2,6,6−ペンタメチル−4−ピペリジル)アミノ)−s−トリアジン−6−イル〕アミノウンデカン等のヒンダードアミン化合物が挙げられる。 Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4 Piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6- Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6 -Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl) -N- (2,2, , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane Compounds.
以下、本発明を合成例、実施例及び比較例によって具体的に説明するが、本発明は以下の実施例により制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely with a synthesis example, an Example, and a comparative example, this invention is not restrict | limited by a following example.
〔合成例1〕化合物No.1の合成
攪拌装置、温度計、窒素導入管及びジムロート冷却管を付けた四つ口1000mlフラスコに、無水マレイン酸−イソブチレン共重合物((株)クラレ製;イソバン10;重量平均分子量165,000)462.5g(カルボン酸無水物として0.3モル)、及びN,N−ジメチルアセトアミドを433g仕込み攪拌、溶解した。次に、この溶液に110〜120℃で2,2,6,6−テトラメチル−4−ピペリジルアミン45.5g(0.29モル)をゆっくり滴下した。滴下終了後、徐々に温度を上げ150〜155℃にて11時間反応させ、イミド化を完了した。反応後、反応系をメタノール300mlで希釈し、アセトン4200mlへ滴下して再沈精製を行った。析出物を濾過、洗浄した後、減圧乾燥して薄黄色固体78.6g(収率91%、重量平均分子量310,000)を得た。得られた薄黄色固体は、IRによる分析により、目的とする中間体であるイミド体であることを確認した。IR分析結果を以下に示す。
<IR分析結果>
3442cm-1(N−H)、1698cm-1(イミド)、1778cm-1(酸無水物)
[Synthesis Example 1] Compound No. 1 Synthesis of 1 Maleic anhydride-isobutylene copolymer (manufactured by Kuraray Co., Ltd .;
<IR analysis results>
3442 cm −1 (N—H), 1698 cm −1 (imide), 1778 cm −1 (acid anhydride)
得られた薄黄色固体78.6g、水197g及びエタノール393gを仕込み加温溶解した。この溶液に40℃で炭酸ナトリウム2.89g(0.027モル)を添加しナトリウム塩とした。次に、12−ケイタングステン酸0.2g及び過酸化水素安定剤(三菱モンサント化成製デイクエスト2046)0.4gを加えて加温した後、55〜60℃で30%過酸化水素水92.7g(0.82モル)を徐々に滴下した。70〜75℃にて7時間反応させ、酸化反応を終了した。反応液をエバポレータにて濃縮して濃縮物とし、濃縮物中の析出物の一部を水洗し濾過して橙色固体(重量平均分子量326,000)を得た。得られた橙色固体は、IR分析により目的物(化合物No.1)であることを確認した。IR分析結果を以下に示す。
<IR分析結果>
1700cm-1(イミド)
78.6 g of the obtained pale yellow solid, 197 g of water and 393 g of ethanol were charged and dissolved by heating. To this solution, 2.89 g (0.027 mol) of sodium carbonate was added at 40 ° C. to obtain a sodium salt. Next, 0.2 g of 12-silicotungstic acid and 0.4 g of hydrogen peroxide stabilizer (Daiquest 2046 manufactured by Mitsubishi Monsanto Kasei) were added and heated, and then 30% hydrogen peroxide solution 92. 7 g (0.82 mol) was gradually added dropwise. The reaction was carried out at 70 to 75 ° C. for 7 hours to complete the oxidation reaction. The reaction solution was concentrated with an evaporator to obtain a concentrate, and a part of the precipitate in the concentrate was washed with water and filtered to obtain an orange solid (weight average molecular weight 326,000). The obtained orange solid was confirmed to be the target product (Compound No. 1) by IR analysis. The IR analysis results are shown below.
<IR analysis results>
1700cm -1 (imide)
〔合成例2〕化合物No.2の合成
合成例1と同様にして得た酸化反応終了後の反応液の濃縮物に、85%リン酸6.5gを水500mlに溶解した溶液を加えた後、テトラヒドロフラン50ml及び飽和食塩水50mlを順に加えて析出物を得た。得られた析出物を濾過、洗浄し減圧乾燥して橙色固体62.0g(収率75%、重量平均分子量325,000)を得た。得られた橙色固体は、IR分析により目的物(化合物No.2)であることを確認した。IR分析結果を以下に示す。また、ESR測定により、得られた化合物No.2の各単位構造に含まれるN−O・化率は61.8%と算出された。
<IR分析結果>
3448cm-1(O−H)、1700cm-1(イミド)
[Synthesis Example 2] Compound No. 2 Synthesis of 2 To the concentrate of the reaction solution obtained in the same manner as in Synthesis Example 1 after completion of the oxidation reaction, a solution obtained by dissolving 6.5 g of 85% phosphoric acid in 500 ml of water was added, followed by 50 ml of tetrahydrofuran and 50 ml of saturated saline. Were added in order to obtain a precipitate. The resulting precipitate was filtered, washed and dried under reduced pressure to obtain 62.0 g of orange solid (yield 75%, weight average molecular weight 325,000). The obtained orange solid was confirmed to be the target product (Compound No. 2) by IR analysis. The IR analysis results are shown below. In addition, the obtained compound No. The NO conversion ratio contained in each unit structure of 2 was calculated to be 61.8%.
<IR analysis results>
3448 cm -1 (OH), 1700 cm -1 (imide)
〔合成例3〕化合物No.3の合成
合成例2で得られた化合物No.2を25.0g、トリエチルアミンを0.17g、及びN,N−ジメチルアセトアミドを270g仕込み加熱攪拌した。ここへ、80℃でエポキシ樹脂(EHPE−3150:ダイセル化学工業(株)製) 2.2gとN,N−ジメチルアセトアミド2.2gとの混合液を仕込み、124〜127℃で50分間反応させた。反応物をメタノール1200g中に投入し、析出物を濾過、メタノール洗浄して固体を得た(20.2g、収率74%)。得られた固体は、IR分析により目的物(化合物No.3)であることを確認した。IR分析結果を以下に示す。また、ESR測定により、得られた化合物No.3の各単位構造に含まれるN−O・化率は54.3%と算出された。
<IR分析結果>
3448cm-1(O−H)、1698cm-1(イミド)
[Synthesis Example 3] Compound No. Synthesis of Compound No. 3 obtained in Synthesis Example 2 2 (25.0 g), triethylamine (0.17 g), and N, N-dimethylacetamide (270 g) were charged and stirred with heating. Here, a mixed liquid of 2.2 g of epoxy resin (EHPE-3150: manufactured by Daicel Chemical Industries, Ltd.) and 2.2 g of N, N-dimethylacetamide was charged at 80 ° C., and reacted at 124 to 127 ° C. for 50 minutes. It was. The reaction product was put into 1200 g of methanol, and the precipitate was filtered and washed with methanol to obtain a solid (20.2 g, yield 74%). The obtained solid was confirmed to be the target product (Compound No. 3) by IR analysis. The IR analysis results are shown below. In addition, the obtained compound No. The NO conversion ratio contained in each unit structure of 3 was calculated to be 54.3%.
<IR analysis results>
3448 cm -1 (OH), 1698 cm -1 (imide)
〔合成例4〕化合物No.4の合成
攪拌装置、温度計、窒素導入管及びジムロート冷却管を付けた四つ口500mlフラスコに、無水マレイン酸−イソブチレン共重合物((株)クラレ製;イソバン04;重量平均分子量60,000)を27.8g(カルボン酸無水物として0.18モル)、メタノール21.7g及び水162.3gを仕込み攪拌した後、室温で2,2,6,6−テトラメチル−4−ピペリジルアミン29.0g(0.18モル)を滴下した。滴下後80〜85℃まで加熱し2時間反応させた。40℃以下まで冷却した後、水酸化リチウム一水和物6.4gを仕込み1時間攪拌した。この溶液にケイタングステン酸0.14g及びデイクエスト2046(三菱モンサント化成(株)製)0.3gを加えた後、55℃に加熱した。そこに30%過酸化水素水51.0g(0.45モル)を55〜60℃の温度に保ちながら約1時間で滴下した後、1時間該温度で攪拌した。反応後、反応系を2800mlのアセトン溶媒中に滴下し、沈殿した結晶をろ別した後、アセトンで洗浄し乾燥して結晶を得た(収量50.6g、収率85%、重量平均分子量130,000)。得られた結晶は、IR分析により目的物(化合物No.4)であることを確認した。IR分析結果を以下に示す。
<IR分析結果>
3450cm-1(N−H)、1635cm-1、1560cm-1(アミド+カルボキシレート)
[Synthesis Example 4] Compound No. 4 Synthesis of 4 A four-necked 500 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a Dimroth condenser tube was charged with a maleic anhydride-isobutylene copolymer (manufactured by Kuraray Co., Ltd .; Isoban 04; 27.8 g (0.18 mol as carboxylic anhydride), 21.7 g of methanol and 162.3 g of water were stirred and stirred, and then 2,2,6,6-tetramethyl-4-piperidylamine 29 at room temperature. 0.0 g (0.18 mol) was added dropwise. After dropping, the mixture was heated to 80 to 85 ° C. and reacted for 2 hours. After cooling to 40 ° C. or lower, 6.4 g of lithium hydroxide monohydrate was added and stirred for 1 hour. To this solution, 0.14 g of silicotungstic acid and 0.3 g of Dequest 2046 (Mitsubishi Monsanto Kasei Co., Ltd.) were added and then heated to 55 ° C. Thereto, 51.0 g (0.45 mol) of 30% aqueous hydrogen peroxide was added dropwise in about 1 hour while maintaining the temperature at 55 to 60 ° C., and the mixture was stirred at that temperature for 1 hour. After the reaction, the reaction system was dropped into 2800 ml of acetone solvent, and the precipitated crystals were filtered off, washed with acetone and dried to obtain crystals (yield 50.6 g, yield 85%, weight average molecular weight 130). , 000). The obtained crystals were confirmed to be the desired product (Compound No. 4) by IR analysis. The IR analysis results are shown below.
<IR analysis results>
3450 cm −1 (N—H), 1635 cm −1 , 1560 cm −1 (amide + carboxylate)
〔合成例5〕化合物No.5の合成
2,2,6,6−テトラメチル−4−ピペリジルアミンの使用量を23.9g(0.15モル)とし、水酸化リチウム一水和物の使用量を8.8gとした以外は、上記合成例4と同様の操作法により結晶を得た(収量45.7g、収率82%、重量平均分子量120,000)。得られた結晶は、IR分析により目的物(化合物No.5)であることを確認した。IR分析結果を以下に示す。
<IR分析結果>
3448cm-1(N−H)、1633cm-1、1560cm-1(アミド+カルボキシレート)
[Synthesis Example 5] Compound No. Synthesis of 5 Except that the amount of 2,2,6,6-tetramethyl-4-piperidylamine used was 23.9 g (0.15 mol) and the amount of lithium hydroxide monohydrate used was 8.8 g Produced crystals by the same procedure as in Synthesis Example 4 (yield 45.7 g, yield 82%, weight average molecular weight 120,000). The obtained crystal was confirmed to be the target product (Compound No. 5) by IR analysis. The IR analysis results are shown below.
<IR analysis results>
3448 cm −1 (N—H), 1633 cm −1 , 1560 cm −1 (amide + carboxylate)
〔実施例1−1〜1−4〕
1.正極の作製
正極活物質としてLiNiO280質量部、導電剤としてアセチレンブラック10質量部、結着剤としてPVDF10質量部、及び試料化合物として合成例1〜4でそれぞれ得られた化合物No.1〜4(表1参照)5質量部の混合物に、N−メチルピロリドンを溶媒として加えてスラリーを調製した。該スラリーを15μm集電体のアルミニウム箔の両面に塗布し、乾燥プレス後、幅55mm、長さ800mmにスリットした後、120℃の真空乾燥を行ない、正極を作製した。
[Examples 1-1 to 1-4]
1. Production of Positive Electrode 80 parts by mass of LiNiO 2 as a positive electrode active material, 10 parts by mass of acetylene black as a conductive agent, 10 parts by mass of PVDF as a binder, and Compound Nos. Obtained in Synthesis Examples 1 to 4 as sample compounds, respectively. A slurry was prepared by adding N-methylpyrrolidone as a solvent to a mixture of 1 to 4 (see Table 1) 5 parts by mass. The slurry was applied to both surfaces of an aluminum foil of a 15 μm current collector, dried and pressed, slit to a width of 55 mm and a length of 800 mm, and then vacuum dried at 120 ° C. to produce a positive electrode.
2.負極の作製
カーボン95質量部及び結着剤5質量部の混合物に、N−メチルピロピドンを溶媒として加えてスラリーを調製した。該スラリーを10μm集電体の銅箔に両面に塗布し、乾燥プレス後、幅60mm、長さ900mmにスリットした後、120℃の真空乾燥を行ない、負極を作製した。
2. Production of Negative Electrode A slurry was prepared by adding N-methylpyrrolidone as a solvent to a mixture of 95 parts by mass of carbon and 5 parts by mass of a binder. The slurry was applied to both sides of a 10 μm current collector copper foil, dried and pressed, slit into a width of 60 mm and a length of 900 mm, and then vacuum dried at 120 ° C. to prepare a negative electrode.
3.非水電解液の調製
エチレンカーボネートとジエチルカーボネートとの体積比1:1の混合溶媒に、LiPF6 を1モル/リットル溶かして非水電解液を調製した。
3. Preparation of Nonaqueous Electrolytic Solution A nonaqueous electrolytic solution was prepared by dissolving 1 mol / liter of LiPF 6 in a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1.
4.非水電解液二次電池の作製
上記正極と上記負極との間に、微孔を有するポリエチレンフィルムからなるセパレータを介在させて、スパイラル状に巻回して極群を形成した。この極群をケースに収納した後、上記非水電解液を注入し、蓋をして密閉し、直径18mm、長さ650mmサイズの非水電解液二次電池を作製した。作製した非水電解液二次電池(円筒型のリチウム二次電池)の内部構造を示す斜視図を図1に、該リチウム二次電池の基本構成を図2に、それぞれ示す。
4). Production of Nonaqueous Electrolyte Secondary Battery A separator made of a polyethylene film having micropores was interposed between the positive electrode and the negative electrode, and was wound spirally to form a pole group. The electrode group was housed in a case, and then the nonaqueous electrolyte solution was injected, covered and sealed, and a nonaqueous electrolyte secondary battery having a diameter of 18 mm and a length of 650 mm was produced. FIG. 1 is a perspective view showing the internal structure of the produced nonaqueous electrolyte secondary battery (cylindrical lithium secondary battery), and FIG. 2 shows the basic configuration of the lithium secondary battery.
(過充電試験)
得られた非水電解液二次電池について、4.1Vまで定電流−定電圧充電を行ない満充電状態とした後、定電流で連続的に電流を流し続けて発煙に至らない場合の最大電流値(許容過充電電流値)を測定した。結果を表1に示す。
(Overcharge test)
About the obtained non-aqueous electrolyte secondary battery, the constant current-constant voltage charge up to 4.1 V is performed to make it fully charged, and then the maximum current when no current is generated due to continuous constant current flow. The value (allowable overcharge current value) was measured. The results are shown in Table 1.
(過充電による発熱量の測定)
上記の方法にて作製した正極及び負極を円形に打ち抜き、これらに、微孔を有するポリエチレンフィルムからなるセパレータを介在させ挟み込むことにより、簡易的なセルを作製した。このセルを4.5Vまで定電流−定電圧充電を行ない満充電状態とした後、集電箔から正極及び負極を剥がし取り、これに一定量のセパレータと電解液を加え、室温〜300℃での発熱量を測定した。結果を表1に示す。尚、表1に示す結果は、下記比較例1における測定値を100とした相対値である。
(Measurement of heat generation due to overcharge)
A simple cell was produced by punching out the positive electrode and negative electrode produced by the above method in a circle and interposing a separator made of a polyethylene film having micropores therebetween. The cell was charged at a constant current-constant voltage up to 4.5 V to be in a fully charged state, and then the positive electrode and the negative electrode were peeled off from the current collector foil, and a certain amount of separator and electrolyte were added thereto. The calorific value of was measured. The results are shown in Table 1. The results shown in Table 1 are relative values with the measured value in Comparative Example 1 below as 100.
〔実施例2−1〜2−2〕
正極に試料化合物を添加せず、負極に試料化合物(表1参照)を添加した以外は、実施例1と同様に、非水電解液二次電池を作製し、過充電試験及び過充電による発熱量の測定を行なった。結果を表1に示す。
[Examples 2-1 to 2-2]
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the sample compound was not added to the positive electrode and the sample compound (see Table 1) was added to the negative electrode. The quantity was measured. The results are shown in Table 1.
〔実施例3−1〜3−2〕
正極に試料化合物を添加せず、試料化合物(表1参照)を添加したポリエチレンフィルムをセパレータとして用いた以外は、実施例1と同様に、非水電解液二次電池を作製し、過充電試験及び過充電による発熱量の測定を行なった。結果を表1に示す。
[Examples 3-1 to 3-2]
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the sample film was not added to the positive electrode and a polyethylene film to which the sample compound (see Table 1) was added was used as a separator. In addition, the amount of heat generated by overcharging was measured. The results are shown in Table 1.
〔比較例1〕
正極に試料化合物を添加しなかった以外は、実施例1と同様に、非水電解液二次電池を作製し、過充電試験及び過充電による発熱量の測定を行なった。結果を表1に示す。
[Comparative Example 1]
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that no sample compound was added to the positive electrode, and an overcharge test and measurement of the amount of heat generated by overcharge were performed. The results are shown in Table 1.
〔比較例2〕
正極に試料化合物として比較化合物1を添加した以外は、実施例1と同様に、非水電解液二次電池を作製し、過充電試験及び過充電による発熱量の測定を行なった。結果を表1に示す。
[Comparative Example 2]
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that
〔比較例3〕
正極に試料化合物として比較化合物2を添加した以外は、実施例1と同様に、非水電解液二次電池を作製し、過充電試験及び過充電による発熱量の測定を行なった。結果を表1に示す。
[Comparative Example 3]
A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that Comparative Compound 2 was added as a sample compound to the positive electrode, and an overcharge test and measurement of the amount of heat generated by overcharge were performed. The results are shown in Table 1.
〔実施例4−1〜4−4及び比較例4−1〜4−3〕正極と非水電解液との親和性試験
表2記載の試料化合物を用いて、実施例1と同様の方法で正極を作製した。得られた正極を、実施例1と同様にして調製した非水電解液に室温で48時間浸漬した後、アルミニウム箔からの正極の剥がれの有無を目視観察し、以下の評価基準により、正極と非水電解液との親和性を評価した。結果を表2に示す。
(評価基準)
○:平滑な表面を維持して剥がれが認められない。
△:電極表面が若干凸凹して剥がれが発生した。
×:剥がれが著しく表面全体が凸凹になった。
[Examples 4-1 to 4-4 and Comparative Examples 4-1 to 4-3] Affinity test between positive electrode and non-aqueous electrolyte In the same manner as in Example 1 using the sample compounds shown in Table 2. A positive electrode was produced. The obtained positive electrode was immersed in a non-aqueous electrolyte prepared in the same manner as in Example 1 at room temperature for 48 hours, and then visually observed for the presence or absence of peeling of the positive electrode from the aluminum foil. The affinity with the non-aqueous electrolyte was evaluated. The results are shown in Table 2.
(Evaluation criteria)
A: A smooth surface is maintained and no peeling is observed.
Δ: The electrode surface was slightly uneven and peeling occurred.
X: Exfoliation was remarkable and the whole surface became uneven.
表1及び表2の結果より明らかなように、正極、負極又はセパレータに、上記一般式(1)又は(2)で示される構成単位のうちの少なくとも1種より構成され平均分子量が1000〜500000であるピペリジル基含有共重合体を添加することにより、過充電に伴う非水電解液二次電池内部の異常反応を阻止し、電池温度の急速な上昇や電池の破損を防止することができる。尚、実施例1〜3において作製した非水電解液二次電池の電池性能に関し、初期電池容量を評価したところ、比較例1において作製した試料化合物無添加の非水電解液二次電池とほぼ同等であった。 As is clear from the results in Tables 1 and 2, the positive electrode, the negative electrode, or the separator is composed of at least one of the structural units represented by the general formula (1) or (2), and the average molecular weight is 1000 to 500,000. By adding the piperidyl group-containing copolymer, the abnormal reaction inside the non-aqueous electrolyte secondary battery due to overcharging can be prevented, and rapid rise in battery temperature and damage to the battery can be prevented. In addition, when the initial battery capacity was evaluated regarding the battery performance of the non-aqueous electrolyte secondary batteries produced in Examples 1 to 3, it was almost the same as the non-aqueous electrolyte secondary battery with no sample compound added produced in Comparative Example 1. It was equivalent.
1 負極
1’ 負極板
1” 負極リード
2 負極集電体
3 正極
3’ 正極板
3” 正極リード
4 正極集電体
5 電解液
6 セパレータ
7 正極端子
8 負極端子
10 非水電解液二次電池
11 ケース
12 絶縁板
13 ガスケット
14 安全弁
15 PTC素子
DESCRIPTION OF
Claims (9)
上記正極、上記負極又は上記セパレータに、下記一般式(1)に示される構成単位及び下記一般式(2)に示される構成単位からなる群から選択される1種以上より構成され平均分子量が1000〜500000であるピペリジル基含有共重合体を添加してなる非水電解液二次電池。
The positive electrode, the negative electrode, or the separator is composed of one or more selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), and has an average molecular weight of 1000. A nonaqueous electrolyte secondary battery obtained by adding a piperidyl group-containing copolymer of ˜500000.
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JPH10154531A (en) * | 1996-11-25 | 1998-06-09 | Toray Ind Inc | Secondary battery |
JPH11102693A (en) * | 1997-09-29 | 1999-04-13 | Hitachi Ltd | Lithium secondary battery |
JP4229510B2 (en) * | 1999-02-15 | 2009-02-25 | 株式会社Adeka | Flame retardant electrolyte and non-aqueous electrolyte secondary battery |
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