JP2007035413A - 非水電解質二次電池及び電池パック - Google Patents
非水電解質二次電池及び電池パック Download PDFInfo
- Publication number
- JP2007035413A JP2007035413A JP2005216177A JP2005216177A JP2007035413A JP 2007035413 A JP2007035413 A JP 2007035413A JP 2005216177 A JP2005216177 A JP 2005216177A JP 2005216177 A JP2005216177 A JP 2005216177A JP 2007035413 A JP2007035413 A JP 2007035413A
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- JP
- Japan
- Prior art keywords
- nonaqueous electrolyte
- negative electrode
- secondary battery
- battery
- lithium
- 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.)
- Granted
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 96
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- DZMOLBFHXFZZBF-UHFFFAOYSA-N prop-2-enyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC=C DZMOLBFHXFZZBF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011149 active material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- -1 allyl dimethyl phosphate Chemical compound 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 23
- 239000007773 negative electrode material Substances 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- GZNJJEODYYLYSA-UHFFFAOYSA-N diethyl prop-2-enyl phosphate Chemical compound CCOP(=O)(OCC)OCC=C GZNJJEODYYLYSA-UHFFFAOYSA-N 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
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- 239000003960 organic solvent Substances 0.000 description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 14
- 229910013063 LiBF 4 Inorganic materials 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 12
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
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- 238000006243 chemical reaction Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
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- 239000002002 slurry Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
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- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
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- MQCJHQBRIPSIKA-UHFFFAOYSA-N prenyl phosphate Chemical compound CC(C)=CCOP(O)(O)=O MQCJHQBRIPSIKA-UHFFFAOYSA-N 0.000 description 4
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- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- IEFUHGXOQSVRDQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F IEFUHGXOQSVRDQ-UHFFFAOYSA-N 0.000 description 3
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- 229910052749 magnesium Inorganic materials 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
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- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
正極と、
常温溶融塩及び下記化2で表されるアリルフォスフェートを含有する非水電解質と
を具備することを特徴とする。
前記非水電解質二次電池は、作動電位が金属リチウム電位に対して0.5V以上となる活物質を含有する負極と、
正極と、
常温溶融塩及び下記化2で表されるアリルフォスフェートを含有する非水電解質と
を具備することを特徴とする。
以下に、本発明の各実施の形態について図面を参照しながら説明する。なお、実施の形態を通して共通の構成には同一の符号を付すものとし、重複する説明は省略する。また、各図は発明の説明とその理解を促すための模式図であり、その形状や寸法、比などは実際の装置と異なる個所があるが、これらは以下の説明と公知の技術を参酌して適宜、設計変更することができる。
正極は、正極活物質を含有し、他に炭素等の電子導電性を有する物質(以下、導電材と称す)や、シート状あるいはペレット状の形状とするための結着剤を含むことができ、電子導電性を有する金属等の基材を集電体として、その集電体に接して用いることもできる。
前記負極は、負極活物質を含有し、導電剤や結着剤等を用いて、ペレット状、薄板状もしくはシート状に成形したものである。
非水電解質は、常温溶融塩と、後述するアリルフォスフェートとを含有する。
セパレータとしては、例えば、ポリエチレン、ポリプロピレン、ポリエステル、セルロース、またはポリフッ化ビニリデン(PVdF)を含む多孔質フィルム、合成樹脂製不織布等を挙げることができる。中でも、ポリエチレン又はポリプロピレンからなる多孔質フィルムは、一定温度において溶融し、電流を遮断することが可能であり、安全性向上の観点から好ましい。また、ポリエステルの一種であるポリエチレンテレフタレート不織布を用いると、溶融塩を含む非水電解質との親和性が高く、出力特性、サイクル特性の点から望ましい。
第二の実施の形態に係る電池パックは、第一の実施の形態に係る電池単体を2つ以上有する。各々の電池単体は電気的に直列もしくは並列に配置され、組電池を為している。
以下、本発明の実施例を、図表を用いて詳細に説明する。以下の実施例1〜5および比較例1〜6は図1に示した電池構造を採用している。
リチウムコバルト酸化物(LiCoO2)粉末90重量%、アセチレンブラック2重量%、グラファイト3重量%、バインダーとしてポリフッ化ビニリデン5重量%をN−メチルピロリドンを溶媒としてスラリー化し、厚さ20μmのアルミニウム箔上に塗布、乾燥後、圧延した。得られた正極シートを直径15mmの円形に切出し、正極を作製した。正極重量は17.8mgであった。得られた正極の充放電電位は、リチウム金属電位に対して約3.0〜4.3Vであった。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かした電解質に、ジエチルアリルフォスフェートを3重量%加えて非水電解質を調整したほかは、実施例1と同様に非水電解質二次電池を作製した。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かした電解質に、ジエチルアリルフォスフェートを1重量%加えて非水電解質を調整したほかは、実施例1と同様に非水電解質二次電池を作製した。
負極活物質としてFeS粉末90重量%、人造黒鉛2.5重量%、アセチレンブラック2.5重量%、ポリフッ化ビニリデン(PVdF)5重量%を、N−メチルピロリドン(NMP)溶液に加えて混合し、得られたスラリーを厚さが20μmのアルミニウム箔に塗布、乾燥後、圧延した。得られた負極シートを直径16mmの円形に切出し、負極とした。負極重量は10.1mgであった。この負極の作動電位は、金属リチウム電位に対して約1.2〜1.9V貴となるものであった。前記負極を用いた以外は、実施例1と同様に非水電解質二次電池を作製した。
N−メチル−N−プロピルピペリジニウムビストリフルオロメタンスルホニルアミドに0.5モル/Lのビストリフルオロメタンスルホニルアミドリチウム(LiTFSI)を溶かした電解質に、ジエチルアリルフォスフェートを1重量%加えて非水電解質を調整したほかは、実施例1と同様に非水電解質二次電池を作製した。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かした電解質に、ジエチルアリルフォスフェートを0.1重量%加えて非水電解質を調整したほかは、実施例1と同様に非水電解質二次電池を作製した。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かして、非水電解質を調製した以外は実施例1と同様にして非水電解質二次電池を作製した。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かした電解質に、リン酸トリメチル(TMP、トリメチルフォスフェート)を5重量%加えて非水電解質を調製したほかは、実施例1と同様に非水電解質二次電池を作製した。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かした電解質に、ジメチルアリルフォスフェート(前述した化3におけるEtをMeに替え、n=1、R=H)を3重量%加えて非水電解質を調製したほかは、実施例1と同様に非水電解質二次電池を作製した。
3000℃焼成のメソフェーズピッチ系繊維状黒鉛粉末87重量%と、平均粒径5μmの人造グラファイト10重量%と、カルボキシメチルセルース1重量%と、スチレン・ブタジエンゴム2重量%とを、水を溶媒としてスラリー化し、銅箔上に塗布、乾燥後、圧延した。得られた負極シートを直径16mmの円形に切出し、負極とした。負極重量は11.4mgであった。この負極の作動電位は、金属リチウム電位に対して約0〜0.4V貴となるものであった。前記負極を用いた以外は、実施例1と同様に非水電解質二次電池を作製した。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かして、非水電解質を調製した以外は実施例4と同様にして非水電解質二次電池を作製した。
N−メチル−N−プロピルピペリジニウムビストリフルオロメタンスルホニルアミドに0.5モル/Lのビストリフルオロメタンスルホニルアミドリチウム(LiTFSI)を溶かして非水電解質を調製したほかは、実施例1と同様に非水電解質二次電池を作製した。
リチウムコバルト酸化物(LiCoO2)粉末90重量%、アセチレンブラック2重量%、グラファイト3重量%、バインダーとしてポリフッ化ビニリデン5重量%をN−メチルピロリドンを溶媒としてスラリー化し、厚さ20μmのアルミニウム箔の両面に塗布・乾燥後、圧延した。塗布量は片面あたりで乾燥後の塗布物重量が90g/m2となるようにした。得られた正極シートを長さ170mm、幅50mmに切出した。長さ150mmを残して、20mm分の塗面を剥がして、アルミニウム箔を露出させ、その部分に長さ80mm、幅4mm、厚さ0.1mmのアルミニウムリボンを超音波溶接で取り付け、正極を得た。得られた正極の充放電電位は、リチウム金属電位に対して約3.0〜4.3Vであった。
正極活物質としてリチウムニッケルコバルトマンガン酸化物(LiNi1/3Co1/3Mn1/3O2)粉末を使用すること以外は、実施例7と同様に非水電解質二次電池を作製した。得られた正極の充放電電位は、リチウム金属電位に対して約3.0〜4.3Vであった。
テトラフルオロホウ酸1−エチル−3−メチルイミダゾリウム(EMI・BF4)に2.0モル/Lのテトラフルオロホウ酸リチウム(LiBF4)を溶かした電解質に、リン酸トリメチル(TMP、トリメチルフォスフェート)を5重量%加えて非水電解質を調製したほかは、実施例7と同様に非水電解質二次電池を作製した。
Claims (5)
- 前記非水電解質中の前記アリルフォスフェートの含有量は、0.1重量%以上3重量%以下であることを特徴とする請求項1に記載の非水電解質二次電池。
- 前記常温溶融塩は、イミダゾリウム骨格を有するカチオンを有することを特徴とする請求項1から2のいずれか1項に記載の非水電解質二次電池。
- 前記正極は、マンガン及びニッケルよりなる群から選択される少なくとも1種類の金属元素を含むリチウム複合酸化物を含有することを特徴とする請求項1から4のいずれか1項に記載の非水電解質二次電池。
- 請求項1〜4いずれか1項記載の非水電解質二次電池の組電池を具備することを特徴とする電池パック。
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Cited By (12)
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