JP2017091715A - Lithium battery and method for manufacturing the same - Google Patents
Lithium battery and method for manufacturing the same Download PDFInfo
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- JP2017091715A JP2017091715A JP2015218237A JP2015218237A JP2017091715A JP 2017091715 A JP2017091715 A JP 2017091715A JP 2015218237 A JP2015218237 A JP 2015218237A JP 2015218237 A JP2015218237 A JP 2015218237A JP 2017091715 A JP2017091715 A JP 2017091715A
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- Prior art keywords
- positive electrode
- negative electrode
- lithium battery
- active material
- lithium
- Prior art date
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- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title description 11
- 238000000034 method Methods 0.000 title description 11
- -1 borate compound Chemical class 0.000 claims abstract description 37
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 239000003660 carbonate based solvent Substances 0.000 claims abstract description 12
- 238000003780 insertion Methods 0.000 claims abstract description 11
- 230000037431 insertion Effects 0.000 claims abstract description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960002645 boric acid Drugs 0.000 claims abstract description 8
- 235000010338 boric acid Nutrition 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- XBVURNWWURAQSY-UHFFFAOYSA-N 2,2,2-trifluoroethoxyboronic acid Chemical compound OB(O)OCC(F)(F)F XBVURNWWURAQSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 21
- 239000000243 solution Substances 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 239000003115 supporting electrolyte Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- DIEXQJFSUBBIRP-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) borate Chemical compound FC(F)(F)COB(OCC(F)(F)F)OCC(F)(F)F DIEXQJFSUBBIRP-UHFFFAOYSA-N 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910012465 LiTi Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000010450 olivine Substances 0.000 description 4
- 229910052609 olivine Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910003286 Ni-Mn Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
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- 238000007086 side reaction Methods 0.000 description 3
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- 239000004332 silver Substances 0.000 description 3
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- 239000002562 thickening agent Substances 0.000 description 3
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 150000007527 lewis bases Chemical group 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 2
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- DZRUNSUYJCQUIG-UHFFFAOYSA-N 2-methylbutan-2-yl hydrogen carbonate Chemical compound CCC(C)(C)OC(O)=O DZRUNSUYJCQUIG-UHFFFAOYSA-N 0.000 description 1
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- 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
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Images
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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウム電池及びその製造方法に関する。 The present invention relates to a lithium battery and a manufacturing method thereof.
従来、リチウム電池用正極活物質として、ＬｉＮｉ0.5Ｍｎ1.5Ｏ4などのＮｉ−Ｍｎスピネルが提案されている（非特許文献１参照）。Ｎｉ−Ｍｎスピネルは約４．６〜４．８Ｖ（vs. Li+/Li）でＬｉ+を挿入脱離することができるため、黒鉛負極と組み合わせた場合には平均電圧約４．６Ｖの電池を構成することができる。しかしながら、Ｎｉ−Ｍｎスピネルを用いたリチウム電池は正極電位が高いため、従来のリチウム電池用の電解液溶媒であるエチレンカーボネートなどを用いると、正極で酸化分解され、耐久性が悪いことがあった。そこで、耐酸性の高いフッ素置換溶媒を用いることが提案されている（非特許文献２参照）。 Conventionally, Ni-Mn spinels such as LiNi 0.5 Mn 1.5 O 4 have been proposed as positive electrode active materials for lithium batteries (see Non-Patent Document 1). Since Ni—Mn spinel can insert and desorb Li + at about 4.6 to 4.8 V (vs. Li + / Li), a battery having an average voltage of about 4.6 V when combined with a graphite negative electrode. Can be configured. However, since the lithium battery using Ni-Mn spinel has a high positive electrode potential, the use of ethylene carbonate or the like, which is a conventional electrolyte solvent for lithium batteries, may cause oxidative decomposition at the positive electrode, resulting in poor durability. . Therefore, it has been proposed to use a fluorine-substituted solvent with high acid resistance (see Non-Patent Document 2).
また、リチウム電池に関するものではないが、ＬｉＦ、ＬｉＣｌ、ＬｉＢｒ、ＬｉＩ、ＣＦ3ＣＯＯＬｉ及びＣ2Ｆ5ＣＯＯＬｉなどのリチウム塩を含む１，２−ジメトキシエタン溶媒中に、フッ素化アリール基やフッ素化アルキルを備えたボレート化合物を加えることが検討されている（非特許文献３参照）。こうすることで、リチウム塩の解離度を高めることができ、溶液のイオン伝導率を高めることができるとしている。 Although not related to lithium batteries, fluorinated aryl groups and fluorinated compounds in 1,2-dimethoxyethane solvents containing lithium salts such as LiF, LiCl, LiBr, LiI, CF 3 COOLi and C 2 F 5 COOLi The addition of borate compounds with alkyl has been studied (see Non-Patent Document 3). By carrying out like this, it is supposed that the dissociation degree of lithium salt can be raised and the ionic conductivity of a solution can be raised.
しかしながら、非特許文献２のリチウム電池では、フッ素置換溶媒を用いることにより高い耐久性を示すとされているものの、電池内でのガス発生の抑制が十分でないことがあり、電池内でのガス発生をより抑制することが望まれていた。非特許文献３では、ボレート化合物の添加によるリチウム塩の解離度向上や溶液のイオン伝導率向上について検討されているだけだった。 However, in the lithium battery of Non-Patent Document 2, although it is said that high durability is exhibited by using a fluorine-substituted solvent, gas generation in the battery may not be sufficiently suppressed. It has been desired to further suppress this. In Non-Patent Document 3, only an improvement in the dissociation degree of the lithium salt and an improvement in the ionic conductivity of the solution by adding a borate compound were studied.
本発明はこのような課題を解決するためになされたものであり、リチウム電池内でのガス発生をより抑制することを主目的とする。 The present invention has been made to solve such a problem, and has as its main object to further suppress gas generation in the lithium battery.
上述した目的を達成するために、本発明者らは鋭意研究した。そして、Ｌｉ挿入脱離電位が４．４Ｖ以上（vs. Li+/Li）の正極活物質を備えたリチウム電池において、カーボネート系溶媒と、支持塩と、所定のボレート化合物を所定量含む電解液を用いると、リチウム電池内でのガス発生をより抑制できることを見出し、本発明を完成するに至った。 In order to achieve the above-mentioned object, the present inventors have intensively studied. In a lithium battery including a positive electrode active material having a Li insertion / release potential of 4.4 V or higher (vs. Li + / Li), an electrolytic solution containing a predetermined amount of a carbonate-based solvent, a supporting salt, and a predetermined borate compound As a result, it was found that gas generation in the lithium battery can be further suppressed, and the present invention has been completed.
即ち、本発明のリチウム電池は、
Ｌｉ挿入脱離電位がリチウム基準で４．４Ｖ以上の正極活物質を含む正極と、
負極活物質を含む負極と、
前記正極と前記負極との間に介在し、カーボネート系溶媒と、支持塩と、オルトホウ酸の３つの水素がフッ素化アルキル基で置換された構造を有するボレート化合物と、を含み、前記ボレート化合物が０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲で含まれる電解液と、
を備えたものである。
That is, the lithium battery of the present invention is
A positive electrode containing a positive electrode active material having a Li insertion / extraction potential of 4.4 V or more based on lithium;
A negative electrode containing a negative electrode active material;
A borate compound that is interposed between the positive electrode and the negative electrode and has a carbonate solvent, a supporting salt, and a borate compound having a structure in which three hydrogen atoms of orthoboric acid are substituted with a fluorinated alkyl group. An electrolytic solution contained in a range of 0.01 mol / L to 0.4 mol / L;
It is equipped with.
本発明のリチウム電池の製造方法は、
Ｌｉ挿入脱離電位がリチウム基準で４．４Ｖ以上の正極活物質を含む正極と、負極活物質を含む負極と、の間に、カーボネート系溶媒と、支持塩と、オルトホウ酸の３つの水素がフッ素化アルキル基で置換された構造を有するボレート化合物と、を含み、前記ボレート化合物が０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲で含まれる電解液を注入するものである。
The method for producing the lithium battery of the present invention comprises:
Three hydrogens of a carbonate-based solvent, a supporting salt, and orthoboric acid are present between a positive electrode containing a positive electrode active material having a Li insertion / release potential of 4.4 V or higher with respect to lithium and a negative electrode containing a negative electrode active material. A borate compound having a structure substituted with a fluorinated alkyl group, and injecting an electrolytic solution containing the borate compound in a range of 0.01 mol / L to 0.4 mol / L.
このリチウム電池及びその製造方法では、リチウム電池内でのガス発生をより抑制できる。こうした効果が得られる理由は、以下のように推察される。例えば、ルイス塩基であるボレート化合物が、孤立電子対を有するカーボネート系溶媒と相互作用することによって、Ｌｉ挿入脱離電位がリチウム基準で４．４Ｖ以上の正極活物質を含む正極を用いた場合でも、正極上でのカーボネート系溶媒の酸化分解を抑制できると考えられる。カーボネート系溶媒の酸化分解によって生じるＨ+は負極に移動して水素ガスを発生させることがあるが、カーボネート系溶媒の酸化分解を抑制することにより、結果として、リチウム電池内でのガス発生を抑制できると考えられる。 In this lithium battery and the manufacturing method thereof, gas generation in the lithium battery can be further suppressed. The reason why such an effect can be obtained is assumed as follows. For example, even when a borate compound that is a Lewis base interacts with a carbonate-based solvent having a lone pair of electrons, a positive electrode containing a positive electrode active material having a Li insertion / release potential of 4.4 V or higher with respect to lithium is used. It is considered that the oxidative decomposition of the carbonate-based solvent on the positive electrode can be suppressed. H + generated by oxidative decomposition of carbonate-based solvent may move to the negative electrode and generate hydrogen gas, but by suppressing oxidative decomposition of carbonate-based solvent, gas generation in the lithium battery is suppressed as a result. It is considered possible.
本発明のリチウム電池は、正極と、負極と、正極と負極との間に介在し、リチウムイオンを伝導する電解液と、を備えている。 The lithium battery of the present invention includes a positive electrode, a negative electrode, and an electrolyte solution that is interposed between the positive electrode and the negative electrode and conducts lithium ions.
本発明のリチウム電池の正極は、Ｌｉ挿入脱離電位がリチウム基準で４．４Ｖ以上の正極活物質を含有している。正極活物質としては、スピネル型リチウムニッケルマンガン酸化物、オリビン型リチウムリン酸コバルト、オリビン型リチウムリン酸ニッケルなどが挙げられる。スピネル型リチウムニッケルマンガン酸化物としては、例えば、ＬｉaＮｉbＭｎcＭｅdＯe（ＭｅはＭｎ，Ｎｉ以外の遷移金属元素、Ａｌ及びアルカリ土類金属から選ばれる少なくとも１種の元素であり、ａ〜ｅは０．９≦ａ≦１．２、０．４５≦ｂ≦０．５５、１．４５≦ｃ≦１．５５、０≦ｄ≦５．００、３．８≦ｅ≦４．２）などが挙げられる。Ｍｅとしての遷移金属は、例えば、Ｖ，Ｔｉ，Ｃｒ，Ｆｅ，Ｃｏ，Ｃｕ等とすることができる。オリビン型リチウムリン酸コバルトとしてはＬｉＣｏＰＯ4などが挙げられ、オリビン型リチウムリン酸ニッケルとしてはＬｉＮｉＰＯ4などが挙げられる。正極活物質としては、上述したもののうち、スピネル型リチウムニッケルマンガン酸化物が好ましく、ＬｉＮｉ0.5Ｍｎ1.5Ｏ4がより好ましい。なお、本発明において、各化学式で示した物質は、化学量論組成のものに限定されず、一部の元素が、過剰であったり、欠損していたり、他の元素で置換されていてもよい。 The positive electrode of the lithium battery of the present invention contains a positive electrode active material having a Li insertion / release potential of 4.4 V or higher with respect to lithium. Examples of the positive electrode active material include spinel type lithium nickel manganese oxide, olivine type lithium cobalt phosphate, and olivine type lithium nickel phosphate. The spinel type lithium-nickel-manganese oxide, for example, Li a Ni b Mn c Me d O e (Me is Mn, a transition metal element other than Ni, is at least one element selected from Al and alkaline earth metal , A to e are 0.9 ≦ a ≦ 1.2, 0.45 ≦ b ≦ 0.55, 1.45 ≦ c ≦ 1.55, 0 ≦ d ≦ 5.00, 3.8 ≦ e ≦ 4 .2). The transition metal as Me can be, for example, V, Ti, Cr, Fe, Co, Cu or the like. Examples of the olivine type lithium cobalt phosphate include LiCoPO 4. Examples of the olivine type lithium nickel phosphate include LiNiPO 4 . As the positive electrode active material, among the above-described materials, spinel type lithium nickel manganese oxide is preferable, and LiNi 0.5 Mn 1.5 O 4 is more preferable. In the present invention, the substance represented by each chemical formula is not limited to the stoichiometric composition, and some elements may be excessive, missing, or substituted with other elements. Good.
この正極は、正極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の正極材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよい。導電材は、正極の電池性能に悪影響を及ぼさない電子伝導性材料であれば特に限定されず、例えば、天然黒鉛（鱗状黒鉛、鱗片状黒鉛）や人造黒鉛などの黒鉛、アセチレンブラック、カーボンブラック、ケッチェンブラック、カーボンウィスカ、ニードルコークス、炭素繊維、金属（銅、ニッケル、アルミニウム、銀、金など）などの１種又は２種以上を混合したものを用いることができる。これらの中で、導電材としては、電子伝導性及び塗工性の観点より、カーボンブラック及びアセチレンブラックが好ましい。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、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、フッ素ゴム等の含フッ素樹脂、或いはポリプロピレン、ポリエチレン等の熱可塑性樹脂、エチレンプロピレンジエンモノマー（ＥＰＤＭ）ゴム、スルホン化ＥＰＤＭゴム、天然ブチルゴム（ＮＢＲ）等を単独で、あるいは２種以上の混合物として用いることができる。また、水系バインダーであるセルロース系やスチレンブタジエンゴム（ＳＢＲ）の水分散体等を用いることもできる。正極活物質、導電材、結着材を分散させる溶剤としては、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、ジエチレントリアミン、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などの有機溶剤を用いることができる。また、水に分散剤、増粘剤等を加え、ＳＢＲなどのラテックスで活物質をスラリー化してもよい。増粘剤としては、例えば、カルボキシメチルセルロース、メチルセルロースなどの多糖類を単独で、あるいは２種以上の混合物として用いることができる。塗布方法としては、例えば、アプリケータロールなどのローラコーティング、スクリーンコーティング、ドクターブレイド方式、スピンコーティング、バーコータなどが挙げられ、これらのいずれかを用いて任意の厚さ・形状とすることができる。集電体としては、アルミニウム、チタン、ステンレス鋼、ニッケル、鉄、焼成炭素、導電性高分子、導電性ガラスなどのほか、接着性、導電性及び耐酸化性向上の目的で、アルミニウムや銅などの表面をカーボン、ニッケル、チタンや銀などで処理したものを用いることができる。これらについては、表面を酸化処理することも可能である。集電体の形状については、箔状、フィルム状、シート状、ネット状、パンチ又はエキスパンドされたもの、ラス体、多孔質体、発泡体、繊維群の形成体などが挙げられる。集電体の厚さは、例えば１〜５００μｍのものが用いられる。 This positive electrode is prepared by mixing a positive electrode active material, a conductive material, and a binder, adding a suitable solvent to form a paste-like positive electrode material, and applying and drying on the surface of the current collector, and if necessary, an electrode You may compress and form in order to raise a density. The conductive material is not particularly limited as long as it is an electron conductive material that does not adversely affect the battery performance of the positive electrode. For example, graphite such as natural graphite (scale-like graphite, scale-like graphite) or artificial graphite, acetylene black, carbon black, What mixed 1 type (s) or 2 or more types, such as ketjen black, carbon whisker, needle coke, carbon fiber, metal (copper, nickel, aluminum, silver, gold, etc.) can be used. Among these, as the conductive material, carbon black and acetylene black are preferable from the viewpoints of electron conductivity and coatability. The binder serves to bind the active material particles and the conductive material particles. For example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluorine-containing resin such as fluorine rubber, or polypropylene, Thermoplastic resins such as polyethylene, ethylene propylene diene monomer (EPDM) rubber, sulfonated EPDM rubber, natural butyl rubber (NBR) and the like can be used alone or as a mixture of two or more. In addition, an aqueous dispersion of cellulose or styrene butadiene rubber (SBR), which is an aqueous binder, can also be used. Examples of the solvent for dispersing the positive electrode active material, the conductive material, and the binder include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethylenetriamine, and N, N-dimethylaminopropylamine. Organic solvents such as ethylene oxide and tetrahydrofuran can be used. Moreover, a dispersing agent, a thickener, etc. may be added to water, and an active material may be slurried with latex, such as SBR. As the thickener, for example, polysaccharides such as carboxymethyl cellulose and methyl cellulose can be used alone or as a mixture of two or more. Examples of the application method include roller coating such as applicator roll, screen coating, doctor blade method, spin coating, bar coater, and the like, and any of these can be used to obtain an arbitrary thickness and shape. Current collectors include aluminum, titanium, stainless steel, nickel, iron, calcined carbon, conductive polymer, conductive glass, and aluminum, copper, etc. for the purpose of improving adhesion, conductivity, and oxidation resistance. A surface treated with carbon, nickel, titanium, silver or the like can be used. For these, the surface can be oxidized. Examples of the shape of the current collector include foil, film, sheet, net, punched or expanded, lath, porous, foam, and formed fiber group. The thickness of the current collector is, for example, 1 to 500 μm.
本発明のリチウム電池の負極は、負極活物質を含有している。負極活物質としては、リチウム、リチウム合金のほか、リチウムイオンを吸蔵・放出可能な炭素質材料、シリコン、シリコン化合物、スズ、スズ化合物、複数の元素を含む複合酸化物、導電性ポリマーなどが挙げられる。炭素質材料は、例えば、コークス類、ガラス状炭素類、グラファイト類、難黒鉛化性炭素類、熱分解炭素類、炭素繊維などが挙げられる。炭素質材料としては、人造黒鉛、天然黒鉛などのグラファイト類が、金属リチウムに近い作動電位を有し、高い作動電圧での充放電が可能であり支持塩としてリチウム塩を使用した場合に自己放電を抑え、且つ充電時おける不可逆容量を少なくできるため、好ましい。複合酸化物としては、例えば、リチウムチタン複合酸化物（例えばＬｉＴｉ2Ｏ4）やリチウムバナジウム複合酸化物（例えばＬｉＶ2Ｏ5）などが挙げられる。負極活物質としては、このうち、炭素質材料や、シリコン、スズ、リチウムチタン複合酸化物などが好ましい。 The negative electrode of the lithium battery of the present invention contains a negative electrode active material. Examples of negative electrode active materials include lithium, lithium alloys, carbonaceous materials capable of inserting and extracting lithium ions, silicon, silicon compounds, tin, tin compounds, composite oxides containing multiple elements, and conductive polymers. It is done. Examples of the carbonaceous material include cokes, glassy carbons, graphites, non-graphitizable carbons, pyrolytic carbons, and carbon fibers. As carbonaceous materials, graphites such as artificial graphite and natural graphite have an operating potential close to that of metallic lithium, can be charged and discharged at a high operating voltage, and self-discharge when lithium salt is used as a supporting salt. This is preferable because the irreversible capacity during charging can be reduced. Examples of the composite oxide include lithium titanium composite oxide (for example, LiTi 2 O 4 ) and lithium vanadium composite oxide (for example, LiV 2 O 5 ). Of these, carbonaceous materials, silicon, tin, lithium titanium composite oxides, and the like are preferable as the negative electrode active material.
この負極は、例えば、負極活物質と集電体とを密着させて形成してもよいし、負極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の負極材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよい。負極に用いられる導電材、結着材、溶剤などは、それぞれ正極で例示したものを用いることができる。負極の集電体には、銅、ニッケル、ステンレス鋼、チタン、アルミニウム、焼成炭素、導電性高分子、導電性ガラス、Ａｌ−Ｃｄ合金などのほか、接着性、導電性及び耐還元性向上の目的で、例えば銅などの表面をカーボン、ニッケル、チタンや銀などで処理したものも用いることができる。これらについては、表面を酸化処理することも可能である。集電体の形状は、正極と同様のものを用いることができる。 This negative electrode may be formed, for example, by adhering a negative electrode active material and a current collector, or by mixing a negative electrode active material, a conductive material, and a binder, and adding an appropriate solvent to form a paste-like negative electrode The material may be applied and dried on the surface of the current collector, and may be compressed to increase the electrode density as necessary. As the conductive material, binder, solvent and the like used for the negative electrode, those exemplified for the positive electrode can be used. The negative electrode current collector includes copper, nickel, stainless steel, titanium, aluminum, calcined carbon, conductive polymer, conductive glass, Al-Cd alloy, etc., as well as improved adhesion, conductivity and reduction resistance. For the purpose, for example, a copper surface treated with carbon, nickel, titanium, silver or the like can be used. For these, the surface can be oxidized. The shape of the current collector can be the same as that of the positive electrode.
本発明のリチウム電池の電解液は、カーボネート系溶媒と、支持塩と、ボレート化合物と、を含む。 The electrolytic solution of the lithium battery of the present invention includes a carbonate solvent, a supporting salt, and a borate compound.
カーボネート系溶媒としては、例えば、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、ビニレンカーボネートなどの環状カーボネートや、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などの鎖状カーボネートなどが挙げられる。また、カーボネート系溶媒は、上述した各カーボネート系溶媒において少なくとも１つの水素原子がフッ素原子で置換されたものとしてもよい。カーボネート系溶媒は、１種を単独で用いてもよいし、２種以上を混合して用いてもよい。カーボネート系溶媒は、環状カーボネートと鎖状カーボネートの両方を含むことが好ましい。また、カーボネート系溶媒は、少なくとも１つの水素原子がフッ素原子で置換されたフッ素化カーボネートを含むことが好ましい。フッ素化カーボネートを含むものでは、リチウム電池の耐久性をより高めることができると考えられる。カーボネート系溶媒は、エチレンカーボネートのうち少なくとも１つの水素原子がフッ素原子で置換されたフッ素化エチレンカーボネートや、エチルメチルカーボネートのうち少なくとも１つの水素原子がフッ素原子で置換されたフッ素化エチルメチルカーボネートがより好ましい。 Examples of the carbonate solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl-n-butyl carbonate, methyl-t-butyl carbonate, di-carbonate, and the like. Examples include chain carbonates such as -i-propyl carbonate and t-butyl-i-propyl carbonate. In addition, the carbonate solvent may be one in which at least one hydrogen atom is substituted with a fluorine atom in each of the carbonate solvents described above. A carbonate type solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. The carbonate-based solvent preferably contains both a cyclic carbonate and a chain carbonate. The carbonate solvent preferably contains a fluorinated carbonate in which at least one hydrogen atom is substituted with a fluorine atom. In the case of containing fluorinated carbonate, it is considered that the durability of the lithium battery can be further improved. Carbonate-based solvents include fluorinated ethylene carbonate in which at least one hydrogen atom is replaced with a fluorine atom in ethylene carbonate, and fluorinated ethyl methyl carbonate in which at least one hydrogen atom in ethyl methyl carbonate is replaced with a fluorine atom. More preferred.
支持塩としては、例えば、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＳｂＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＦＳＯ2）2、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＣ（ＣＦ3ＳＯ2）3、ＬｉＳｉＦ6、ＬｉＡｌＦ4、ＬｉＳＣＮ、ＬｉＣｌ、ＬｉＦ、ＬｉＢｒ、ＬｉＩ、ＬｉＡｌＣｌ4などのリチウム塩が挙げられる。このうち、ＬｉＰＦ6や、ＬｉＦＳＩ（上述したＬｉＮ（ＦＳＯ2）2）などが好ましい。支持塩は、電解液中の濃度が０．１ｍｏｌ／Ｌ以上５ｍｏｌ／Ｌ以下であることが好ましく、０．５ｍｏｌ／Ｌ以上２ｍｏｌ／Ｌ以下であることがより好ましい。支持塩の濃度が０．１ｍｏｌ／Ｌ以上では、十分な電流密度を得ることができ、５ｍｏｌ／Ｌ以下では、電解液をより安定させることができる。 As the supporting salt, for example, LiPF 6, LiClO 4, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiN (FSO 2) 2, LiN (CF 3 SO 2) 2, LiC (CF 3 SO 2) 3 , and lithium salts such as LiSiF 6 , LiAlF 4 , LiSCN, LiCl, LiF, LiBr, LiI, and LiAlCl 4 . Of these, LiPF 6 and LiFSI (LiN (FSO 2 ) 2 described above) are preferable. The concentration of the supporting salt in the electrolytic solution is preferably 0.1 mol / L or more and 5 mol / L or less, and more preferably 0.5 mol / L or more and 2 mol / L or less. If the concentration of the supporting salt is 0.1 mol / L or more, a sufficient current density can be obtained, and if it is 5 mol / L or less, the electrolytic solution can be made more stable.
ボレート化合物は、オルトホウ酸（Ｂ（ＯＨ）3）の３つの水素が、フッ素化アルキル基で置換された構造を有している。フッ素化アルキル基は、アルキル基の有する水素のうちの１つ以上がフッ素で置換された構造であればよく、一部の水素がフッ素で置換された構造でもよいし、全ての水素がフッ素で置換された構造でもよい。フッ素化アルキル基は、少なくとも、アルキル基の末端の炭素に結合する水素のうちの１つ以上がフッ素で置換された構造であることがより好ましい。アルキル基は、直鎖でもよいし分岐鎖を有していてもよく、炭素数は１〜９であることが好ましい。アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基などが挙げられる。また、これらのアルキル基は置換基を有していてもよい。このボレート化合物は、下記式（１）で表されるものとしてもよい。 The borate compound has a structure in which three hydrogen atoms of orthoboric acid (B (OH) 3 ) are substituted with a fluorinated alkyl group. The fluorinated alkyl group may have a structure in which one or more of hydrogen atoms of the alkyl group are substituted with fluorine, may have a structure in which part of hydrogen is substituted with fluorine, or all hydrogen is fluorine. It may be a substituted structure. More preferably, the fluorinated alkyl group has a structure in which at least one hydrogen bonded to carbon at the terminal of the alkyl group is substituted with fluorine. The alkyl group may be linear or branched, and preferably has 1 to 9 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Moreover, these alkyl groups may have a substituent. This borate compound may be represented by the following formula (1).
式（１）において、フッ素化アルキル基である、Ｃx1Ｈy1Ｆz1、Ｃx2Ｈy2Ｆz2及びＣx3Ｈy3Ｆz3、は、全てが同じでもよいし、２つが同じで１つが異なっていてもよいし、全てが異なっていてもよい。ｘ１，ｘ２及びｘ３は、それぞれ、１以上９以下であればよいが、６以下が好ましく、５以下がより好ましく、４以下がさらに好ましく、１以上２以下が一層好ましい。ｙ１，ｙ２及びｙ３は、それぞれ、０以上１８以下であればよいが、１２以下が好ましく、７以下がより好ましく、３以下がさらに好ましく、０以上２以下が一層好ましい。ｚ１，ｚ２及びｚ３は、それぞれ、１以上１９以下であればよいが、１３以下が好ましく、１１以下がより好ましく、７以下がさらに好ましく、１以上５以下が一層好ましい。ボレート化合物は、ｘ１，ｘ２及びｘ３が全て２で、ｙ１，ｙ２及びｙ３が全て２で、ｚ１，ｚ２及びｚ３が全て３である、（２，２，２−トリフルオロエチル）ボレートであることがより好ましい。 In the formula (1), C x1 H y1 F z1 , C x2 H y2 F z2 and C x3 H y3 F z3 which are fluorinated alkyl groups may all be the same, or two are the same and one is different Or all of them may be different. x1, x2 and x3 may each be 1 or more and 9 or less, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and still more preferably 1 or more and 2 or less. y1, y2 and y3 may be 0 or more and 18 or less, respectively, preferably 12 or less, more preferably 7 or less, further preferably 3 or less, and further preferably 0 or more and 2 or less. z1, z2 and z3 may be 1 or more and 19 or less, respectively, preferably 13 or less, more preferably 11 or less, still more preferably 7 or less, and still more preferably 1 or more and 5 or less. The borate compound is (2,2,2-trifluoroethyl) borate in which x1, x2 and x3 are all 2, y1, y2 and y3 are all 2, and z1, z2 and z3 are all 3. Is more preferable.
電解液には、ボレート化合物が、０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲で含まれる。このうち、０．０２ｍｏｌ／Ｌ以上が好ましく、０．０３ｍｏｌ／Ｌ以上がより好ましい。また、０．３ｍｏｌ／Ｌ以下が好ましく、０．２ｍｏｌ／Ｌ以下がより好ましい。こうした範囲であれば、リチウム電池内でのガス発生をより抑制できるし、高温耐久性をより高めることができる。また、０．４ｍｏｌ／Ｌ以下であれば、負極抵抗の増大を抑制し、電池としての抵抗の上昇を抑制できる。 The electrolyte solution contains a borate compound in a range of 0.01 mol / L to 0.4 mol / L. Among these, 0.02 mol / L or more is preferable, and 0.03 mol / L or more is more preferable. Moreover, 0.3 mol / L or less is preferable and 0.2 mol / L or less is more preferable. If it is such a range, the gas generation | occurrence | production within a lithium battery can be suppressed more, and high temperature durability can be improved more. Moreover, if it is 0.4 mol / L or less, the increase in negative electrode resistance can be suppressed and the raise of the resistance as a battery can be suppressed.
本発明のリチウム電池は、正極と負極との間にセパレータを備えていてもよい。セパレータとしては、リチウム電池の使用範囲に耐えうる組成であれば特に限定されないが、例えば、ポリプロピレン製不織布やポリフェニレンスルフィド製不織布などの高分子不織布、ポリエチレンやポリプロピレンなどのオレフィン系樹脂の薄い微多孔膜が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。 The lithium battery of the present invention may include a separator between the positive electrode and the negative electrode. The separator is not particularly limited as long as it has a composition that can withstand the range of use of the lithium battery. Is mentioned. These may be used alone or in combination.
本発明のリチウム電池の形状は、特に限定されないが、例えばコイン型、ボタン型、シート型、積層型、円筒型、偏平型、角型などが挙げられる。また、電気自動車等に用いる大型のものなどに適用してもよい。図１は、本発明のリチウム電池の一例を示す模式図である。このリチウム電池１０は、集電体１１に正極活物質１２を形成した正極シート１３と、集電体１４の表面に負極活物質１７を形成した負極シート１８と、正極シート１３と負極シート１８との間に設けられたセパレータ１９と、正極シート１３と負極シート１８の間を満たす電解液２０と、を備えたものである。このリチウム電池１０は、正極シート１３と負極シート１８との間にセパレータ１９を挟み、これらを捲回して円筒ケース２２に挿入し、正極シート１３に接続された正極端子２４と負極シート１８に接続された負極端子２６とを配設して形成されている。ここでは、正極活物質１２は、Ｌｉ挿入脱離電位がリチウム基準で４．４Ｖ以上である。また、電解液２０は、カーボネート系溶媒と、支持塩と、オルトホウ酸の３つの水素がフッ素化アルキル基で置換された構造を有するボレート化合物と、を含み、ボレート化合物は０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲で含まれる。
The shape of the lithium battery of the present invention is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type. Moreover, you may apply to the large sized thing etc. which are used for an electric vehicle etc. FIG. 1 is a schematic view showing an example of the lithium battery of the present invention. The
本発明のリチウム電池の製造方法では、正極と負極との間に電解液を注入する。正極は、Ｌｉ挿入脱離電位がリチウム基準で４．４Ｖ以上の正極活物質を含むものであればよく、上述したリチウム電池の正極などを用いることができる。負極は、負極活物質を含むものであればよく、上述したリチウム電池の負極などを用いることができる。電解液は、カーボネート系溶媒と、支持塩と、オルトホウ酸の３つの水素がフッ素化アルキル基で置換された構造を有するボレート化合物と、を含み、前記ボレート化合物が０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲で含むものであればよく、上述したリチウム電池の電解液などを用いることができる。なお、本発明のリチウム電池は、こうした製造方法で製造されたものに限定されず、正極と負極との間に電解液を介在させることができる製造方法で製造されたものであればよい。例えば、電解液中に正極や負極を配置してもよいし、あらかじめ電解液を含浸させた正極や負極を用いてリチウム電池を製造してもよい。リチウム電池の製造時に用いる電解液中のボレート化合物の濃度が０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲であれば、その後の充放電などで電解液中のボレート化合物濃度が変化しても、リチウム電池内でのガス発生を抑制できると考えられる。 In the method for producing a lithium battery of the present invention, an electrolytic solution is injected between the positive electrode and the negative electrode. The positive electrode only needs to include a positive electrode active material having a Li insertion / release potential of 4.4 V or higher with respect to lithium, and the positive electrode of the lithium battery described above can be used. The negative electrode should just contain a negative electrode active material, and the negative electrode of the lithium battery mentioned above etc. can be used for it. The electrolytic solution includes a carbonate-based solvent, a supporting salt, and a borate compound having a structure in which three hydrogen atoms of orthoboric acid are substituted with a fluorinated alkyl group, and the borate compound is 0.01 mol / L or more and 0.0. What is necessary is just to include in the range of 4 mol / L or less, and the electrolyte solution etc. of the lithium battery mentioned above can be used. In addition, the lithium battery of this invention is not limited to what was manufactured with such a manufacturing method, What is necessary is just to be manufactured with the manufacturing method which can interpose electrolyte solution between a positive electrode and a negative electrode. For example, a positive electrode or a negative electrode may be disposed in the electrolytic solution, or a lithium battery may be manufactured using a positive electrode or a negative electrode impregnated with an electrolytic solution in advance. If the concentration of the borate compound in the electrolytic solution used at the time of manufacturing the lithium battery is in the range of 0.01 mol / L or more and 0.4 mol / L or less, the concentration of the borate compound in the electrolytic solution changes due to subsequent charge / discharge or the like. It is also considered that gas generation in the lithium battery can be suppressed.
以上説明した本発明のリチウム電池及びその製造方法によれば、リチウム電池内でのガス発生をより抑制できる。こうした効果が得られる理由は、以下のように推察される。例えば、上述した非特許文献２のリチウム電池では、フッ素化エチレンカーボネート溶媒（以下ＦＥＣとも称する）を用いることで、耐酸性を高めることができ、Ｌｉ挿入脱離電位がリチウム基準で４．６〜４．８Ｖの正極を用いたリチウム電池の耐久性を高めることができる。しかし、非特許文献２のリチウム電池では、正極でＦＥＣが酸化分解されてＣＯ2とＨＦが生成し、Ｈ+が負極に移動し、負極で還元されて水素ガスが生成すると考えられる。これに対して、本発明のリチウム電池では、オルトホウ酸の３つの水素がフッ素化アルキル基で置換された構造を有するボレート化合物を適量含むため、こうした正極上での副反応を抑制できると考えられる。より具体的には、例えば、ルイス塩基であるボレート化合物が、孤立電子対を有するカーボネート系溶媒と相互作用することによって、正極上でのカーボネート系溶媒の酸化分解が抑制され、結果として、リチウム電池内でのガス発生を抑制できると考えられる。また、本発明のリチウム電池によれば、正極上での副反応を抑制できるため、副反応に伴う正負極間での容量ずれによる電池容量の低下も抑制できると考えられる。 According to the lithium battery and the manufacturing method thereof of the present invention described above, gas generation in the lithium battery can be further suppressed. The reason why such an effect can be obtained is assumed as follows. For example, in the above-described lithium battery of Non-Patent Document 2, acid resistance can be increased by using a fluorinated ethylene carbonate solvent (hereinafter also referred to as FEC), and the Li insertion / release potential is 4.6 to The durability of a lithium battery using a 4.8V positive electrode can be increased. However, in the lithium battery of Non-Patent Document 2, it is considered that FEC is oxidized and decomposed at the positive electrode to generate CO 2 and HF, H + moves to the negative electrode, and is reduced at the negative electrode to generate hydrogen gas. On the other hand, the lithium battery of the present invention contains an appropriate amount of a borate compound having a structure in which three hydrogen atoms of orthoboric acid are substituted with a fluorinated alkyl group. Therefore, it is considered that such a side reaction on the positive electrode can be suppressed. . More specifically, for example, the borate compound which is a Lewis base interacts with a carbonate solvent having a lone pair of electrons, thereby suppressing the oxidative decomposition of the carbonate solvent on the positive electrode, resulting in a lithium battery. It is thought that gas generation inside can be suppressed. Moreover, according to the lithium battery of this invention, since the side reaction on a positive electrode can be suppressed, it is thought that the fall of the battery capacity by the capacity shift between positive and negative electrodes accompanying a side reaction can also be suppressed.
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
以下には、本発明のリチウム電池を具体的に作製した例について、実施例として説明する。 Below, the example which produced the lithium battery of this invention concretely is demonstrated as an Example.
［実施例１］
（電池の作製）
モノフルオロエチレンカーボネート（ＭＦＥＣ）とメチル−２，２，２−トリフルオロエチルカーボネート（ＭＴＦＥＣ）を体積比でＭＦＥＣ：ＦＴＦＥＣ＝３：７の割合で含む混合溶媒中に、ＬｉＰＦ6を１．１Ｍの濃度となるように含む混合溶液を準備した。この混合溶液１００ｍＬに３．０８ｇ（０．０５ｍｏｌ／Ｌ）のトリス（２，２，２−トリフルオロエチル）ボレート（Ａｌｄｒｉｃｈ製）を添加して、電解液を調整した。
[Example 1]
(Production of battery)
In a mixed solvent containing monofluoroethylene carbonate (MFEC) and methyl-2,2,2-trifluoroethyl carbonate (MTFEC) in a volume ratio of MFEC: FTFEC = 3: 7, LiPF 6 was added in an amount of 1.1 M. A mixed solution containing a concentration was prepared. To 100 mL of this mixed solution, 3.08 g (0.05 mol / L) of tris (2,2,2-trifluoroethyl) borate (manufactured by Aldrich) was added to prepare an electrolytic solution.
正極活物質としてのＬｉＮｉ0.5Ｍｎ1.5Ｏ4を９０質量％、導電材としてのカーボンブラックを８質量％、結着材としてのポリフッ化ビニリデンを２質量％の割合で混合し、分散媒としてのＮ−メチル−２−ピロリドンを適量添加して分散させて、スラリー状正極合材を得た。このスラリー状正極合材を、１５μｍ厚のアルミニウム箔集電体の両面に塗布、乾燥させた後、ロールプレスで高密度化し、正極シートとした。なお、正極活物質の付着量は、片面当たり６．０ｍｇ／ｃｍ2とした。 90% by mass of LiNi 0.5 Mn 1.5 O 4 as the positive electrode active material, 8% by mass of carbon black as the conductive material, and 2% by mass of polyvinylidene fluoride as the binder were mixed to form N as a dispersion medium. -A suitable amount of methyl-2-pyrrolidone was added and dispersed to obtain a slurry-like positive electrode mixture. The slurry-like positive electrode mixture was applied to both sides of a 15 μm thick aluminum foil current collector and dried, and then densified with a roll press to obtain a positive electrode sheet. In addition, the adhesion amount of the positive electrode active material was 6.0 mg / cm 2 per side.
負極活物質としての非晶質コート黒鉛を９８質量％、結着剤としてのスチレンブタジエンゴムを１質量％、増粘剤としてのカルボキシメチルセルロースナトリウムを１質量％の割合で混合し、水を適量添加して分散させて、スラリー状負極合材を得た。このスラリー状負極合材を、１０μｍ厚の銅箔集電体の両面に塗布、乾燥させた後、ロールプレスで高密度化し、負極シートとした。なお、負極活物質の付着量は、片面当たり４．０ｍｇ／ｃｍ2とした。 98% by mass of amorphous coated graphite as a negative electrode active material, 1% by mass of styrene butadiene rubber as a binder, and 1% by mass of sodium carboxymethylcellulose as a thickener, and an appropriate amount of water is added. And dispersed to obtain a slurry-like negative electrode mixture. The slurry-like negative electrode mixture was applied to both sides of a 10 μm thick copper foil current collector, dried, and then densified with a roll press to obtain a negative electrode sheet. In addition, the adhesion amount of the negative electrode active material was 4.0 mg / cm 2 per side.
正極シートに正極集電タブリードを熔接して正極とし、負極シートには負極集電タブリードを熔接して負極とした。これらの正極及び負極の間に、ポリプロピレン／ポリエチレン／ポリプロピレン３層構造で２０μｍ厚の微多孔膜セパレータを挟み、捲回してロール電極体を作製した。このロール電極体を、外装缶及びキャップよりなる、ニッケルメッキした鉄製の円筒形状の電池ケースに挿入した。電池ケースのキャップ側に配置した正極集電タブに、正極集電タブリードを熔接するとともに、外装缶の底に配置した負極集電タブに負極集電タブリードを熔接した。そして、電解液を電池ケース内に含浸させ、キャップにかしめ加工を施すことにより電池ケースを密閉し、円筒型の電池を作製した。 A positive electrode current collector tab lead was welded to the positive electrode sheet to make a positive electrode, and a negative electrode current collector tab lead was welded to the negative electrode sheet to make a negative electrode. A roll electrode body was produced by sandwiching a microporous membrane separator having a polypropylene / polyethylene / polypropylene three-layer structure and having a thickness of 20 μm between the positive electrode and the negative electrode and winding it. This roll electrode body was inserted into a nickel-plated iron cylindrical battery case made of an outer can and a cap. The positive electrode current collector tab lead was welded to the positive electrode current collector tab arranged on the cap side of the battery case, and the negative electrode current collector tab lead was welded to the negative electrode current collector tab arranged on the bottom of the outer can. Then, the battery case was impregnated in the battery case, and the cap was caulked to seal the battery case, thereby producing a cylindrical battery.
（電池のコンディショニング）
得られた電池を用い、２０℃で活性化充放電を行った。１サイクル目は、定電流方式で、電流密度０．３ｍＡ／ｃｍ2（０．３Ｃ相当）の定電流で上限電圧４．９Ｖまで充電した。その後、定電流方式で、電流密度０．３ｍＡ／ｃｍ2で下限電圧３．５Ｖまで放電した。２サイクル目は定電流−定電圧方式で、０．３ｍＡ／ｃｍ2で定電流充電し、４．９Ｖに達した後に４．９Ｖでの定電圧充電を１時間行った。その後、定電流方式で電流密度０．３ｍＡ／ｃｍ2で下限電圧３．５Ｖまで放電した。このときの放電容量をＣiniとした。
(Battery conditioning)
Activation charging / discharging was performed at 20 degreeC using the obtained battery. In the first cycle, the battery was charged to a maximum voltage of 4.9 V with a constant current method and a constant current with a current density of 0.3 mA / cm 2 (equivalent to 0.3 C). Thereafter, the battery was discharged at a current density of 0.3 mA / cm 2 to a lower limit voltage of 3.5 V by a constant current method. In the second cycle, a constant current-constant voltage method was used, and constant current charging was performed at 0.3 mA / cm 2. After reaching 4.9 V, constant voltage charging at 4.9 V was performed for 1 hour. Thereafter, the battery was discharged to a lower limit voltage of 3.5 V at a current density of 0.3 mA / cm 2 by a constant current method. The discharge capacity at this time was Cini.
（電池の高温サイクル耐久試験）
コンディショニング後の電池を用い、６０℃の環境温度、２Ｃ相当の電流で定電流充放電試験を行った。上限電圧を４．９Ｖ、下限電圧を３．５Ｖとし、サイクル数は２００サイクルとした。２００サイクル後の電池を２０℃の環境温度で定電流−定電圧方式で、０．３ｍＡ／ｃｍ2で定電流充電し、４．９Ｖに達した後に４．９Ｖでの定電圧充電を１時間行った。その後、定電流方式で電流密度０．３ｍＡ／ｃｍ2で下限電圧３．５Ｖまで放電した。このときの放電容量をＣ200とし、Ｃ200／Ｃiniを容量維持率とした。
(Battery high-temperature cycle durability test)
Using the conditioned battery, a constant current charge / discharge test was performed at an ambient temperature of 60 ° C. and a current corresponding to 2C. The upper limit voltage was 4.9 V, the lower limit voltage was 3.5 V, and the number of cycles was 200 cycles. The battery after 200 cycles was charged at a constant current-constant voltage method at an ambient temperature of 20 ° C. at a constant current of 0.3 mA / cm 2 , and after reaching 4.9 V, it was charged at a constant voltage of 4.9 V for 1 hour. went. Thereafter, the battery was discharged to a lower limit voltage of 3.5 V at a current density of 0.3 mA / cm 2 by a constant current method. The discharge capacity at this time was C200, and C200 / Cini was the capacity retention rate.
（ガス量測定）
コンディショニング後、高温サイクル耐久試験の前後において、以下のようにガス量の測定を行った。電池を３．５Ｖまで放電した状態で注射筒が接続されたテフロン製密閉容器に入れて密閉し、密閉したままニードルで電池缶に穴をあけ、バルブを開いて注射筒に出てきたガスの容積から電池内発生ガス量を測定した。
(Gas volume measurement)
After conditioning, the amount of gas was measured as follows before and after the high temperature cycle durability test. With the battery discharged to 3.5 V, place it in a Teflon sealed container to which a syringe is connected, seal it, and make a hole in the battery can with a needle, open the valve, and open the valve. The amount of gas generated in the battery was measured from the volume.
［実施例２］
トリス（２，２，２−トリフルオロエチル）ボレートの濃度を０．１ｍｏｌ／Ｌとした電解液を用いた以外は、実施例１と同様とした。
[Example 2]
The procedure was the same as Example 1 except that an electrolytic solution in which the concentration of tris (2,2,2-trifluoroethyl) borate was 0.1 mol / L was used.
［実施例３］
負極活物質としてＬｉＴｉ2Ｏ4を用い、コンディショニング及び高温サイクル耐久試験において上限電圧を３．４Ｖ、下限電圧を２．０Ｖとした以外は、実施例１と同様とした。
[Example 3]
It was the same as Example 1 except that LiTi 2 O 4 was used as the negative electrode active material and the upper limit voltage was set to 3.4 V and the lower limit voltage was set to 2.0 V in the conditioning and high-temperature cycle durability test.
［実施例４］
トリス（２，２，２−トリフルオロエチル）ボレートの濃度を０．１ｍｏｌ／Ｌとした電解液を用い、負極活物質としてＬｉＴｉ2Ｏ4を用い、コンディショニング及び高温サイクル耐久試験において上限電圧を３．４Ｖ、下限電圧を２．０Ｖとした以外は、実施例１と同様とした。
[Example 4]
An electrolytic solution in which the concentration of tris (2,2,2-trifluoroethyl) borate was 0.1 mol / L was used, LiTi 2 O 4 was used as the negative electrode active material, and the upper limit voltage was set to 3 in the conditioning and high-temperature cycle durability test. The same as Example 1 except that the lower limit voltage was set to 0.4V and 2.0V.
［比較例１］
トリス（２，２，２−トリフルオロエチル）ボレートを含まない混合溶液を電解液に用いた以外は、実施例１と同様とした。
[Comparative Example 1]
The same procedure as in Example 1 was conducted except that a mixed solution containing no tris (2,2,2-trifluoroethyl) borate was used as the electrolyte.
［比較例２］
トリス（２，２，２−トリフルオロエチル）ボレートの濃度を０．５ｍｏｌ／Ｌとした電解液を用いた以外は、実施例１と同様とした。
[Comparative Example 2]
The procedure was the same as Example 1 except that an electrolytic solution in which the concentration of tris (2,2,2-trifluoroethyl) borate was 0.5 mol / L was used.
［比較例３］
トリス（２，２，２−トリフルオロエチル）ボレートを含まない混合溶液を電解液に用い、負極活物質としてＬｉＴｉ2Ｏ4を用い、コンディショニング及び高温サイクル耐久試験において上限電圧を３．４Ｖ、下限電圧を２．０Ｖとした以外は、実施例１と同様とした。
[Comparative Example 3]
A mixed solution not containing tris (2,2,2-trifluoroethyl) borate is used as the electrolyte, LiTi 2 O 4 is used as the negative electrode active material, and the upper limit voltage is 3.4 V and the lower limit in conditioning and high-temperature cycle durability tests. The same as Example 1 except that the voltage was 2.0V.
［実験結果］
表１に実験結果をまとめた。なお、表１において、ガス量は、比較例１の初期ガス量を１としたときの相対ガス量とした。負極に黒鉛を用いた比較例１、実施例１、実施例２の比較から、トリス（２，２，２−トリフルオロエチル）ボレートを添加することで、初期ガス量低減及び耐久後ガス量低減が確認された。また、それに伴って、高温サイクル耐久試験の容量維持率の向上も見られた。耐久後のガス成分を分析すると、実施例１や実施例２では比較例１に比して、ＣＯ2及びＨ2がより減少していることがわかった。このことから、トリス（２，２，２−トリフルオロエチル）ボレートの添加により、正極上での溶媒の分解が抑制されてＣＯ2の発生量が減るとともに、溶媒の酸化分解によって生じるＨＦの量が減少したために、負極上でのＨ2発生も抑制されてＨ2発生量が減ったと考えられた。
[Experimental result]
Table 1 summarizes the experimental results. In Table 1, the gas amount is the relative gas amount when the initial gas amount in Comparative Example 1 is 1. From the comparison of Comparative Example 1, Example 1 and Example 2 using graphite as the negative electrode, by adding tris (2,2,2-trifluoroethyl) borate, the initial gas amount is reduced and the post-endurance gas amount is reduced. Was confirmed. Along with this, an improvement in the capacity retention rate of the high-temperature cycle durability test was also observed. Analysis of the gas components after the endurance revealed that CO 2 and H 2 were reduced more in Example 1 and Example 2 than in Comparative Example 1. From this, the addition of tris (2,2,2-trifluoroethyl) borate suppresses the decomposition of the solvent on the positive electrode, thereby reducing the amount of CO 2 generated and the amount of HF generated by the oxidative decomposition of the solvent. Therefore, it was considered that the generation of H 2 on the negative electrode was suppressed and the amount of H 2 generation was reduced.
また、負極に、黒鉛に代えてＬｉＴｉ2Ｏ4を用いた場合にも、同様の効果が得られた。このことから、負極の種類は特に限定されないことがわかった。 The same effect was obtained when LiTi 2 O 4 was used for the negative electrode instead of graphite. From this, it was found that the type of the negative electrode is not particularly limited.
一方、トリス（２，２，２−トリフルオロエチル）ボレートを０．５ｍｏｌ／Ｌ添加した比較例２は初期のガス量は減少したものの、耐久後のガス量や、高温耐久試験の容量維持率が悪化した。比較例２では、耐久後の電池抵抗が上昇していた。この理由は、例えば、トリス（２，２，２−トリフルオロエチル）ボレートの電解液中の割合が高いと、何らかの新たな反応が生じて電極表面に被膜のようなものを形成し、Ｌｉイオンの通過を阻害するためと推察された。 On the other hand, in Comparative Example 2 in which 0.5 mol / L of tris (2,2,2-trifluoroethyl) borate was added, the initial gas amount decreased, but the gas amount after durability and the capacity retention rate of the high temperature durability test Worsened. In Comparative Example 2, the battery resistance after endurance increased. This is because, for example, if the ratio of tris (2,2,2-trifluoroethyl) borate in the electrolyte is high, a new reaction occurs and a film-like material is formed on the electrode surface. It was inferred to inhibit the passage of.
なお、本発明は上述した実施例に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 In addition, this invention is not limited to the Example mentioned above at all, and as long as it belongs to the technical scope of this invention, it cannot be overemphasized that it can implement with a various aspect.
本発明は、電池産業の分野に利用可能である。 The present invention can be used in the field of the battery industry.
１０ リチウム電池、１１ 集電体、１２ 正極活物質、１３ 正極シート、１４ 集電体、１７ 負極活物質、１８ 負極シート、１９ セパレータ、２０ 電解液、２２ 円筒ケース、２４ 正極端子、２６ 負極端子。
DESCRIPTION OF
Claims (8)
負極活物質を含む負極と、
前記正極と前記負極との間に介在し、カーボネート系溶媒と、支持塩と、オルトホウ酸の３つの水素がフッ素化アルキル基で置換された構造を有するボレート化合物と、を含み、前記ボレート化合物が０．０１ｍｏｌ／Ｌ以上０．４ｍｏｌ／Ｌ以下の範囲で含まれる電解液と、
を備えたリチウム電池。 A positive electrode containing a positive electrode active material having a Li insertion / extraction potential of 4.4 V or more based on lithium;
A negative electrode containing a negative electrode active material;
A borate compound that is interposed between the positive electrode and the negative electrode and has a carbonate solvent, a supporting salt, and a borate compound having a structure in which three hydrogen atoms of orthoboric acid are substituted with a fluorinated alkyl group. An electrolytic solution contained in a range of 0.01 mol / L to 0.4 mol / L;
Lithium battery equipped with.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012174546A (en) * | 2011-02-22 | 2012-09-10 | Kaneka Corp | Nonaqueous electrolyte secondary battery |
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| JP2012174546A (en) * | 2011-02-22 | 2012-09-10 | Kaneka Corp | Nonaqueous electrolyte secondary battery |
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