JP2017027944A - Lithium ion battery - Google Patents
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 16
- 239000010935 stainless steel Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052718 tin Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 11
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 31
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 28
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007774 positive electrode material Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 49
- 239000006185 dispersion Substances 0.000 description 29
- 238000007600 charging Methods 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- 238000007599 discharging Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- -1 lithium transition metal compound Chemical class 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920006369 KF polymer Polymers 0.000 description 2
- 229910008090 Li-Mn-O Inorganic materials 0.000 description 2
- 229910006369 Li—Mn—O Inorganic materials 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910017326 LixMn Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
Abstract
Description
本発明は、水系電解液でも２V級の放電が可能なリチウムイオン電池に関する。 The present invention relates to a lithium ion battery capable of 2V class discharge even with an aqueous electrolyte.
リチウムイオン電池は、利点として、高電圧で高エネルギー密度を達成できるため、小型化が可能である。そのことから、ビデオカメラ等の家電製品や、ノート型パソコン、携帯電話機等の携帯型電子機器、電動工具、電動アシスト自転車などの電源として広く用いられている。また最近では、電気自動車（ＥＶ）やハイブリッド電気自動車（ＨＥＶ）などに搭載される大型電池へも応用されつつある。 Since the lithium ion battery can achieve a high energy density at a high voltage as an advantage, it can be miniaturized. Therefore, it is widely used as a power source for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones, power tools, and power-assisted bicycles. Recently, it is also being applied to large batteries mounted on electric vehicles (EV) and hybrid electric vehicles (HEV).
しかし、これら実用化されているリチウムイオン電池は、エチレンカーボネート、ジエチレンカーボネートやプロピレンカーボネートと言った引火性のある溶媒を含有する非水系電解液を使用した非水系リチウムイオン電池である。このため、引火や爆発の危険があり、安全性の問題を潜在的に抱えている。事実、非水系のリチウムイオン電池の発火事故は後を絶たず、その対策のための費用は増大し続けている。
そのような状況の中で、人命に直結するような重大な事故に発展する可能性が高い、電気自動車やハイブリッド電気自動車などは高い安全性を求められるため、自動車業界への非水系電解液リチウムイオン電池の普及は遅れている。
However, these lithium ion batteries in practical use are nonaqueous lithium ion batteries using a nonaqueous electrolytic solution containing a flammable solvent such as ethylene carbonate, diethylene carbonate, and propylene carbonate. For this reason, there is a danger of ignition and explosion, and there is a potential safety problem. In fact, non-aqueous lithium-ion batteries have been ignited continually, and the cost of countermeasures continues to increase.
Under such circumstances, non-aqueous electrolyte lithium for the automobile industry is highly demanded for electric vehicles and hybrid electric vehicles, which are likely to develop into serious accidents that directly affect human life. The spread of ion batteries is delayed.
このため、引火性や爆発の危険性がない水系の電解液電池が提案されている。
例えば、特許文献１では、電極物質として、遷移金属酸化物等のリチウムが可逆的に挿入抽出可能な挿入化合物にリチウムを挿入した化合物、例えばスピネルLixMn2O4を使用することが提案されている。より具体的な電極構成として、チタン棒にLi-Mn-O系の電極ペーストを塗布して得たTi-(Li-Mn-O)-Ti積層体を作成したことが記載されている。
正極を形成する電極ペーストは、リチウムを挿入種とするリチウム遷移金属化合物と、ポリフッ化ビニリデンと、カーボンブラックで構成されている。電解液は溶媒として水、電解質として水酸化リチウムと塩化リチウムの混合物で構成されている。
For this reason, a water-based electrolyte battery without flammability or explosion risk has been proposed.
For example,
The electrode paste that forms the positive electrode is composed of a lithium transition metal compound using lithium as an insertion species, polyvinylidene fluoride, and carbon black. The electrolytic solution is composed of water as a solvent and a mixture of lithium hydroxide and lithium chloride as an electrolyte.
特許文献２では、正極、負極ともに集電体として、アルミニウム、ステンレス、銅、白金等の金属やカーボンなどの導電性の高い固体の箔等を用い、その上に各々、正極物質及び負極物質を固定する。
正極物質は、リチウムイオンを挿脱する物質、ポリフッ化ビニリデンやポリテトラフルオロエチレンなどの結着剤、及び黒鉛粉末、カーボンブラックなどの導電性付与剤で構成されている。負極物質も、リチウムイオンを挿脱する物質、結着剤、導電性付与剤とからなる。リチウムイオンを挿脱する物質としては、遷移金属とリチウムとの複合酸化物やジスルフィド等の有機物が挙げられている。電解液は、中性リチウム塩の水溶液が使用されている。
In
The positive electrode material is composed of a material that inserts and removes lithium ions, a binder such as polyvinylidene fluoride and polytetrafluoroethylene, and a conductivity imparting agent such as graphite powder and carbon black. The negative electrode material also includes a material that inserts and removes lithium ions, a binder, and a conductivity-imparting agent. Examples of the substance that inserts and removes lithium ions include complex oxides of transition metals and lithium, and organic substances such as disulfides. As the electrolytic solution, an aqueous solution of a neutral lithium salt is used.
非特許文献１は、正極集電体としてニッケルメッシュを用い、ここにマンガン酸リチウム、結着剤のポリテトラフルオロエチレン、及び導電助剤のアセチレンブラックを混合したものをプレスして正極としている。負極は亜鉛、電解液は硫酸亜鉛と硫酸リチウムの水溶液を用いている。 Non-Patent Literature 1 uses a nickel mesh as a positive electrode current collector, and presses a mixture of lithium manganate, a binder polytetrafluoroethylene, and a conductive auxiliary agent acetylene black to form a positive electrode. The negative electrode uses zinc and the electrolyte uses an aqueous solution of zinc sulfate and lithium sulfate.
しかし、これらの水系電解液リチウムイオン電池は、安全性は高いものの、水の電気分解により気泡が発生して電圧が上がらないという問題があった。また、気泡の発生は、セルの密封の妨げになるという問題もあった。そこで、高い電圧の水系電解液リチウムイオン電池の実用化には、これらの問題を解決する必要があった。 However, although these aqueous electrolyte lithium ion batteries have high safety, there is a problem that bubbles are generated due to electrolysis of water and the voltage does not increase. In addition, there is a problem that the generation of bubbles hinders cell sealing. Therefore, it was necessary to solve these problems for practical application of a high voltage aqueous electrolyte lithium ion battery.
本発明者らは、今回鋭意工夫の末、リチウムイオンを含む電解液を使用した、起電力が２V級のリチウム電池を発明した。すなわち、正極、負極及び電解液として特定の材料を組み合わせることにより、電解液が水溶液を主体とした水系電解液で構成されていながら、起電力が２V級のリチウム電池を得ることができたのである。 The inventors of the present invention have invented a lithium battery having an electromotive force of 2 V class using an electrolyte containing lithium ions as a result of diligent efforts. That is, by combining specific materials as the positive electrode, the negative electrode, and the electrolytic solution, a lithium battery having an electromotive force of 2 V can be obtained while the electrolytic solution is composed of an aqueous electrolytic solution mainly composed of an aqueous solution. .
すなわち、本発明は、
（１）(a)少なくとも正極、負極、及び電解液を有し、
(b)正極が、少なくとも正極集電体及び正極集電体被覆物から成り、
(c)正極集電体が、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうち一種以上から成り、
(d)負極が、亜鉛、スズ、カドミウム、鉛、水銀、水素吸収蔵合金のうち一種以上から成り、且つ、
(e)電解液が、硝酸リチウムの水溶液である、
(f)リチウムイオン電池、
（２）(a)少なくとも正極、負極、及び電解液を有し、
(b)正極が、少なくとも正極集電体及び正極集電体被覆物から成り、
(c)正極集電体が、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうち一種以上から成り、
(d)負極が、亜鉛、スズ、カドミウム、鉛、水銀、水素吸収蔵合金のうち一種以上から成り、且つ、
(e)電解液が、硝酸リチウム及び硫酸リチウムの水溶液である、
(f)リチウムイオン電池、
（３）(a)少なくとも正極、負極、及び電解液を有し、
(b)正極が、少なくとも正極集電体及び正極集電体被覆物から成り、
(c)正極集電体が、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうち一種以上から成り、
(d)負極が、亜鉛、スズ、カドミウム、鉛、水銀、水素吸収蔵合金のうち一種以上から成り、且つ、
(e)電解液が、硝酸イオン、硫酸イオン及びリチウムイオンを含有する、
(f)リチウムイオン電池、
（４）負極が亜鉛及びスズのうち一種以上であることを特徴とする上記（１）〜（３）のいずれかに記載のリチウムイオン電池、
（５）起電力が２．０Ｖ以上である上記（１）〜（４）のいずれかに記載のリチウムイオン電池、
（６）正極活物質がリチウム金属酸化物である上記（１）〜（５）のいずれかに記載のリチウムイオン電池、に存する。
That is, the present invention
(1) (a) having at least a positive electrode, a negative electrode, and an electrolyte solution;
(b) the positive electrode comprises at least a positive electrode current collector and a positive electrode current collector coating;
(c) the positive electrode current collector is composed of one or more of aluminum, titanium, stainless steel, nickel and carbon;
(d) the negative electrode is composed of one or more of zinc, tin, cadmium, lead, mercury, hydrogen absorbing alloy, and
(e) the electrolyte is an aqueous solution of lithium nitrate;
(f) lithium ion battery,
(2) (a) having at least a positive electrode, a negative electrode, and an electrolyte,
(b) the positive electrode comprises at least a positive electrode current collector and a positive electrode current collector coating;
(c) the positive electrode current collector is composed of one or more of aluminum, titanium, stainless steel, nickel and carbon;
(d) the negative electrode is composed of one or more of zinc, tin, cadmium, lead, mercury, hydrogen absorbing alloy, and
(e) the electrolyte is an aqueous solution of lithium nitrate and lithium sulfate,
(f) lithium ion battery,
(3) (a) having at least a positive electrode, a negative electrode, and an electrolyte,
(b) the positive electrode comprises at least a positive electrode current collector and a positive electrode current collector coating;
(c) the positive electrode current collector is composed of one or more of aluminum, titanium, stainless steel, nickel and carbon;
(d) the negative electrode is composed of one or more of zinc, tin, cadmium, lead, mercury, hydrogen absorbing alloy, and
(e) the electrolytic solution contains nitrate ion, sulfate ion and lithium ion,
(f) lithium ion battery,
(4) The lithium ion battery according to any one of (1) to (3), wherein the negative electrode is at least one of zinc and tin.
(5) The lithium ion battery according to any one of (1) to (4), wherein the electromotive force is 2.0 V or more,
(6) The lithium ion battery according to any one of (1) to (5), wherein the positive electrode active material is a lithium metal oxide.
本発明により、安全性に優れ、かつ高い起電力を有するリチウムイオン電池を得ることができる。 According to the present invention, a lithium ion battery having excellent safety and high electromotive force can be obtained.
本発明におけるリチウムイオン電池とは、リチウムイオンを含む電解液を使用した電池であって、少なくとも、正極、負極及び電解液を有するものをいう。本発明では、これらの各構成部分が、特定の材料から成ることを特徴とする。
また、水系リチウムイオン電池とは、水系電解液、すなわち電解液が溶媒として水を主成分とするものを用いたリチウムイオン電池をいう。
電池の構造は、正極と負極とを物理的に絶縁し、正極と負極の間を電解液で満たしたものとすればよく、従来知られている各種の構造を採用することができる。
本発明のリチウムイオン電池の構成の一例を、図１に示すが、この形態に限られることはない。図中、１は正極、２は正極集電体、３は正極集電体被覆物、４は負極、５は電解液である。６は活物質、７は導電性付与材、８はバインダーである。９は外部回路である。
The lithium ion battery in the present invention is a battery using an electrolytic solution containing lithium ions, and has at least a positive electrode, a negative electrode, and an electrolytic solution. In the present invention, each of these components is made of a specific material.
The aqueous lithium ion battery refers to an aqueous electrolytic solution, that is, a lithium ion battery using an electrolytic solution containing water as a main component as a solvent.
The structure of the battery may be such that the positive electrode and the negative electrode are physically insulated, and the space between the positive electrode and the negative electrode is filled with an electrolytic solution, and various known structures can be employed.
An example of the configuration of the lithium ion battery of the present invention is shown in FIG. 1, but is not limited to this form. In the figure, 1 is a positive electrode, 2 is a positive electrode current collector, 3 is a positive electrode current collector coating, 4 is a negative electrode, and 5 is an electrolyte. 6 is an active material, 7 is a conductivity imparting material, and 8 is a binder. Reference numeral 9 denotes an external circuit.
〔正極〕
本発明では、正極は、図１の様に、少なくとも正極集電体と正極集電体被覆物とで構成されたものである。
[Positive electrode]
In the present invention, as shown in FIG. 1, the positive electrode is composed of at least a positive electrode current collector and a positive electrode current collector coating.
〔正極集電体〕
集電体とは、電池において電気を取り出す端子のことをいい、本発明では、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうちの一種以上を用いる。これらの材料は、陽極酸化に対して耐性のある導電性の高い物質である。もっとも優れているのは、ニッケルであり、次にチタン、アルミニウム、ステンレス、炭素の順番である。
[Positive electrode current collector]
The current collector refers to a terminal for taking out electricity in the battery. In the present invention, one or more of aluminum, titanium, stainless steel, nickel, and carbon are used. These materials are highly conductive substances that are resistant to anodization. The most excellent is nickel, followed by titanium, aluminum, stainless steel, and carbon.
〔正極集電体被覆物〕
正極集電体被覆物は、集電体の少なくとも一部を被覆するものであり、少なくとも(i)正極活物質、(ii)バインダー、(iii)導電性付与材とから構成され、通常は、これらの成分のみで十分である。
正極活物質としては、リチウム金属酸化物（例えば、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、ニッケルマンガンコバルト酸リチウム等、リチウムイオンが挿入、脱離する物質）等、従来よりリウチムイオン電池に用いられてきた各種の材料から選択することができる。より好ましくは、コバルト酸リチウム、ニッケル酸リチウム及びニッケルマンガンコバルト酸リチウムである。最も好ましくはコバルト酸リチウム及びニッケルマンガンコバルト酸リチウムである。
バインダーは、正極活物質と導電性付与材とを一体化し成形し集電体に付着させる機能を有するものであれば足り、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ブチラール、スチレン・ブタジエンゴム（ＳＢＲ）等の、正極集電体に密着しかつ耐水性のある物質を用いることができる。
導電性付与材としては、例えば、カーボンブラック、カーボンナノチューブのような炭素材などで、導電性が得られれば特に制限はない。
[Positive electrode current collector coating]
The positive electrode current collector coating covers at least a part of the current collector, and is composed of at least (i) a positive electrode active material, (ii) a binder, and (iii) a conductivity imparting material. Only these components are sufficient.
As the positive electrode active material, lithium metal oxides (for example, lithium cobalt oxide, lithium manganate, lithium nickelate, lithium nickel manganese cobaltate, etc., a material from which lithium ions are inserted and desorbed), etc., have been conventionally used for lithium ion batteries. It can be selected from various materials that have been used. More preferred are lithium cobaltate, lithium nickelate, and nickel manganese lithium cobaltate. Most preferred are lithium cobaltate and nickel manganese lithium cobaltate.
It is sufficient that the binder has a function of integrating the positive electrode active material and the conductivity-imparting material, and forming and adhering it to the current collector. For example, polyvinylidene fluoride (PVDF), butyral, styrene-butadiene rubber (SBR) A substance that adheres to the positive electrode current collector and has water resistance, such as, can be used.
As the conductivity imparting material, for example, a carbon material such as carbon black or carbon nanotube is used, and there is no particular limitation as long as conductivity is obtained.
〔正極集電体被覆物の混合物の作製方法〕
一般に、（１）正極集電体被覆物を構成する物質を乳鉢やミキサーのような混合器で混合する方法、（２）正極集電体被覆物を構成する物質をN−メチル−２−ピロリドンや水のような液体中で混練し、混合する方法、及び（３）導電性付与材をN−メチル−２−ピロリドンや水のような液体中に分散剤等を使用し事前に分散させた導電性付与材の分散体と正極活物質とバインダーを混錬し、混合する方法がある。
これらの方法のうち、（１）の方法は、連続生産できないため量産化には不向きであり、また均一な混合が難しいため、性能にも限界がある。（２）及び（３）の方法は、そのような問題がないため、より優れている。特に（３）の方法が、分散が困難な導電性付与材を予め均一に分散することにより性能を向上させることができるため、好ましい。
（３）における事前に導電性付与材の分散体の作製方法としては、特開２０１１−７０９０８号公報、特開２０１４−１０７１９１号公報に記載されているような方法も適用できる。また、正極活物質、バインダー、導電性付与材の種類の選定も、これらの特許文献に記載の材料から選択することも可能である。
[Method for producing mixture of cathode current collector coating]
In general, (1) a method of mixing the material constituting the positive electrode current collector coating with a mixer such as a mortar or a mixer, and (2) the material constituting the positive electrode current collector coating is N-methyl-2-pyrrolidone. A method of kneading and mixing in a liquid such as water or water, and (3) the conductivity imparting material is dispersed in advance in a liquid such as N-methyl-2-pyrrolidone or water using a dispersant or the like. There is a method in which a dispersion of a conductivity imparting material, a positive electrode active material, and a binder are kneaded and mixed.
Among these methods, the method (1) is not suitable for mass production because it cannot be continuously produced, and it is difficult to perform uniform mixing, so that the performance is limited. The methods (2) and (3) are more excellent because there are no such problems. In particular, the method (3) is preferred because the performance can be improved by uniformly dispersing in advance a conductivity imparting material that is difficult to disperse.
As a method for preparing a dispersion of a conductivity imparting material in advance in (3), methods described in JP 2011-70908 A and JP 2014-107191 A can also be applied. In addition, the types of the positive electrode active material, the binder, and the conductivity imparting material can also be selected from the materials described in these patent documents.
〔正極の作製方法〕
正極集電体被覆物の混合方法が上記の（１）の時は、正極集電体とともに圧縮成形する。正極集電体被覆物の混合方法が上記（２）又は（３）の時は、正極集電体上にアプリケーターやダイコーターやコンマコーターのような塗布機で塗布し、乾燥機で溶媒を乾燥させる。後者の方が、各成分が均一に混合でき、性能がより優れるため望ましい。
[Method for producing positive electrode]
When the method of mixing the positive electrode current collector coating is (1) above, compression molding is performed together with the positive electrode current collector. When the method of mixing the positive electrode current collector coating is (2) or (3) above, apply it on the positive electrode current collector with an applicator such as an applicator, die coater or comma coater, and dry the solvent with a dryer. Let The latter is desirable because the components can be mixed uniformly and the performance is better.
〔負極〕
本発明では、亜鉛、スズ、カドミウム、鉛、水銀及び水素吸収蔵合金のうち一種以上から選択する。これらは水素過電圧が高く優れている。特に好ましいのは、亜鉛及びスズである。
本発明では、これらの物質が集電体として機能すると同時に電子の授受を行うので、さらに活物質層を設ける必要がない。しかし、さらに集電体として機能する部材を付加しても構わない。例えば、図２に示す構造では、ステンレス製の押さえ部材１０は、正極集電体被覆物と、亜鉛等から成る負極とを、電解液と接触させるための固定手段として機能すると同時に、電気を取り出す端子である集電体としても機能している。
[Negative electrode]
In this invention, it selects from 1 or more types among zinc, tin, cadmium, lead, mercury, and a hydrogen absorbing alloy. These are excellent in hydrogen overvoltage. Particularly preferred are zinc and tin.
In the present invention, since these substances function as a current collector and exchange electrons at the same time, there is no need to provide an active material layer. However, a member that functions as a current collector may be added. For example, in the structure shown in FIG. 2, the pressing
〔電解液〕
溶媒はリチウムイオン電池において使用されている溶媒を使用することができる。特に本発明では溶媒を水として水系のリチウムイオン電池とした場合でも高い電圧を得ることができることが特徴である。必要に応じて界面活性剤のような添加剤や陽極酸化を抑制する添加剤を加えても問題ない。
電解質は硝酸リチウム、又は硝酸リチウムと硫酸リチウムとの混合物を使用する。すなわち、これらの物質を水溶液とし、硝酸イオンとリチウムイオンとを存在させるか、又は硝酸イオン、硫酸イオン及びリチウムイオンを存在させる。これにより、気泡の発生を抑えることができ、高い電圧を得ることができる上に密封したパッケージングが可能である。
硝酸リチウムを使用する場合、すなわち硝酸イオンとリチウムイオンを存在させる場合には、硝酸リチウムの濃度は高い方が、放電時間が長くなるので好ましい。具体的には２mol/リットル以上、飽和濃度未満が適切である。
また、硫酸イオン、硝酸イオン及びリチウムイオンを存在させる場合には、硝酸イオン濃度は０．０５mol/リットル以上であれば足り、かつ飽和濃度未満が適切である。硫酸イオン濃度は高いほうが好ましいが、１mol/リットル以上であれば足り、かつ飽和濃度未満が適切である。リチウムイオンの濃度は２．０５mol/リットル以上、かつ飽和濃度未満が適切である。
[Electrolyte]
As the solvent, a solvent used in a lithium ion battery can be used. In particular, the present invention is characterized in that a high voltage can be obtained even when an aqueous lithium ion battery is used with a solvent as water. There is no problem even if an additive such as a surfactant or an additive for suppressing anodization is added as necessary.
As the electrolyte, lithium nitrate or a mixture of lithium nitrate and lithium sulfate is used. That is, these substances are made into aqueous solutions and nitrate ions and lithium ions are present, or nitrate ions, sulfate ions and lithium ions are present. Thereby, generation | occurrence | production of a bubble can be suppressed, a high voltage can be obtained, and the sealed packaging is possible.
When lithium nitrate is used, that is, when nitrate ions and lithium ions are present, a higher concentration of lithium nitrate is preferable because the discharge time becomes longer. Specifically, 2 mol / liter or more and less than the saturation concentration are appropriate.
When sulfate ions, nitrate ions, and lithium ions are present, the nitrate ion concentration need only be 0.05 mol / liter or more, and less than the saturation concentration is appropriate. A higher sulfate ion concentration is preferred, but 1 mol / liter or more is sufficient, and less than a saturated concentration is appropriate. The lithium ion concentration is suitably 2.05 mol / liter or more and less than the saturation concentration.
本発明では正極集電体と負極と電解液を以上のように、特定の物質で構成し、それらを組み合わせることによって意外にも非常に優れた効果が表れることが分かった。すなわち、水系のリチウムイオン電池において、従来達成できなかった２Ｖ以上という高い起電力を得ることができる。 In the present invention, it has been found that the positive current collector, the negative electrode, and the electrolytic solution are composed of specific substances as described above, and a surprisingly excellent effect appears by combining them. In other words, in an aqueous lithium ion battery, a high electromotive force of 2 V or more, which has not been achieved in the past, can be obtained.
次に、この発明の具体的な実施例について説明する。 Next, specific examples of the present invention will be described.
＜実施例１＞
〔導電性付与材の分散体の作製〕
溶媒（ＮＭＰ：三菱化学（株）製）７８．５ｇと分散剤（「メトローズＳＭ−４」（商品名）：信越化学（株）製）１．５ｇと導電性付与材（「デンカブラック粒状」（商品名）：電気化学工業（株）製のアセチレンブラック）２０ｇを直径１ｍｍのジルコニアビーズ（「ＹＴＺボール」（商品名）：（株）ニッカトー製）３００ｇとともに、Ｓ−ボトル広口丸形２５０ｃｃに仕込み、ペイントコンディショナー（「ペイントシェーカー」（商品名）：浅田鉄工（株）製）で２時間分散を行い、導電性付与材の分散体として、「分散体１」を得た。
<Example 1>
[Preparation of dispersion of conductivity imparting material]
78.5 g of solvent (NMP: manufactured by Mitsubishi Chemical Corporation), 1.5 g of dispersant (“Metroze SM-4” (trade name): manufactured by Shin-Etsu Chemical Co., Ltd.) and conductivity imparting material (“Denka Black Granular”) (Product Name): 20 g of acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd. and 300 g of zirconia beads having a diameter of 1 mm (“YTZ ball” (product name): manufactured by Nikkato Co., Ltd.) into 250-cc S-bottle Hiroguchi round shape The dispersion was performed for 2 hours using a paint conditioner (“Paint Shaker” (trade name) manufactured by Asada Tekko Co., Ltd.), and “
〔正極集電体被覆物の混合物の作製〕
正極活物質として、コバルト酸リチウム（「セルシードＣ１０Ｎ」（商品名）：日本化学工業（株）製）１９．１ｇとバインダー（「ＫＦポリマーＬ＃７２０８」（商品名）：クレハ化学（株）製ＰＶＤＦ。ＰＶＤＦを８ｗｔ％含有）３．７５ｇ（樹脂固形分：０．３ｇ）と分散体１を３．０ｇ（アセチレンブラック含有量：０．６ｇ）仕込み、スパチュラで予備撹拌したのち、遊星攪拌機（「ＡＲＥ−３１０」（商品名）：（株）シンキー製）で自転２０００ｒｐｍ、公転８００ｒｐｍで１分間混錬し、混合した。
[Preparation of mixture of cathode current collector coating]
As a positive electrode active material, 19.1 g of lithium cobaltate (“Cell Seed C10N” (trade name): manufactured by Nippon Chemical Industry Co., Ltd.) and a binder (“KF Polymer L # 7208” (trade name): manufactured by Kureha Chemical Co., Ltd.) PVDF (containing 8 wt% of PVDF) 3.75 g (resin solid content: 0.3 g) and 3.0 g of dispersion 1 (acetylene black content: 0.6 g) were charged, pre-stirred with a spatula, and then a planetary stirrer ( “ARE-310” (trade name): manufactured by Shinky Co., Ltd., kneaded at 2000 rpm for rotation and 800 rpm for 1 minute, and mixed.
〔正極の作製〕
正極集電体被覆物の混合物をアルミニウム箔（アルミニウム箔、厚さ２０μｍ：宝泉（株）製）にアプリケーター（「ＳＡ−２０４ マイクロメーター付フィルムアプリケーター」（商品名）：テスター産業（株）製）で塗布した。その後、１００℃の温風乾燥機（「ＤＮ６００」（商品名）：ヤマト科学（株）製）で３０分間乾燥させた。その後、正極と電解液の接液用開口部分より大きく切り取り正極とした。
[Production of positive electrode]
The mixture of the positive electrode current collector coating is applied to an aluminum foil (aluminum foil,
〔負極〕
亜鉛箔（厚さ０．１ｍｍ：（株）ニラコ製）を負極と電解液の接液用開口部分より大きく切り取り負極とした。
[Negative electrode]
A zinc foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was cut out larger than the opening for contact with the negative electrode and the electrolyte solution to obtain a negative electrode.
〔電解液の作製〕
１０００ｃｃメスフラスコに硝酸リチウム（硝酸リチウム特級：ナカライテスク（株）製）４１３．７ｇを仕込み、イオン交換水で１０００ｃｃにメスアップし、６ｍｏｌ／リットルの硝酸リチウム水溶液を作製した。
(Preparation of electrolyte)
413.7 g of lithium nitrate (lithium nitrate special grade: manufactured by Nacalai Tesque Co., Ltd.) was charged into a 1000 cc volumetric flask and made up to 1000 cc with ion-exchanged water to prepare a 6 mol / liter lithium nitrate aqueous solution.
〔電池の作製〕
以上により作成した正極、負極及び電解液を用い、図２に示すリチウムイオン電池を組み立て、以下の試験に使用した。図中、１０はキャップ、１１は電解液充填セル、１２は正極押さえ、１３は負極押さえ、１４はバンドである。セルの形状は直方体で、向かい合った一組の側面の下部には開口部分１５が設けられ、正極及び負極が、電解液と接触するようになっている。正極及び負極は各々、正極押さえ及び負極押さえによりセルの開口部分に押さえつけられた状態で、ゴム製のバンドで締め付けられることにより固定されている。正極押さえ及び負極押さえは、導線を介して外部回路に接続し、通電可能となっている。
セルは、上部から電解液を注入した後、キャップで封入する構造になっている。
開口部分の設けられた一組の側面の間の距離、すなわち電極間距離は１８ｍｍ、開口部分の面積は０．７８５ｃｍ２、セルの素材はPEEK（ポリエーテルエーテルケトン）製、正極押さえ及び負極押さえはステンレス製である。
[Production of battery]
The lithium ion battery shown in FIG. 2 was assembled using the positive electrode, the negative electrode, and the electrolyte prepared as described above, and used for the following tests. In the figure, 10 is a cap, 11 is an electrolyte-filled cell, 12 is a positive electrode holder, 13 is a negative electrode holder, and 14 is a band. The shape of the cell is a rectangular parallelepiped, and an
The cell has a structure in which an electrolytic solution is injected from above and sealed with a cap.
The distance between a pair of side surfaces provided with the opening, that is, the distance between the electrodes is 18 mm, the area of the opening is 0.785 cm 2 , and the material of the cell is made of PEEK (polyether ether ketone). Is made of stainless steel.
〔充電方法〕
ポテンショスタット（「ＰＳ−０４」（商品名）：（株）東邦技研製）で開回路電位から２．５Vまで１０ｍV／ｓで掃引し、２．５Vで１２００秒間保持して充電完了とした。
[Charging method]
A potentiostat (“PS-04” (trade name): manufactured by Toho Giken Co., Ltd.) was swept from the open circuit potential to 2.5 V at 10 mV / s and held at 2.5 V for 1200 seconds to complete charging.
〔放電、確認方法〕
充電後起電力をテスター（「カードハイテスタ３２４４」（商品名）：日置電機（株）製）で測定し、その後モーター（「Ａ１２５」（商品名）：日精電機（株）製）に接続し、モーターが回転することを確認した。
その時、モーターの回転時間を測定した。
〔気泡発生の確認方法〕
気泡発生の確認方法は、図２の電池においてキャップ１０を開け、目視で電解液表面に気泡が浮かび上がってきていないかを確認した。
[Discharge, confirmation method]
After charging, the electromotive force was measured with a tester (“Card Hi Tester 3244” (trade name) manufactured by Hioki Electric Co., Ltd.), and then connected to a motor (“A125” (trade name) manufactured by Nissei Electric Co., Ltd.). Confirmed that the motor rotates.
At that time, the rotation time of the motor was measured.
[Confirmation method of bubble generation]
As for the method for confirming the generation of bubbles, the
以上の充放電テストの態様の概念図を、図３に示す。図中、１６はスイッチ、１７はポテンショスタット、１８はモーター、１９は導線、２０はリチウムイオン電池、２１はテスタである。 FIG. 3 shows a conceptual diagram of the above charge / discharge test mode. In the figure, 16 is a switch, 17 is a potentiostat, 18 is a motor, 19 is a conductor, 20 is a lithium ion battery, and 21 is a tester.
＜実施例２＞
正極集電体としてチタン箔（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 2>
A battery was prepared in the same manner as in Example 1 except that titanium foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the positive electrode current collector, and charging and discharging were performed in the same manner.
＜実施例３＞
正極集電体としてＳＵＳ３０４板（ＪＩＳ Ｇ ４３０５ 厚さ１．０ｍｍ：日本テストパネル（株）製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 3>
A battery was prepared in the same manner as in Example 1 except that a SUS304 plate (JIS G 4305 thickness 1.0 mm: manufactured by Nippon Test Panel Co., Ltd.) was used as the positive electrode current collector, and charging and discharging were performed in the same manner. .
＜実施例４＞
正極集電体としてニッケル板（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 4>
A battery was prepared in the same manner as in Example 1 except that a nickel plate (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the positive electrode current collector, and charging and discharging were performed in the same manner.
＜実施例５＞
正極集電体としてグラッシーカーボン（厚さ１．０ｍｍ：（株）ニラコ製）炭素板を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 5>
A battery was prepared in the same manner as in Example 1 except that a glassy carbon (thickness 1.0 mm: manufactured by Nilaco Corporation) carbon plate was used as the positive electrode current collector, and charging and discharging were performed in the same manner.
＜実施例６＞
負極としてスズ箔（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 6>
A battery was prepared in the same manner as in Example 1 except that tin foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the negative electrode, and charging and discharging were performed in the same manner.
＜実施例７＞
〔電解液の作製〕
１００ｃｃメスフラスコに硝酸リチウム（硝酸リチウム：ナカライテスク（株）製）４１．４ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、２ｍｏｌ／リットルの硝酸リチウム水溶液を作製した。
電解液として、この２ｍｏｌ／リットルの硝酸リチウム溶液を使用した以外は、実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 7>
(Preparation of electrolyte)
41.4 g of lithium nitrate (lithium nitrate: manufactured by Nacalai Tesque Co., Ltd.) was charged into a 100 cc volumetric flask and made up to 100 cc with ion-exchanged water to prepare a 2 mol / liter lithium nitrate aqueous solution.
A battery was prepared in the same manner as in Example 1 except that this 2 mol / liter lithium nitrate solution was used as the electrolytic solution, and charged and discharged in the same manner.
＜実施例８＞
〔導電性付与材の分散体の作製〕
溶媒（ＮＭＰ：三菱化学（株）製）９３．５ｇと分散剤（「エスレックＢ ＢＬ−１０」（商品名）：積水化学工業（株）製）１．５ｇと導電性付与材（「ＦＬＯＴＵＢＥ９１１０」（商品名）：Ｃｎａｎｏ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ製の粉状カーボンナノチューブ）５ｇを直径１ｍｍのジルコニアビーズ（「ＹＴＺボール」（商品名）：（株）ニッカトー製）３００ｇとともに、Ｓ−ボトル広口丸形２５０ｃｃに仕込み、ペイントコンディショナー（「ペイントシェーカー」（商品名）：浅田鉄工（株）製）で５時間分散を行い、導電性付与材の分散体として、「分散体２」を得た。
導電性付与剤の分散体として、分散体２を使用した以外は、実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 8>
[Preparation of dispersion of conductivity imparting material]
93.5 g of solvent (NMP: manufactured by Mitsubishi Chemical Co., Ltd.) and a dispersant (“ESREC B BL-10” (trade name): manufactured by Sekisui Chemical Co., Ltd.) and a conductivity imparting material (“FLOTUBE 9110”) (Product Name): 5 g of Cano Technology Limited powdered carbon nanotubes together with 300 g of 1 mm diameter zirconia beads (“YTZ ball” (trade name): manufactured by Nikkato Co., Ltd.) into 250 cc S-bottle wide-mouth round 250 cc Then, dispersion was performed for 5 hours with a paint conditioner (“Paint Shaker” (trade name): manufactured by Asada Tekko Co., Ltd.), and “
A battery was prepared in the same manner as in Example 1 except that
＜実施例９＞
正極活物質として、ニッケルマンガンコバルト酸リチウム（「ＮＭＥ−１１００」（商品名）：戸田工業（株）製）を使用した以外は、実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 9>
A battery was prepared in the same manner as in Example 1 except that lithium nickel manganese cobaltate (“NME-1100” (trade name): manufactured by Toda Kogyo Co., Ltd.) was used as the positive electrode active material. Discharge was performed.
＜実施例１０＞
導電性付与材の分散体として、分散体２を使用し、正極活物質として、マンガン酸リチウム（「ＨＰＭ７０５１」（商品名）：戸田工業（株）製）を使用した以外は、実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 10>
Example 1 with the exception that
＜実施例１１＞
〔導電性付与材の分散体の作製〕
溶媒（ＮＭＰ：三菱化学（株）製）７９．０ｇと分散剤（「ＰＶＰ Ｋ−１５」（商品名）：アイエスピー・ジャパン（株）製）１．０ｇと導電性付与材（「トーカブラック＃５５００」（商品名）：東海カーボン（株）製のカーボンブラック）２０ｇを直径１ｍｍのジルコニアビーズ（「ＹＴＺボール」（商品名）：（株）ニッカトー製）３００ｇとともに、Ｓ−ボトル広口丸形２５０ｃｃに仕込み、ペイントコンディショナー（「ペイントシェーカー」（商品名）：浅田鉄工（株）製）で２時間分散を行い、導電性付与材の分散体として、「分散体３」を得た。
<Example 11>
[Preparation of dispersion of conductivity imparting material]
79.0 g of solvent (NMP: manufactured by Mitsubishi Chemical Corporation), 1.0 g of dispersant (“PVP K-15” (trade name): manufactured by IPS Japan Co., Ltd.) and conductivity imparting material (“Toka Black”) # 5500 "(trade name): carbon black manufactured by Tokai Carbon Co., Ltd.) together with 300 g of zirconia beads having a diameter of 1 mm (" YTZ ball "(trade name): manufactured by Nikkato Co., Ltd.) and S-bottle Hiroguchi round shape The dispersion was charged at 250 cc and dispersed for 2 hours with a paint conditioner (“Paint Shaker” (trade name) manufactured by Asada Tekko Co., Ltd.) to obtain “
導電性付与剤の分散体として、分散体３を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
A battery was prepared in the same manner as in Example 1 except that
＜実施例１２＞
〔導電性付与材の分散体の作製〕
溶媒としてイオン交換水８０．５ｇと分散剤（「セロゲン５Ａ」（商品名）：第一工業製薬（株）製）１．５ｇと導電性付与材（「デンカブラック粒状」（商品名）：電気化学工業（株）製アセチレンブラック）１８．０ｇを直径１ｍｍのジルコニアビーズ（「ＹＴＺボール」（商品名）：（株）ニッカトー製）３００ｇとともに、Ｓ−ボトル広口丸形２５０ｃｃに仕込み、ペイントコンディショナー（「ペイントシェーカー」（商品名）：浅田鉄工（株）製）で２時間分散を行い、導電性付与材の分散体として、「分散体４」を得た。
<Example 12>
[Preparation of dispersion of conductivity imparting material]
80.5 g of ion-exchanged water as a solvent, 1.5 g of a dispersant (“Serogen 5A” (trade name): manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a conductivity-imparting material (“Denka Black Granule” (trade name): Electric 18.0 g of acetylene black manufactured by Chemical Industry Co., Ltd., together with 300 g of zirconia beads having a diameter of 1 mm (“YTZ ball” (trade name): manufactured by Nikkato Co., Ltd.) into 250 cc S-bottle wide-mouth round shape, paint conditioner ( “Paint shaker” (trade name: manufactured by Asada Tekko Co., Ltd.) was used for dispersion for 2 hours to obtain “
〔正極集電体被覆物の混合物の作製〕
正極活物質として、コバルト酸リチウム（「セルシードＣ１０Ｎ」（商品名）：日本化学工業（株）製）１９．１ｇとバインダー（「ＴＤＲ２００１」（商品名）：ＪＳＲ（株）製スチレン・ブタジエンゴム（ＳＢＲ）エマルション）０．８ｇ（ＳＢＲ固形分：０．３ｇ）と分散体４を３．３ｇ（アセチレンブラック含有量：０．６ｇ）とイオン交換水１．０ｇを仕込み、スパチュラで予備撹拌したのち、遊星攪拌機（「ＡＲＥ−３１０」（商品名）：（株）シンキー製）で自転２０００ｒｐｍ、公転８００ｒｐｍで１分間混錬し、混合した。
導電性付与材の分散体として分散体４を用い、正極集電体被覆物の混合物として上記のものを用いた以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
[Preparation of mixture of cathode current collector coating]
As a positive electrode active material, 19.1 g of lithium cobalt oxide ("Cellseed C10N" (trade name): manufactured by Nippon Chemical Industry Co., Ltd.) and a binder ("TDR2001" (trade name): styrene butadiene rubber (manufactured by JSR Corporation) ( (SBR) emulsion) 0.8 g (SBR solid content: 0.3 g), 3.3 g of dispersion 4 (acetylene black content: 0.6 g) and 1.0 g of ion-exchanged water were charged, and after pre-stirring with a spatula The mixture was kneaded with a planetary stirrer (“ARE-310” (trade name): manufactured by Sinky Co., Ltd.) at 2000 rpm for rotation and 800 rpm for 1 minute and mixed.
A battery was prepared in the same manner as in Example 1 except that the
＜実施例１３＞
バインダーとしてブチラール樹脂（「エスレックＳＨ−３」（商品名）：積水化学工業（株）製）を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 13>
A battery was prepared in the same manner as in Example 1 except that butyral resin (“ESREC SH-3” (trade name): manufactured by Sekisui Chemical Co., Ltd.) was used as a binder, and charging and discharging were performed in the same manner.
＜実施例１４＞
〔正極集電体被覆物の混合物の作製〕
溶媒（ＮＭＰ：三菱化学（株）製）６．０ｇと導電性付与材（「デンカブラック粉状」（商品名：電気化学工業（株）製アセチレンブラック）を遊星攪拌機（「ＡＲＥ−３１０」（商品名）：（株）シンキー製）で自転２０００ｒｐｍ、公転８００ｒｐｍで１分間混錬した。そこに、正極活物質として、コバルト酸リチウム（「セルシードＣ１０Ｎ」（商品名）：日本化学工業（株）製）１９．１ｇとバインダー（「ＫＦポリマーＬ＃７２０８」（商品名）：クレハ化学（株）製。ＰＶＤＦを８ｗｔ％含有）３．７５ｇ（樹脂固形分：０．３ｇ）を添加し、スパチュラで予備撹拌したのち、遊星攪拌機（「ＡＲＥ−３１０」（商品名）：（株）シンキー製）で自転２０００ｒｐｍ、公転８００ｒｐｍで１分間混錬し、混合して正極集電体被覆物の混合物を得た。
正極集電体被覆物の混合物の作製方法以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 14>
[Preparation of mixture of cathode current collector coating]
A planetary stirrer (“ARE-310”) (6.0 g of a solvent (NMP: manufactured by Mitsubishi Chemical Corporation) and a conductivity-imparting material (“DENKA BLACK POWDER” (trade name: acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd.)) (Product name): manufactured by Shinky Co., Ltd., and kneaded for 1 minute at a rotational speed of 2000 rpm and revolution of 800 rpm, and as a positive electrode active material, lithium cobaltate ("Cellseed C10N" (trade name): Nippon Chemical Industry Co., Ltd. 19.1 g and a binder (“KF polymer L # 7208” (trade name): manufactured by Kureha Chemical Co., Ltd. containing 8 wt% PVDF) 3.75 g (resin solid content: 0.3 g) were added, and a spatula was added. , And then kneaded with a planetary stirrer (“ARE-310” (trade name): manufactured by Sinky Co., Ltd.) at a rotation speed of 2000 rpm and a revolution speed of 800 rpm for 1 minute, and mixed to cover the positive electrode current collector. To give a mixture of.
A battery was prepared in the same manner as in Example 1 except for the method of preparing the mixture of the positive electrode current collector coating, and charging and discharging were performed in the same manner.
＜比較例１＞
正極集電体として亜鉛箔（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 1>
A battery was prepared in the same manner as in Example 1 except that zinc foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the positive electrode current collector, and charging and discharging were performed in the same manner.
＜比較例２＞
正極集電体としてスズ箔（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative example 2>
A battery was prepared in the same manner as in Example 1 except that tin foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the positive electrode current collector, and charging and discharging were performed in the same manner.
＜比較例３＞
負極としてニッケル箔（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 3>
A battery was prepared in the same manner as in Example 1 except that nickel foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the negative electrode, and charging and discharging were performed in the same manner.
＜比較例４＞
負極としてグラッシーカーボン（厚さ１．０ｍｍ：（株）ニラコ製）炭素を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative example 4>
A battery was prepared in the same manner as in Example 1 except that glassy carbon (thickness 1.0 mm: manufactured by Nilaco Co., Ltd.) carbon was used as the negative electrode, and charging and discharging were performed in the same manner.
＜比較例５＞
負極としてチタン箔（厚さ０．１ｍｍ：（株）ニラコ製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 5>
A battery was prepared in the same manner as in Example 1 except that titanium foil (thickness 0.1 mm: manufactured by Nilaco Co., Ltd.) was used as the negative electrode, and charging and discharging were performed in the same manner.
＜比較例６＞
負極としてＳＵＳ３０４板（ＪＩＳ Ｇ ４３０５ 厚さ１．０ｍｍ：日本テストパネル（株）製）を使用した他は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 6>
A battery was prepared in the same manner as in Example 1 except that a SUS304 plate (JIS G 4305 thickness 1.0 mm: manufactured by Nippon Test Panel Co., Ltd.) was used as the negative electrode, and charging and discharging were performed in the same manner.
＜比較例７＞
〔電解液の作製〕
１００ｃｃメスフラスコに硫酸リチウム（硫酸リチウム：キシダ化学（株）製）２２．０ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、２ｍｏｌ／リットルの硫酸リチウム水溶液を作製した。
電解液として、この２ｍｏｌ／リットルの硫酸リチウム溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 7>
(Preparation of electrolyte)
22.0 g of lithium sulfate (lithium sulfate: manufactured by Kishida Chemical Co., Ltd.) was charged into a 100 cc volumetric flask and made up to 100 cc with ion-exchanged water to prepare a 2 mol / liter lithium sulfate aqueous solution.
A battery was prepared in the same manner as in Example 1 except that this 2 mol / liter lithium sulfate solution was used as the electrolytic solution, and charged and discharged in the same manner.
＜比較例８＞
〔電解液の作製〕
１００ｃｃメスフラスコに塩化リチウム（塩化リチウム：東京化成工業（株）製）２５．４ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、６ｍｏｌ／リットルの塩化リチウム水溶液を作製した。
電解液として、この６ｍｏｌ／リットルの塩化リチウム溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 8>
(Preparation of electrolyte)
Into a 100 cc volumetric flask, 25.4 g of lithium chloride (lithium chloride: manufactured by Tokyo Chemical Industry Co., Ltd.) was charged and made up to 100 cc with ion-exchanged water to prepare a 6 mol / liter lithium chloride aqueous solution.
A battery was prepared in the same manner as in Example 1 except that this 6 mol / liter lithium chloride solution was used as the electrolytic solution, and charged and discharged in the same manner.
＜実施例１５＞
〔電解液の作製〕
１００ｃｃのメスフラスコに硫酸リチウム（硫酸リチウム：キシダ化学（株）製）２２．０ｇと硝酸リチウム（（硝酸リチウム：ナカライテスク（株）製）２０．７ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、２ｍｏｌ／リットル硫酸リチウム、１ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この２ｍｏｌ／リットル硫酸リチウム、１ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 15>
(Preparation of electrolyte)
Into a 100 cc volumetric flask, 22.0 g of lithium sulfate (lithium sulfate: manufactured by Kishida Chemical Co., Ltd.) and 20.7 g of lithium nitrate ((lithium nitrate: manufactured by Nacalai Tesque)) were charged, and the volume was increased to 100 cc with ion-exchanged water. Then, 2 mol / liter lithium sulfate and 1 mol / liter lithium nitrate aqueous solution were prepared.
A battery was prepared in the same manner as in Example 1 except that this 2 mol / liter lithium sulfate and 1 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charged and discharged in the same manner.
＜実施例１６＞
〔電解液の作製〕
１００ｃｃのメスフラスコに硫酸リチウム（硫酸リチウム：キシダ化学（株）製）２２．０ｇと硝酸リチウム（（硝酸リチウム：ナカライテスク（株）製）１０．４ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、２ｍｏｌ／リットル硫酸リチウム、０．５ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この２ｍｏｌ／リットル硫酸リチウム、０．５ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 16>
(Preparation of electrolyte)
Into a 100 cc volumetric flask, 22.0 g of lithium sulfate (lithium sulfate: manufactured by Kishida Chemical Co., Ltd.) and 10.4 g of lithium nitrate ((lithium nitrate: manufactured by Nacalai Tesque)) were charged, and the volume was increased to 100 cc with ion-exchanged water. Then, 2 mol / liter lithium sulfate and 0.5 mol / liter lithium nitrate aqueous solution were prepared.
A battery was prepared in the same manner as in Example 1 except that this 2 mol / liter lithium sulfate and 0.5 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charged and discharged in the same manner.
＜実施例１７＞
〔電解液の作製〕
１００ｃｃのメスフラスコに硫酸リチウム（硫酸リチウム：キシダ化学（株）製）２２．０ｇと硝酸リチウム（（硝酸リチウム：ナカライテスク（株）製）２．１ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、２ｍｏｌ／リットル硫酸リチウム、０．１ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この２ｍｏｌ／リットル硫酸リチウム、０．１ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 17>
(Preparation of electrolyte)
Into a 100 cc volumetric flask, 22.0 g of lithium sulfate (lithium sulfate: manufactured by Kishida Chemical Co., Ltd.) and 2.1 g of lithium nitrate ((lithium nitrate: manufactured by Nacalai Tesque)) were charged, and the volume was increased to 100 cc with ion-exchanged water. Then, 2 mol / liter lithium sulfate and 0.1 mol / liter lithium nitrate aqueous solution were prepared.
A battery was prepared in the same manner as in Example 1 except that this 2 mol / liter lithium sulfate and 0.1 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charged and discharged in the same manner.
＜実施例１８＞
〔電解液の作製〕
１００ｃｃのメスフラスコに硫酸リチウム（硫酸リチウム：キシダ化学（株）製）１１．０ｇと硝酸リチウム（（硝酸リチウム：ナカライテスク（株）製）２．１ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、１ｍｏｌ／リットル硫酸リチウム、０．１ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この１ｍｏｌ／リットル硫酸リチウム、０．１ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 18>
(Preparation of electrolyte)
A 100 cc volumetric flask was charged with 11.0 g of lithium sulfate (lithium sulfate: manufactured by Kishida Chemical Co., Ltd.) and 2.1 g of lithium nitrate ((lithium nitrate: manufactured by Nacalai Tesque)), and the volume was increased to 100 cc with ion-exchanged water. Then, 1 mol / liter lithium sulfate and 0.1 mol / liter lithium nitrate aqueous solution were prepared.
A battery was prepared in the same manner as in Example 1 except that this 1 mol / liter lithium sulfate and 0.1 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charged and discharged in the same manner.
＜実施例１９＞
〔電解液の作製〕
１００ｃｃのメスフラスコに硫酸リチウム（硫酸リチウム：キシダ化学（株）製）１１．０ｇと硝酸リチウム（（硝酸リチウム：ナカライテスク（株）製）１．０ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、１ｍｏｌ／リットル硫酸リチウム、０．０５ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この１ｍｏｌ／リットル硫酸リチウム、０．０５ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Example 19>
(Preparation of electrolyte)
A 100 cc volumetric flask was charged with 11.0 g of lithium sulfate (lithium sulfate: manufactured by Kishida Chemical Co., Ltd.) and 1.0 g of lithium nitrate ((lithium nitrate: manufactured by Nacalai Tesque)), and the volume was increased to 100 cc with ion-exchanged water. Then, 1 mol / liter lithium sulfate and 0.05 mol / liter lithium nitrate aqueous solution were prepared.
A battery was prepared in the same manner as in Example 1 except that this 1 mol / liter lithium sulfate and 0.05 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charged and discharged in the same manner.
＜比較例９＞
〔電解液の作製〕
１００ｃｃのメスフラスコに塩化リチウム（塩化リチウム：東京化成工業（株）製）４．２ｇと硝酸リチウム（（硝酸リチウム：ナカライテスク（株）製）２０．７ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、１ｍｏｌ／リットル塩化リチウム、１ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この１ｍｏｌ／リットル塩化リチウム、１ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 9>
(Preparation of electrolyte)
Into a 100 cc volumetric flask, 4.2 g of lithium chloride (lithium chloride: manufactured by Tokyo Chemical Industry Co., Ltd.) and 20.7 g of lithium nitrate ((lithium nitrate: manufactured by Nacalai Tesque)) were charged, and the volume was adjusted to 100 cc with ion-exchanged water. 1 mol / liter lithium chloride, 1 mol / liter lithium nitrate aqueous solution was prepared.
A battery was prepared in the same manner as in Example 1 except that this 1 mol / liter lithium chloride and 1 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charging and discharging were performed in the same manner.
＜比較例１０＞
〔電解液の作製〕
１００ｃｃのメスフラスコに水酸化リチウム（水酸化リチウム一水和物：和光純薬工業（株）製）４．２ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、１ｍｏｌ／リットル水酸化リチウム水溶液を作製した。
電解液として、この１ｍｏｌ／リットル水酸化リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 10>
(Preparation of electrolyte)
Into a 100 cc volumetric flask was charged 4.2 g of lithium hydroxide (lithium hydroxide monohydrate: manufactured by Wako Pure Chemical Industries, Ltd.), made up to 100 cc with ion-exchanged water, and a 1 mol / liter lithium hydroxide aqueous solution was added. Produced.
A battery was prepared in the same manner as in Example 1 except that this 1 mol / liter lithium hydroxide aqueous solution was used as the electrolytic solution, and charged and discharged in the same manner.
＜比較例１１＞
〔電解液の作製〕
１００ｃｃのメスフラスコに水酸化リチウム（水酸化リチウム一水和物：和光純薬工業（株）製）４．２ｇと１．０ｇを仕込み、イオン交換水で１００ｃｃにメスアップし、１ｍｏｌ／リットル水酸化リチウム、０．０５ｍｏｌ／リットル硝酸リチウム水溶液を作製した。
電解液として、この１ｍｏｌ／リットル水酸化リチウム、０．０５ｍｏｌ／リットル硝酸リチウム水溶液を使用した以外は実施例１と同様にして電池を作成し、同様に充電、放電を行った。
<Comparative Example 11>
(Preparation of electrolyte)
4.2 g and 1.0 g of lithium hydroxide (lithium hydroxide monohydrate: manufactured by Wako Pure Chemical Industries, Ltd.) are charged into a 100 cc volumetric flask, and the volume is increased to 100 cc with ion-exchanged water. Lithium oxide, 0.05 mol / liter lithium nitrate aqueous solution was prepared.
A battery was prepared in the same manner as in Example 1 except that this 1 mol / liter lithium hydroxide and 0.05 mol / liter lithium nitrate aqueous solution were used as the electrolytic solution, and charged and discharged in the same manner.
以上の実施例及び比較例における使用材料、並びに測定された起電力及びモーター回転時間を、表１〜４に示す。 The materials used in the above Examples and Comparative Examples, and the measured electromotive force and motor rotation time are shown in Tables 1 to 4.
正極集電体のみを変化させた実施例１〜５と比較例１〜２とを比較すると、正極集電体としてアルミニウム、チタン、ステンレス、ニッケル、及び炭素から選択すれば、充放電が可能であり、しかも２ボルト以上の高い起電力を得ることができるが、正極集電体として亜鉛、スズを用いた場合には充放電しないことがわかる。 Comparing Examples 1 to 5 and Comparative Examples 1 and 2 in which only the positive electrode current collector was changed, charging and discharging are possible if the positive electrode current collector is selected from aluminum, titanium, stainless steel, nickel, and carbon. In addition, a high electromotive force of 2 volts or more can be obtained, but it is understood that charging and discharging are not performed when zinc or tin is used as the positive electrode current collector.
負極のみを変化させた実施例６〜７と比較例３〜６とを比較すると、負極として亜鉛、スズから選択すれば充放電可能であり、しかも２ボルト以上の高い起電力を得ることができるが、負極としてチタン、ステンレス、ニッケル、炭素を用いた場合は充放電しないことがわかる。これら負極として充放電可能な材質と充放電しない材質とは、水素化電圧の点で差がある。すなわち、負極として充放電可能な材質は、充放電しない材質に比べて、大幅に高い水素過電圧を持っていることが特徴である。したがって、充放電可能な材質と同等の高い水素過電圧が特徴であるカドミウム、鉛、水銀、水素吸蔵合金も、充放電可能であることが合理的に推測できる。 Comparing Examples 6 to 7 and Comparative Examples 3 to 6 in which only the negative electrode was changed, charging and discharging are possible if zinc or tin is selected as the negative electrode, and a high electromotive force of 2 volts or more can be obtained. However, when titanium, stainless steel, nickel, or carbon is used as the negative electrode, it is understood that charging / discharging is not performed. There is a difference in the hydrogenation voltage between the material that can be charged and discharged as the negative electrode and the material that is not charged and discharged. That is, a material that can be charged and discharged as a negative electrode is characterized by having a significantly higher hydrogen overvoltage than a material that does not charge and discharge. Therefore, it can be reasonably estimated that cadmium, lead, mercury, and a hydrogen storage alloy, which are characterized by a high hydrogen overvoltage equivalent to a chargeable / dischargeable material, can also be charged / discharged.
したがって、正極集電体としてアルミニウム、チタン、ステンレス、ニッケル、及び炭素のうち１種以上を用い、且つ、負極として亜鉛、スズ、カドミウム、鉛、水銀、及び水素吸蔵合金のうち１種以上を用いることが、水系で２ボルト以上の高い起電力を有するリチウムイオン電池を得るための条件であることがわかる。
さらに、実施例１と比較例７〜８の結果から、電解液として硝酸リチウムの水溶液を用いれば、充電時に気泡の発生がなく、水系で２ボルト以上の高い起電力を有するリチウムイオン電池を得ることができることがわかる。
Accordingly, at least one of aluminum, titanium, stainless steel, nickel, and carbon is used as the positive electrode current collector, and at least one of zinc, tin, cadmium, lead, mercury, and a hydrogen storage alloy is used as the negative electrode. This is a condition for obtaining a lithium ion battery having a high electromotive force of 2 volts or more in an aqueous system.
Furthermore, from the results of Example 1 and Comparative Examples 7-8, if an aqueous solution of lithium nitrate is used as the electrolyte, a lithium ion battery having no electrolysis during charging and having a high electromotive force of 2 volts or more in an aqueous system is obtained. You can see that
以上から、正極集電体としてアルミニウム、チタン、ステンレス、ニッケル、及び炭素のうち１種以上を用い、負極として亜鉛、スズ、カドミウム、鉛、水銀、及び水素吸蔵合金のうち１種以上を用い、且つ電解液として硝酸リチウムの水溶液を用いれば、充電時に気泡の発生がなく、水系で２ボルト以上の高い起電力を有するリチウムイオン電池を得ることができることがわかる。
また、実施例１と７の結果から、電解液に硝酸リチウムの水溶液を用いた場合の硝酸リチウム塩の濃度すなわち硝酸イオンの濃度は高い方が起電力が高く電池性能が優れていることがわかる。
また、実施例１５〜１９の結果からは、電解液に硝酸イオン、硫酸イオン及びリチウムイオンを含有させた場合の硫酸イオン濃度は高いほど性能が良く、硝酸イオン濃度は非常に少なく０．０５モル/リットル以上であれば十分に良好な電池性能が発現していることがわかる。
From the above, using one or more of aluminum, titanium, stainless steel, nickel, and carbon as the positive electrode current collector, using one or more of zinc, tin, cadmium, lead, mercury, and hydrogen storage alloy as the negative electrode, In addition, when an aqueous solution of lithium nitrate is used as the electrolytic solution, it is understood that there is no generation of bubbles during charging, and a lithium ion battery having a high electromotive force of 2 volts or more in an aqueous system can be obtained.
Further, from the results of Examples 1 and 7, it is understood that the higher the concentration of lithium nitrate, that is, the concentration of nitrate ions, in the case of using an aqueous solution of lithium nitrate as the electrolyte, the higher the electromotive force and the better the battery performance. .
Further, from the results of Examples 15 to 19, the higher the sulfate ion concentration when the electrolyte solution contains nitrate ion, sulfate ion and lithium ion, the better the performance, and the very low nitrate ion concentration is 0.05 mol. It can be seen that a sufficiently good battery performance is exhibited when the capacity is 1 / liter or more.
実施例１、８及び１１の結果からは、導電性付与材としてカーボンブラックやカーボンナノチューブなど各種の炭素材料を用いることができること、特にアセチレンブラックを用いれば、高い起電力が得られ、電池性能が優れることがわかる。
実施例１、９及び１０からは、正極活物質として従来から知られているリチウム金属化合物であるコバルト酸リチウム、ニッケルマンガンコバルト酸リチウム、マンガン酸リチウムといった各種の化合物が使用できることがわかる。
実施例１、１２及び１３からは、バインダーとして正極集電体に密着性のあるＰＶＤＦ、ＳＢＲといった各種の材料を使用できることがわかる。
From the results of Examples 1, 8 and 11, it is possible to use various carbon materials such as carbon black and carbon nanotubes as the conductivity-imparting material. In particular, if acetylene black is used, high electromotive force can be obtained and battery performance is improved. It turns out that it is excellent.
Examples 1, 9 and 10 show that various compounds such as lithium cobaltate, nickel manganese lithium cobaltate, and lithium manganate, which are lithium metal compounds conventionally known as positive electrode active materials, can be used.
From Examples 1, 12 and 13, it can be seen that various materials such as PVDF and SBR having adhesion to the positive electrode current collector can be used as the binder.
実施例１及び１４からは、正極集電体被覆物を作成するための前述の方法のうち、（２）正極集電体被覆物を構成する物質をN−メチル−２−ピロリドンや水のような液体中で混練し、混合する方法、及び（３）導電性付与材をN−メチル−２−ピロリドンや水のような液体中に分散剤等を使用し事前に分散させた導電性付与材の分散体と正極活物質とバインダーを混錬し、混合する方法、のいずれも使用可能であること、がわかる。また、導電性付与材の分散に分散剤を用いていない実施例１４に比べて実施例１の方が優れた結果を得ていることから、特に（３）の方法が、より優れた性能を得られることがわかる。これは、一般に均一な分散が困難な微細粒子である導電性付与材を、より均一化しておくことにより一層性能を発揮できるためと推測される。したがって、（２）や（３）の方法のほうが、前述の（１）正極集電体被覆物を構成する物質を乳鉢やミキサーのような混合器で混合する方法、に比べて、より優れた性能を発揮できることが推測できる。 From Examples 1 and 14, among the above-described methods for preparing the positive electrode current collector coating, (2) the substance constituting the positive electrode current collector coating is N-methyl-2-pyrrolidone or water. A method of kneading and mixing in a simple liquid, and (3) a conductivity imparting material in which the conductivity imparting material is dispersed in advance in a liquid such as N-methyl-2-pyrrolidone or water It can be seen that any of the dispersion method, the positive electrode active material, and the binder can be kneaded and mixed. In addition, since the result of Example 1 is superior to Example 14 in which a dispersant is not used for dispersing the conductivity imparting material, the method (3) has particularly superior performance. It turns out that it is obtained. This is presumed to be because performance can be further enhanced by making the conductivity imparting material, which is generally fine particles difficult to uniformly disperse, more uniform. Therefore, the methods (2) and (3) are superior to the method (1) in which the material constituting the positive electrode current collector coating is mixed with a mixer such as a mortar or a mixer. It can be estimated that performance can be demonstrated.
本発明により、起電力が高く、かつ安全性に優れたリチウムイオン電池を得ることができる。 According to the present invention, a lithium ion battery having high electromotive force and excellent safety can be obtained.
１ 正極
２ 正極集電体
３ 正極集電体被覆物
４ 負極
５ 電解液
６ 正極活物質
７ 導電性付与材
８ バインダー
９ 外部回路
１０ キャップ
１１ 電解液充填セル
１２ 正極押さえ
１３ 負極押さえ
１４ バンド
１５ 開口部分
１６ スイッチ
１７ ポテンショスタット
１８ モーター
１９ 導線
２０ リチウムイオン電池
２１ テスタ
DESCRIPTION OF
Claims (6)
(b)正極が、少なくとも正極集電体及び正極集電体被覆物から成り、
(c)正極集電体が、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうち一種以上から成り、
(d)負極が、亜鉛、スズ、カドミウム、鉛、水銀、水素吸収蔵合金のうち一種以上から成り、且つ、
(e)電解液が、硝酸リチウムの水溶液である、
(f)リチウムイオン電池。 (a) having at least a positive electrode, a negative electrode, and an electrolytic solution,
(b) the positive electrode comprises at least a positive electrode current collector and a positive electrode current collector coating;
(c) the positive electrode current collector is composed of one or more of aluminum, titanium, stainless steel, nickel and carbon;
(d) the negative electrode is composed of one or more of zinc, tin, cadmium, lead, mercury, hydrogen absorbing alloy, and
(e) the electrolyte is an aqueous solution of lithium nitrate;
(f) Lithium ion battery.
(b)正極が、少なくとも正極集電体及び正極集電体被覆物から成り、
(c)正極集電体が、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうち一種以上から成り、
(d)負極が、亜鉛、スズ、カドミウム、鉛、水銀、水素吸収蔵合金のうち一種以上から成り、且つ、
(e)電解液が、硝酸リチウム及び硫酸リチウムの水溶液である、
(f)リチウムイオン電池。 (a) having at least a positive electrode, a negative electrode, and an electrolytic solution,
(b) the positive electrode comprises at least a positive electrode current collector and a positive electrode current collector coating;
(c) the positive electrode current collector is composed of one or more of aluminum, titanium, stainless steel, nickel and carbon;
(d) the negative electrode is composed of one or more of zinc, tin, cadmium, lead, mercury, hydrogen absorbing alloy, and
(e) the electrolyte is an aqueous solution of lithium nitrate and lithium sulfate,
(f) Lithium ion battery.
(b)正極が、少なくとも正極集電体及び正極集電体被覆物から成り、
(c)正極集電体が、アルミニウム、チタン、ステンレス、ニッケル及び炭素のうち一種以上から成り、
(d)負極が、亜鉛、スズ、カドミウム、鉛、水銀、水素吸収蔵合金のうち一種以上から成り、且つ、
(e)電解液が、硝酸イオン、硫酸イオン及びリチウムイオンを含有する、
(f)リチウムイオン電池。 (a) having at least a positive electrode, a negative electrode, and an electrolytic solution,
(b) the positive electrode comprises at least a positive electrode current collector and a positive electrode current collector coating;
(c) the positive electrode current collector is composed of one or more of aluminum, titanium, stainless steel, nickel and carbon;
(d) the negative electrode is composed of one or more of zinc, tin, cadmium, lead, mercury, hydrogen absorbing alloy, and
(e) the electrolytic solution contains nitrate ion, sulfate ion and lithium ion,
(f) Lithium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019021514A (en) * | 2017-07-18 | 2019-02-07 | トヨタ自動車株式会社 | Negative electrode current collector, negative electrode, and aqueous lithium ion secondary battery |
| JP2020021609A (en) * | 2018-07-31 | 2020-02-06 | 株式会社豊田中央研究所 | Aqueous solution secondary battery |
| WO2020054099A1 (en) | 2018-09-13 | 2020-03-19 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, vehicle, and stationary power supply |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995021470A1 (en) * | 1994-02-03 | 1995-08-10 | Moli Energy (1990) Limited | Aqueous rechargeable battery |
| US20100221596A1 (en) * | 2009-02-06 | 2010-09-02 | Huggins Robert A | Systems, methods of manufacture and use involving lithium and/or hydrogen for energy-storage applications |
| JP2013062135A (en) * | 2011-09-13 | 2013-04-04 | Toyota Motor Corp | Air cell |
| JP2014515546A (en) * | 2011-06-03 | 2014-06-30 | ▲蘇▼州宝▲時▼得▲電▼▲動▼工具有限公司 | battery |
| JP2015095431A (en) * | 2013-11-14 | 2015-05-18 | 株式会社豊田中央研究所 | Aqueous solution-type secondary battery |
| CN205052863U (en) * | 2015-07-02 | 2016-03-02 | 广西中烟工业有限责任公司 | River system lithium ion battery electron cigarette |
-
2016
- 2016-07-22 JP JP2016144932A patent/JP2017027944A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995021470A1 (en) * | 1994-02-03 | 1995-08-10 | Moli Energy (1990) Limited | Aqueous rechargeable battery |
| US20100221596A1 (en) * | 2009-02-06 | 2010-09-02 | Huggins Robert A | Systems, methods of manufacture and use involving lithium and/or hydrogen for energy-storage applications |
| JP2014515546A (en) * | 2011-06-03 | 2014-06-30 | ▲蘇▼州宝▲時▼得▲電▼▲動▼工具有限公司 | battery |
| JP2013062135A (en) * | 2011-09-13 | 2013-04-04 | Toyota Motor Corp | Air cell |
| JP2015095431A (en) * | 2013-11-14 | 2015-05-18 | 株式会社豊田中央研究所 | Aqueous solution-type secondary battery |
| CN205052863U (en) * | 2015-07-02 | 2016-03-02 | 广西中烟工业有限责任公司 | River system lithium ion battery electron cigarette |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019021514A (en) * | 2017-07-18 | 2019-02-07 | トヨタ自動車株式会社 | Negative electrode current collector, negative electrode, and aqueous lithium ion secondary battery |
| US10998547B2 (en) | 2017-07-18 | 2021-05-04 | Toyota Jidosha Kabushiki Kaisha | Negative electrode current collector, negative electrode, and aqueous lithium ion secondary battery |
| JP2020021609A (en) * | 2018-07-31 | 2020-02-06 | 株式会社豊田中央研究所 | Aqueous solution secondary battery |
| WO2020054099A1 (en) | 2018-09-13 | 2020-03-19 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, vehicle, and stationary power supply |
| US11251436B2 (en) | 2018-09-13 | 2022-02-15 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, vehicle, and stationary power supply |
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