JP2012074167A - Electrode for lithium ion secondary battery and manufacturing method thereof, and lithium ion secondary battery - Google Patents
Electrode for lithium ion secondary battery and manufacturing method thereof, and lithium ion secondary battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 33
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000007772 electrode material Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000010298 pulverizing process Methods 0.000 claims abstract description 4
- 239000002003 electrode paste Substances 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 3
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 17
- 239000011245 gel electrolyte Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 10
- 229920000447 polyanionic polymer Polymers 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- -1 nickel metal hydride Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 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
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 229920001798 poly[2-(acrylamido)-2-methyl-1-propanesulfonic acid] polymer Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920006369 KF polymer Polymers 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- NEKSMZUJCUEYAR-UHFFFAOYSA-M lithium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Li+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C NEKSMZUJCUEYAR-UHFFFAOYSA-M 0.000 description 1
- OHGICEXGYYWLRO-UHFFFAOYSA-N lithium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound [Li].OS(=O)(=O)CC(C)(C)NC(=O)C=C OHGICEXGYYWLRO-UHFFFAOYSA-N 0.000 description 1
- ZKIAYSOOCAKOJR-UHFFFAOYSA-M lithium;2-phenylethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 ZKIAYSOOCAKOJR-UHFFFAOYSA-M 0.000 description 1
- BKOLBAQLWMWQMZ-UHFFFAOYSA-M lithium;ethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=C BKOLBAQLWMWQMZ-UHFFFAOYSA-M 0.000 description 1
- OWHKPASDYFOLTA-UHFFFAOYSA-M lithium;methyl 2-methylprop-2-enoate;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O.COC(=O)C(C)=C OWHKPASDYFOLTA-UHFFFAOYSA-M 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウムイオン二次電池用電極及びその製造方法、並びに該電極を用いたリチウムイオン二次電池に関する。 The present invention relates to an electrode for a lithium ion secondary battery, a manufacturing method thereof, and a lithium ion secondary battery using the electrode.
リチウムイオン二次電池は、鉛蓄電池、ニッケル水素電池に比べて、エネルギー密度及び起電力が高いという特徴を有するため、小型、軽量化が要求される携帯電話やノートパソコン等の電源として広く使用されている。現在、これらの機器に使用されているリチウムイオン二次電池の多くには、電解液として、リチウム塩を有機溶媒に溶解させた非水系電解液が使用されている。
しかしながら、非水系電解液を使用した二次電池は、有機溶媒の液漏れに伴う充放電サイクル寿命特性の低下や、負極から正極方向に成長するデンドライドの析出に伴う内部短絡発生などの危険性を有しており、最悪の場合、発火事故の原因ともなる。一方で、近年は、リチウムイオン二次電池を電力貯蔵用の大型定置用電源や電気自動車用の電源として利用することが期待されており、リチウムイオン二次電池のさらなる高エネルギー密度化と安全性の向上が強く望まれている。
Lithium ion secondary batteries are characterized by high energy density and electromotive force compared to lead-acid batteries and nickel metal hydride batteries, so they are widely used as power sources for mobile phones and laptop computers that require small size and light weight. ing. Currently, in many of the lithium ion secondary batteries used in these devices, a nonaqueous electrolytic solution in which a lithium salt is dissolved in an organic solvent is used as the electrolytic solution.
However, secondary batteries using non-aqueous electrolytes have a risk of deterioration of charge / discharge cycle life characteristics due to leakage of organic solvent and occurrence of internal short circuit due to precipitation of dendrites growing from the negative electrode to the positive electrode. In the worst case, it may cause a fire accident. On the other hand, in recent years, it has been expected that lithium ion secondary batteries will be used as large stationary power sources for power storage and power sources for electric vehicles. Improvement is strongly desired.
そこで、電解質として固体又はゲル状のものを利用する系が考案され、さかんに研究が進められている。これらの電解質を使用することにより、電解液の揮発拡散や液漏れが防止されるため、電池としての信頼性、安全性が向上する。さらに、電解質自体を薄膜化、積層化することが容易となるため、プロセス性の向上とパッケージの簡略化が期待されている。
リチウムイオン二次電池の基本構造は、電解液又は固体もしくはゲル状電解質と、正極活物質を含む正極と、負極活物質を含む負極とから構成されている。正極及び負極は、活物質を含む組成物を集電体に塗布して乾燥させることで作製され、前記組成物は集電体の片面及び両面のいずれに塗布されても良い。両面塗布の場合に、電極は積層構造を有し、これによりリチウムイオン二次電池の大容量化が可能となる。
Therefore, a system utilizing a solid or gel electrolyte is devised, and research is being conducted rapidly. By using these electrolytes, volatile diffusion and leakage of the electrolytic solution are prevented, so that reliability and safety as a battery are improved. Furthermore, since the electrolyte itself can be easily thinned and laminated, it is expected to improve processability and simplify the package.
The basic structure of a lithium ion secondary battery includes an electrolytic solution or a solid or gel electrolyte, a positive electrode including a positive electrode active material, and a negative electrode including a negative electrode active material. The positive electrode and the negative electrode are produced by applying a composition containing an active material to a current collector and drying it, and the composition may be applied to either one or both sides of the current collector. In the case of double-sided coating, the electrode has a laminated structure, which makes it possible to increase the capacity of the lithium ion secondary battery.
リチウムイオン二次電池において電解液を使用する場合には、電解液が電極の細孔部にまで浸透するため、リチウムイオンが効率よく移動できる。しかし、固体又はゲル状電解質を使用する場合には、固体又はゲル状であるがゆえに、これら電解質と電極との間の界面抵抗が大きくなり、充放電特性が不充分となって電池の大容量化が困難であるという問題点があった。 When using an electrolytic solution in a lithium ion secondary battery, the electrolytic solution penetrates into the pores of the electrode, so that lithium ions can move efficiently. However, when a solid or gel electrolyte is used, since it is solid or gel, the interfacial resistance between the electrolyte and the electrode is increased, resulting in insufficient charge / discharge characteristics and a large capacity of the battery. There was a problem that it was difficult to make it.
そこで、これら問題点を解決しようとする技術が種々検討されている。特許文献１には、固体電解質と電極活物質との間に、この固体電解質と電極活物質を含む中間層が設けられたリチウムイオン二次電池が開示されている。また、特許文献２には、固体電解質を加熱融解したものを電極に塗布し、電極と電極を貼り合わせて得られたリチウムイオン二次電池が開示されている。これら特許文献では、電極と固体電解質との間の界面抵抗を低減できるため、充放電特性の改善やエネルギー密度の増加などの電池特性の向上が可能であるとされている。
Therefore, various techniques for solving these problems have been studied.
しかし、これら特許文献で開示されているリチウムイオン二次電池は、製造時に固体電解質又は電極表面に、さらに電解質材料を塗布するという手法が必要であり、製造方法が煩雑で、しかも界面抵抗の低減や電池の大容量化も不十分であるという問題点があった。 However, the lithium ion secondary batteries disclosed in these patent documents require a technique in which an electrolyte material is further applied to the solid electrolyte or electrode surface at the time of production, and the production method is complicated and the interface resistance is reduced. In addition, there is a problem that the capacity of the battery is not sufficient.
本発明は上記事情に鑑みてなされたものであり、簡便に製造でき、固体電解質又はゲル状電解質を使用した場合であっても、充分な電池性能が得られるリチウムイオン二次電池を提供することを課題とする。 The present invention has been made in view of the above circumstances, and provides a lithium ion secondary battery that can be easily manufactured and can provide sufficient battery performance even when a solid electrolyte or a gel electrolyte is used. Is an issue.
上記課題を解決するため、
本発明は、ポリアニオン型リチウム塩を含有することを特徴とするリチウムイオン二次電池用電極を提供する。
本発明のリチウムイオン二次電池用電極においては、前記ポリアニオン型リチウム塩が、ポリカルボン酸リチウム塩及びポリスルホン酸リチウム塩からなる群から選択される一種以上であることが好ましい。
また、本発明は、上記本発明の電極を備えたことを特徴とするリチウムイオン二次電池を提供する。
また、本発明は、上記本発明のリチウムイオン二次電池用電極の製造方法であって、電極活物質及びポリアニオン型リチウム塩水溶液を混合し、得られた混合物を乾燥及び粉砕して粉体を作製する工程と、該粉体、結着剤及び導電剤を混合して電極用ペーストを作製する工程と、を有することを特徴とするリチウムイオン二次電池用電極の製造方法を提供する。
To solve the above problem,
The present invention provides an electrode for a lithium ion secondary battery comprising a polyanion type lithium salt.
In the lithium ion secondary battery electrode of the present invention, the polyanion type lithium salt is preferably at least one selected from the group consisting of a polycarboxylic acid lithium salt and a polysulfonic acid lithium salt.
The present invention also provides a lithium ion secondary battery comprising the electrode of the present invention.
The present invention also relates to a method for producing an electrode for a lithium ion secondary battery according to the present invention, wherein an electrode active material and a polyanion type lithium salt aqueous solution are mixed, and the resulting mixture is dried and pulverized to obtain a powder. There is provided a method for producing an electrode for a lithium ion secondary battery, comprising a step of producing, and a step of producing an electrode paste by mixing the powder, a binder and a conductive agent.
本発明によれば、簡便に製造でき、固体電解質又はゲル状電解質を使用した場合であっても、充分な電池性能が得られるリチウムイオン二次電池が得られる。 According to the present invention, a lithium ion secondary battery can be obtained that can be easily manufactured and can provide sufficient battery performance even when a solid electrolyte or a gel electrolyte is used.
以下、本発明について詳しく説明する。
＜リチウムイオン二次電池用電極＞
本発明のリチウムイオン二次電池用電極は、ポリアニオン型リチウム塩を含有することを特徴とする。ここで、「ポリアニオン型リチウム塩を含有する」とは、電極の構成成分としてポリアニオン型リチウム塩が含まれることを指し、例えば、電極表面にポリアニオン型リチウム塩が単に付着している場合など、電極からのポリアニオン型リチウム塩の脱離を自在に行える場合を除く。
このような電極を使用することで、固体電解質又はゲル状電解質を使用した場合であっても、充分な電池性能が得られるリチウムイオン二次電池が得られる。また、かかるリチウムイオン二次電池は、簡便に製造できる。
The present invention will be described in detail below.
<Electrode for lithium ion secondary battery>
The electrode for a lithium ion secondary battery of the present invention is characterized by containing a polyanionic lithium salt. Here, “containing a polyanion-type lithium salt” means that a polyanion-type lithium salt is included as a component of the electrode. For example, when the polyanion-type lithium salt is simply attached to the electrode surface, the electrode Excludes cases where polyanion-type lithium salts can be freely detached from
By using such an electrode, it is possible to obtain a lithium ion secondary battery capable of obtaining sufficient battery performance even when a solid electrolyte or a gel electrolyte is used. Such a lithium ion secondary battery can be easily manufactured.
本発明のリチウムイオン二次電池用電極としては、前記ポリアニオン型リチウム塩を含有する電極用ペーストが集電体上に塗布され、乾燥されたものを、好ましいものとして例示できる。 As a lithium ion secondary battery electrode of the present invention, a preferable example is one in which the electrode paste containing the polyanionic lithium salt is applied on a current collector and dried.
ポリアニオン型リチウム塩は、特に限定されず、ポリマー構造中に複数のアニオン部及び該アニオン部と塩を形成するリチウムカチオン（リチウムイオン、Ｌｉ＋）を含むものであれば、いずれも好適に使用できる。好ましいものとしては、酸のリチウム塩である部位を複数含むものが例示でき、該酸としては、カルボン酸及びスルホン酸が例示できる。
すなわち、ポリアニオン型リチウム塩の好ましいものとしては、ポリカルボン酸リチウム塩及びポリスルホン酸リチウム塩が例示できる。
The polyanionic lithium salt is not particularly limited, and any polyanionic lithium salt can be suitably used as long as it includes a plurality of anion portions and a lithium cation (lithium ion, Li + ) that forms a salt with the anion portion in the polymer structure. . Preferred examples include those containing a plurality of sites that are lithium salts of acids, and examples of the acids include carboxylic acids and sulfonic acids.
That is, preferable examples of the polyanion type lithium salt include polycarboxylic acid lithium salt and polysulfonic acid lithium salt.
前記ポリカルボン酸リチウム塩の好ましいものとしては、ポリ（（メタ）アクリル酸リチウム）、ポリマレイン酸リチウム、ポリフマル酸リチウム、ポリムコン酸リチウム、ポリソルビン酸リチウム、ポリ（アクリロニトリル−ブタジエン−アクリル酸リチウム）共重合体、ポリ（ｔｅｒｔ−ブチルアクリレート−エチルアクリレート−メタクリル酸リチウム）共重合体、ポリ（エチレン−アクリル酸リチウム）共重合体、ポリ（メチルメタクリレート−メタクリル酸リチウム）共重合体が例示でき、ポリ（アクリル酸リチウム）がより好ましい。なお、本明細書において、「（メタ）アクリル酸」は、「アクリル酸」及び「メタクリル酸」の双方を指すものとする。 Preferred examples of the lithium polycarboxylic acid salt include poly ((meth) lithium acrylate), lithium polymaleate, lithium polyfumarate, lithium polymuconate, lithium polysorbate, and poly (acrylonitrile-butadiene-lithium acrylate) copolymer. Examples thereof include poly (tert-butyl acrylate-ethyl acrylate-lithium methacrylate) copolymer, poly (ethylene-lithium acrylate) copolymer, and poly (methyl methacrylate-lithium methacrylate) copolymer. Lithium acrylate) is more preferred. In the present specification, “(meth) acrylic acid” refers to both “acrylic acid” and “methacrylic acid”.
前記ポリスルホン酸リチウム塩の好ましいものとしては、ポリ（２−アクリルアミド−２−メチル−１−プロパンスルホン酸リチウム）、ポリ（スチレンスルホン酸リチウム）、ポリ（ビニルスルホン酸リチウム）、ポリ（パーフルオロスルホン酸リチウム）が例示できる。ポリ（パーフルオロスルホン酸リチウム）としては、ポリ（パーフルオロアルケンスルホン酸リチウムや、下記一般式（１）で表されるものが例示できる。 Preferred examples of the lithium polysulfonate include poly (2-acrylamido-2-methyl-1-propanesulfonate), poly (lithium styrenesulfonate), poly (lithium vinylsulfonate), and poly (perfluorosulfone). Lithium acid) can be exemplified. Examples of poly (lithium perfluorosulfonate) include poly (lithium perfluoroalkene sulfonate) and those represented by the following general formula (1).
前記ポリアニオン型リチウム塩は、一種を単独で使用しても良いし、二種以上を併用しても良い。二種以上を併用する場合には、その組み合わせ及び比率は目的に応じて適宜選択すれば良い。 The polyanion type lithium salt may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio may be appropriately selected according to the purpose.
本発明のリチウムイオン二次電池用電極としては、前記ポリアニオン型リチウム塩で被覆された電極活物質を含有するものが例示できる。そして、かかる電極活物質を含むこと以外は、従来の電極と同様の構成とすることができ、例えば、かかる電極活物質、導電剤、結着剤等が配合されてなる電極用ペーストが、集電体上に塗布され、乾燥されたものが例示できる。電極用ペーストが乾燥され、形成された層は、集電体の片面のみに設けられていても良いし、両面に設けられていても良い。 Examples of the electrode for a lithium ion secondary battery of the present invention include those containing an electrode active material coated with the polyanion type lithium salt. The composition can be the same as that of the conventional electrode except that such an electrode active material is included. For example, an electrode paste containing such an electrode active material, a conductive agent, a binder, and the like is collected. The thing apply | coated and dried on the electrical conductor can be illustrated. The layer formed by drying the electrode paste may be provided only on one side of the current collector, or may be provided on both sides.
前記電極活物質のうち、正極用活物質としては、エネルギー密度が高く、リチウムイオンの可逆的な脱離及び進入を可能とする機能に優れた、リチウムを含有する遷移金属酸化物が好ましい。このような正極用活物質として、具体的には、ＬｉＣｏＯ２等のコバルト複合酸化物；ＬｉＭｎ２O４等のマンガン複合酸化物；ＬｉＮｉＯ２等のニッケル複合酸化物；これら酸化物からなる群から選択される二種以上の混合物；ＬｉＮｉＯ２等のニッケル複合酸化物においてニッケル（Ｎｉ）の一部がコバルト（Ｃｏ）やマンガン（Ｍｎ）に置換された複合酸化物；ＬｉＦｅＰＯ４、ＬｉＦｅＶＯ４等の鉄複合酸化物等が例示できる。 Among the electrode active materials, the positive electrode active material is preferably a lithium-containing transition metal oxide having a high energy density and an excellent function of allowing reversible desorption and entry of lithium ions. Specifically, as such a positive electrode active material, a cobalt composite oxide such as LiCoO 2 ; a manganese composite oxide such as LiMn 2 O 4 ; a nickel composite oxide such as LiNiO 2 ; a group consisting of these oxides A mixture of two or more selected; a composite oxide in which a part of nickel (Ni) is substituted with cobalt (Co) or manganese (Mn) in a nickel composite oxide such as LiNiO 2 ; LiFePO 4 , LiFeVO 4, etc. Examples thereof include iron complex oxides.
前記電極活物質のうち、負極用活物質としては、リチウムイオンの可逆的な進入及び脱離を可能とする材料であれば特に限定されないが、好ましいものとして炭素材料が例示できる。そして、かかる炭素材料として具体的には、天然黒鉛、アモルファスカーボン、グラファイト、メソカーボンマイクロビーズ、メソフェーズピッチ系炭素繊維、樹脂単体を炭化処理した炭素材等が例示できる。 Among the electrode active materials, the negative electrode active material is not particularly limited as long as it is a material that allows reversible entry and detachment of lithium ions, but a carbon material can be exemplified as a preferable material. Specific examples of such carbon materials include natural graphite, amorphous carbon, graphite, mesocarbon microbeads, mesophase pitch-based carbon fibers, and carbon materials obtained by carbonizing a resin simple substance.
前記電極活物質の平均粒径は、０．５〜５０μｍであることが好ましく、１〜３０μｍであることがより好ましい。 The average particle diameter of the electrode active material is preferably 0.5 to 50 μm, and more preferably 1 to 30 μm.
前記導電剤は、各種カーボンブラックであれば特に限定されない。具体的には、アセチレンブラック、ケッチェンブラック、気相法炭素繊維（ＶＧＣＦ）等が例示できる。
前記導電剤は、負極の場合、添加しなくても良い。
The conductive agent is not particularly limited as long as it is various carbon blacks. Specific examples include acetylene black, ketjen black, vapor grown carbon fiber (VGCF), and the like.
In the case of a negative electrode, the conductive agent may not be added.
前記結着剤は、前記活物質及び導電剤を集電体に結着させるものであれば特に限定されない。具体的には、ポリフッ化ビニリデン（ＰＶＤＦ）、スチレンブタジエン共重合ゴム（ＳＢＲ）、ポリテトラフルオロエチレン(ＰＴＦＥ)、ポリイミド等が例示できる。 The binder is not particularly limited as long as it binds the active material and the conductive agent to the current collector. Specific examples include polyvinylidene fluoride (PVDF), styrene butadiene copolymer rubber (SBR), polytetrafluoroethylene (PTFE), and polyimide.
前記集電体のうち、正極集電体の材質としては、例えば、アルミニウムが好ましく、負極集電体の材質としては、例えば、銅が好ましい。 Among the current collectors, the positive electrode current collector is preferably made of aluminum, for example, and the negative electrode current collector is preferably made of copper, for example.
本発明のリチウムイオン二次電池用電極は、あらかじめポリアニオン型リチウム塩を含有しているので、固体電解質又はゲル状電解質を使用した場合であっても、得られるリチウムイオン二次電池は、これら電解質と電極との間の界面抵抗が効果的に抑制され、充放電特性に優れるなど、充分な電池性能を有する。 Since the electrode for a lithium ion secondary battery of the present invention contains a polyanion-type lithium salt in advance, even when a solid electrolyte or a gel electrolyte is used, the obtained lithium ion secondary battery is prepared by using these electrolytes. Interfacial resistance between the electrode and the electrode is effectively suppressed, and the battery performance is sufficient, such as excellent charge / discharge characteristics.
＜リチウムイオン二次電池用電極の製造方法＞
本発明のリチウムイオン二次電池用電極は、例えば、前記電極活物質及びポリアニオン型リチウム塩水溶液を混合し、得られた混合物を乾燥及び粉砕して粉体を作製する工程と、該粉体、結着剤及び導電剤を混合して電極用ペーストを作製する工程と、を有する方法で製造できる。
前記製造方法の一例について、フローチャートを図１に示す。
<Method for producing electrode for lithium ion secondary battery>
The electrode for a lithium ion secondary battery of the present invention includes, for example, a step of mixing the electrode active material and a polyanion-type lithium salt aqueous solution, and drying and pulverizing the obtained mixture to produce a powder; And a step of preparing a paste for an electrode by mixing a binder and a conductive agent.
A flowchart of an example of the manufacturing method is shown in FIG.
前記電極活物質と混合するポリアニオン型リチウム塩は、電極活物質１００質量部に対して０．００１〜２０質量部であることが好ましく、０．０１〜１０質量部であることがより好ましい。 The polyanionic lithium salt mixed with the electrode active material is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the electrode active material.
前記電極活物質及びポリアニオン型リチウム塩水溶液を混合する方法は、特に限定されず、ボールミル、ホモジナイザー、スターラー、超音波分散機、自公転ミキサー等を使用する方法が例示できる。
得られた混合物は、乾燥機を使用して乾燥させれば良く、乾燥温度は水を除去できるように、例えば、８０〜１００℃程度とすれば良い。また、乾燥は、常圧下及び減圧下のいずれで行っても良い。そして、乾燥時間は、乾燥温度に応じて適宜調節すれば良い。
混合物の粉砕は、例えば、粉砕機や乳鉢を使用して行えば良い。
The method for mixing the electrode active material and the polyanionic lithium salt aqueous solution is not particularly limited, and examples thereof include a method using a ball mill, a homogenizer, a stirrer, an ultrasonic disperser, a self-revolving mixer, and the like.
The obtained mixture may be dried using a dryer, and the drying temperature may be, for example, about 80 to 100 ° C. so that water can be removed. The drying may be performed under normal pressure or reduced pressure. And drying time should just adjust suitably according to drying temperature.
The mixture may be pulverized using, for example, a pulverizer or a mortar.
前記混合物を乾燥及び粉砕して得られた粉体は、前記ポリアニオン型リチウム塩で被覆された電極活物質が主成分であると考えられる。かかる粉体の平均粒径は、混合に供する前の前記電極活物質の平均粒径と同様であることが好ましい。 The powder obtained by drying and pulverizing the mixture is considered to be mainly composed of the electrode active material coated with the polyanionic lithium salt. The average particle size of the powder is preferably the same as the average particle size of the electrode active material before being subjected to mixing.
前記粉体、結着剤及び導電剤を混合して電極用ペーストを作製する工程は、従来と同様の方法で行うことができる。例えば、前記粉体、結着剤及び導電剤を、溶媒存在下で混合し、電極用ペーストを作製する方法が例示できる。 The step of preparing the electrode paste by mixing the powder, the binder, and the conductive agent can be performed by a method similar to the conventional method. For example, a method of preparing the electrode paste by mixing the powder, the binder and the conductive agent in the presence of a solvent can be exemplified.
前記結着剤の配合量は、特に限定されないが、前記電極活物質１００質量部に対して１〜３０質量部であることが好ましい。
また、前記導電剤の配合量も特に限定されないが、前記結着剤の配合量と同様で良い。
Although the compounding quantity of the said binder is not specifically limited, It is preferable that it is 1-30 mass parts with respect to 100 mass parts of said electrode active materials.
Further, the blending amount of the conductive agent is not particularly limited, but may be the same as the blending amount of the binder.
混合時に使用する溶媒は、各配合成分と反応しないものであれば特に限定されない。溶媒は、例えば、前記結着剤の種類に応じて選択することが好ましく、結着剤がＰＶＤＦである場合には、好ましいものとしてＮ−メチル−２−ピロリドン（ＮＭＰ）が例示でき、結着剤がＳＢＲ又はＰＴＦＥである場合には、好ましいものとして水が例示できる。 The solvent used at the time of mixing will not be specifically limited if it does not react with each compounding component. The solvent is preferably selected according to, for example, the type of the binder. When the binder is PVDF, N-methyl-2-pyrrolidone (NMP) can be exemplified as a preferable binder. When the agent is SBR or PTFE, water can be exemplified as a preferable one.
本発明のリチウムイオン二次電池用電極は、例えば、前記電極用ペーストを前記集電体上に塗布して、乾燥させることで得られる。
電極用ペーストの塗布方法は特に限定されないが、電極用ペーストを均一に塗布できる方法が好ましく、ドクターブレード、アプリケーター、バーコータ等を使用する塗布方法が例示できる。
乾燥は、常圧下及び減圧下のいずれで行っても良い。
乾燥温度は、電極用ペーストの溶媒成分を除去できる温度であれば良く、例えば、８０〜１４０℃とすることが好ましい。乾燥時間は、乾燥温度に応じて適宜調節すれば良い。
The electrode for a lithium ion secondary battery of the present invention can be obtained, for example, by applying the electrode paste on the current collector and drying it.
The method for applying the electrode paste is not particularly limited, but a method capable of uniformly applying the electrode paste is preferable, and examples thereof include a doctor blade, an applicator, a bar coater and the like.
Drying may be performed under normal pressure or reduced pressure.
The drying temperature should just be the temperature which can remove the solvent component of the paste for electrodes, for example, it is preferable to be 80-140 degreeC. What is necessary is just to adjust drying time suitably according to drying temperature.
乾燥後の電極において、集電体上の前記電極用ペーストから形成される層の厚さは、目的とする電池容量に応じて適宜調節すれば良いが、通常は２０〜３００μｍであることが好ましい。そして、かかる層の厚さは、例えば、電極用ペーストの塗布量で調節でき、さらに、ロールプレス機等のプレス機を使用して、乾燥中又は乾燥後の電極用ペーストを圧縮成形することでも調節できる。 In the electrode after drying, the thickness of the layer formed from the electrode paste on the current collector may be appropriately adjusted according to the target battery capacity, but is usually preferably 20 to 300 μm. . The thickness of the layer can be adjusted by, for example, the amount of the electrode paste applied, and further, by using a press machine such as a roll press machine, the electrode paste during or after drying may be compression molded. Can be adjusted.
前記電極用ペーストは、目的とする電池の構成に応じて、集電体の片面のみに塗布しても良いし、両面に塗布しても良い。 The electrode paste may be applied to only one side of the current collector or may be applied to both sides depending on the configuration of the target battery.
＜リチウムイオン二次電池及びその製造方法＞
本発明のリチウムイオン二次電池は、上記本発明の電極を備えたことを特徴とし、固体電解質又はゲル状電解質を備えたものが好適である。
本発明のリチウムイオン二次電池は、本発明の電極を備えたこと以外は、従来のリチウムイオン二次電池と同様の構成とすることができ、例えば、その形状は、円筒型、角型、コイン型、シート型等、種々のものに調節できる。
<Lithium ion secondary battery and manufacturing method thereof>
The lithium ion secondary battery of the present invention is characterized by including the electrode of the present invention, and preferably includes a solid electrolyte or a gel electrolyte.
The lithium ion secondary battery of the present invention can have the same configuration as that of the conventional lithium ion secondary battery except that the electrode of the present invention is provided. For example, the shape thereof is cylindrical, rectangular, Various types such as a coin type and a sheet type can be adjusted.
図２は、本発明のリチウムイオン二次電池を例示する概略断面図である。
ここに示すリチウムイオン二次電池１は、コイン型であり、ケース１４内において正極１１、電解質膜１２及び負極１３がこの順に積層され、この積層体が絶縁性ガスケット１５を介してキャップ１６で密封され、概略構成されている。ただし、ここに示すリチウムイオン二次電池は、本発明の一例を示すに過ぎず、本発明はここに示すものに何ら限定されるものではない。
FIG. 2 is a schematic cross-sectional view illustrating a lithium ion secondary battery of the present invention.
The lithium ion
本発明のリチウムイオン二次電池は、公知の方法に従って、例えば、グローブボックス内又は乾燥空気雰囲気下で、電解質及び本発明の電極を使用して製造すれば良い。 What is necessary is just to manufacture the lithium ion secondary battery of this invention using an electrolyte and the electrode of this invention according to a well-known method, for example in a glove box or dry air atmosphere.
本発明のリチウムイオン二次電池は、上記本発明の電極を使用することにより、固体電解質又はゲル状電解質を使用した場合であっても、例えば製造時において、電解質又は電極表面に、さらに電解質材料を塗布する等の操作が不要なので、従来のリチウムイオン二次電池よりも簡便に製造できる。そして、電極がポリアニオン型リチウム塩を含有していることにより、充分な電池性能が得られ、大容量化も容易である。 The lithium ion secondary battery of the present invention uses the electrode of the present invention, so that even when a solid electrolyte or a gel electrolyte is used, the electrolyte material is further added to the electrolyte or the electrode surface, for example, at the time of production. Therefore, it can be manufactured more easily than conventional lithium ion secondary batteries. And since an electrode contains polyanion-type lithium salt, sufficient battery performance is obtained and large capacity | capacitance is also easy.
以下、具体的実施例により、本発明についてさらに詳しく説明する。ただし、本発明は、以下に示す実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
＜原料・部材の製造＞
［製造例１］
（ポリ（アクリル酸リチウム）（ＰＡｃ−Ｌｉ）の製造）
ポリアクリル酸（ＰＡｃ）（１０．０ｇ、１３８．８ｍｍｏｌ）を丸底フラスコに量り取り、これを１００ｍＬの蒸留水に溶解させた。水酸化リチウム・一水和物（ＬｉＯＨ・Ｈ２Ｏ）（５．９９ｇ、１３９．５ｍｍｏｌ）を６０ｍＬの蒸留水に溶かした溶液を、これにゆっくりと滴下した。室温で２４時間撹拌した後、ロータリーエバポレーターで得られた溶液を濃縮した。濃縮した溶液を５００ｍＬのメタノールにゆっくりと滴下し、析出した固体をメタノールで洗浄することで、白色のＰＡｃ−Ｌｉを得た。
<Manufacture of raw materials and components>
[Production Example 1]
(Production of poly (lithium acrylate) (PAc-Li))
Polyacrylic acid (PAc) (10.0 g, 138.8 mmol) was weighed into a round bottom flask and dissolved in 100 mL of distilled water. A solution of lithium hydroxide monohydrate (LiOH.H 2 O) (5.99 g, 139.5 mmol) dissolved in 60 mL of distilled water was slowly added dropwise thereto. After stirring for 24 hours at room temperature, the solution obtained on a rotary evaporator was concentrated. The concentrated solution was slowly added dropwise to 500 mL of methanol, and the precipitated solid was washed with methanol to obtain white PAc-Li.
［製造例２］
（ポリ（２−アクリルアミド−２−メチル−１−プロパンスルホン酸リチウム）（ＰＡＭＰＳ−Ｌｉ）の製造）
ポリ（２−アクリルアミド−２−メチル−１−プロパンスルホン酸）（ＰＡＭＰＳ）１５質量％水溶液（３３．３ｇ、２４．１ｍｍｏｌ）を丸底フラスコに量り取り、水酸化リチウム・一水和物（ＬｉＯＨ・Ｈ２Ｏ）（１．０５ｇ、２４．６ｍｍｏｌ）を６０ｍＬの蒸留水に溶かした溶液を、これにゆっくりと滴下した。室温で２４時間撹拌した後、ロータリーエバポレーターで溶液を濃縮した。濃縮した溶液を４００ｍＬの２−プロパノールにゆっくりと滴下し、析出した固体を２−プロパノールで洗浄することで、淡黄色のポリ（２−アクリルアミド−２−メチル−１−プロパンスルホン酸リチウム（ＰＡＭＰＳ−Ｌｉ）を得た。
[Production Example 2]
(Production of poly (2-acrylamido-2-methyl-1-propanesulfonic acid lithium) (PAMPS-Li))
A 15% by mass aqueous solution (33.3 g, 24.1 mmol) of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) was weighed into a round bottom flask, and lithium hydroxide monohydrate (LiOH A solution of H 2 O) (1.05 g, 24.6 mmol) dissolved in 60 mL of distilled water was slowly added dropwise thereto. After stirring for 24 hours at room temperature, the solution was concentrated on a rotary evaporator. The concentrated solution was slowly added dropwise to 400 mL of 2-propanol, and the precipitated solid was washed with 2-propanol to obtain a pale yellow poly (2-acrylamido-2-methyl-1-propanesulfonate lithium (PAMPS- Li) was obtained.
［製造例３］
（電解質膜の製造）
濃度が１０質量％のＰＶｄＦ−ＨＦＰ（ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体）テトラヒドロフラン溶液（５．０ｇ）、製造例１で得られたＰＡｃ−Ｌｉ（０．４５ｇ）、ＢＦ３Ｏ（Ｃ２Ｈ５）２（０．８２ｇ）、有機溶媒としてエチエンカーボネート（ＥＣ）及びγ−ブチロラクトン（ＧＢＬ）の混合溶媒（ＥＣ：ＧＢＬ＝３０：７０（体積比））（４．５ｇ）をサンプル瓶に量り取り、テトラヒドロフラン（５ｍＬ）を加えた後、４８時間攪拌した。ＰＡｃ−Ｌｉが完全に溶解していることを確認した後、得られた溶液をポリテトラフルオロエチレン製のシャーレ（直径５．０ｃｍ）にキャスティングした。次いで、前記シャーレを真空デシケータ内に移し、ここに乾燥窒素を２Ｌ／分の流量で流しながら２４時間以上乾燥させることによって、固体電解質膜を得た。
[Production Example 3]
(Manufacture of electrolyte membrane)
PVdF-HFP (polyvinylidene fluoride-hexafluoropropylene copolymer) tetrahydrofuran solution (5.0 g) having a concentration of 10% by mass, PAc-Li (0.45 g) obtained in Production Example 1, BF 3 O (C 2 H 5 ) 2 (0.82 g), and a mixed solvent (EC: GBL = 30: 70 (volume ratio)) (4.5 g) of an ethylene solvent (EC) and γ-butyrolactone (GBL) as an organic solvent is a sample. The solution was weighed into a bottle and tetrahydrofuran (5 mL) was added, followed by stirring for 48 hours. After confirming that PAc-Li was completely dissolved, the obtained solution was cast into a petri dish (diameter: 5.0 cm) made of polytetrafluoroethylene. Next, the petri dish was transferred into a vacuum desiccator, and dried for 24 hours or more while flowing dry nitrogen at a flow rate of 2 L / min to obtain a solid electrolyte membrane.
＜電極の製造＞
［実施例１］
（ＰＡｃ−Ｌｉを含有する電極の製造）
正極用活物質であるコバルト酸リチウム（ＬｉＣｏＯ２）（日本化学工業社製セルシードＣ−５Ｈ、平均粒径６．７μｍ）１０ｇと、製造例１で得られたＰＡｃ−Ｌｉの１質量％水溶液１０ｇとを秤量し、これを自公転ミキサーで１分間混合して、コバルト酸リチウムがＰＡｃ−Ｌｉで被覆された正極用の混合物を得た。
また、負極用活物質であるグラファイト（日本黒鉛工業社製ＣＧＢ−１０、平均粒径１２．１３μｍ）１０ｇと、製造例１で得られたＰＡｃ−Ｌｉの１質量％水溶液１０ｇとを秤量し、これを自公転ミキサーで１分間混合して、グラファイトがＰＡｃ−Ｌｉで被覆された負極用の混合物を得た。
次いで、得られた正極用及び負極用の前記混合物を、それぞれ乾燥機を使用して８０℃で１時間乾燥させた後、乳鉢で粉砕して、正極用及び負極用の粉体を得た。この時、粉体の平均粒径は、活物質の元の平均粒径と同等程度とした。
次いで、得られた正極用の粉体８．９ｇ、ポリフッ化ビニリデン（ＰＶＤＦ）（クレハ社製ＫＦポリマー＃１１２０、Ｎ−メチル−２−ピロリドン（ＮＭＰ）溶媒、固形分１２質量％）を固形分換算で０．６ｇ、アセチレンブラック（電気化学工業社製デンカブラック）０．５ｇ、ＮＭＰ１０ｇを秤量して、自公転ミキサーで１分間混合し、さらに超音波ホモジナイザーで５分間混合し、自公転ミキサーで１分間脱泡することで、正極用ペーストを得た。
また、得られた負極用の粉体９．０ｇ、前記ＰＶＤＦを固形分換算で１．０ｇ、ＮＭＰ８ｇを秤量して、自公転ミキサーで１分間混合し、さらに超音波ホモジナイザーで５分間混合し、自公転ミキサーで１分間脱泡することで、負極用ペーストを得た。
次いで、アプリケーターを使用して、得られた正極用ペーストを厚さ２０μｍのアルミ箔に塗布し、１２０℃で３０分程度加熱した後、ロールプレス機で圧縮成形し、さらに８０℃１２時間減圧乾燥することで、ＰＡｃ−Ｌｉを含有する厚さが５０μｍの正極を得た。
また、アプリケーターを使用して、得られた負極用ペーストを厚さ２０μｍの銅箔に塗布し、１２０℃で３０分程度加熱した後、ロールプレス機で圧縮成形し、さらに８０℃１２時間減圧乾燥することで、ＰＡｃ−Ｌｉを含有する厚さが３０μｍの負極を得た。
得られた電極の組成を表１に示す。
<Manufacture of electrodes>
[Example 1]
(Production of electrode containing PAc-Li)
10 g of lithium cobalt oxide (LiCoO 2 ) (Nippon Chemical Industry Co., Ltd. cell seed C-5H, average particle size 6.7 μm), which is an active material for the positive electrode, and 10 g of a 1% by mass aqueous solution of PAc-Li obtained in Production Example 1 Were weighed and mixed for 1 minute with a self-revolving mixer to obtain a mixture for a positive electrode in which lithium cobaltate was coated with PAc-Li.
In addition, 10 g of graphite (CGB-10 manufactured by Nippon Graphite Industry Co., Ltd., average particle size 12.13 μm) as an active material for a negative electrode and 10 g of a 1% by mass aqueous solution of PAc-Li obtained in Production Example 1 were weighed. This was mixed with a self-revolving mixer for 1 minute to obtain a negative electrode mixture in which graphite was coated with PAc-Li.
Next, the obtained positive electrode and negative electrode mixtures were each dried at 80 ° C. for 1 hour using a dryer, and then pulverized in a mortar to obtain positive electrode and negative electrode powders. At this time, the average particle size of the powder was set to be approximately the same as the original average particle size of the active material.
Next, 8.9 g of the obtained powder for positive electrode, polyvinylidene fluoride (PVDF) (Kureha KF polymer # 1120, N-methyl-2-pyrrolidone (NMP) solvent, solid content: 12% by mass) 0.6 g in terms of conversion, 0.5 g of acetylene black (Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd.) and 10 g of NMP are weighed and mixed for 1 minute with a self-revolving mixer, and further mixed for 5 minutes with an ultrasonic homogenizer. By degassing for 1 minute, a positive electrode paste was obtained.
In addition, 9.0 g of the obtained negative electrode powder, 1.0 g of the PVDF in terms of solid content, and 8 g of NMP were weighed, mixed for 1 minute with a self-revolving mixer, and further mixed for 5 minutes with an ultrasonic homogenizer, A negative electrode paste was obtained by defoaming for 1 minute with a self-revolving mixer.
Next, using an applicator, the obtained positive electrode paste was applied to an aluminum foil having a thickness of 20 μm, heated at 120 ° C. for about 30 minutes, then compression-molded with a roll press, and further dried under reduced pressure at 80 ° C. for 12 hours. As a result, a positive electrode containing PAc-Li and having a thickness of 50 μm was obtained.
Also, using an applicator, the obtained negative electrode paste was applied to a copper foil having a thickness of 20 μm, heated at 120 ° C. for about 30 minutes, then compression-molded with a roll press, and further dried under reduced pressure at 80 ° C. for 12 hours. As a result, a negative electrode containing PAc-Li and having a thickness of 30 μm was obtained.
Table 1 shows the composition of the obtained electrode.
［実施例２］
（ＰＡＭＰＳ−Ｌｉを含有する電極の製造）
正極用活物質であるコバルト酸リチウム（日本化学工業社製セルシードＣ−５Ｈ、平均粒径６．７μｍ）１０ｇと、製造例２で得られたＰＡＭＰＳ−Ｌｉの１質量％水溶液１０ｇとを秤量し、これを自公転ミキサーで１分間混合して、コバルト酸リチウムがＰＡＭＰＳ−Ｌｉで被覆された正極用の混合物を得た。
また、負極用活物質であるグラファイト（日本黒鉛工業社製ＣＧＢ−１０、平均粒径１２．１３μｍ）１０ｇと、製造例２で得られたＰＡＭＰＳ−Ｌｉの１質量％水溶液１０ｇとを秤量し、これを自公転ミキサーで１分間混合して、グラファイトがＰＡＭＰＳ−Ｌｉで被覆された負極用の混合物を得た。
以下、ＰＡｃ−Ｌｉで被覆された正極用及び負極用の混合物に代えて、得られた正極用及び負極用の前記混合物を使用したこと以外は、実施例１と同様の方法で、ＰＡＭＰＳ−Ｌｉを含有する正極及び負極をそれぞれ得た。
得られた電極の組成を表１に示す。
[Example 2]
(Production of electrode containing PAMPS-Li)
10 g of lithium cobaltate (Nippon Kagaku Kogyo cell seed C-5H, average particle size 6.7 μm) as an active material for the positive electrode and 10 g of a 1% by mass aqueous solution of PAMPS-Li obtained in Production Example 2 were weighed. This was mixed for 1 minute with a self-revolving mixer to obtain a mixture for a positive electrode in which lithium cobaltate was coated with PAMPS-Li.
Also, 10 g of graphite (CGB-10 manufactured by Nippon Graphite Industry Co., Ltd., average particle size 12.13 μm) as an active material for the negative electrode and 10 g of a 1% by mass aqueous solution of PAMPS-Li obtained in Production Example 2 were weighed. This was mixed for 1 minute by a self-revolving mixer to obtain a negative electrode mixture in which graphite was coated with PAMPS-Li.
Hereinafter, in place of the mixture for positive electrode and negative electrode coated with Pac-Li, the same method as in Example 1 was used except that the obtained mixture for positive electrode and negative electrode was used, and PAMPS-Li A positive electrode and a negative electrode containing each were obtained.
Table 1 shows the composition of the obtained electrode.
＜従来の電極の製造＞
［比較例１］
前記正極用及び負極用の粉体に代えて、コバルト酸リチウム（日本化学工業社製セルシードＣ−５Ｈ、平均粒径６．７μｍ）及びグラファイト（日本黒鉛工業社製ＣＧＢ−１０、平均粒径１２．１３μｍ）をそれぞれ使用して、正極用ペースト及び負極用ペーストを作製したこと以外は、実施例１と同様の方法で、ポリアニオン型リチウム塩を含有しない従来の正極及び負極をそれぞれ製造した。
得られた電極の組成を表１に示す。
<Manufacture of conventional electrodes>
[Comparative Example 1]
Instead of the positive electrode and negative electrode powders, lithium cobalt oxide (Nippon Kagaku Kogyo Co., Ltd. cell seed C-5H, average particle size 6.7 μm) and graphite (Nippon Graphite Kogyo Co., Ltd. CGB-10, average particle size 12) A conventional positive electrode and negative electrode not containing a polyanionic lithium salt were produced in the same manner as in Example 1 except that a positive electrode paste and a negative electrode paste were prepared using .13 μm respectively.
Table 1 shows the composition of the obtained electrode.
＜リチウムイオン二次電池の製造＞
［実施例３］
（ＰＡｃ−Ｌｉを含有する電極を備えたリチウムイオン二次電池の製造）
実施例１で得られたＰＡｃ−Ｌｉを含有する正極及び負極、並びに製造例３で得られた固体電解質膜を使用し、不活性ガス又は乾燥空気雰囲気下で、図２に示すコイン型のリチウムイオン二次電池を製造した。より具体的には、正極及び負極は直径１６ｍｍの大きさ、電解質膜は直径１７ｍｍの大きさに、それぞれ切断した。そして、コイン型電池のケース内で正極、電解質膜及び負極をこの順に積層し、絶縁性ガスケットを介してステンレス製のキャップにより密封した。
<Manufacture of lithium ion secondary batteries>
[Example 3]
(Manufacture of a lithium ion secondary battery provided with an electrode containing PAc-Li)
Using the positive electrode and negative electrode containing PAc-Li obtained in Example 1 and the solid electrolyte membrane obtained in Production Example 3, coin-type lithium shown in FIG. 2 in an inert gas or dry air atmosphere An ion secondary battery was manufactured. More specifically, the positive electrode and the negative electrode were cut to a diameter of 16 mm, and the electrolyte membrane was cut to a diameter of 17 mm. Then, the positive electrode, the electrolyte membrane and the negative electrode were laminated in this order in the case of the coin-type battery, and sealed with a stainless steel cap through an insulating gasket.
［実施例４］
（ＰＡＭＰＳ−Ｌｉを含有する電極を備えたリチウムイオン二次電池の製造）
実施例１で得られたＰＡｃ−Ｌｉを含有する正極及び負極に代えて、実施例２で得られたＰＡＭＰＳ−Ｌｉを含有する正極及び負極を使用したこと以外は、実施例３と同様の方法で、コイン型のリチウムイオン二次電池を製造した。
[Example 4]
(Manufacture of a lithium ion secondary battery equipped with an electrode containing PAMPS-Li)
The same method as in Example 3, except that the positive electrode and negative electrode containing PAMPS-Li obtained in Example 2 were used instead of the positive electrode and negative electrode containing PAc-Li obtained in Example 1. Thus, a coin-type lithium ion secondary battery was manufactured.
［比較例２］
（従来の電極を備えたリチウムイオン二次電池の製造）
実施例１で得られたＰＡｃ−Ｌｉを含有する正極及び負極に代えて、比較例１で得られた、ポリアニオン型リチウム塩を含有しない従来の正極及び負極を使用したこと以外は、実施例３と同様の方法で、コイン型のリチウムイオン二次電池を製造した。
[Comparative Example 2]
(Manufacture of lithium ion secondary batteries with conventional electrodes)
Example 3 except that instead of the positive electrode and negative electrode containing PAc-Li obtained in Example 1, the conventional positive electrode and negative electrode not containing polyanionic lithium salt obtained in Comparative Example 1 were used. A coin-type lithium ion secondary battery was manufactured in the same manner as described above.
＜電池性能（レート特性）の評価＞
上記各実施例及び比較例のリチウムイオン二次電池について、２５℃の環境下で上限電圧４．２Ｖまで充電した後、下限電圧２．５Ｖまで定電流放電するという操作を繰り返す充放電サイクルを行った。ここで、充放電時の電流量は０．２Ｃ、１Ｃ、３Ｃとした。ここで「１Ｃ」とは、活物質量より算出した容量を１時間で充放電するのに必要な電流量であり、同様に「０．２Ｃ」とは５時間、「３Ｃ」とは２０分で、それぞれ充放電するのに必要な電流量である。そして、この充放電サイクルの１０回目の放電容量を測定し、電流量が０．２Ｃの場合の放電容量を１００とした時の、電流量が１Ｃと３Ｃの場合の放電容量の比率をそれぞれ求めて、レート特性を評価した。結果を表２に示す。
<Evaluation of battery performance (rate characteristics)>
About the lithium ion secondary battery of each said Example and comparative example, after charging to the upper limit voltage 4.2V in a 25 degreeC environment, the charge / discharge cycle which repeats the operation of carrying out constant current discharge to the lower limit voltage 2.5V was performed It was. Here, the amount of current during charging and discharging was set to 0.2C, 1C, and 3C. Here, “1C” is the amount of current required to charge and discharge the capacity calculated from the amount of active material in 1 hour. Similarly, “0.2C” is 5 hours, and “3C” is 20 minutes. Thus, the amount of current required to charge and discharge each. Then, the discharge capacity at the 10th charge / discharge cycle is measured, and the ratio of the discharge capacity when the current amount is 1C and 3C when the discharge capacity when the current amount is 0.2C is assumed to be 100. The rate characteristics were evaluated. The results are shown in Table 2.
表２から明らかなように、本発明の電極を使用することで、電解質が固体であっても、電池のレート特性が大きく改善されており、電池性能が大きく向上することが確認できた。電解質がゲル状であっても同様の効果が得られる。 As is apparent from Table 2, it was confirmed that by using the electrode of the present invention, the rate characteristics of the battery were greatly improved even when the electrolyte was solid, and the battery performance was greatly improved. The same effect can be obtained even if the electrolyte is gel.
本発明は、リチウムイオン二次電池に利用可能である。 The present invention can be used for a lithium ion secondary battery.
１・・・リチウムイオン二次電池、１１・・・正極、１２・・・電解質膜、１３・・・負極、１４・・・ケース、１５・・・絶縁性ガスケット、１６・・・キャップ
DESCRIPTION OF
Claims (4)
電極活物質及びポリアニオン型リチウム塩水溶液を混合し、得られた混合物を乾燥及び粉砕して粉体を作製する工程と、該粉体、結着剤及び導電剤を混合して電極用ペーストを作製する工程と、
を有することを特徴とするリチウムイオン二次電池用電極の製造方法。 It is a manufacturing method of the electrode for lithium ion secondary batteries according to claim 1 or 2,
Mixing the electrode active material and the polyanionic lithium salt aqueous solution, drying and pulverizing the resulting mixture to produce a powder, and mixing the powder, binder and conductive agent to produce an electrode paste And a process of
The manufacturing method of the electrode for lithium ion secondary batteries characterized by having.
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| WO2015029248A1 (en) * | 2013-09-02 | 2015-03-05 | 株式会社日立製作所 | Negative electrode active material-coating material, negative electrode material using same, negative electrode, lithium ion secondary battery, battery system, monomer, and method for synthesizing monomer |
| WO2015029247A1 (en) * | 2013-09-02 | 2015-03-05 | 株式会社日立製作所 | Negative electrode active material-coating material, negative electrode material using same, negative electrode, lithium ion secondary battery and battery system |
| WO2015052809A1 (en) * | 2013-10-10 | 2015-04-16 | 株式会社日立製作所 | Negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries using same, lithium ion secondary battery and battery system |
| WO2015118676A1 (en) * | 2014-02-10 | 2015-08-13 | 株式会社日立製作所 | MATERIAL FOR Li BATTERIES |
| WO2023119990A1 (en) * | 2021-12-24 | 2023-06-29 | パナソニックＩｐマネジメント株式会社 | Negative electrode for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
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| US10355279B2 (en) | 2013-10-10 | 2019-07-16 | Hitachi, Ltd. | Negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries using same, lithium ion secondary battery and battery system |
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