JP6281154B2 - Negative electrode sheet of lithium ion secondary battery and lithium ion secondary battery - Google Patents
Negative electrode sheet of lithium ion secondary battery and lithium ion secondary battery Download PDFInfo
- Publication number
- JP6281154B2 JP6281154B2 JP2013204912A JP2013204912A JP6281154B2 JP 6281154 B2 JP6281154 B2 JP 6281154B2 JP 2013204912 A JP2013204912 A JP 2013204912A JP 2013204912 A JP2013204912 A JP 2013204912A JP 6281154 B2 JP6281154 B2 JP 6281154B2
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- ion secondary
- lithium ion
- negative electrode
- electrode sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 37
- 239000005751 Copper oxide Substances 0.000 claims description 37
- 229910000431 copper oxide Inorganic materials 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000000835 fiber Substances 0.000 claims description 20
- 239000011149 active material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 2
- 229960002218 sodium chlorite Drugs 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- 239000010949 copper Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910002992 LiNi0.33Mn0.33Co0.33O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemically Coating (AREA)
- Chemical Treatment Of Metals (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、リチウムイオン二次電池などの非水系電池に関する。より詳細には、酸化銅により被覆された多孔構造の支持体を備える電極シートを負極として使用する非水系電池に関する。 The present invention relates to a non-aqueous battery such as a lithium ion secondary battery. More specifically, the present invention relates to a non-aqueous battery using an electrode sheet provided with a porous support coated with copper oxide as a negative electrode.
非水系電池の負極は、一般的に金属箔などの集電体上にスラリー状の電極活物質層形成用塗工液を塗布し、熱風乾燥などにより乾燥させ、ロールプレスにより作成している。活物質としてカーボン負極が一般的に使用されているが、容量が低いのでより高容量で安全性に優れるものが求められている。
特許文献１には、真空蒸着法により、基板（銅板など）上にスズ薄膜を形成したリチウムイオン二次電池用負極材料の製造方法が開示されている。
特許文献２および特許文献３には、正極、負極及び非水系のイオン伝導体からなる電池において、前記負極が負極活物質の主成分としてリチウムイオンのインターカレーション・デインターカレーション可能な黒鉛よりなり、さらにこの電極内に酸化銅を含むリチウムイオン二次電池が開示されている。
The negative electrode of a non-aqueous battery is generally prepared by applying a slurry-like electrode active material layer-forming coating solution on a current collector such as a metal foil, drying it by hot air drying, and the like, and rolling it. A carbon negative electrode is generally used as an active material. However, since the capacity is low, a high capacity and excellent safety are required.
Patent Document 1 discloses a method for producing a negative electrode material for a lithium ion secondary battery in which a tin thin film is formed on a substrate (such as a copper plate) by a vacuum deposition method.
In Patent Document 2 and Patent Document 3, in a battery comprising a positive electrode, a negative electrode, and a non-aqueous ion conductor, the negative electrode is made of graphite capable of intercalation / deintercalation of lithium ions as a main component of the negative electrode active material. Further, a lithium ion secondary battery containing copper oxide in the electrode is disclosed.
特許文献１においては、スズ膜が検討されているが、充放電の際の膨潤収縮で満足するものが得られていない。また、特許文献２および３では、金属酸化物（酸化銅）が、理論容量が高いことから負極の活物質に一部組み込むことが検討されているが、カーボン電極の一部の改良に留まっている。 In Patent Document 1, a tin film has been studied, but a film satisfying swelling and shrinkage at the time of charge / discharge has not been obtained. In Patent Documents 2 and 3, the metal oxide (copper oxide) has been studied to be partially incorporated into the active material of the negative electrode because of its high theoretical capacity. Yes.
本発明者らは、酸化銅の形状をコントロールすることにより、高容量化可能な電極が得られるのではないかと考え、酸化銅の形状コントロールによる高容量化を発明が解決しようとする課題に設定した。 The present inventors think that an electrode capable of increasing the capacity can be obtained by controlling the shape of the copper oxide, and setting the capacity by controlling the shape of the copper oxide is set as a problem to be solved by the invention. did.
本発明者等は、上記の課題について鋭意検討の結果、電極を構成する導電性支持体を多孔化するとともに、該支持体を酸化銅の先細薄片密集体で被覆することにより高容量化が達成されることを見出し、本発明に到達した。本発明第１の構成は、多孔構造の導電性支持体が酸化銅の先細薄片密集体により被覆された電極シートである。 As a result of intensive studies on the above problems, the inventors of the present invention achieved a high capacity by making the conductive support constituting the electrode porous and covering the support with a tapered thin piece of copper oxide. As a result, the present invention has been reached. The first configuration of the present invention is an electrode sheet in which a conductive support having a porous structure is covered with a tapered thin piece dense assembly of copper oxide.
上記の電極シートにおいて、前記多孔構造の導電性支持体が空隙率３０〜９０％であることが好ましい。 Said electrode sheet WHEREIN: It is preferable that the electroconductive support body of the said porous structure is 30 to 90% of porosity.
上記の電極シートにおいて、前記酸化銅の先細薄片の長さが０．６μｍ以上であることが好ましい。 Said electrode sheet WHEREIN: It is preferable that the length of the said copper oxide taper piece is 0.6 micrometer or more.
上記の電極シートにおいて、前記支持体が多孔構造の金属よりなることが好ましい。 In the above electrode sheet, the support is preferably made of a porous metal.
上記の電極シートにおいて、前記支持体が金属薄膜に覆われた有機繊維よりなることが好ましい。 Said electrode sheet WHEREIN: It is preferable that the said support body consists of organic fiber covered with the metal thin film.
上記の電極シートにおいて、前記金属薄膜がメッキ処理により形成されていることが好ましい。 In the electrode sheet, the metal thin film is preferably formed by a plating process.
上記の電極シートにおいて、前記酸化銅の先細薄片密集体が黒化層であることが好ましく、前記黒化層が水酸化ナトリウムと亜塩素酸ナトリウムによる黒化処理液含浸法によるのが好ましい。 In the above electrode sheet, it is preferable that the copper oxide tapered thin dense body is a blackening layer, and the blackening layer is preferably formed by a blackening treatment liquid impregnation method using sodium hydroxide and sodium chlorite.
本発明第２の構成は、前記の電極シートを負極として使用した非水系電池である。 The second configuration of the present invention is a non-aqueous battery using the electrode sheet as a negative electrode.
本発明第１の構成によれば、酸化銅を先細薄片の形状で密集体として支持体を被覆するので、特許文献２、３に開示されている、微粉末の酸化銅をバインダーとブレンドし、ペーストにして塗布したものよりも高容量化が可能であり、しかも、支持体を多孔体とすることで反応場が増大し酸化銅から取り出せる電気量が増加する。しかも、本発明においては、集電体と活物質が強く一体化しており活物質で生じる電気をスムーズに集電体へ取り出せる。また、本発明においては、活物質層が充放電により膨張収縮しても崩壊しにくいという特性を有する。 According to the first configuration of the present invention, since the copper oxide is coated as a dense body in the form of a thin thin piece and the support is coated, the fine powdered copper oxide disclosed in Patent Documents 2 and 3 is blended with a binder, The capacity can be increased as compared with the case where the paste is applied, and the reaction field is increased and the amount of electricity that can be extracted from the copper oxide is increased by making the support a porous body. In addition, in the present invention, the current collector and the active material are strongly integrated, and electricity generated by the active material can be smoothly taken out to the current collector. Moreover, in this invention, it has the characteristic that it is hard to collapse even if an active material layer expands and contracts by charging / discharging.
本発明第２の構成によれば、本発明に係る非水系電池は、酸化銅がリチウムよりも還元電位が高いので、リチウム析出による短絡発生がなく、安全性に優れる。また、同様の効果で使用されている負極活物質のチタン酸リチウムに比べて容量も大きいという特性がある。 According to the second configuration of the present invention, since the non-aqueous battery according to the present invention has a reduction potential higher than that of lithium, copper oxide does not cause a short circuit due to lithium deposition and is excellent in safety. Further, it has a characteristic that its capacity is larger than that of lithium titanate, which is a negative electrode active material used for the same effect.
本発明においては、非水系電池を構成する電極シートが、酸化銅の先細薄片密集体により被覆された、多孔構造の導電性支持体から構成されている。
本発明における非水系電池とは、リチウムイオン電池のほか、他のアルカリ金属を活物質とする電池を含み、また、一次電池および二次電池の両者を包含する。以下、リチウムイオン二次電池を中心にして記載する。
In this invention, the electrode sheet which comprises a non-aqueous battery is comprised from the electroconductive support body of the porous structure coat | covered with the taper-thin piece compact of copper oxide.
The non-aqueous battery in the present invention includes, in addition to a lithium ion battery, a battery using another alkali metal as an active material, and includes both a primary battery and a secondary battery. Hereinafter, description will be made focusing on the lithium ion secondary battery.
リチウムイオン二次電池は、負極層、電解質層、正極層とから構成される。負極層は、負極材料と固体電解質を含有する。本発明において、負極材料は、多孔構造の導電性支持体から構成される。 A lithium ion secondary battery includes a negative electrode layer, an electrolyte layer, and a positive electrode layer. The negative electrode layer contains a negative electrode material and a solid electrolyte. In the present invention, the negative electrode material is composed of a porous conductive support.
（多孔構造の導電性支持体）
本発明に係る電極シートは、多孔構造の導電性支持体から構成されている。本発明において、多孔構造とは、好ましくは、３次元網目状の多孔構造、または連結孔を有する多孔構造である。逆に、３次元網目状の多孔構造、または連結孔を有する多孔構造であれば、負極活物質の膨張収縮を効果的に抑制することができ、サイクル劣化を抑制することができるため好ましい。また、多孔構造とすることで酸化銅皮膜の表面積が増大するため、充放電に寄与しないロス分が減少し、より効率的な電極となる。本発明において支持体の導電性は、支持体を導電性金属で構成するか、支持体基材に導電性金属を被覆することにより付与されることができる。
(Electroconductive support with porous structure)
The electrode sheet according to the present invention is composed of a conductive support having a porous structure. In the present invention, the porous structure is preferably a three-dimensional network porous structure or a porous structure having connecting holes. Conversely, a three-dimensional network-like porous structure or a porous structure having connecting holes is preferable because expansion and shrinkage of the negative electrode active material can be effectively suppressed and cycle deterioration can be suppressed. In addition, since the surface area of the copper oxide film is increased by adopting a porous structure, the amount of loss that does not contribute to charging and discharging is reduced, resulting in a more efficient electrode. In the present invention, the conductivity of the support can be imparted by constituting the support with a conductive metal or coating the support substrate with the conductive metal.
支持体が導電性金属から形成される場合には、多数の小孔のある金属板あるいは金属箔、金属網状メッシュ、金属繊維からなる多孔体が挙げられる。
支持体を構成する導電性金属としては、アルミニウム、ニッケル、鉄、ステンレス鋼、チタン、銅などの金属材料が挙げられる。これらの金属材料は、１種単独で用いてもよいし、２種以上併用してもよい。なかでも、電子伝導性、電池作動電位という観点からは、銅、ニッケル、ステンレスが好ましく、特に銅が好ましい。
支持体の空隙率は、３０〜９０％であることが好ましく、４０〜９０％であることがより好ましい。空隙率が小さすぎると高容量化を得にくくなる傾向にあるので好ましくなく、空隙率が大きすぎると、支持体としての力学特性が不十分となり、また単位体積当たりの容量が低下する傾向にあることから好ましくない。
When the support is made of a conductive metal, a metal plate or metal foil having a large number of small holes, a metal mesh, and a porous body made of metal fibers can be used.
Examples of the conductive metal constituting the support include metal materials such as aluminum, nickel, iron, stainless steel, titanium, and copper. These metal materials may be used alone or in combination of two or more. Of these, copper, nickel, and stainless steel are preferable from the viewpoint of electron conductivity and battery operating potential, and copper is particularly preferable.
The porosity of the support is preferably 30 to 90%, more preferably 40 to 90%. If the porosity is too small, it tends to be difficult to obtain a high capacity. This is not preferable, and if the porosity is too large, the mechanical properties as a support are insufficient, and the capacity per unit volume tends to decrease. That is not preferable.
導電性金属を被覆する支持体基材としては、有機繊維から形成される支持体基材が挙げられる。該繊維表面に金属層を形成する場合には、有機繊維層として、織編物、不織布形状を用いて、メッキ、蒸着、金属粉末を塗布したものが好ましい。
本発明において支持体基材を形成するために、用いられる有機繊維としては、ポリプロピレン、ポリエチレン、ポリエチレンテレフタレート、ポリアミドなどからなる合成繊維やセルロース繊維などの有機繊維が挙げられ、電池の種類や電解液の種類に応じて適宜選定される。
上記の有機繊維は、編織布や乾式または湿式不織布(紙)などの多孔性の有機繊維層を形成し、その片面または両面に導電性金属を、メッキ、蒸着、金属粉末の塗布などのより有機繊維層の少なくとも一部、好ましくは全面に層状に付着させることにより導電性の多孔性支持体を形成することができる。
Examples of the support base material that covers the conductive metal include a support base material formed from organic fibers. When the metal layer is formed on the fiber surface, the organic fiber layer is preferably a woven or knitted fabric or non-woven fabric shape coated with plating, vapor deposition or metal powder.
In order to form the support substrate in the present invention, examples of the organic fibers used include synthetic fibers made of polypropylene, polyethylene, polyethylene terephthalate, polyamide, and the like, and organic fibers such as cellulose fibers. It is selected as appropriate according to the type.
The above organic fiber forms a porous organic fiber layer such as a woven fabric or a dry or wet nonwoven fabric (paper), and is coated with a conductive metal on one or both sides thereof, and more organic, such as plating, vapor deposition, or application of metal powder. A conductive porous support can be formed by adhering at least part of the fiber layer, preferably the entire surface, in a layered manner.
(有機繊維層の導電性金属層の形成)
有機繊維層の目付としては、１０〜１００ｇ／ｍ２、より好ましくは、２０〜８０ｇ／ｍ２の範囲内にあるのが好ましく、目付けが小さすぎると力学特性が劣り加工時の工程張力に耐えられなくなる場合があるので好ましくなく、大きすぎると一定厚みにした時に密度が高くなりすぎ、目標とする空間を保持できなくなる傾向にある点で好ましくない。有機繊維層の厚みとしては、０．０２〜０．２０ｍｍ、より好ましくは、０．０５〜０．１５ｍｍの範囲内にあるのが好ましく、厚みが小さすぎると力学特性が不十分となり、工程で不具合が発生する場合があるので好ましくなく、厚みが大きすぎると電池内の容積を占有してしまい、密度当たりの容量として劣った電池になる場合があるので好ましくない。空隙率としては、３０〜９０％、より好ましくは、４０〜９０％の範囲内にあるのが好ましく、空隙率が小さすぎると高容量化しにくくなる場合があるので好ましくなく、空隙率が大きすぎると支持体としての力学特性が不十分となり、また単位体積あたりの容量が低下してしまう場合がある点で好ましくない。
(Formation of conductive metal layer of organic fiber layer)
The basis weight of the organic fiber layer is preferably in the range of 10 to 100 g / m 2 , more preferably 20 to 80 g / m 2. If the basis weight is too small, the mechanical properties are inferior and the process tension at the time of processing is tolerated. Since it may not be possible, it is not preferable. If it is too large, the density becomes too high when the thickness is made constant, which is not preferable in that the target space tends not to be maintained. The thickness of the organic fiber layer is preferably 0.02 to 0.20 mm, more preferably 0.05 to 0.15 mm. If the thickness is too small, the mechanical properties become insufficient. It is not preferable because a problem may occur, and if the thickness is too large, the volume in the battery is occupied, and the battery may be inferior in capacity per density. The porosity is preferably 30 to 90%, more preferably in the range of 40 to 90%. If the porosity is too small, it may be difficult to increase the capacity, which is not preferable, and the porosity is too large. In addition, the mechanical properties as a support are insufficient, and the capacity per unit volume may be reduced.
有機繊維層上への導電性金属被覆層を形成する金属としては、前記のアルミニウム、ニッケル、銅、チタン、鉄、ステンレス系金属、銅等の導電性金属を挙げることができる。上述の導電性金属の中でも、電気抵抗値が比較的低いものが好ましい。このような導電性金属としては、アルミニウム、銅等が挙げられる。
好ましくは、有機繊維層への導電性金属被覆層の形成は、公知の電解めっき法を利用することができる。なお、不織布に電解めっきを施す前に、有機繊維層表面に導電性を有する層を形成する。この導電性層を形成する手段として、無電解めっき法、スパッタリング法を利用することができる。上記の導電性層としては、４g/m2ないし９g/m2程度とすることが好ましい。そして、導電性を付与した有機繊維層に導電性金属のめっき浴を用いて電解メッキを施すことで、有機繊維表面に導電性金属の被覆層が形成された多孔性金属層を作製することができる。めっき浴としては、ワット浴、塩化浴、スルファミン酸浴が挙げられる。
上記の導電性金属の被覆量は、２０〜１００ｇ／ｍ２、好ましくは３０〜８０ｇ／ｍ２の範囲内にあるのが好ましく、被覆量が小さすぎると皮膜強度が弱くなり、部分剥離等が発生する場合があるので好ましくなく、被覆量が大きすぎると空隙の確保がしにくくなる場合があるので好ましくない。また、導電性金属層が形成された有機繊維層の空隙率は、３０〜９０％、より好ましくは、４０〜８０％の範囲内にあるのが好ましく、空隙率が小さすぎると高容量化をしにくくなる場合があるので好ましくなく、空隙率が大きすぎると力学特性が不十分となり、単位体積当たりの容量が低下する場合があるので好ましくない。
Examples of the metal that forms the conductive metal coating layer on the organic fiber layer include the above-described conductive metals such as aluminum, nickel, copper, titanium, iron, stainless steel, and copper. Among the conductive metals described above, those having a relatively low electrical resistance value are preferred. Examples of such conductive metals include aluminum and copper.
Preferably, the formation of the conductive metal coating layer on the organic fiber layer can utilize a known electrolytic plating method. In addition, before performing electroplating on a nonwoven fabric, the layer which has electroconductivity is formed in the organic fiber layer surface. As means for forming the conductive layer, an electroless plating method or a sputtering method can be used. The conductive layer is preferably about 4 g / m 2 to 9 g / m 2 . Then, by applying electroplating to the organic fiber layer imparted with conductivity using a plating bath of conductive metal, a porous metal layer having a conductive metal coating layer formed on the surface of the organic fiber can be produced. it can. Examples of the plating bath include a watt bath, a chloride bath, and a sulfamic acid bath.
The coating amount of the conductive metal is preferably in the range of 20 to 100 g / m 2 , preferably 30 to 80 g / m 2. If the coating amount is too small, the film strength becomes weak and partial peeling or the like occurs. Since it may occur, it is not preferable, and when the coating amount is too large, it may be difficult to secure voids, which is not preferable. The porosity of the organic fiber layer on which the conductive metal layer is formed is preferably in the range of 30 to 90%, more preferably 40 to 80%. If the porosity is too small, the capacity is increased. This is not preferable because it may be difficult to do so, and if the porosity is too large, the mechanical properties become insufficient, and the capacity per unit volume may decrease, which is not preferable.
（酸化銅被覆）
導電性多孔性支持体への酸化銅の先細薄片密集体被覆は、黒化処理により行われる。この黒化処理は、濃度５５〜９０ｇ／ｌ（より好ましくは６５〜８０ｇ／ｌ）のＮａＯＨと、濃度７０〜９０ｇ／ｌ（より好ましくは７５〜８５ｇ／ｌ）のＮａＣｌＯ２と、を含有する黒化処理液を７０〜１００℃（より好ましくは７５〜９５℃）に加熱し、当該黒化処理液に支持体を３〜５分浸漬して行なう。このような黒化処理を施した支持体上には、酸化銅からなる微細な先細薄片密集体からなる皮膜が形成される。
黒化処理の前には、導電性支持体の脱脂工程および酸洗工程を行うのが好ましい。脱脂工程は、支持体表面を６５〜７０℃の界面活性剤で３０〜９０秒間洗浄し、表面の脂成分が除去される。酸洗工程は、支持体を０．５ｍｏｌ／ｌの硫酸水溶液に３０〜９０秒間浸漬し、表面の酸化層を除去することが好ましい。
(Copper oxide coating)
The conductive porous support is coated with a taper-thin piece dense assembly of copper oxide by a blackening treatment. This blackening treatment contains NaOH having a concentration of 55 to 90 g / l (more preferably 65 to 80 g / l) and NaClO 2 having a concentration of 70 to 90 g / l (more preferably 75 to 85 g / l). The blackening treatment liquid is heated to 70 to 100 ° C. (more preferably 75 to 95 ° C.), and the support is immersed in the blackening treatment liquid for 3 to 5 minutes. On the support subjected to such a blackening treatment, a film made of a fine tapered thin piece dense body made of copper oxide is formed.
Prior to the blackening treatment, it is preferable to perform a degreasing step and a pickling step of the conductive support. In the degreasing step, the surface of the support is washed with a surfactant at 65 to 70 ° C. for 30 to 90 seconds to remove the fat component on the surface. In the pickling step, it is preferable to immerse the support in a 0.5 mol / l sulfuric acid aqueous solution for 30 to 90 seconds to remove the oxide layer on the surface.
先細薄片の長さとしては、０．６〜２．０μｍ、より好ましくは、０．７〜１．５μｍの範囲内にあるのが好ましい。長さが小さすぎると高容量化を得にくくなるので好ましくなく、長さが大きすぎると集電体である銅との距離が離れすぎ効率が落ちる場合がある点で好ましくない。先細薄片の長さは、黒化処理液の濃度を変えることにより調整することができる。 The length of the tapered thin piece is preferably 0.6 to 2.0 μm, more preferably 0.7 to 1.5 μm. If the length is too small, it is difficult to obtain a high capacity, and it is not preferable, and if the length is too large, the distance from the current collector copper is too far away, which is not preferable because the efficiency may decrease. The length of the tapered thin piece can be adjusted by changing the concentration of the blackening treatment liquid.
（電解質層）
リチウムイオン二次電池を構成する電解質層は、特に限定はなく、本技術分野において公知の電解質が使用できる。
(Electrolyte layer)
The electrolyte layer constituting the lithium ion secondary battery is not particularly limited, and an electrolyte known in this technical field can be used.
（正極層）
本発明において、リチウムイオン二次電池に用いられる正極としては、例えば集電体上に正極活物質やバインダーを含む電極活物質層が形成された公知の正極を使用できる。正極の集電体の材料としては、導電性を有する材料であれば特に制限されないが、例えばアルミニウム、ニッケル、銅などが挙げられる。
正極活物質としては、例えば一般式ＬｉＭｘＯｙ（ただし、Ｍは金属であり、ｘおよびｙ、は金属Ｍと酸素Ｏの組成比である）で表される金属酸リチウム化合物が用いられる。具体的には、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）、オリビン型リン酸鉄リチウム（ＬｉＦｅＰＯ４）などが挙げられる。なお、Ｍは複数の金属であってもよく、例えばＬｉＭ１ ｐＭ２ ｑＭ３ ｒＯｙ（ただし、ｐ＋ｑ＋ｒ＝ｘである）で表される化合物、具体的にはＬｉＮｉ０．３３Ｍｎ０．３３Ｃｏ０．３３Ｏ２などを正極活物質として用いることもできる。
正極に用いられるバインダーとしては、ＰＶＤＦ、ＳＢＲなどが挙げられる。正極の電極活物質層は、導電助剤を含んでいてもよい。導電助剤を含むことにより、正極の導電性がより向上し、電池性能をより高めることができる。導電助剤としては、黒鉛、カーボンブラック、カーボンナノチューブ、グラフェン、フラーレンが挙げられる。これら導電助剤は、１種単独で用いてもよいし、２種以上を併用してもよい。２種以上併用する場合、その組み合わせや比率は目的に応じて適宜選択すればよい。
(Positive electrode layer)
In the present invention, as the positive electrode used in the lithium ion secondary battery, for example, a known positive electrode in which an electrode active material layer containing a positive electrode active material and a binder is formed on a current collector can be used. The material of the positive electrode current collector is not particularly limited as long as it is a conductive material, and examples thereof include aluminum, nickel, and copper.
As the positive electrode active material, for example, a metal acid lithium compound represented by the general formula LiM x O y (where M is a metal and x and y are composition ratios of the metal M and oxygen O) is used. Specifically, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), olivine type lithium iron phosphate (LiFePO 4 ), and the like can be given. M may be a plurality of metals, for example, a compound represented by LiM 1 p M 2 q M 3 r O y (where p + q + r = x), specifically, LiNi 0.33 Mn 0 .33 Co 0.33 O 2 or the like can also be used as the positive electrode active material.
Examples of the binder used for the positive electrode include PVDF and SBR. The electrode active material layer of the positive electrode may contain a conductive additive. By including a conductive additive, the conductivity of the positive electrode is further improved, and the battery performance can be further improved. Examples of the conductive aid include graphite, carbon black, carbon nanotube, graphene, and fullerene. These conductive assistants may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio may be appropriately selected according to the purpose.
例えば、リチウムイオン電池は、上述した負極層、電解質層及び正極層を貼り合せ、接合することで製造できる。接合する方法としては、各部材を積層し、加圧・圧着する方法や、２つのロール間を通して加圧する方法（ｒｏｌｌｔｏ ｒｏｌｌ）等がある。また、接合面にイオン伝導性を有する活物質や、イオン伝導性を阻害しない接着物質を介して接合してもよい。 For example, a lithium ion battery can be manufactured by bonding and bonding the above-described negative electrode layer, electrolyte layer, and positive electrode layer. As a method of joining, there are a method of laminating each member, pressurizing and pressure bonding, a method of pressurizing between two rolls (rollto roll), and the like. Moreover, you may join to the joining surface through the active material which has ion conductivity, and the adhesive material which does not inhibit ion conductivity.
（用途）
本発明に係る非水系電池は、携帯情報端末、携帯電子機器、家庭用小型電力貯蔵装置、
モーターを電力源とする自動二輪車、電気自動車、ハイブリッド電気自動車等の電池として用いることができる。
(Use)
A non-aqueous battery according to the present invention includes a portable information terminal, a portable electronic device, a small electric power storage device for home use,
It can be used as a battery for a motorcycle, an electric vehicle, a hybrid electric vehicle or the like using a motor as a power source.
以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.
（充放電特性の評価方法）
三極式ビーカーセルを用いて、対極及び参照極として金属リチウム板（（株）レアメタリック製、厚さ１ｍｍ、純度９９．９％）、電解液として１Ｍのリチウムビストリフルオロメタンスルホニルアミド（ＬｉＴＦＳＡ）を支持塩とするプロピレンカーボネート（ＰＣ）溶液（（株）キシダ化学製）を用いた。電解液の温度としては、３０℃とした。なお、充放電測定装置（北斗電工（株）製、ＨＪ１００１ＳＭ８Ａ）により、電流密度０．３４Ａ／ｇで、０．００５〜３．０Ｖｖｓ．Ｌｉ／Ｌｉ＋の電位幅で充放電を繰り返し、５回目のサイクルにおける放電容量[酸化銅１ｇ当たりの放電容量（ｍＡｈ）]およびシート１ｍ２当たりの放電容量（ｍＡｈ）を評価した。
(Evaluation method of charge / discharge characteristics)
Using a tripolar beaker cell, a metallic lithium plate (made by Rare Metallic, thickness 1 mm, purity 99.9%) as a counter electrode and a reference electrode, and 1M lithium bistrifluoromethanesulfonylamide (LiTFSA) as an electrolyte A propylene carbonate (PC) solution (manufactured by Kishida Chemical Co., Ltd.) was used. The temperature of the electrolyte was 30 ° C. In addition, with a charge / discharge measuring device (HJ1001SM8A, manufactured by Hokuto Denko Co., Ltd.), a current density of 0.34 A / g, 0.005 to 3.0 Vvs. Charging / discharging was repeated with a potential width of Li / Li + , and the discharge capacity [discharge capacity per 1 g of copper oxide (mAh)] and the discharge capacity per 1 m 2 of sheet (mAh) in the fifth cycle were evaluated.
（酸化銅の先細薄片体の長さの測定方法）
支持体上の先細薄片体の長さを走査電子顕微鏡[日本電子(株)、ＪＳＭ−６７０１Ｆ]を用いて観察することにより測定した。
(Measuring method of the length of copper oxide taper piece)
The length of the tapered thin piece on the support was measured by observing using a scanning electron microscope [JEOL Ltd., JSM-6701F].
（空隙率）
本発明において、空隙率とは、シート全体の体積中に占める空隙の容積の割合である。
(Porosity)
In the present invention, the porosity is the ratio of the volume of the voids in the entire volume of the sheet.
＜実施例１＞
ＰＰ／ＰＥ紙（ダイワボウ社製：ＰＰ ０．５ｄｒ×５ｍｍ、ＮＢＦ １．５ｄｒ×５ｍｍ；目付２９ｇ／ｍ２；厚さ０．１５ｍｍ：密度０．１９ｇ／ｃｍ３：空隙率８６％)に、通常の無電解メッキ法にて、銅付着量８４ｇ／ｍ２、付着後の空隙率７９．５％の多孔構造の導電性支持体を作製した。
得られた支持体に下記のようにして酸化銅の先細薄片(長さ:１μｍ)の密集体からなる活物質を付着（付着量９．８ｇ／ｍ２）させて電極シートを作製した。
黒化処理液[日立化成(株)製] ＨＩＳＴ−５００Ａ、ＨＩＳＴ−５００Ｂ，ＨＩＳＴ−５００Ｃを１．７：０．６：１の割合でブレンドした８０℃の浴で処理し、酸化銅膜を形成した。形成された酸化銅被覆面の走査型電子顕微鏡写真を図1に示し、得られた電極シートの放電容量の測定結果を表1に示す。
<Example 1>
PP / PE paper (Daiwabo Co., Ltd .: PP 0.5dr × 5mm, NBF 1.5dr × 5mm; basis weight 29g / m 2 ; thickness 0.15mm: density 0.19g / cm 3 : porosity 86%) A conductive support with a porous structure having a copper adhesion amount of 84 g / m 2 and a porosity of 79.5% after adhesion was produced by a normal electroless plating method.
An active material composed of a dense copper oxide thin piece (length: 1 μm) was adhered to the obtained support (attachment amount 9.8 g / m 2 ) as described below to prepare an electrode sheet.
Blackening treatment solution [manufactured by Hitachi Chemical Co., Ltd.] HIST-500A, HIST-500B, and HIST-500C were treated in an 80 ° C. bath blended at a ratio of 1.7: 0.6: 1 to form a copper oxide film. Formed. A scanning electron micrograph of the formed copper oxide-coated surface is shown in FIG. 1, and the measurement results of the discharge capacity of the obtained electrode sheet are shown in Table 1.
＜実施例２＞
実施例１におけるＰＰ／ＰＥ紙の代わりに、銅網（目付５６９．６ｇ／ｍ２：厚さ０．１１ｍｍ：密度５．１８ｇ／ｃｍ3：空隙率４１．９％）を用いて、該銅網上に 実施例1と同様にして黒化処理を行って、酸化銅の先細薄片（長さ１μｍ）密集体からなる活物質(付着量６．２ｇ／ｍ２)が形成された電極シートを作製した。
得られた電極シートの放電容量の測定結果を表1に示す。
<Example 2>
In place of the PP / PE paper in Example 1, a copper net (569.6 g / m 2 per unit area: thickness 0.11 mm: density 5.18 g / cm 3 : porosity 41.9%) was used. A blackening treatment was performed on the net in the same manner as in Example 1 to form an electrode sheet on which an active material (attachment amount 6.2 g / m 2 ) composed of a dense copper oxide thin piece (length 1 μm) was formed. Produced.
Table 1 shows the measurement results of the discharge capacity of the obtained electrode sheet.
＜実施例３＞
実施例２と同じ銅網（目付５６９．６ｇ／ｍ２：厚さ０．１１ｍｍ：密度５．１８ｇ／ｃｍ３：空隙率４１．９％）を用いて、該銅網上に下記条件で黒化処理を行って、酸化銅の先細薄片（長さ０．８μｍ）からなる活物質（付着量５．９ｇ／ｍ２）が形成された電極シートを作製した。
黒化処理液[日立化成（株）製] ＨＩＳＴ−５００Ａ、ＨＩＳＴ−５００Ｂ、ＨＩＳＴ−５００Ｃを１．７：０．４：１の割合でブレンドした８０℃の浴で処理し、酸化銅膜を形成した。得られた電極シートの放電容量の測定結果を表1に示す。
<Example 3>
Using the same copper mesh as in Example 2 (weight per unit: 569.6 g / m 2 : thickness 0.11 mm: density 5.18 g / cm 3 : porosity 41.9%), black was formed on the copper mesh under the following conditions. The electrode sheet in which the active material (adhesion amount 5.9 g / m 2 ) made of the tapered thin piece (length 0.8 μm) of copper oxide was formed was prepared.
Blackening treatment solution [manufactured by Hitachi Chemical Co., Ltd.] HIST-500A, HIST-500B, HIST-500C were treated in an 80 ° C. bath blended at a ratio of 1.7: 0.4: 1, and a copper oxide film was formed. Formed. Table 1 shows the measurement results of the discharge capacity of the obtained electrode sheet.
＜比較例１＞
実施例２における銅網と同じ銅網を用いて、酸化銅にＰＶＤＦを混合してペースト状にしたものからなる球状(径１μｍ)の活物質(付着量５．９ｇ／ｍ２)が該銅網上に形成された電極シートを作製した。
得られた電極シートの放電容量の測定結果を表1に示す。
<Comparative Example 1>
Using the same copper mesh as the copper mesh in Example 2, a spherical active material (adhesion amount 5.9 g / m 2 ) composed of a paste formed by mixing PVDF with copper oxide is the copper mesh. An electrode sheet formed on a net was produced.
Table 1 shows the measurement results of the discharge capacity of the obtained electrode sheet.
＜比較例２＞
実施例２における銅網の代わりに銅板（厚み０．０２ｍｍ、密度８．９２ｇ／ｃｍ３）を用いて、該銅板上に 実施例1と同様にして黒化処理を行って、酸化銅の先細薄片（長さ１μｍ）密集体からなる活物質(付着量２．８ｇ／ｍ２)が形成された電極シートを作製した。
得られた電極シートの放電容量の測定結果を表1に示す。
<Comparative example 2>
Using a copper plate (thickness 0.02 mm, density 8.92 g / cm 3 ) in place of the copper net in Example 2, blackening treatment was performed on the copper plate in the same manner as in Example 1 to taper the copper oxide. An electrode sheet on which an active material (attachment amount 2.8 g / m 2 ) composed of a dense piece (length: 1 μm) was formed was produced.
Table 1 shows the measurement results of the discharge capacity of the obtained electrode sheet.
実施例１では、ＰＰ／ＰＥ紙上に銅を８４ｇ／ｍ２メッキした支持体に、酸化銅の先細薄片（長さ１μｍ）密集体が被覆された電極では、高い放電容量が得られた。この結果から、実施例１の電極は、充放電容量が高く、充放電サイクル特性に優れたリチウムイオン二次電池を得ることができることが分かる。
実施例２および実施例３では、銅網（５６９．６ｇ／ｍ２：空隙率４１．９％）上に先細薄片(長さ１μｍ)の酸化銅または先細薄片（長さ０．８μｍ）の酸化銅を被覆した電極では、充放電容量がいずれも高く、充放電サイクル特性に優れたリチウムイオン二次電池を得ることができることが分かる。
In Example 1, a high discharge capacity was obtained with an electrode in which a copper oxide taped thin piece (length: 1 μm) was coated on a support obtained by plating 84 g / m 2 of copper on PP / PE paper. From this result, it can be seen that the electrode of Example 1 has a high charge / discharge capacity, and a lithium ion secondary battery excellent in charge / discharge cycle characteristics can be obtained.
In Example 2 and Example 3, the copper oxide (569.6 g / m 2 : porosity 41.9%) on the copper oxide or taper (length 0.8 μm) of taper flakes (length 1 μm) It can be seen that the electrode coated with copper has a high charge / discharge capacity, and a lithium ion secondary battery excellent in charge / discharge cycle characteristics can be obtained.
比較例１では、１μｍ径の球状の酸化銅であるために、放電容量が小さく、電池負極の容量の点で不十分である。
比較例２では、支持体が多孔体ではなく、厚さ０．０２ｍｍの銅板であるために、電極シート放電容量が小さく、電極負極として容量が不十分である。
In Comparative Example 1, since the spherical copper oxide having a diameter of 1 μm is used, the discharge capacity is small and the capacity of the battery negative electrode is insufficient.
In Comparative Example 2, since the support is not a porous body but a copper plate having a thickness of 0.02 mm, the electrode sheet discharge capacity is small and the capacity as an electrode negative electrode is insufficient.
本発明は、導電性のある多孔構造の支持体が酸化銅の先細薄片密集体により被覆された電極シートを提供することにより、この電極シートを負極に用いる非水系電池（リチウムイオン二次電池）の高容量化が図られるので、非水系電池を駆動電源として用いる電子機器に用いることができる。 The present invention provides a non-aqueous battery (lithium ion secondary battery) using the electrode sheet as a negative electrode by providing an electrode sheet in which a conductive porous structure support is coated with a taper thin piece of copper oxide. Therefore, it can be used for an electronic device that uses a non-aqueous battery as a drive power source.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013204912A JP6281154B2 (en) | 2013-09-30 | 2013-09-30 | Negative electrode sheet of lithium ion secondary battery and lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013204912A JP6281154B2 (en) | 2013-09-30 | 2013-09-30 | Negative electrode sheet of lithium ion secondary battery and lithium ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015069902A JP2015069902A (en) | 2015-04-13 |
| JP6281154B2 true JP6281154B2 (en) | 2018-02-21 |
Family
ID=52836355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013204912A Active JP6281154B2 (en) | 2013-09-30 | 2013-09-30 | Negative electrode sheet of lithium ion secondary battery and lithium ion secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6281154B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6778291B1 (en) * | 2019-03-04 | 2020-10-28 | ナミックス株式会社 | Negative current collector of copper foil and lithium ion battery containing it and its manufacturing method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5927755B2 (en) * | 2010-09-30 | 2016-06-01 | 凸版印刷株式会社 | Lithium ion battery and method for producing lithium ion battery |
-
2013
- 2013-09-30 JP JP2013204912A patent/JP6281154B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015069902A (en) | 2015-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6367390B2 (en) | Production of large capacity prism lithium ion alloy anode | |
| JP5975347B2 (en) | ELECTRODE BODY FOR STORAGE ELEMENT AND STORAGE ELEMENT | |
| WO2013140942A1 (en) | All-solid-state lithium secondary battery | |
| JP5119277B2 (en) | ELECTRODE FOR LITHIUM SECONDARY BATTERY AND METHOD FOR PRODUCING THE SAME | |
| JP5416128B2 (en) | Non-aqueous secondary battery | |
| JP5985137B2 (en) | Manufacturing method of non-aqueous secondary battery | |
| JP5372881B2 (en) | Lithium secondary battery having a stress relaxation layer | |
| WO2013125485A1 (en) | All-solid-state lithium secondary battery | |
| Im et al. | Two-dimensional, P-doped Si/SiOx alternating veneer-like microparticles for high-capacity lithium-ion battery composite | |
| KR20230050395A (en) | Negative plate and secondary battery | |
| JP2011233349A (en) | Nonaqueous secondary battery | |
| JPWO2017104583A1 (en) | All-solid-state secondary battery, electrode sheet for all-solid-state secondary battery, and production method thereof | |
| JP6672971B2 (en) | Method of manufacturing electrode body | |
| JP2016184484A (en) | Negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP6567289B2 (en) | Lithium ion secondary battery | |
| JP2016046058A (en) | Nonaqueous electrolyte secondary battery and separator therefor | |
| JP4973892B2 (en) | Capacitors | |
| JP4973882B2 (en) | Capacitors | |
| JP2013077734A (en) | Electrode and method of manufacturing the same | |
| JP6844602B2 (en) | electrode | |
| JP6281154B2 (en) | Negative electrode sheet of lithium ion secondary battery and lithium ion secondary battery | |
| JP2003331823A (en) | Nonaqueous electrolyte secondary battery and method of manufacturing the battery | |
| KR102056455B1 (en) | Negative electrode and secondary battery comprising the negative electrode | |
| JP2015173030A (en) | Porous collector and method for manufacturing porous collector | |
| JP2019220357A (en) | Electrode for lithium ion secondary battery, and lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160721 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170407 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170411 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170612 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171205 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171228 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6281154 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |