TW201044677A - Lithium ion secondary battery, electrode for the battery, and electrodeposited copper foil for the electrode for the battery - Google Patents

Abstract

Disclosed is an electrodeposited copper foil for a negative electrode for a lithium ion secondary battery, which enables the production of a lithium ion secondary battery that has a high energy density, rarely undergoes the reduction in capacity even when a charge-discharge cycle is repeated, has a long service life, and can be reduced in size. Specifically disclosed is an electrodeposited copper foil for an electrode current collector of a lithium ion secondary battery, which has a tensile strength of 400 N/mm2 or more and a stretch ratio of not less than 4.5% and less than 13%, in which the surface that forms an active material layer capable of absorbing/releasing lithium electrochemically or chemically has a surface roughness (Ra) of 0.01 to 1 μ m.

Description

[Technical Field] The present invention relates to a lithium ion secondary battery comprising a non-aqueous electrolysis having irregularities and a negative electrode material for forming a negative electrode active material layer on a surface of a negative electrode. The electric box used in the secondary battery is an electrolytic steel foil of the electrode collector.先前 ❹ [Prior Art] A positive electrode, a surface of a negative electrode collector composed of a copper box having a smooth surface, coated with carbon particles as a negative electrode active material layer, and a counter electrode and a non-aqueous electrolyte The secondary battery system is now used in a mobile phone type 1 personal computer or the like. In the negative electrode of the ion secondary battery, a rust preventive treatment was carried out using an electrolytic copper foil which was produced by electrolysis and which was treated with the same. In the copper case which is the negative electrode collector for the above-mentioned plasma ion secondary battery, as shown in Patent Document 1, it is suppressed by using a copper box which reduces the difference in surface roughness between the shiny side and the rough side (both sides of the copper case) The battery charge and discharge efficiency is reduced. The electrolytic copper box for reducing the difference in the roughness of the surface of the shiny surface and the rough surface is appropriately selected and added to the electrolyte by various water-soluble high-sub substances, various surfactants, various organic sulfur systems. It is produced by a compound, chloride ion, or the like. For example, Patent Document 2 discloses that the use of a compound having a sulfhydryl group, a chloride ion, a low molecular weight 3 201044677 gel having a molecular weight of 1 Å or less, and a polymer of a polymer polysaccharide are used in the electrolytic solution. The method is made/faced, coated with carbon particles, and the feed solution steel box is attached to the surface of the copper drop. /pressed to become the collector of the negative electrode (electrically, the tensile strength of the electrolytic copper flute is 3〇riU j, . . , ^ ^ v/ i\ // JJ] J j] ^ jf ^ .逑 谪厣 谪厣 ΐ # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # # The first one - the human battery is still capacity, such as Shi Xi, Xi, etc., as a negative school, alloyed in Zhong Zhiming, Li literature 3). / / #子_Secondary battery (refer to the purpose of high-capacity lithium as a purpose _ by... or sputtering method in copper: (negative) Shi Xi' formed as a non-crystalline stone film or microcage The active material produced by the method of culturing, for example, 4 films, was found to exhibit good charge and discharge cycle characteristics: = 'close to the collector, and therefore, .., ^, refer to Patent Document 4). In recent years, it has also been developed: by the combination of hydrazine and imine (4), _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ It is coated on a copper crucible, and the electricity used in this type of ion secondary battery is erroneously occluded by lithium. In addition, upon discharge, the volume is expanded by about 4 t of discharge I to release the clock ions to contract. Therefore, due to the expansion and contraction with charge and discharge, the volume of the active material f layer is micronized, and the phenomenon of 201044677 is peeled off by the collector. The repetition of the discharge causes the active material to have a large effect at the collector due to charging, and the expansion and contraction of the volume of the layer occurs. - The force wrinkles at the collector, and when the charge and discharge are performed many times. Some problems have occurred. Fragmentation

When the wrinkles of the collector are changed, the problem of the decrease in the body occupied by the stomach electrode occurs. In addition, it maintains long-term stable battery performance. [Patent Literature] In the case of $, the electrode is stored in a battery and the energy per unit volume is dense, and the collector is not able to be broken. [Patent Document 1] Patent No. 3742144 [Patent Document 2] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Problem] As described above, in the state in which (4) the collector electrode of the active material of the main forming tool is used as the set electrode, the axe is used in the state of the battery. The charge-discharge reaction causes the active material It # :::: two to have a large stress in the collector, and occurs in the shape of the collector = shape. In addition, there are many times of repeated charging and discharging. 5 201044677 When electricity is used, there is a problem that the foil is broken as a collector. Wrinkles in the collector are observed in the battery. The energy density in the battery cannot be maintained. The 矽, 锗 or the secondary battery can be maintained. It is provided as the target *I, when the deformation of the text 4 is

In the meantime, there is a so-called thunder ^^彳± 士 A occupies a larger volume, and each single degree decreases pE1 day from the flat m-bar and "bull m < screaming occurs. This is caused by the collector's break , stable battery performance between long turns.

The present invention provides _ pick-up, 1 + I ', and the kind of illusion is used in the collector electrode which is used for collecting the active component of tin as the main component, and the ion of the negative electrode of the two objects is not collected in the collector. A bell-ion secondary battery that does not cause breakage of the collector, and which has a long-term stable performance, is used as an electrode for a battery and an electrolytic copper tube constituting the electrode. [Means for Solving the Problem] The electrolytic copper box for an ion secondary battery electrode of the present invention has a tensile strength of 4 _ / coffee 2 or more, an elongation of 4 5% : less than 13% above The surface roughness Ra of the surface of the active material layer which can be electrochemically or chemically occluded and entangled is 0. 〇1~1 M m. The above-mentioned electrolytic copper foil forming the above-mentioned active material layer is hunted; the forged oxygen phase growth method, the surname method or the grinding method is used to carry out the rough surface. In addition, the surface of the above-mentioned electrolytic steel sheet forming the active material layer is particularly preferably a surface which is roughened by copper as a main component by electroplating. Preferably, the powdered copper plating layer caused by the electroplating of copper is not on the powdered 201044677 copper plating layer so as not to impair the uneven shape thereof. Copper electric money (coated electric ore) to form a surface formed by a copper plating layer. The electrode for a secondary secondary battery of the present invention is deposited on the collector and can be electrochemically or chemically occluded. An electrode for a lithium ion secondary battery formed by the active material layer, wherein the collector is composed of an electrolytic copper box, and the tensile strength of the copper pig is 4〇〇N/mm2 or more, and the elongation is 4 '5/0 or more and less than 13%', and the surface roughness Ra of the above-mentioned collector surface of the active material layer 〇 is 01 to 1/1/m. The ion secondary battery of the present invention is Stacking on the collector can be electric: or chemically absorbing and releasing The clock ion battery formed by the active material layer of the clock is characterized in that the collector is composed of an electrolytic copper box, and the tensile strength of the copper box is 4 (Wlong 2 or more, the elongation is 45%) The surface roughness of the collector surface of the active material layer is less than 13%, and the surface roughness of the collector surface of the active material layer is 1 to 1/1/m. The active material of the electrode for the ion secondary battery is Shi Xi, wrong. Or, the "tin" is used as a main component. / [Effect of the Invention] If the copper ion flute is used for the electrode of the chain ion secondary battery of the present invention, it is possible to provide a state in which the copper sway is used as a collector. The deformation of the stem, the I wrinkle, etc. occurs during charge and discharge, and the energy density per unit volume of the lithium ion secondary battery can be increased, and the collector is not broken. Therefore, the clock ion is stabilized for a long time and is stable. The battery of the present invention is a battery of the present invention. The human battery is used in the negative electrode of the battery, and the electrolytic copper is dissolved before use. Therefore, it is possible to provide a collector 7 without being charged or discharged. 201044677 Wrinkles, etc. Deformation, can raise the 曰 ^ 〇 ION ion primary battery per unit volume said 1 degree, and the bungee is not broken ~ 杲棰 not broken 'Therefore, the lithium ion secondary battery that is expected to be stable for a long time. EMBODIMENT OF THE INVENTION The copper ion of the lithium ion secondary battery of the present invention can be electrolyzed or oxidized to absorb and release lithium, and the copper is deposited on the surface thereof, and is characterized by: Its tensile strength is 诹4 υ(10)/Μ, and the elongation is 4.5% or more and less than 13%. Yiwei and the surface roughness h of the electrolytic copper enamel after she smashed the rough surface. 4. The copper foil for lithium ion secondary battery electrode of the invention is made of electrolytic copper having a tensile strength of 1: wide or more, an elongation of 4.5% or more, and less than m, and the electrolytic copper is used as Therefore, even if it is subjected to the stress of expansion and contraction of the active material layer due to the release of the bell, it becomes a collector, and deformation or breakage such as wrinkles does not occur. #In the state of using the electrolytic copper of the negative electrode collector with a tensile strength lower than 4 Å/_2, 'the stress of expansion and contraction of the active material layer due to the release of the clock during charging and discharging, In the episode, wrinkles occur. In addition, even if the tensile strength is 400 N/W and ±, the "J shape" is repeated, and when the charge and discharge cycles are repeated a plurality of times, the hair and the collector (box) are broken. In order not to break, it is necessary to have an elongation of 4. W or more and less than 13%. ▲When the elongation of the electrolytic copper box is less than 45%, the breakage occurs when the charge and discharge cycles are repeated repeatedly. On the other hand, if the extension of 201044677 exceeds m, the breakage of the box does not occur, but due to the manufacturing principle of the electrolytic copper box, the tendency of the tensile strength to increase and the elongation decrease Because, in reality, it is not easy to manufacture a tensile strength of more than /mm2 and an elongation of more than 13%. The copper crucible for the electrode of the ion secondary battery of the present invention is a copper crucible for electrochemically or chemically absorbing and releasing the active material of the bell on the surface thereof and protecting the electrode for the ion secondary battery. The tensile strength of the copper box is Ο

The upper side of the G side has an elongation of more than 4.5% and is less than m, and the unevenness of the surface of the active material layer, that is, the surface roughness is "〇. 〇1 〜1 // m 〇 by the collector The surface roughness Ra of the surface becomes 〇_〇1 to ... to alleviate the influence of the copper box on the expansion and contraction of the active material layer due to the charge and discharge cycle. It happens to prevent the effect of breaking. That is to say, 'as shown in Figure 1(a), 'the rough surface is made to be the material: Cao: 1...the roughened electrolytic copper box (collector)" When the activity is formed and θ 21 is formed, the active material layer is formed by placing an active material on the unevenness formed on the surface of the roughened electrolytic copper foil (collector) u. As shown in Fig. 1 (b), when the lithium ion battery (collector) u which forms the active material layer 21 is used as a negative ion electrode for charging and discharging the ion secondary battery, the active material is refined. The volume "expanded by the absorption of lithium ions by the bio-bee" makes the active material layer 21 dense. The receiver, as shown by HI and the active material ^,1, releases lithium ions and shrinks the active material during the first discharge, and is an island shape along the roughened 9 201044677 electrolytic copper pig. The concave portion forms a crack and is separated along the convex portion. In the active material layer 21, the active material is re-expanded by charging of the receiver to narrow the crack. However, 'then even the heavy gentleman Qiu Ba Gua also enters the charge and discharge, so that the cracked mouth ρ knife becomes the expansion and contraction of the slow electrolysis m...the island-shaped part of the 'lowering rough surface% and copper mooring (collector) 11 The entire body of the body is skewed to prevent wrinkles and the like from being formed as a polarized electrolytic copper box U. The clever-to-be-thick surface has the effect of preventing breakage. The above effect is that when the surface crude sugar k is not lower than 〇. 01 # m, it does not have an effect, even if the Ra is 1 meg ^ ' effect is saturated. Further, in order to roughen the surface of the copper foil so that the wax Ka becomes 1 # m or more, it becomes inexpensive and becomes impractical. In the present invention, the tensile strength and elongation, the 呷 系 借 乂 乂 乂 乂 乂 乂 乂 乂 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗 粗The value measured by the method determined by Japanese Industrial Standard 〇iS K 6251). Further, the surface roughness degree Ra is an arithmetic surface roughness obtained by Japanese Industrial Standards (chest 94), for example, a value measured by a surface roughness meter. Lithium ion two of the present invention:: heavy snow, ice field A & 'The negative electrode is used in the electrolytic copper foil to have a tensile strength of 4 gang / 2 or more, an elongation of 4 > 5% or more, less than (four) and form an activity. The surface roughness of the material layer, that is, the surface roughness of Ra is 〇. (H~1/zm collector (, liver liver remnant) surface, the accumulation can be electrochemically or chemically occluded. The active material layer forms a negative electrode on the surface 10 201044677. The adhesion of the collector and the active material layer can be improved by the surface roughness Ra of the collector surface being 0 〇1, and The effect of the copper box on the contraction of the active material caused by the charge and discharge cycle 'prevents enemies and the like in the copper box as the collector: and has the effect of preventing breakage. ' Ο ο

The electrolysis steel book for the electrode of the ion secondary battery of the present invention is obtained by using an aqueous solution of copper sulfate monosulfate as a thunder; the IL vowel is composed of a platinum group element or its oxidation, and is formed into an insoluble anode and opposite direction. The electrolyte is supplied between the cathode drums of the anode, and the cathode drum is rotated at a constant rate, and the DC current is applied between the two electrodes at the same time. On the table of the cathode drum & ^ -,

Copper is precipitated, and the copper is peeled off from the surface of the cathode drum, and the copper is scraped, and the wood is made by continuous winding. The electrolysis (4) of the present invention can be carried out by electrolysis (4) of a sulfuric acid electrode by an ion, a molecular weight of two: a compound having a scouring group, a chloride, and a low molecular weight hydrazine and a high molecular polysaccharide 2, and a thiourea is added. It is produced by using polypropylene glycol, polyethylene glycol, dimethyl ether or polyvinyl alcohol. , face = face = = industry: 1 electrolytic copper is connected to the positive surface of the cathode drum, and the opposite side is called "rough surface". The electrolytic copper box manufactured by the box is called " Untreated electrolytic copper in order to make the surface of the surface of the untreated electrolytic steel box rough. U1~1 # m, therefore, Hawthorn two; Su want to treat the surface of the untreated electrolytic copper foil 11 201044677 Electroplating method and gas phase formation "The roughening treatment system can be suitably carried out by a pore phase growth method, a residual method, a polishing method, or the like. The recording method and the vapor phase growth method are used to form a surface having a thin % of relief and a cold surface as a method of roughening the electric ore method. In addition, it is used as a vapor phase growth method and an electroless ore method. This. The ruthenium plating method, the CVD method, and the steaming method can be applied to the surface of the crude electrolytic copper foil caused by the electric shovel method, and the method of the gentleman in the untreated electric ore film. (4) The copper alloy, etc. (4) is the main component. ^ The method of roughening by electrolysis (4) is the most common method = Patent Document 5 (曰本特公昭I_号) is used for the printed circuit. That is, the 'face' of the electric iron used by the melon is the rough-faced copper electricity ◎: the so-called "scorch electric ore" to form the powder ore" without damaging its concave and convex shape, in essence, the pile:: makes the powder Granular steel is a method of roughening the so-called sore-like copper. It is a method of forming a ruthenium as a main component by a vapor phase growth method by means of a method or (4) in an unformed: the system is preferably composed of copper or a steel alloy or the like. The roughening caused by the quotation method is suitable for the method caused by physics ::: (4). Further, as a method of grinding by sand blasting, etc., by grinding or the like, or by 201044677, the active material layer of the present invention is absorbing and releasing the substance of the bell, β is alloyed by lithium. The active material 吸 吸 系列 矽 矽 锗 锗 锗 锗 锗 锗 锗 锗 锗 锗 锗 锗 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛 蛛矽, 锗; 5瓴m u. Which is best to use = tin. Therefore, the active material layer used in the present invention is a layer of a main component, particularly preferably a layer. ❹ 〇: The active material layer of the invention of the second invention is preferably amorphous, and the ruthenium layer is preferably a non-crystalline layer or a microcrystalline layer. The active material layer of the present invention is formed as In the state of the film, it can be formed by ===mine method, steaming method, spray method or electroplating method. Even in this method, it is preferably formed by the method of (4) and the method of splashing money. In the state of the coating type, it is made into a slurry by the active material and the binder. Formed by cloth, dried and stamped. The 'collector of the present invention is preferably thinner, ... preferably metal', especially electrolysis mi. The active layer can be deposited on one or both sides of the collector. In the state in which the active material layer is formed on both sides of the collector, the surface roughness of the two sides of the collector is preferably m". The active material 1 of the present invention may be first occluded or added with lithium. In the formation of the active material layer, 'addition of lithium. That is to say, by forming the active layer of the bell, the active material layer contains. In addition, after the active material layer is opened, the active material is The layer 'absorbs or adds lithium. The method for occluding or adding lithium to the active material layer is a series of electrochemical methods and methods for storing or adding lithium. In the present invention, it is preferable to use a diffusion layer in the active material layer. Ingredients 13 201044677 copper). The adhesion between the collector and the active material layer can be improved by diffusing the components of the collector layer in the active material layer. The diffusion is not alloyed to the element of the copper or the like as a collector component. In the state of diffusion, Inhibition and alloying, therefore, it is possible to suppress the expansion/contraction of the film caused by the charge-discharge reaction, and it is possible to suppress the occurrence of stress such as the peeling of the active material layer by the collector. The lithium ion secondary battery of the present invention includes a negative electrode composed of the electrode for a lithium ion secondary battery of the present invention, a substance for occluding and releasing lithium, and a positive electrode for the active material and a nonaqueous electrolyte. The non-aqueous electrolyte used in the H-ion secondary battery of this month is also desolved in the solvent to the solute of the solute, and the solvent is used as the solvent system of the non-aqueous electrolyte. The solvent of the battery is not particularly limited, but, for example, a cyclic carbonate or a dimercapto carbonate such as ethylene carbonate, propylene carbonate, butylene carbonate or ethylene carbonate. , a chain carbonate such as 1 ethyl carbonate ▲ based carbon 酉夂 S 曰. It is preferable to use a mixture of a cyclic carbonate and a chain carbonate. Further, a chain of three or more of the above-mentioned cyclic carbonate, hydrazine, 2-diethyl ether solvent or butyl di ethoxy ethene may be used. A mixed solvent such as vinegar. :: The solute system which is a non-aqueous electrolyte is used for the secondary electricity of the clock ion: the quality is not particularly limited. For example, (10), coffee, 'j ^ UN (CF3S0^ -LiN(C2F5SO〇2.LiN) (CF3S〇2) 2) 'LiC ( CF3S〇2) 3 ^ LiC ( C2F5S〇^ T - AFT · r1n r 5^U2) 3 > LiAsFe ' ΐ2Βΐ°Πΐ°, Ll2Bl2C1]2, etc. Especially best Use LiXFy 201044677 (in the chemical formula 'X series P, As, Sb, B, Bi, A1, Ga or In, when X is P, As or Sb, y is 6 and X is B, Bi, A1, Ga Or when 'y is 4') and lithium perfluorinated alkyl sulfonate imine LiN (C»F2»+ iS〇2) (CnF2n+, S〇2) (in the chemical formula, m and n are independent The ground becomes an integer of 1 = 4.) or the clock fluorinated alkylsulfonic acid methylate LiC (CpF2p + Α〇2) (CqF2q+1S〇2) (crF2r+1S〇2) (in the chemical formula, p, q and r are each independently a mixed solute of 丨=4.) Even among these, it is particularly preferable to use a mixed solute of UPFe and UN (C2F5S〇2) 2 . The electrolyte system can be used in polyethylene oxide, polyacrylonitrile, poly I Ethylene and a polymer electrolyte, etc. to the gel polymer electrolyte impregnated with an electrolytic solution or an electrolyte.

Inorganic solid bismuth II of Li I, LisN, etc.: The electrolyte of the ion secondary battery is as long as the U compound which is found to be an ionic conductive solute and dissolves and keeps the solvent of the chelating compound from being solved by the charging of the battery. Can be used without restrictions. In the case of the voltage at the time of storage or in the case of storage, it is also used as a metal oxide for the positive electrode, 2, UMn2, and the like. And, in addition to: Electrochemical insertion and disengagement: < Outside, if it is used. If it is qualitative, it can also be used for the purpose of suppressing the deformation or breakage of the collector (4) due to the charge and discharge of 15 201044677 by the present invention, and improving the unit volume per unit of the secondary ion battery. An ion secondary battery having an energy density and maintaining long performance. [Examples] The present invention will be described in more detail below with reference to the accompanying Examples. However, the invention is not limited to the following examples, and may be appropriately modified and carried out without departing from the scope of the invention. [Examples 1 to 3] [Production of untreated copper foil] An additive of the composition shown in Table i was added to an acidic copper electrolytic bath of copper 7 〇 13 〇 g / 1 - sulfuric acid 80 to 14 g/l. In the table, Mps is a 3-mercapto-1-propanone sodium sulphate, and HEC (a polymer polysaccharide) is a low molecular weight gel having a molecular weight of 3, _ ethyl octyl. Further, ppG is a polypropylene glycol, PEGDME is a polyethylene glycol dimethyl group, and m is a polyvinyl alcohol. (9) MPS, HEC (polymer polysaccharides), gum, ethylene sulfur veins, polypropylene glycol, polyethylene glycol dimethyl bond, polyethylene glycol and chloride ions to the concentration shown in Table i, prepared H uses an electrolyte. In the material, the concentration of the vapor ions is adjusted to be 30_'. However, the concentration of the chloride ions is appropriately changed by the electrolysis conditions, and is not limited to this concentration. Using a prepared electrolyte, the noble electrode is coated with a noble metal oxide at the anode, and the cathode is made of a titanium rotating drum, at the electrolysis conditions (current density, liquid temperature) shown by the electrolysis box. Untreated copper foil [Table 1] 16 201044677 Electrolyte composition and electrolysis conditions

In the case of the electric charge, the powder was applied without damaging the adhesion. Comparative Example 3: Heating in a nitrogen atmosphere at 350 t x 60 minutes [Production of the working electrode (negative electrode)] Electrolytic copper shown in Table 1. The surface of the box A1 is electroplated by electro-convex copper to form a powdery copper plating layer. On the copper-plated layer, a dense copper plating (coating plating, uneven shape) is used to form a surface-formed electrolytic copper foil which is improved in powdered copper and electrolytic copper, and becomes a collector a. Initially, in the electrolytic copper foil A1 The state, as a weight of 22/zmn, is then applied to the electromagnet (10) to make the thickness 25", as the collector al. In addition, the steel y of the steel y... Copper plating (breaking electroplating powder granular key conditions: - as below. Thickness-making conditions caused by steel winding conditions, dense sulfuric acid steel sulfuric acid added | J liquid temperature and current density treatment 110' 30 10, 80g / L "160g / L Appropriate amount -60 °c 5〇A/dm2 20 seconds 17 201044677 Tight copper electric ore copper sulfate sulfuric acid temperature current density processing time

(Cover plating) Conditions: 200g / L 90 ~ 130g / L 30 ~ 60 〇 C 1 0 ~ 30A / dm2 2 ~ 2 0 seconds _ then 'on the surface of the electrolytic steel box A2, A3, the same as the collector al Perform burnt electric keys and abundance &,, and break the plating to make collectors a2 and a3. The thick sounds of the collectors ai and a2, a3, > ± , seven ^ tensile strength, elongation and surface roughness Ra, Rz are shown in Table 2. [Table 2 Table 2 Collector Thickness (// m) Ra (β m) Rz (// m) Tensile Strength m / nun2) Elongation (%) Example 1 A1 25.4 0. 69 3. 50 707 480 Implementation Example 2 Example 3 6. 5 12 9 a2 QQ 25. 1 0. 59 3. 32 - Comparative Example 1 α. 〇bl 25. 3 "25. 0 0. 60 0. 56 3. 41 3. 28 420 1 4. 5 Comparative Example 2 Κ9 338 L 8. 0 Comparative Example 3 U u ----. b3 25. 8 0. 65 ___3. 70 479 3. 6 25.8 0. 65 3. 70 220 5 On the occasion, Ma 7: ί * 丄, 〇. ϊ AN, . , ,. A.",,, ^, ~ meaning, value, tensile strength and elongation are using tensile testing machine (INSTR〇N 佶 佶. l The value of the U is "measured". In addition, the surface roughness Ra and Rz are determined by the method of J:TM, using the stylus type table: thick:: (SE-3C type manufactured by Otaru Research Institute) Measured value 彳 Next, on the collectors 31 and a2, a thin film of a very active material. Sputtering conditions / becomes a negative 1 basket · argon (Ar), 201044677 money emulsion flow rate: iL substrate temperature: room Temperature (no twisting), anti-f pressure UPa (1·Hidden W), high-frequency power: said. Shi Xi 4 film system is stacked until its thickness becomes 5, m In the case of the Raschig film obtained in the Raman (Ra called the spectroscopic analysis of the leaf, the peak near the ^ is detected, but no nearby bee is detected. From this, it is known that the stone is obtained. The film is a non-crystalline dream film. Ο Ο 切割 切割 切割 石 石 石 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 薄膜 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石(1) The celestial pole and the working electrode of Example 2 (collector..., Example 3 (collector a3) (negative electrode). [Production of Vi cat battery] The action pole is used in an atmosphere of argon gas. In the lower box, II is a two-electrode Vicat (V) battery. The Vicat battery is wrongly placed in the glass container and the old electrolyte. It is composed of a pole, a working electrode and a gin. As a method of electrolysis (IV), a metal is dissolved in a solvent having a volume ratio of 3:7, and the mixture of ethylene carbonate and diethyl carbonate is dissolved. Lithium and reference poles use lithium [Evaluation of charge and discharge cycle characteristics] = Vicat made as described above The battery, after reaching 〇V(vs.u/Ll+)tr, causes the potential of the working electrode to discharge, so that the potential of the working pole, and then, the constant current of the current reaches the potential of 2V (v.Li/Li+ ) for 201044677, 'evaluate the discharge capacity and initial rate per unit area. In addition, the so-called initial; ^ 彳 & clothing charge and discharge effect ah gong gong dynasty charge and discharge efficiency (based on the following formula to calculate / / electrical efficiency) initial charge and discharge efficiency (%) = initial xl00 electric valley The results of the evaluation of the 1-stage charging capacity are shown in Table 3. [Table 3] Example 1 Example 2 Example 3 Comparative Example 1 Comparatively known 2 ---- Comparative Example 3 Initial discharge capacity (mAh/cm2 ~~ "76 " (%1 95.

[Evaluation of Electrode Thickness The thickness of the Αk ^ . , 疋 before and after the charge and discharge test and after the charge and discharge test, the thickness of the ψ ψ + 士, before and after the charge and discharge test. Further, the thickness of the central portion and the four corners of the total of five points was measured at 5 points, and the average value was used as the thickness of the electrode. The evaluation results are shown in Table 4.

20 201044677 [Comparative Examples 1 and 2, 3] As the collector Μ, b2, b3, the use of the table j and the electrolysis condition f ray # 衣1 is not the electrolyte composition: condition (electricity, liquid temperature) The electrolysis produced (4) B3 'For the electrolytic copper foil β1, β2, β3 Court* is made by the electrolytic plating of the same copper as the 1st of the 1st phase... the phase is in the real case., 9 κο 成粗Surface processing, making collector bl and b2, b3. The collector bl and b2, b 4 ώ φ η * thickness, tensile strength, elongation, and surface "degrees Ra, Rz" are shown in Table 2. Ο Ο

On the collectors bl and b2, h?·^ t· , Q 3 , the same as in the first and second embodiments, the amorphous ruthenium film is formed, and the phase cup is exemplified by the examples 1 and 2, and 3 The working electrode of Comparative Example 1 (collector (1) and Comparative Example 2 (collector b2), b3) was produced. (4) " (collective use of these roles and phase rv. +, shoot) in 16 cases 1 and 2, 3 to make Vicat lca battery, the initial discharge capacity and love for each Vicat battery日古'+ & in Table 3. Electrical efficiency, the results, and the display are clearly shown by the results shown by: "Even in the example" 2 and any of the electrodes of Comparative Examples 1 and 2, , also obtained 3.5mAh / cm degree of thunderbolt π, in the discharge valley, serving more than 94% of the initial charge and discharge effect that this system is also roughened by the surface of any type of collector, and by Since the active material layer is formed in a slit in the thickness direction and separated into a columnar shape, the active material layer does not peel or collapse, and is in close contact with the collector. _In addition, even the working poles of Comparative Examples i and 2, In the same manner, the thicknesses of Examples 1 & 2, 3 were measured, and the thicknesses before and after the charge and discharge test were measured. The thickness changes before and after the charge and discharge test were determined. Table 4 shows the results of 21 201044677. It is clearly shown that the working poles of Examples 1 and 2 and qm丄3 are compared Compared with the working poles of Examples i and 3, the thickness change before and after the charge and discharge test is significantly smaller. This is because of the action poles in Examples 1 and 2, sd, and the thickness changes only due to charge and discharge. The active material expands and contracts to change the thickness, and even in the charge and discharge test, the collector does not cause deformation such as sensation, etc. In contrast, the comparative example 3 and 3 = wrinkles occur in the collector. Increase the thickness variation. "Comparative Example 2 is the thickness change before and after charge and discharge 疋 at 3 〇〇: after the human cycle, 'breaking at '羯' is observed. This is because the system is used for electrolytic copper in collector b2| The tensile strength is relatively large. Therefore, due to the charge and discharge: the wrinkles caused by the reduction are small, but the elongation is small, and the household is easy to break. Changed to female field, and 呷 hand double, therefore, Asian did not observe the break after 3 cycles, but the strength of the anti-smashing force became smaller, so the wrinkles became more pronounced. And the wrinkles are generated in the collector, therefore, the tensile The degree must be 400 N/mm2 or more. + / 2, / or above. In addition, even if the tensile strength is 4 〇〇 n / mm or more, the elongation is not 4 years old. ), in the collector, the deformation, the literary specialization, the county 曰 疋 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有Moreover, since the foil is not broken, therefore, it is preferable to use an electrolytic copper foil having a tensile strength of 400 N/_2 or more and an elongation of 4· and less than 3%. The material layer 201044677 is sad. 'The electrolytic copper foil used in the collector has a large tensile strength and a large elongation. % can prevent the occurrence of wrinkles only by the high tensile strength, but when the elongation is small, β is repeatedly subjected to the charge and discharge cycle, and the tensile strength is large and the elongation is also increased. The shape of the electrolytic copper foil is removed to prevent the occurrence of wrinkles, and the pig does not break. ~ In addition, in the state of using an active material composed of bismuth or tin, ^ also gives the same result. According to the present invention, it is possible to suppress the occurrence of wrinkles or the like in the collector due to charge and discharge, and it is possible to improve the energy density per unit volume of the battery of the ion-ion battery, even if the charging (four) cycle is repeated repeatedly. A lithium-ion secondary battery that can be miniaturized and has a long life and can be miniaturized. [Simple description of the map]

Fig. 1 (a) to (c) showing the state of the lithium ion secondary battery of the present invention in the state of electricity and discharge using the copper foil for electrodes. [Description of main component symbols] 11~ rough surfaced electrolytic steel box. 21~active material layer. twenty three

Claims (1)

201044677 VII. Patent application scope: 1.—The kind of clock ion _ _A _ . One ''electrolytic copper foil for human battery electrode' The electrolysis copper box for the above electrode' has a tensile strength of 2 and is 40ON / mm or more, and the elongation is 4 R % or more, go to:,,#; 1 Q 〇/ 卜 ° 'The surface roughness Ra of the surface of the active material layer which can be electrochemically or chemically absorbed and released. · 01~1 " m. For example, the electrolytic copper foil for lithium ion secondary battery electrode according to the first patent of the patent dry circumference, wherein the Jiejie electric surface is formed by electroplating, cypress, and soil surface growth, etching or grinding. The surface of the face is made by law. 3. In the copper-clad case I for the secondary battery electrode of the second section of the patent application scope i, the electrolyzed copper of the active material f layer is formed: the surface is made of copper as a main component by electroplating The surface formed by the particles. 4. The surface of the electrolyzed copper falling on the electrode material layer of the second active battery electrode of the second embodiment of the patent application is formed by the electroplating method using particles of copper as a main component. Surface 5. The surface of the electrolyzed copper falling on the electrode material of the above-mentioned active material layer is formed by electroplating with copper, as in the patent application scope The powdery copper electroplated tantalum powdered copper plating layer is formed on the surface of the copper plating layer without impairing the density of the uneven shape: copper electricity: (coating plating). X6. The lithium ion secondary electric power repelling copper foil according to the second aspect of the patent application, wherein the surface of the electrolytic copper foil forming the active material layer is caused by electroplating of copper The powdery granular copper plating layer is formed on the surface of the granular copper plating layer so as not to impair the uneven shape of the steel layer by the steel plating layer of φ < steel plating 201044677 (coating plating). - Long ion two (four) (four) electrode, electrochemically or chemically absorbing on the collector, releasing the active material layer of the clock, h is a collector system composed of electrolytic copper flute, and its tensile strength is extended by the thief. The rate is more than 5%, less than 丨qo, 乂, mass μ $ & . 隹 ° ° and form the surface of the above-mentioned active ribbed layer of the surface of the collector's surface "biometric system 〇.01~ 1 ".. Shen patents her lithium ion around the seventh item _ which, Xin, ω 仏 邴卞 - - 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人The main component. 9. A secondary ion of the bell ion / μ ^ , , /, can be deposited on the collector can be electro-chemical or chemically occluded in the release, a ... " 4 lithium active material layer The negative electrode, / 2 steel slab, has a tensile strength of 400 N / mm or more, an elongation ratio of f /amp; ^ , . 5 / ° or more, less than 13%, and the formation of the aforementioned active material layer ~bm. ', surface roughness of the extreme surface 〇.〇1 〇25