CN103403934B - The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body and the manufacture method of positive electrode for nonaqueous electrolyte secondary battery - Google Patents

The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body and the manufacture method of positive electrode for nonaqueous electrolyte secondary battery Download PDF

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Publication number
CN103403934B
CN103403934B CN201180052263.1A CN201180052263A CN103403934B CN 103403934 B CN103403934 B CN 103403934B CN 201180052263 A CN201180052263 A CN 201180052263A CN 103403934 B CN103403934 B CN 103403934B
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collector body
positive electrode
aforementioned
manufacture method
secondary battery
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CN103403934A (en
Inventor
秋山大作
石田辉和
高桥胜
矢熊纪子
大串亮
出口友香里
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MEC Co Ltd
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MEC Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides manufacture method and the manufacture method of positive electrode for nonaqueous electrolyte secondary battery of the positive electrode for nonaqueous electrolyte secondary battery collector body of the electronic conductivity that can promote between active substance and collector body.The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body of the present invention is the manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body on the surface with etchant roughening treatment aluminum current collecting substrate, it is characterised in that: aforementioned etchant is by selected more than one in the alkaline aqueous solution system etchant comprising alkali source and amphoteric metal ion and the ferric ion water solution system etchant comprising ferric ion source, cupric ion source, manganese ion source and mineral acid.

Description

The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body and nonaqueous electrolyte The manufacture method of anode of secondary cell
Technical field
The present invention be the positive electrode collector about the rechargeable nonaqueous electrolytic battery being used in lithium rechargeable battery etc. it Manufacture method and the manufacture method of positive pole.
Background technology
Rechargeable nonaqueous electrolytic battery because of may heavy load electric discharge, can reuse by charging, and as portable electricity Source is used for the e-machine miscellaneous such as mobile phone, notebook computer.Along with in order to realize these electronic machines step by step Miniaturization/the lightweight of device, for the rechargeable nonaqueous electrolytic battery as portable power sources, it is desirable to and smallerization/lightweight/ The requirement of high-energy-density is the most surging.
And in recent years under the rise of petroleum resources, the surging background of International Geophysical environmental protection movement, electric automobile, Hybrid vehicle, fuel cell car etc. enjoy to be gazed at, and its some is practical.In these drive systems, as benefit It is integral for helping with the secondary cell of power supply etc., and expect can urgency of corresponding automobile start/the anxious height output accelerated two Primary cell.Due to such background, in prospect secondary cell, energy density is the highest and can represent the nonaqueous electrolyte two of high output Primary cell.
Respond among the rechargeable nonaqueous electrolytic battery of these requirements, especially with lithium rechargeable battery because of available high energy Metric density and be widely used, in significantly growing up in market.
Lithium rechargeable battery the most generally on the collector body constituted with aluminum etc., formation comprises lithium cobalt oxidation The active matter of the transistion metal compound containing lithium such as thing, lithium nickel oxide, lithium manganese oxide, oxide/lithium ferrite, iron lithium phosphate Matter layer.Such as, in following patent documentation 1, record to prevent because of the dilation etc. of the active substance along with discharge and recharge The adherence making the interface of active substance and collector body deteriorates, make collector body surface after hydrochloric acid Anodic Oxidation is roughened again, The manufacture method of the positive pole of active material layer is formed in this roughening face.
Prior art document
Patent documentation
Patent documentation 1 Japanese Unexamined Patent Publication 2008-210564 publication
Summary of the invention
Technical problem
But, inventor finds through investigation, and the manufacture method of the positive pole in past has lifting active substance and collector body Between the difficulty of electronic conductivity.
The present invention is because above-mentioned truth, it is provided that can promote the non-aqueous of electronic conductivity between active substance and collector body The manufacture method of electrolyte secondary battery positive electrode collector and the manufacture method of positive electrode for nonaqueous electrolyte secondary battery.
Technical scheme
The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body of the present invention, for etchant roughening treatment aluminum The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body on the surface of current collecting substrate processed, aforementioned etchant is for by comprising The alkaline aqueous solution system etchant of alkali source and amphoteric metal ion and sulphur compound and comprise ferric ion source, cupric from More than one etchants selected in the ferric ion water solution system etchant of component, manganese ion source and mineral acid, aforementioned Sulphur compound is more than one sulphur compounds selected by the sulphur compound by thiosulfuric acid ion and carbon number 1～7, aforementioned trivalent The content of iron ion source, iron ion accounts for 1.5～9.0 weight %, the content of aforementioned cupric ion source, copper ion account for 0.05～ 1.0 weight %.
The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery of the present invention, lives for being formed on aluminum positive electrode collector The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery of property material layer, the most aforementioned aluminum positive electrode collector is with above-mentioned The positive electrode collector obtained by manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body of invention, then at aforementioned positive electrode Abovementioned reactive species layer is formed on the surface of the roughened process of collector body.
Also, the invention described above it " aluminum " can be for by aluminum institute constitutor, also can be for by aluminium alloy institute constitutor.And this explanation In " aluminum " for refer to aluminum or aluminum alloy.
Invention effect
The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body of the foundation present invention and nonaqueous electrolyte secondary The manufacture method of positive electrode for battery, because of the surface with special etch agent roughening treatment aluminum current collecting substrate, and adds collector body With the contact area of active substance, it is considered to promote the electronic conductivity between active substance and collector body.
Accompanying drawing explanation
Fig. 1 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting embodiment 1 of 45 ° Retouch formula electron micrograph.
Fig. 2 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting embodiment 2 of 45 ° Retouch formula electron micrograph.
Fig. 3 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting embodiment 3 of 45 ° Retouch formula electron micrograph.
Fig. 4 is with multiplying power: 10000 times, pinch shadow angles: the roughening face of the collector body of the condition shooting embodiment 3 of surface Sweep electron microscope photograph.
Fig. 5 is with multiplying power: the sweep electron microscope phase in the cross section of the collector body of the condition shooting embodiment 3 of 3500 times Sheet.
Fig. 6 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting embodiment 4 of 45 ° Retouch formula electron micrograph.
Fig. 7 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting embodiment 5 of 45 ° Retouch formula electron micrograph.
Fig. 8 is with multiplying power: 3500 times, pinch shadow angles: the scan-type on the collector body surface of the condition shooting comparative example 1 of 45 ° Electron micrograph.
Fig. 9 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting comparative example 2 of 45 ° Retouch formula electron micrograph.
Figure 10 is for multiplying power: 3500 times, pinch shadow angles: sweeping of the roughening face of the collector body of the condition shooting comparative example 3 of 45 ° Retouch formula electron micrograph.
Figure 11 is with multiplying power: 3500 times, pinch shadow angles: the roughening face of the collector body of the condition of 45 ° shooting embodiment 12 it Sweep electron microscope photograph.
Figure 12 is with multiplying power: 10000 times, pinch shadow angles: the roughening of the collector body of the condition shooting embodiment 12 of surface The sweep electron microscope photograph in face.
Figure 13 is with multiplying power: the sweep electron microscope in the cross section of the collector body of the condition shooting embodiment 12 of 3500 times Photograph.
Figure 14 is with multiplying power: 3500 times, pinch shadow angles: the roughening face of the collector body of the condition of 45 ° shooting embodiment 13 it Sweep electron microscope photograph.
Figure 15 is with multiplying power: 10000 times, pinch shadow angles: the roughening of the collector body of the condition shooting embodiment 13 of surface The sweep electron microscope photograph in face.
Figure 16 is with multiplying power: the sweep electron microscope in the cross section of the collector body of the condition shooting embodiment 13 of 3500 times Photograph.
Detailed description of the invention
[aluminum current collecting substrate]
The aluminum current collecting substrate (hereinafter referred merely to as " base material ") of the present invention can be used in as long as non-aqueous solution electrolysis can be used in The positive pole of electrolitc secondary cell, i.e. without limit especially, can use variously-shaped person.Such as foil-like, porous metals shape, perforation gold can be used Belong to shape, foaming metal shape, the base material of the shape such as netted, from the point of view of forming the viewpoint in uniform roughening face, preferably foil-like base material. Also, can be used in the thickness of the base material of the present invention by obtaining abundant intensity from the viewpoint of, more than preferably 10 μm, more preferably 15 More than μm.Also, by promote active substance loading from the viewpoint of, below preferably 50 μm, below more preferably 30 μm.
[etchant]
In the present invention, the etchant of roughening treatment base material, for using by aforementioned base water solution system etchant and aforementioned three Valency iron ion water solution system etchant is selected more than one.In the present invention, because of with aforementioned special etch agent roughening treatment aluminum The surface of current collecting substrate processed, adds the contact area of collector body and active substance, and is considered to promote active substance and collection Electronic conductivity between electricity body.From the point of view of viewpoint by the good roughening shape obtaining applicable electronics conduction, etchant is preferable Use aforementioned base water solution system etchant.Hereinafter, illustrate to be used in each composition of the etchant of the present invention.
(alkaline aqueous solution system etchant)
First, alkaline aqueous solution system etchant is described.Alkaline aqueous solution system etchant for comprise alkali source and amphoteric metal from Son, can contain sulphur compound, oxidant, various additives etc. according to need.
＜ alkali source ＞
Alkali source is not particularly limited, by the deliquescent viewpoint of aluminum and reduce from the viewpoint of cost, preferably NaOH, KOH. From the viewpoint of the content of alkali source is by obtaining good roughening shape, preferable hydroxide ion accounts for more than 0.60 weight %, more excellent Select more than 1.45 weight %, also will be more than more preferably 2.50 weight %.Also, come by the viewpoint obtaining suitable roughening treatment speed Seeing, the content of alkali source, preferably hydroxide ion account for below below 22.80 weight %, more preferably 16.30 weight %, also more excellent Select below 12.25 weight %.
＜ amphoteric metal ion ＞
As long as be i.e. not particularly limited beyond amphoteric metal ion Al ion, can illustrate Zn ion, Pb ion, Sn ion, Sb ion, Cd ion etc., from the point of view of the viewpoint of the good roughening shape and reduction carrying capacity of environment that obtain applicable electronics conduction, Preferably Zn ion, Sn ion, more preferably Zn ion.The content of amphoteric metal ion, by obtaining the good of applicable electronics conduction From the point of view of the viewpoint of roughening shape, more than preferably 0.2 weight %, more than more preferably 0.5 weight %, also will more preferably 1.0 weight % Above.Also, from the viewpoint of by obtaining appropriate roughening treatment speed, the content of amphoteric metal ion preferably 6.0 weight % with Under, below more preferably 4.4 weight %, also will be below more preferably 3.5 weight %.
Via allotment amphoteric metal ion source, alkaline aqueous solution system etchant can contain amphoteric metal ion.Both sexes gold Belong to ionogenic example, in the situation of Zn ion source, zinc nitrate, Firebrake ZB, zinc chloride, zinc sulfate, zinc bromide, alkalescence can be enumerated Zinc carbonate, zinc oxide, zinc sulfide etc..Also, in the situation of Sn ion source, stannic chloride (IV), stannic chloride (II), tin acetate can be enumerated (II), Tin tetrabromide. (II), diphosphonic acid stannum (II), tin oxalate (II), stannum oxide (II), Tin tetraiodide. (II), STANNOUS SULPHATE CRYSTALLINE (II), sulfuration Stannum (IV), stearic stannum (II) etc..
＜ sulphur compound ＞
Can be used in the alkaline aqueous solution system etchant of the present invention, just be fitted via the roughening treatment carrying out densification From the viewpoint of closing the good roughening shape of electronics conduction, the most adjustable sulphur compound.In allotment sulphur compound situation, by From the viewpoint of identical, more than the content of sulphur compound preferably 0.05 weight %, more than more preferably 0.1 weight %, also more excellent Select more than 0.2 weight %.From the viewpoint of identical, below the content of sulphur compound preferably 25.0 weight %, more preferably 20.0 Below weight %, also will be below more preferably 15.0 weight %.
Sulphur compound is not particularly limited, by obtain be suitable for electronics conduction good roughening shape from the viewpoint of, preferably By more than one selected by the sulphur compound of thiosulfuric acid ion and carbon number 1～7, more preferably by thiosulfuric acid ion and carbon number More than one selected by the sulphur compound of 1～3.Wherein, via allocating its ion source, alkaline aqueous solution system etchant can contain There is thiosulfuric acid ion plasma.
The sulphur compound of above-mentioned carbon number 1～7 can enumerate thiourea (carbon number 1), THIOGLYCOLLIC ACID ammonium (carbon number 2), THIOGLYCOLLIC ACID (carbon Several 2), sulfur glycerol (carbon number 3), L-Thioproline (carbon number 4), dithiodiglycol acid (carbon number 4), β, β '-sulfur are for dipropyl Acid (carbon number 5), N, N-diethyl-dithio amidocarbonic acid sodium trihydrate (carbon number 5), 3,3 '-dithiodipropionic acid (carbon number 6), 3,3 '-dithio dipropyl alcohol (carbon number 6), o-toluene thiophenol (carbon number 7), toluene-ω-thiol (carbon number 7) etc..
＜ oxidant ＞
Can be used in the alkaline aqueous solution system etchant of the present invention, in order to be re-dissolved in the roughening treatment of aluminum with aluminum The amphoteric metal on substrate surface, the most adjustable oxidant is separated out during substitution reaction.In the situation of allotment oxidant, by both sexes From the viewpoint of the re-dissolved of metal, more than the content of oxidant preferably 0.5 weight %, more than more preferably 1.0 weight %, also Will be more than more preferably 2.0 weight %.Also, by obtain being suitable for electronics conduction be well roughened shape from the viewpoint of, oxidant Below content preferably 10.0 weight %, below more preferably 8.4 weight %, also will be below more preferably 6.0 weight %.
Aforementioned oxidizer can enumerate the chloric acid such as chlorous acid, hypochlorous acid and salt thereof, permanganate, chromate, bichromate, cerium (IV) peroxide, the nitrate ion such as the oxidizing metal salts such as salt, compound containing nitro, hydrogen peroxide, persulfate Deng.Wherein from the point of view of the viewpoint by the stability in alkaline aqueous solution system etchant, preferably nitrate ion.
Via allotment nitrate ion source, alkaline aqueous solution system etchant can contain nitrate ion.The model in nitrate ion source Example can enumerate nitric acid, sodium nitrate, potassium nitrate, barium nitrate, calcium nitrate, ammonium nitrate, zinc nitrate etc..
Can be used in the alkaline aqueous solution system etchant of the present invention, in order to prevent because the surface contaminants such as fingerprint make roughening Uneven and interfacial agent can be added, also can add other additives according to need.Other additives, can illustrate to suppress adjoint The dissolving of aluminum and produce the additive of spot, the such as azole such as hydramine, imidazoles such as monoethanolamine, diethanolamine, triethanolamine, Hydroxy carboxylic acid and the salt etc. of they such as citric acid, malic acid, gluconic acid.Adding the situation that these other one-tenth divides, its content About preferably 0.1～5 weight %.
The alkaline aqueous solution system etchant of the present invention can be used in, be dissolved in deionized water etc. by by aforementioned each composition And can easily allocate.
(ferric ion water solution system etchant)
Then explanation ferric ion water solution system etchant.Ferric ion water solution system etchant is for comprising ferric iron Ion source, cupric ion source, manganese ion source and mineral acid, can comprise various additives etc. according to need.
＜ ferric ion source ＞
The ferric ion source of the ferric ion water solution system etchant that can be used in the present invention is by the one-tenth of aluminum oxidation Point.Ferric nitrate (III), iron sulfate (III), iron chloride (III) etc. can be enumerated in aforementioned ferric ion source.Aforementioned ferric ion Among source, from the point of view of the point that chlorination ferric iron is excellent with regard to dissolubility, cheap preferably.
The content in aforementioned ferric ion source, preferably iron ion account for 1.5～9.0 weight %, more preferably 2.5～7.0 weights Amount %, also will more preferably 4.0～6.0 weight %.If more than aforementioned content 1.5 weight %, then the coarsening rate of aluminum can be prevented (dissolution velocity) reduces.On the other hand, if aforementioned content is below 9.0 weight %, because coarsening rate can be made to maintain suitably, and energy It is roughened equably.
＜ cupric ion source ＞
The cupric ion source of the ferric ion water solution system etchant of the present invention can be used in, for for removing rapidly Remove to be formed at the composition of the oxide-film of substrate surface before treatment.Aforementioned cupric ion source can enumerate copper sulfate (II), chlorination Copper (II), copper nitrate (II), Copper hydrate (II) etc..Among aforementioned cupric ion source, copper sulfate is with regard to excellent from the point of view of cheap point Choosing.
The content of cupric ion source, preferably copper ion account for 0.05～1.0 weight %, more preferably 0.10～0.8 weight %, Also will more preferably 0.15～0.4 weight %.If more than aforementioned content 0.05 weight %, can easily remove oxide skin(coating).Separately On the one hand, if aforementioned content is below 1.0 weight %, can prevent the metallic copper of substrate surface from replacing and separate out.
＜ manganese ion source ＞
The manganese ion source of the ferric ion water solution system etchant of the present invention can be used in, for for the most uneven And it is roughened the composition of substrate surface equably.Manganese sulfate, manganese chloride, manganese acetate, manganous fluoride, nitric acid can be enumerated in aforementioned manganese ion source Manganese etc..Among aforementioned manganese ion source, manganese sulfate and manganese chloride are with regard to preferred from the point of view of cheap point.
The content in manganese ion source, preferably manganese ion account for 0.02～1.5 weight %, more preferably 0.06～0.6 weight %, also want More preferably 0.10～0.5 weight %.If aforementioned content is more than 0.02 weight %, then can give full play to add the effect in manganese ion source Really.On the other hand, if aforementioned content is below 1.5 weight %, cost is the most easily reduced.
＜ mineral acid ＞
The mineral acid of the ferric ion water solution system etchant of the present invention can be used in, for dissolving quilt with ferric ion The composition of the aluminum of oxidation.Aforementioned inorganic acid can be enumerated hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, be crossed chloric acid, sulfanilic acid etc..Aforementioned inorganic Almost without stink among acid, from the point of view of cheap point, preferably sulfuric acid.
The content of aforementioned inorganic acid preferably 5～30 weight %, more preferably 7～25 weight %, also will more preferably 12～18 weights Amount %.If more than aforementioned content 5 weight %, then can prevent the coarsening rate (dissolution velocity) of aluminum from reducing.On the other hand, if front Stating content is below 30 weight %, because preventing from separating out the crystallization of aluminium salt when liquid temperature reduces, and can promote workability.
Can be used in the ferric ion water solution system etchant of the present invention, in order to prevent because of surface contaminants such as fingerprints Make roughening uneven and interfacial agent can be added, also can add other additives according to need.
The ferric ion water solution system etchant of the present invention, by aforementioned each composition being dissolved in deionized water etc. and Can easily modulate.
Then, the method illustrating to use above-mentioned etchant roughening treatment substrate surface.First, illustrate to use alkaline aqueous solution It it is the situation of etchant.
When using the etchant roughening treatment of alkaline aqueous solution system, in object to be processed substrate surface organic oil etc. substantially Situation about polluting, after carrying out oils and fats, carries out using the roughening treatment of aforementioned ferric ion water solution system etchant. Coarsing processing method can be enumerated by processing methods such as dipping, sprayings.Treatment temperature preferably 20～40 DEG C, process the time preferably 10～ About 300 seconds.General washing can be carried out after aforementioned processing, be dried.
In the present invention, after using alkaline aqueous solution system etchant to carry out roughening treatment, preferably to remove the both sexes gold of precipitation For the purpose of genus, clean to roughening face pickling.As long as the acid solubilized amphoteric metal being used in pickling clean is i.e. not particularly limited, preferably special Not with by aqueous solution of nitric acid, aqueous sulfuric acid and containing sulphuric acid and the aqueous solution of hydrogen peroxide are selected more than one are water-soluble Liquid processes roughening face.If removing in the amphoteric metal of substrate surface precipitation, then because can carry out being passivated again of substrate surface simultaneously, and The non-oxidizability to high potential can be promoted.The process of aqueous solution can be enumerated and be processed with dipping, spraying etc..Treatment temperature is preferred 20～40 DEG C, process preferably about 5～40 seconds time.Common washing can be carried out after aforementioned processing, be dried.
Using the situation of aqueous solution of nitric acid, from the viewpoint of removing the performance of amphoteric metal and the corrosivity to aluminum, The concentration of nitric acid preferably 5～65 weight %, more preferably 25～45 weight %.Using the situation of aqueous sulfuric acid, by removing two The performance of property metal and to the corrosivity of aluminum from the viewpoint of, the concentration of sulphuric acid preferably 5～60 weight %, more preferably 20～40 weights Amount %.
Using the situation containing sulphuric acid with the aqueous solution of hydrogen peroxide, by removing the performance of amphoteric metal and the corruption to aluminum From the viewpoint of erosion property, the concentration of sulphuric acid preferably 5～60 weight %, more preferably 20～40 weight %.From the viewpoint of identical, The concentration of hydrogen peroxide preferably 1～40 weight %, more preferably 5～30 weight %.
In the present invention, above-mentioned pickling is clean, particularly with by aqueous solution of nitric acid, aqueous sulfuric acid and containing sulphuric acid and mistake After more than one aqueous solutions selected in the aqueous solution of hydrogen oxide process roughening face, also further this process face can be carried out sun Pole oxidation processes (alumite process).After carrying out aforementioned anodizing process, the non-oxidizability to high potential can be promoted further.
Also, in the present invention, after using the etchant roughening treatment of alkaline aqueous solution system, also can use selected from hydrochloric acid, hydrogen bromine Halogen acids such as acid or comprise the alkaline aqueous solution of hydroxide by more than one metals selected in alkalies and alkaline earth The roughening face of cleaning.If carrying out with halogen acids or alkaline aqueous solution, roughening face is to be cleaned, because roughening face is etched slightly, and controlled The shape in roughening face processed.Thereby, the size of the positive active material particle used and the roughening face shape that shape is appropriate can be formed Shape.In order to form the roughening face with deeper recess, preferably process with halogen acids.Also, aforementioned base water solution system does not comprises The aqueous solution of amphoteric metal ion.
Former state halogen acids clean situation, from the point of view of the viewpoint of the shape in the roughening face of being easily controlled, preferably use halogen Change the halogen acids that concentration is 1～35 weight % of hydrogen.From the viewpoint of halogen acids is by cost and usability, preferably hydrochloric acid.
Former state halogen acids clean situation, processing method can be enumerated and process with dipping, spraying etc..Treatment temperature is preferred 20～40 DEG C, process preferably about 5～300 seconds time.Common washing can be carried out after aforementioned processing, be dried.
Former state alkaline aqueous solution clean situation, from the viewpoint of the shape in the roughening face of being easily controlled, preferably make With the alkaline aqueous solution that the concentration of hydroxide is 1～48 weight %.From the viewpoint of hydroxide is by cost and usability, excellent Select potassium hydroxide, sodium hydroxide.
Former state alkaline aqueous solution clean situation, processing method can be enumerated and process with dipping, spraying etc..Treatment temperature Preferably 20～40 DEG C, process preferably about 5～300 seconds time.Common washing can be carried out after aforementioned processing, be dried.Also, with Aforementioned base aqueous solution cleans the situation in roughening face, preferably clean with pickling further to the roughening face after cleaning.In aforementioned base The process of water solution system etchant can remove the amphoteric metal of precipitation.Use the clean acid of aforementioned pickling and treatment conditions etc., for The above-mentioned pickling carried out for the purpose of removing amphoteric metal situation only is identical.
Then, illustrate to use the situation of ferric ion water solution system etchant.Using ferric ion water solution system The situation of etchant, the situation that the substrate surface organic oil etc. in object to be processed substantially pollutes, after carrying out oils and fats, carry out Use the roughening treatment of aforementioned ferric ion water solution system etchant.Coarsing processing method can be enumerated with dipping, spraying Etc. processing method.Treatment temperature preferably 20～30 DEG C, processes preferably about 10～300 seconds time.Can lead to after aforementioned processing Normal washing, it is dried.
If using ferric ion water solution system etchant to carry out roughening treatment, having the concavo-convex of substrate surface and becoming careful Situation, in the case, only the most careful being partly dissolved is removed with the sodium hydrate aqueous solution about concentration 1～5 weight % Go.In this situation, after processing with sodium hydrate aqueous solution, preferably remove the spot residuing in surface with dilute nitric acid dissolution. Ferric ion water solution system etchant after roughening base material is neutralized, because of can through adding sodium hydroxide, calcium hydroxide etc. Easily coagulation is in the aluminum of dissolving again by Shen Dian, therefore liquid waste processing is easy.
To use aforementioned base water solution system etchant or the roughening treatment of ferric ion water solution system etchant, make base Material surface coarsening becomes concaveconvex shape.The now weight that depth direction etch quantity (meltage) is the aluminum dissolved of aluminum, by than The situation that weight calculates with surface area, preferably 0.1～3.0 μm, more preferably 0.2～2.5 μm, also will more preferably 0.5～2.0 μm.Erosion If quarter measures within the above range, then can obtain being suitable for the good roughening shape of electronics conduction.Etch quantity can mat treatment temperature and The process time etc. adjust.
Also, in the present invention, use aforementioned base water solution system etchant or the roughening of ferric ion water solution system etchant When processing base material, can the substrate surface of whole of roughening treatment, also partly roughening treatment can only form the face of active material layer.
Also, the present invention also can merge the process of use aforementioned base water solution system etchant and use ferric ion water The process of solution system etchant.Processing sequence now does not limit.Also, in the range of the effect not undermining the present invention, also Can merge and use the Wet-type etching with other etchants and various dry-etching.
Positive electrode for nonaqueous electrolyte secondary battery collector body (hereinafter referred merely to as " the collection obtained through above-mentioned roughening treatment Electricity body "), by forming active material layer on the surface of this roughening treatment, available rechargeable nonaqueous electrolytic battery is with just Pole (hereinafter referred merely to as " positive pole ").Hereinafter, with an embodiment of the manufacture method of positive pole, illustrate that lithium rechargeable battery is with just The example of pole.
As long as the active substance of active material layer constituting lithium ion secondary battery anode have can occlusion/releasing lithium it Function is i.e. not particularly limited, and can illustrate metal sulfide positive electrode for it.Specifically, lithium and cobalt oxides, lithium nickel can be used Oxide, lithium manganese oxide, oxide/lithium ferrite, nickel/cobalt composite oxide (binary system positive electrode) containing lithium, containing lithium it The olivine-type transition gold containing lithium such as nickel manganese cobalt composite oxide (ternary system anode material) or iron lithium phosphate and lithium phosphate manganese etc. The transistion metal compound containing lithium such as genus phosphate；The transistion metal compounds such as manganese dioxide；The carbonaceous materials such as fluorographite Deng.More specifically, LiCoO can be used2、LiNiO2、LiMn2O4、LiFeO2、LiFePO4, and the nonstoichiometric compound of they It is substituted by the transistion metal compound of other transition metal, MnO with a part for transition metal they comprised2、TiS2、 FeS2、Nb3S4、Mo3S4、CoS2、V2O5、P2O5、CrO3、V3O3、TeO2、GeO2Deng.They can use independent a kind, also can merge 2 Plant used above.Wherein, from the point of view of the viewpoint excellent by thermostability, capacity, output characteristics, the transition metal of lithium is preferably comprised Compound.And iron lithium phosphate and the transistion metal compound containing other lithiums are in a ratio of electronics conduction resistance height, if using with this The bright collector body obtained by method, can promote the electronic conductivity comprising between the active substance of iron lithium phosphate and collector body. It is to say, use the high active substance of electronics conduction resistance as iron lithium phosphate, according to the present invention, because of add collector body and The contact area of active substance, is also considered to promote the electronic conductivity between active substance and collector body.
The constituent material of active material layer also can use conductive agent.As long as conductive agent is in the charge and discharge of the active substance of use If electric potential does not play the electronic conductivity material of chemical change, what can.Such as can individually or as a mixture contain There are graphite-like, acetylene black, conductive carbon black (ketjen black), the channel process such as native graphite (flaky graphite etc.), Delanium Carbon black, furnace black, the metal powders such as conducting fibre class, carbon tetrafluoride, aluminum such as carbon black class, carbon fiber, metallic fiber such as black dim, hot Conductive metal oxide class, the polyphenylene derivatives etc. such as electric conductivity whisker class, titanium oxide such as end class, zinc oxide, potassium titanate are organic Conductive material etc..Among these conductive agents particularly good for Delanium, acetylene black.Though the addition of conductive agent is not particularly limited, But relative to active substance 100 weight portion, preferably 1～50 weight portions, more preferably 1～30 weight portions.
The method forming active material layer on the roughening treatment face of collector body is not particularly limited, and can use well known Active material layer forming method, such as, can use modulation to be mixed with the serosity of active substance, conductive agent, solid and solvent, This serosity is coated on the surface of roughened process of collector body, then is dried the method formed.
Above-mentioned solid can use over any solid for forming positive pole, can suitably use polyvinylidene fluoride (PVDF), polyamidoimide, politef, polyethylene, polypropylene, polymethyl methacrylate etc..Relative to active matter Matter 100 weight portion, the content of solid preferably 1～20 weight portion, more preferably 1～10 weight portions.
Above-mentioned solvent can use over any solvent for forming positive pole, such as, can suitably use N-methyl-2-pyrroles Pyridine ketone (NMP), dimethylformamide (DMF), dimethyl acetylamide, butanone, oxolane, acetone, ethanol, ethyl acetate Deng.Also, serosity can be made an addition to by being used in the well known any additive forming positive pole in the past.
Above-mentioned serosity is come in the viewpoint of suitable scope by the thickness of the active material layer obtained by making in the viscosity of 25 DEG C See, preferably more than 1000mPa s, more preferably more than 2000mPa s.Also, from the viewpoint of by the coating to collector body, on State preferred below the 15000mPa s of viscosity, more preferably below 10000mPa s.And the thickness of active material layer be usually 1 μm with More than upper, preferably 3 μm, the most usually below 100 μm, below preferably 80 μm, below more preferably 60 μm.
From the viewpoint of preferably serum viscosity, the solids content concn of serosity preferably 20～60 weight %, more preferably 25～55 weight %.
The positive pole obtained according to above method, in the manufacture processing procedure of lithium rechargeable battery with negative pole, dividing plate lamination (or Winding) together.Then, inject this laminate (or coiling body) via by electrolyte and polymer dielectric etc., manufacture lithium Ion secondary battery.
One of the present invention described above embodiment, but the present invention is not limited to above-mentioned embodiment.Such as, above-mentioned reality Execute for being illustrated on base material the example of the method directly forming active material layer in form, but also can be formed by graphite on base material In the intermediate layer of composition, on this intermediate layer, form active material layer.
Also, for the example of lithium ion secondary battery anode is described in above-mentioned embodiment, but the present invention is by optimization Collector body surface structure also controls the interface between collector body/active material layer (or intermediate layer), promotes active substance and current collection The technology of the electronic conductivity between body, is not limited to lithium ion secondary battery anode.The most also magnesium ion two it is applicable to Positive electrode for nonaqueous electrolyte secondary battery beyond the lithium rechargeable batteries such as primary cell and calcium ion secondary cell.
[embodiment]
Then, embodiments of the present invention are described together with comparative example.But intangibility of the present invention is interpreted into and is defined in following enforcement Example.
(making of collector body)
First, the aqueous solution of the composition shown in modulomenter 1.By aluminium foil (thickness 20 μ of defined in JIS A1050H H18 M) impregnated in obtained aqueous solution (30 DEG C) and shaken, only washing after the etch quantity shown in etching table 1, then soak Stain is in the aqueous solution of nitric acid (30 DEG C) of 35 weight %, and is shaken 20 seconds, then washes, is dried.Use scanning electron shows Micro mirror (SEM) observe obtained by collector body among, the roughening face of the collector body of embodiment 1～5 and comparative example 1～3.Now SEM photograph is shown in Fig. 1～10.Any embodiment is all roughened equably, but comparative example 2 and comparative example 3 are uneven concavo-convex Shape.
[table 1]
(making of positive pole)
First, mixing LiMn2O4(64.0 weight %), acetylene black (3.6 weight %), polyvinylidene fluoride (4.0 weights Amount %) and N-methyl-2-Pyrrolizidine ketone (28.4 weight %) to modulate positive active material serosity.Then, above-mentioned serosity is coated with It is distributed on the roughening face of above-mentioned collector body, then is dried, obtain being formed with the active material layer of thickness 60 μm on collector body Positive pole (14mm × 20mm).And the density of the active material layer of obtained positive pole is 2.4g/cm3。
(mensuration of AC impedance (AC Impendance))
Use the battery test system 147060BEC type of Solarton company, under the environment of 25 DEG C, to above-mentioned positive pole Apply the alternating current of 0.1Hz, 1.0Hz, 1kHz, 20kHz, measure AC impedance now.Result is shown in table 2.And high-frequency range AC impedance suppress because of the ionic conduction in receptor 1 activity material layer, and have easily shadow by the resistance conducted essentially from electronics The tendency of sound.
[table 2]
0.1Hz 1.0Hz 1kHz 20kHz
Embodiment 1 5.107Ω 3.974Ω 1.707Ω 1.286Ω
Embodiment 2 5.015Ω 3.841Ω 1.537Ω 1.094Ω
Embodiment 3 4.924Ω 3.788Ω 1.352Ω 0.941Ω
Embodiment 4 5.058Ω 4.006Ω 1.629Ω 1.212Ω
Embodiment 5 5.104Ω 3.941Ω 1.556Ω 1.175Ω
Embodiment 6 5.118Ω 4.003Ω 1.764Ω 1.225Ω
Embodiment 7 4.938Ω 3.847Ω 1.541Ω 1.169Ω
Embodiment 8 4.985Ω 3.830Ω 1.494Ω 1.099Ω
Embodiment 9 4.931Ω 3.825Ω 1.381Ω 0.993Ω
Embodiment 10 5.084Ω 4.104Ω 1.717Ω 1.296Ω
Embodiment 11 4.940Ω 3.776Ω 1.359Ω 0.961Ω
Comparative example 1 5.201Ω 4.229Ω 1.902Ω 1.375Ω
Comparative example 2 5.226Ω 4.197Ω 1.949Ω 1.437Ω
Comparative example 3 5.183Ω 4.078Ω 1.852Ω 1.306Ω
As Ru Biao2Suo Shi, in the frequency range of more than 1kHz, any embodiment all can reduce exchange resistance compared with comparative example Anti-.
(making of test cell)
First, mixing mesophase micro-carbon ball (65.7 weight %), acetylene black (1.4 weight %), polyvinylidene fluoride (3.5 Weight %) and N-methyl-2-Pyrrolizidine ketone (29.4 weight %) to modulate negative electrode active material serosity.Then, by above-mentioned serosity Coat rolling of thickness 20 μm to prolong on Copper Foil (process of non-surface), then be dried, obtain being formed with thickness on Copper Foil in rolling to prolong The negative pole (14mm × 21mm) of the active material layer of 35 μm.And the density of the active material layer of obtained negative pole is 1.3g/ cm3.Then, above-mentioned negative pole is used, with the method institute identical with the manufacture method of the positive pole used in above-mentioned Based on AC Impedance Measurements The positive pole for preparing, Porous polyethylene dividing plate and by the LiPF of 1M6It is dissolved in carbonic acid and stretches ethyl ester (EC) and Ethyl methyl carbonate (MEC) electrolyte that mixed solvent (Capacity Ratio is EC:MEC=3:7) forms, assembles test cell.Now, relative area (electrode effective area) is set to 2.8cm2, packaging material use aluminum laminated material.
(with electric current stop method measure internal resistance)
Use Solarton company battery test system 147060BEC type, according to following methods carry out internal resistance it Measure.First, after making above-mentioned test cell become fully charged state, under the environment of 25 DEG C, carry out 0.5C (with 2 hours completely The magnitude of current of electric discharge) electric discharge of load, after starting to discharge 12 minutes, stop electric discharge, change in voltage time thus carries out battery The mensuration of internal resistance.Now, the voltage component that the moment while stopping electric discharge replying is set to impedance components (ohmic Component), the voltage component the most slowly replied is set to equilibrium composition, by it with in being set to obtain with the electric current method of stopping Portion's resistance.Result is shown in table 3.Also, impedance components is to represent the resistance essentially from electronics conduction, equilibrium composition represents main next Resistance from the ionic conduction of inside battery.
[table 3]
Impedance components Equilibrium composition The internal resistance obtained with the electric current method of stopping
Embodiment 1 3.92Ω 4.46Ω 8.38Ω
Embodiment 2 3.71Ω 4.48Ω 8.19Ω
Embodiment 3 3.61Ω 4.52Ω 8.13Ω
Embodiment 4 3.89Ω 4.46Ω 8.35Ω
Embodiment 5 3.83Ω 4.43Ω 8.26Ω
Embodiment 6 3.97Ω 4.46Ω 8.43Ω
Embodiment 7 3.79Ω 4.51Ω 8.30Ω
Embodiment 8 3.82Ω 4.49Ω 8.31Ω
Embodiment 9 3.66Ω 4.50Ω 8.16Ω
Embodiment 10 3.92Ω 4.47Ω 8.39Ω
Embodiment 11 3.71Ω 4.50Ω 8.21Ω
Comparative example 1 4.39Ω 4.39Ω 8.78Ω
Comparative example 2 4.00Ω 4.52Ω 8.52Ω
Comparative example 3 4.12Ω 4.50Ω 8.62Ω
Use LiMn2O4As arbitrary active substance
As Ru Biao3Suo Shi, any embodiment all can reduce the resistance of impedance components compared with comparative example.Thus result is true Recognize and can promote the electronic conductivity between active substance and collector body according to the present invention.
Then, illustrate to evaluate use above-described embodiment and the collector body of comparative example, and use iron lithium phosphate as active matter The result of the internal resistance of the battery of matter.
First, mixing olivine-type iron lithium phosphate (56.3 weight %), acetylene black (5.3 weight %), polyvinylidene fluoride (4.6 weight %) and N-methyl-2-Pyrrolizidine ketone (33.8 weight %) are to modulate positive active material serosity.Then, by above-mentioned On the roughening face of each collector body that serosity coats above-described embodiment and comparative example, then it is dried, is obtained shape on collector body Become to have the positive pole (14mm × 20mm) of the active material layer of thickness 50 μm.And the density of the active material layer of obtained positive pole is 2.0g/cm3。
Then, make test cell same as described above, with the electric current method of stopping same as described above carry out internal resistance it Measure.Result is shown in table 4.
[table 4]
Impedance components Equilibrium composition The internal resistance obtained with the electric current method of stopping
Embodiment 1 5.92Ω 8.63Ω 14.55Ω
Embodiment 2 5.33Ω 8.81Ω 14.14Ω
Embodiment 3 5.19Ω 8.44Ω 13.63Ω
Embodiment 4 5.63Ω 9.14Ω 14.77Ω
Embodiment 5 5.57Ω 8.73Ω 14.30Ω
Embodiment 6 6.71Ω 8.92Ω 15.63Ω
Embodiment 7 5.42Ω 9.11Ω 14.53Ω
Embodiment 8 5.61Ω 8.90Ω 14.51Ω
Embodiment 9 5.24Ω 9.04Ω 14.28Ω
Embodiment 10 7.89Ω 9.23Ω 17.12Ω
Embodiment 11 5.41Ω 8.91Ω 14.32Ω
Comparative example 1 24.00Ω 9.04Ω 33.04Ω
Comparative example 2 43.41Ω 8.74Ω 52.15Ω
Comparative example 3 25.36Ω 8.85Ω 34.21Ω
Use olivine-type iron lithium phosphate as arbitrary active substance
As Ru Biao4Suo Shi, embodiment all can be greatly reduced the resistance of impedance components compared with arbitrary comparative example.Thus Results verification can promote the electronic conductivity between active substance and collector body according to the present invention.
Then, use the nickel manganese cobalt composite oxide containing lithium as active substance, illustrate to evaluate the high rate discharge of battery The result of characteristic.
(making of the collector body of embodiment 12)
First, modulation and the aqueous solution of above-described embodiment 2 same composition.The aluminium foil of defined in JIS A1050H H18 (thickness 20 μm) impregnated in obtained aqueous solution (30 DEG C) and shaken, and only etches 1.0 μm and (is equivalent to 2.70g/m2) Etch quantity after wash.Then, impregnated in the hydrochloric acid (hydrogen cloride concentration: 7 weight %) of 25 DEG C, shaken 30 seconds After wash again, be dried, obtain the collector body of embodiment 12.Enforcement obtained by using sweep electron microscope (SEM) to observe The roughening face of the collector body of example 12.SEM photograph now is shown in Figure 11～13.
(making of the collector body of embodiment 13)
First, modulation and the aqueous solution of above-described embodiment 2 same composition.By the aluminium foil of defined in JIS A1050H H18 (thickness 20 μm) impregnated in obtained aqueous solution (30 DEG C) and shaken, and only etches 1.0 μm and (is equivalent to 2.70g/m2) Etch quantity after wash.Then, impregnated in the sodium hydrate aqueous solution (25 DEG C) of 5 weight %, after being shaken 2 minutes Washing, impregnated in further in the aqueous solution of nitric acid (30 DEG C) of 35 weight %, is shaken 20 seconds, then washes, is dried, and obtains reality Execute the collector body of example 13.The roughening face of the collector body of the embodiment 13 obtained by using sweep electron microscope (SEM) to observe. SEM photograph now is shown in Figure 14～16.
The collector body of obtained embodiment 12,13 and the collector body of above-described embodiment 3 and comparative example 1 is used just to make Pole, makes test cell with this, evaluates the high-rate discharge characteristic of battery.It is shown in detail as follows.
(making of positive pole)
Mixing LiNi1/3Mn1/3Co1/3O2(42.8 weight %), acetylene black (3.5 weight %), polyvinylidene fluoride (3.5 weights Amount %) and N-methyl-2-Pyrrolizidine ketone (50.2 weight %) modulate positive active material serosity.Then, by above-mentioned collector body Be stamped into diameter 10mm discoid after, on its roughening face, be coated with above-mentioned serosity, be dried again, obtain being formed on collector body The positive pole of the active material layer of thickness 20 μm.And the density of the active material layer of obtained positive pole is 1.8g/cm3。
(making of test cell)
The discoid negative pole (diameter 16mm) preparing to be constituted using lithium metal, as negative pole, uses this negative pole, above-mentioned positive pole, many Hole matter polyethylene dividing plate and by the LiPF of 1M6It is dissolved in carbonic acid and stretches ethyl ester (EC) and the mixed solvent of Ethyl methyl carbonate (DMC) The electrolyte of (Capacity Ratio is EC:DMC=1:1), puts into the battery (trade name: HC planar cells) of Bao Quan company, Make test cell.
(evaluation of high-rate discharge characteristic)
After above-mentioned test cell is placed 8 hours under the environment of 25 DEG C, sequentially carry out shown in table 5 under the environment of 25 DEG C Circulation 1～circulation 7.Then the discharge capacity sustainment rate of 5C, 10C and 15C is calculated with following formula.Result is shown in table 6.Also, be used for The discharge capacity of the circulation 1,5～7 of the calculating of discharge capacity sustainment rate, measures actual measurement obtained by 3 times in each circulation Averagely.
Discharge capacity × 100 of the discharge capacity/circulation 1 of the discharge capacity sustainment rate (%) of 5C=circulation 5
Discharge capacity × 100 of the discharge capacity/circulation 1 of the discharge capacity sustainment rate (%) of 10C=circulation 6
Discharge capacity × 100 of the discharge capacity/circulation 1 of the discharge capacity sustainment rate (%) of 15C=circulation 7
[table 5]
[table 6]
Use LiNi1/3Mn1/3Co1/3O2As arbitrary active substance
As shown in table 6, embodiment relative to arbitrary comparative example 1 for greatly improving discharge capacity sustainment rate.It speculates Because of electronic conductivity between active substance and collector body in embodiment, and improve current collecting efficiency therefore.

Claims (7)

1. a manufacture method for positive electrode for nonaqueous electrolyte secondary battery collector body, it is with etchant roughening treatment aluminum collection The manufacture method of the positive electrode for nonaqueous electrolyte secondary battery collector body on the surface of electricity base material,
Aforementioned etchant is by the alkaline aqueous solution system etchant comprising alkali source and amphoteric metal ion and sulphur compound and to comprise Selected by the ferric ion water solution system etchant of ferric ion source, cupric ion source, manganese ion source and mineral acid More than one etchants,
Aforementioned sulphur compound is more than one sulphur compounds selected by the sulphur compound by thiosulfuric acid ion and carbon number 1～7,
The content in aforementioned ferric ion source, iron ion accounts for 1.5～9.0 weight %, the content of aforementioned cupric ion source, copper from Son accounts for 0.05～1.0 weight %.
The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body the most according to claim 1, it is characterised in that Aforementioned etchant is aforementioned base water solution system etchant.
The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body the most according to claim 1, it is characterised in that The content of the aforementioned sulphur compound in aforementioned base water solution system etchant is 0.05～25.0 weight %.
The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body the most according to claim 1, it is characterised in that Aforementioned base water solution system etchant comprises nitrate ion further.
The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body the most according to claim 1, it is former After stating the surface of alkaline aqueous solution system etchant roughening treatment aforementioned aluminum current collecting substrate, with water-soluble by aqueous solution of nitric acid, sulphuric acid Liquid and more than one aqueous solutions selected by aqueous solution containing sulphuric acid with hydrogen peroxide process roughening face.
The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body the most according to claim 1, it is former After stating the surface of alkaline aqueous solution system etchant roughening treatment aforementioned aluminum current collecting substrate, with by halogen acids and comprise by alkali gold More than one aqueous solutions selected by alkaline aqueous solution of the hydroxide of more than one metals selected by genus and alkaline-earth metal The roughening face of process.
The manufacture method of positive electrode for nonaqueous electrolyte secondary battery collector body the most according to claim 1, it is characterised in that When the surface of roughening treatment aforementioned aluminum current collecting substrate, the etch quantity in depth direction is 0.1～3.0 μm.
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