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CN103384930A - Method for producing electrodes - Google Patents

Method for producing electrodes Download PDF

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Publication number
CN103384930A
CN103384930A CN2012800087926A CN201280008792A CN103384930A CN 103384930 A CN103384930 A CN 103384930A CN 2012800087926 A CN2012800087926 A CN 2012800087926A CN 201280008792 A CN201280008792 A CN 201280008792A CN 103384930 A CN103384930 A CN 103384930A
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Prior art keywords
metallic substrates
organic acid
metal substrate
electrode
acid
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CN2012800087926A
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Inventor
蒂姆·舍弗尔
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LI TEC VERMOEGENSVERWALTUNGS GmbH
Li Tec Battery GmbH
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LI TEC VERMOEGENSVERWALTUNGS GmbH
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a method for producing an electrode, in particular a negative electrode, of an electrochemical cell having a metal substrate, wherein the method includes the steps of treating the metal substrate with UV irradiation and treating the metal substrate using an organic acid.

Description

Method for the manufacture of electrode
Technical field
The full content of priority requisition DE 10 2,011 011 154.9 is by reference as the application's part.
The present invention relates to a kind of method of the electrode for the manufacture of electrochemical cell, especially make the method for negative electrode.Described electrochemical cell can be preferred for providing power for the automobile with motor, and this motor preferably has hybrid power and/or adopts external charge (" plug in ") to drive.
Background technology
Electrochemical cell, especially lithium storage battery due to its high-energy-density and high power capacity as accumulator in device for mobile communication, for example mobile phone, use at power tool or at electrically driven (operated) automobile and in having the automobile of hybrid power.In these different application, especially in the Automobile drive field, these electrochemical cells must satisfy high request: high as far as possible capacitance and energy density, it keeps stable through a large amount of charging and discharging circulations, has simultaneously light as far as possible weight.
Often directly depend on ageing of electrode the useful life of electrochemical cell, especially depends on the aging of negative electrode.Electrochemical cell loses its capacity and power in ageing process.Described process occurs in mostly habitual electrochemical cell to a certain extent, and depends on significantly use state (temperature, condition of storage, charged state etc.), but also depends on quality and the technique of material during the electrochemical cell course of processing.Therefore, the very pure material of high-quality processing can access very long-lived electrochemical cell, and they are also only aging slightly through the long time, and therefore loses in time very little capacity and power.
Because the material purity of using often is subject to restriction physics or chemistry, for example because of the reason of synthesis technique, therefore storage battery production person's primary and foremost purpose is, obtain more high-quality and therefore more long-lived electrochemical cell by optimizing electrode production process, as for example as described in the document EP 2 006 942.
Especially, the quality of adhering to for electrochemical cell of the electrochemical active material on metal substrate surface is crucial.From well known in the prior art, by corona treatment, namely use the surface of chromatosulfuric acid etching metal substrate, can strengthen electrochemical active material and adhere to the lip-deep of metallic substrates.Yet the main shortcoming of the method is the use of chromatosulfuric acid, and it is highly toxic for human and environment, and will cause producing in the following process of electrochemical cell the pollution that can not put up with.
Summary of the invention
According to prior art, target of the present invention is to provide a kind of Innovative method for the manufacture of the electrode of long-life electrochemical cell, especially negative electrode.
The described method that invention relates to is achieved by the instruction of independent claims.Preferred embodiment of the present invention is the content of dependent claims.
In order to solve described problem, below describe a kind of manufacturing in detail for the method for method, the especially negative electrode of the electrode of electrochemical cell, it comprises by UV irradiation and with organic acid, metallic substrates is processed.
The method that relates to of invention has advantages of the environmental sound of realization and reliable clean metal substrate, and described method has especially been improved the adhering to of electrochemical active material of metal substrate surface, and makes electrochemical cell have long useful life.
" electrochemical cell " refers to various forms of electric energy storage equipments.So term especially defines once or the electrochemical cell of quadric form, but also comprises the accumulator of other form, for example electric capacity.On meaning of the present invention, electrochemical cell preferably is interpreted as lithium-ion battery.
Electronics is exported in term " negative electrode " expression, electrode with customer, when for example motor is communicated with.Therefore negative electrode is anode according to this criterion.Correspondingly term " positive electrode " refer to electrode and customer, electron gain when for example motor is communicated with.Therefore positive electrode is negative electrode according to this criterion.
Electrode by making according to method of the present invention, be positive electrode and/or negative electrode, have at least a metal collector and have at least a kind of electrochemical active material.
Term " electrochemical active material " refers to a kind of storage or supply ion, especially cation, preferably material of lithium ion of being suitable for.
In one embodiment, electrochemical active material is a kind of active material of cathode.
In a preferred embodiment, electrochemical material is a kind of active material of positive electrode.Described active material of positive electrode is carbon containing preferably.
In one embodiment, except metallic substrates and electrochemical active material (preferably, active material of positive electrode) outside, the electrode of the method manufacturing that relates to according to invention also comprises at least a additive, preferably be used for improving the additive of electric conductivity, for example additive of carbon-Ji, for example carbon black, and/or a kind of additive of redox reaction, described additive reduces, preferably minimizes, preferably prevents the damage of electrochemical active material when electrochemical cell transships.
Term " metallic substrates " preferably refers to parts " electrode substrate " and " collector electrode " of electrode.Described metallic substrates is suitable for herein the application of active material and is mainly metalline, is preferably all metalline.
Described metallic substrates is at least part of film or network structure or fabric of being set to preferably, preferably has the alloy of copper or cupric.
The method that invention relates to preferably has step: metal pretreated substrate, the surface of metallic substrates particularly, thereby with respect to the application of active material with to process the metallic substrates life period with organic acid poor, in particular, substrate is cleaned at least in part, preferably cleans fully.
Term " time difference " refers to, is using organic acid, the processing on the surface of clean metal substrate especially at least in part, particularly this metallic substrates and and be applied to electrochemical active material on pretreated metallic substrates between, interval dt of described time difference〉0.At least part of clean metal substrate of organic acid is especially used in described processing, occurs electrochemical active material is applied to before on pretreated metallic substrates.Described processing especially with at least part of clean metal substrate of organic acid and with reactive compound be applied to pretreated, especially the time difference between on the collector electrode of at least part of cleaning is preferably up to dt=3 hour, is preferably up to 2 hours, is preferably up to 1 hour.
In a preferred embodiment, in preliminary treatment, especially clean at least in part with organic acid the surface of this metallic substrates, particularly this metallic substrates and reactive compound is applied to this is pretreated, the time difference between the metallic substrates of especially at least part of cleaning is 30 to 40 minutes, preferably 35 minutes (+/-2 minutes).
In preliminary treatment, especially clean at least in part with organic acid the surface of this metallic substrates, particularly this metallic substrates and reactive compound is applied to this is pretreated, the time difference between the metallic substrates of especially at least part of cleaning has advantage: can especially effectively clean, wherein, being preferably up to 50% impurity is removed, and particularly preferably high impurity to 100% metallic substrates is by from substrate, and especially the surface of metallic substrates removes.
With the substrate of organic acid clean metal with apply the method step on the surface of the further processing metallic substrates that can carry out again other between electrochemical active material, for example as drying steps.
Term " organic acid " refers to a kind of compound of chemistry, it has acid group O=X-OH, namely comprises central atom (X), and the OH base is coupled by the singly-bound between the oxygen atom O of central atom X and OH base, and comprise another oxygen atom, it is connected with central atom X by two keys.Described central atom X selects in can the nonmetal or semimetal from the periodic table of chemical element (PSE) applicable, realizes being connected with an oxygen atom by setting up two keys, and is connected with the oxygen atom of OH base by setting up the singly-bound realization simultaneously.Central atom X is preferably selected from the group of carbon, sulphur, phosphorus, silicon, wherein carbon particularly preferably.
In addition, central atom X is additional other a atom also, carbon atom preferably, and it is the organic alternative compositions that is selected from alkyl or aryl, outside de-carbon and water atom, it also comprises the hetero-atom that other are additional, preferably can be nitrogen, oxygen, sulphur or phosphorus.Term " organic acid " does not use odd number, and it can relate to multiple organic acid mixture.
If organic acid is " solid " acid, namely under reference condition (25 ℃, 1.031bar) be solid forms, preferably before use it is dissolved in suitable solution.Described organic acid and/or solution preferably have and are less than 20% water content, preferably have to be less than 10% water content, preferably have to be less than 5% water content, preferably have to be less than 2% water content, particularly preferably have 1% or water content still less.Described organic acid is preferred to be selected like this, and it decomposes when UV irradiation or temperature rising.The catabolite that preferred described organic acid generates when UV irradiation is at least part of is gaseous state.Preferred catabolite is as CO 2Or water.
In one embodiment, organic acid is selected from the group of the mixture of acetic acid, butanedioic acid, fumaric acid, citric acid, maleic acid, oxalic acid, lactic acid, pyruvic acid, second two succinic acid (Oxalbersteinsaeure), oxaloacetic acid (Oxalessigsaeure), ethanedioic acid (Oxalsaeure) or its combination.
In a preferred embodiment, it is oxalic acid (also being called ethanedioic acid) that organic acid---has other components---alternatively.
Advantage with organic acid, especially oxalic acid is that organic acid can decompose by for example heating or UV irradiation.Therefore the organic acid analyte that produces is mainly CO 2Can remove or remove with simple method with water.In addition, have an organic acid environment original just simpler, and have lower danger with respect to the environment that chromatosulfuric acid is for example arranged, as be used in when using the corona etching.The environment in this especially related " dustless space " is widely used in the manufacture process of electrochemical cell.
In a particularly preferred embodiment with " anhydrous " oxalic acid as described organic acid, it is sold on market with cas number 144-62-7.Here " anhydrous " refers to that the water content of oxalic acid is equal to or less than 1%.
In another particularly preferred embodiment with " anhydrous " oxalic acid as described organic acid, and at least part of NMP(N-N-methyl-2-2-pyrrolidone N-that is dissolved in), the water content that described NMP has preferably be less than 100ppm(1,000,000/), preferably be less than 60ppm, preferably be less than 30ppm, preferably be less than 10ppm, and be pure, and so-called " battery quality " is mainly not contain amine impurity.
Use anhydrous organic acid, especially anhydrous oxalic acid to have advantage: can be especially effectively and easily at least in part, preferably remove fully impurity, especially its lip-deep impurity in metallic substrates, and especially when with copper foil during as metallic substrates.The impurity on the surface of described metallic substrates can be owing to storing, transport, packing or cause in the manufacture process of metallic substrates.Impurity for example may adversely affect, and electroactive substance is attached on the surface of metallic substrates, therefore cause electrochemical cell " aging " rapidly, perhaps even adversely affect the function of metallic substrates, namely by or obtain or supply with electronics to electrochemical active material, this adverse effect for example can show as, and interior resistance raises and the capacity that loses electrochemical cell of therefore following and the form of power.
In one embodiment, metallic substrates is film copper or cupric, especially the thin slice of copper (foil).In the mill, for example in the operation of rolling or cutting process, the surface of the collector electrode of copper foil is often contained material grease and/or greasy, is especially had the material pollution of butter or grit.In addition, the surface of the film of cupric, especially copper foil, for a long time with the passivation layer passivation at least in part that especially forms by oxidation under surrounding air contacts, this passivation layer comprises the cupric oxide Cu that also is regarded as impurity in one embodiment 2O。Therefore use has organic substituent organic acid and has advantage, because organically grease-contained and/or greasy material is at least part of according to chemical process " similar mixing " (similar substance dissolves is in similar material), preferred whole being dissolved in organic acid, thus its surface from metallic substrates can be removed.Use another advantage of organic acid to be, described passivation layer, comprise cupric oxide Cu in one embodiment 2The passivation layer of O at least in part, preferably be removed fully.Preferably, further reaction no longer occurs with organic acid in the surface of the metallic substrates on processed surface, particularly at least part of cleaning with clearing up.
In a particularly preferred embodiment, metallic substrates be the film of cupric, especially with copper foil as metallic substrates, and the surface of this metallic substrates is subject to containing material, especially butter grease and/or greasy and/or at least part of cupric oxide Cu that comprises at least in part 2The pollution of the passivation layer of O, and at least in part, preferably fully by organic acid, preferably anhydrous oxalic acid is processed, thereby and at least partially, preferably fully remove these impurity.
The term of verb and noun " cleaning " is interpreted as: preferably from metal substrate surface remove high to 50%, be preferably up to 70%, be preferably up to 100% impurity, yet preferred 5%, 10%, 15%, 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 80%, 85%, 90%, 95% the impurity of removing from metal substrate surface at least.
The term of verb and noun " processing " is interpreted as: the metal surface of preferred as many as 50%, preferred as many as 70%, preferred as many as 100% is contacted, especially by its infiltration with organic acid, wherein, in each example, the surface of preferred at least 5%, 10%, 15%, 20%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 80%, 85%, 90%, 95% metallic substrates contacts with organic acid, especially by its infiltration.
In one embodiment, realize infiltrating metal substrate surface with organic acid by spray (Bespruehen) metal substrate surface with organic acid.
In another embodiment, by realizing infiltrating metal substrate surface with organic acid with organic acid cast (Begiessen) metal substrate surface.
In another embodiment, realize infiltrating metal substrate surface with organic acid by soak (Tauchbad) metal substrate surface with organic acid.
In another embodiment, utilize a device to realize infiltrating metal substrate surface with organic acid, roll for example, its surface is infiltrated by organic acid, and therefore the surface by metallic substrates contacts with the surface of described device and makes that organic acid is at least part of to be transferred on metal substrate surface.
In another embodiment, by realizing processing metal substrate surface with organic acid with steam evaporation (Bedampfen), described steam have organic acid or consisting of.Can realize like this treatment surface especially uniformly, especially essentially no " wetting (wetting) " or " wetting removal (de-wetting) " effect.Described processing preferably is at least under 85 ℃, 100 ℃, 150 ℃ in temperature to be carried out.Described processing can form vapor stream, and described steam with certain pressure intensity is applied on pending surface, thereby reaches the cleaning effect of machinery.In each example, this pressure preferably is at least 1bar, 2bar, 5bar, 10bar, 25bar, 50bar, 100bar, 200bar or 500bar, but the pressure on described metallic substrates or ambient pressure also can be 1bar.The cross section of described vapor stream can be plane AD, and this plane is equivalent to the plane AO on pending plane at least.Also may and preferably described cross section AD be equivalent to a part of f(AD=f*AO of plane AO), f is preferably at least or be at most 0.5,0.25,0.1,0.05.The cross-sectional area of described vapor stream is preferred respectively is square, profiles banded or lines substantially.
The processing of described metallic substrates especially to its cleaning, is preferably also used plasma and is realized, plasma jet especially, especially with respect to the ambient pressure of metallic substrates under 0.05bar and 1bar.Plasma is a kind of gas, and it is partly or entirely by charged particle freely, as being comprised of ion or electronics, and for example obtains by the electric treatment of in alternating magnetic field, gas being carried out, for example, and the plasma system that can obtain on market.Described plasma can utilize oxygen or organic acid manufacturing.Wherein temperature can be selected arbitrarily, especially substantially equals room temperature.This makes it possible to provide a kind of more flexible and gentle purification.
May and preferably, described organic acid, especially has the organic acid vapor stream and pending surface is moved relative to each other, preferably has fixing speed, to reach result especially uniformly, preferably, for example pending surface is mobile with respect to organic acid (or vapor stream), and perhaps organic acid (or vapor stream) moves with respect to pending surface.
In one embodiment, the step that infiltrates metal substrate surface is the other method step afterwards, and it utilizes mechanically actuated operation, for example vibrations, and organic acid is evenly distributed in metal substrate surface.
In one embodiment, when being evenly distributed in metal substrate surface, organic acid infiltrates metal substrate surface with organic acid.
In one embodiment, method is the mechanical cleaning metal substrate surface, and the friction of device that for example can be by utilizing brush or yarn fabric realizes.Described mechanical friction step can be before infiltrating metal substrate surface with organic acid, infiltrate with organic acid metal substrate surface during or simultaneously, or follow after infiltrating step.
In a preferred embodiment, infiltrate metal substrate surface, organic acid be evenly distributed in the method step of metal substrate surface and the step of mechanical cleaning metal substrate surface is bonded in an independent method step with organic acid, this step for example can be implemented by having the organic acid vapor stream, or utilize movably shelf storage to be full of the organic acid brush and realize, thereby the surface of metallic substrates can be infiltrated constantly by organic acid, and by applying organic acid with contacting of metal substrate surface.Wherein said displaceable brush for example carries out circular motion on the surface of metallic substrates, and organic acid is evenly distributed in metal substrate surface thus.Be applied to the optional pressure of metal substrate surface by brush, metal substrate surface is also simultaneously by mechanical cleaning.
Described organic acid is preferably up to 30 seconds in the time of staying of metal substrate surface, 5 minutes, be preferably up to 30 minutes, be preferably up to 60 minutes, be preferably up to 2 hours.But the described organic acid time of staying also can be longer or shorter.
In addition, inventing the method that relates to comprises with UV Irradiation metallic substrates.
In one embodiment, before processing metallic substrates with organic acid, it is carried out UV irradiation.
In another embodiment, after processing metallic substrates with organic acid, it is carried out UV irradiation.
In a preferred embodiment, before processing metallic substrates with organic acid and afterwards it is carried out UV irradiation.
In a preferred embodiment, except metallic substrates, also electrochemical active material is carried out UV irradiation.
Described UV x ray irradiation x on electrochemical active material can be tightly before being applied to active material on metallic substrates, perhaps has a predetermined time with it poor.
Described UV irradiation to metallic substrates and electrochemical active material adheres to the generation favorable influence to electrochemical active material on metallic substrates.By UV irradiation, can remove organic dirt (contaminants) from the surface by oxidation at least in part.Generate catabolite, for example CO therebetween 2And water.Therefore, by UV irradiation, at least part of clean metal substrate surface, and the adhesive force of at least part of increase metal substrate surface.
Another advantage of UV irradiation metallic substrates is, the lip-deep organic acid---after applying step---that is present in potentially metallic substrates can partly preferably can all decompose by organic acid at least by UV irradiation it is removed.This produces particularly advantageous effect, generates volatile catabolite under the UV effect of irradiation, as certain gas, for example CO 2Water also can be used as the catabolite that the UV effect of irradiation forms in addition.Can remove easily these catabolites in follow-up step, and can not cause damage in electrochemical cell.
For example mercury vapor lamp is suitable for the radiation source as UV, as Cooper-Hewitt lamp or UV light-emitting diode.The UV ray is that wavelength is the electromagnetic irradiation of 1nm-380nm.
Method preferably comprises step: dry described metallic substrates, namely reduce or remove accumulating in the liquid of metal substrate surface, especially water.Described drying steps can carry out before the UV Irradiation and/or afterwards.In addition described drying steps can be before processing with organic acid and/or before and/or carry out afterwards.
The method that invention relates to preferably comprises step: to the metal substrate surface coating, the UV Irradiation is preferably used on wherein said surface with electrochemical active material, and/or processes with organic acid.And then it is favourable further processing with UV irradiation after the coating step.
In one embodiment, invent the electrochemical cell that relates to and have at least an electrode, the method manufacturing that it relates to by invention.This electrode is negative electrode preferably, it comprises metallic substrates, described metallic substrates preferred disposition becomes to comprise copper, and it makes sheet or film, and be preferably up to 30%, be preferably up to 50%, be preferably up to 70%, be preferably up to the total surface of 100% described metallic substrates by the electroactive substance coating, coating integratedly preferably, wherein electroactive substance is carbon containing, graphite or amorphous graphite or " hard carbon " or their mixture of preferred selective freezing.
Also comprise in another embodiment extra adhesive, described adhesive plays and improves effect bonding between electroactive substance and metallic substrates.This adhesive preferably comprise polymer, preferably comprise fluorinated polymer, preferably comprise Kynoar (Poly-vinylidenfluorid), described polymer is with trade mark Kynar
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Solef
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Kureha
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Figure BDA00003663579900094
Sell.
Description of drawings
Fig. 1 is the schematic diagram of an embodiment.
Embodiment
Embodiment according to the method for the manufacture of electrode of the present invention comprises following step:
Step (11): supplying metal substrate, the preferably electrode of copper metal electrode or cupric.Step (12): afterwards, process described metallic substrates, especially by the described metal substrate surface of UV radiation treatment.Step (21): supply organic acid, especially oxalic acid.Step (22): be dissolved in NMP described organic acid is at least part of subsequently.Described step (11) and/or step (12) can with step (21) and/or (22) executed in parallel.But execution in step (11) and/or step (12) also can be independent of each other in time with execution in step (21) and/or step (22), perhaps have the time difference with execution in step (21) and/or step (22).Therefore for example also can execution in step (11) and step (21) after manner of execution step (22) again, and then manner of execution step (12).
Step (30): will be dissolved in the organic acid in NMP, the anhydrous organic acid that preferably is dissolved in NMP is applied to the metal substrate surface that UV processed.
Step (40): at least in part from the surface of metallic substrates remove apply step (30) be dissolved in NMP in organic acid.If step (30) is carried out with the time interval with respect to step (40), is favourable.Can reach more effective cleaning thus.
Step (50): utilize the UV radiation treatment to utilize metal substrate surface in the step (40) of organic acid cleaning.
Step (71): the supply electrochemical active material, in particular for the electrochemical active material of anode, and step (72): with UV radiation treatment electrochemical active material.Described step (71) and (72) can be in time point execution arbitrarily.But particularly advantageously be, when step (72) is carried out followed by step (60), described step (60) comprises carrying out coating according to the surface of before this step (12), (30), (40) and (50) pretreated metallic substrates, especially described pretreated metallic substrates.
Step (80): the metallic substrates of electroactive substance coating is arranged in step (60) by the UV radiation treatment.Step (80) is optional step.

Claims (8)

1. method for the manufacture of the electrode of electrochemical cell, the method for the negative electrode of electrochemical cell especially, it has metallic substrates, it is characterized in that, and the method comprises the steps:
By the described metallic substrates of UV radiation treatment; And,
By processing described metallic substrates with organic acid.
2. the method for claim 1, is characterized in that, described metallic substrates comprises copper, and preferred, the film of cupric or copper foil.
3. the method according to any one of the preceding claims, is characterized in that, the UV irradiation of described metallic substrates was carried out before or after processing metallic substrates with organic acid or before processing metallic substrates with organic acid and carry out afterwards.
4. the method according to any one of the preceding claims, is characterized in that, described organic acid is anhydrous oxalic acid.
5. method as claimed in claim 4, is characterized in that, described oxalic acid is dissolved in anhydrous NMP.
6. the method according to any one of the preceding claims, is characterized in that, before with electrochemical active material, metallic substrates being applied 30-40 minute, execution was processed metallic substrates with organic acid.
7. method as claimed in claim 6, is characterized in that, with UV radiation treatment electrochemical active material.
8. one kind is used for the electrode of cleaning electrochemical cell, the method for the metallic substrates of negative electrode especially, it is characterized in that, described method comprises the steps:
By UV radiation treatment metallic substrates, and
By processing metallic substrates with organic acid.
CN2012800087926A 2011-02-14 2012-01-26 Method for producing electrodes Pending CN103384930A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063142A (en) * 1994-12-01 2000-05-16 Canon Kabushiki Kaisha Process for producing a rechargeable lithium battery having an improved anode coated by a film containing a specific metal oxide material
JP2000192260A (en) * 1998-12-25 2000-07-11 Toyo Aluminium Kk Manufacturing method of metal foil laminate for etching and etched metal foil
CN1969409A (en) * 2004-04-15 2007-05-23 Fmc公司 Composite materials of nano-dispersed silicon and tin and methods of making the same
US20090098457A1 (en) * 2007-10-15 2009-04-16 Samsung Electronics Co., Ltd. Electrode for secondary battery, manufacturing method thereof and secondary battery employing the same
CN101595541A (en) * 2006-10-17 2009-12-02 麦斯韦尔技术股份有限公司 The electrode that is used for energy storing device
CN101685853A (en) * 2008-09-23 2010-03-31 深圳市比克电池有限公司 Lithium ion battery preparation method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63218150A (en) * 1987-03-06 1988-09-12 Toshiba Battery Co Ltd Thin battery
US8231810B2 (en) * 2004-04-15 2012-07-31 Fmc Corporation Composite materials of nano-dispersed silicon and tin and methods of making the same
US20090029251A1 (en) 2006-03-02 2009-01-29 Mamoru Baba Secondary battery, manufacturing method thereof and system thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063142A (en) * 1994-12-01 2000-05-16 Canon Kabushiki Kaisha Process for producing a rechargeable lithium battery having an improved anode coated by a film containing a specific metal oxide material
JP2000192260A (en) * 1998-12-25 2000-07-11 Toyo Aluminium Kk Manufacturing method of metal foil laminate for etching and etched metal foil
CN1969409A (en) * 2004-04-15 2007-05-23 Fmc公司 Composite materials of nano-dispersed silicon and tin and methods of making the same
CN101595541A (en) * 2006-10-17 2009-12-02 麦斯韦尔技术股份有限公司 The electrode that is used for energy storing device
US20090098457A1 (en) * 2007-10-15 2009-04-16 Samsung Electronics Co., Ltd. Electrode for secondary battery, manufacturing method thereof and secondary battery employing the same
CN101685853A (en) * 2008-09-23 2010-03-31 深圳市比克电池有限公司 Lithium ion battery preparation method

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