CN109056011A - A kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil - Google Patents
A kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil Download PDFInfo
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- CN109056011A CN109056011A CN201810703557.XA CN201810703557A CN109056011A CN 109056011 A CN109056011 A CN 109056011A CN 201810703557 A CN201810703557 A CN 201810703557A CN 109056011 A CN109056011 A CN 109056011A
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- copper foil
- anode
- cathode
- lithium ion
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a kind of preparation methods applied to high capacity lithium ion cells cathode micropore copper foil, belong to electrolytic copper foil technical field.The preparation method includes that foil rack is equipped with electrolytic cell, there is anode plate in the electrolytic cell, the anode slot is connected by the anode of copper bar and power supply, the cathode roll connecting with power cathode is equipped with above the anode slot, it is characterised in that gather numerous pin marks on the anode plate.It is used cooperatively by the anode plate of the pulse power and numerous pin marks that gather, the micropore copper foil for producing high-capacity lithium ion cell has the advantages that thickness is suitable, is unlikely to deform and not cracky；The micropore copper foil is coated with suitable for coating machine, and negative electrode material can be made not easily to fall off.Porosity 20%, 10 microns of aperture can satisfy the market demand completely.
Description
Technical field
The invention belongs to electrolytic copper foils to process technical field, more particularly to a kind of applied to high-capacity lithium ion cell
The preparation method of cathode micropore copper foil.
Background technique
Lithium ion battery is most active and fastest-rising battery product in current Battery Market, is come from development trend
It sees, the significant challenge that battery manufacturers face is always constant demand of the consumer to bigger energy density, either volume
Energy density or gravimetric energy density.
In existing lithium ion battery, electrojet body of the usual aluminium foil as anode is coated with positive electrode in aluminium foil surface,
Form anode；Electrojet body of the copper foil as cathode is coated with negative electrode material in copper foil surface, forms cathode；Positive electrode and negative electrode are logical
It crosses after diaphragm separates and overlaps, form lithium ion battery.
Most common negative electrode material is usually graphite, silicon-carbon cladding, grapheme material etc. in lithium ion battery industry at present
High-capacity battery, negative current collector are usually copper foil, are coated with negative electrode material on copper foil two sides, form cathode.But due to coating
The technical restriction of technique, the negative electrode material thickness for being coated on copper foil two sides is often inconsistent, or even differs greatly.Use lithium ion
When battery, electrochemical reaction occurs with the positive electrode of corresponding position respectively for the negative electrode material on copper foil two sides, and usually relatively thin is negative
Electrochemical reaction occurs for pole and anode to when all consumption, and reaction also stops therewith；Meanwhile thicker cathode continues to
Reaction is participated in provide electric energy.But the electric energy provided at this time is less, reduces the working efficiency of battery to a certain extent,
The actual needs for meeting people thus is tended not to, and is resulted in waste of resources.
At present in technology, there is a kind of battery made of porous copper foil, the copper foil in the battery can be connected to copper foil two sides
Reaction tank, specifically:, will be another by through-hole after negative electrode material completely consumes in the reaction tank of the relatively thin side of negative electrode material
The reaction material migration of side comes, and realizes the reaction tank simultaneous reactions of copper foil two sides.But the production of current through-hole copper foil
There are certain defects for equipment.The existing equipment for preparing porous copper foil has following several, first is that mold, is carried out using mold to copper foil
Punching, the disadvantage is that mold precision prescribed is high, and mold is easy to damage, and causes manufacturing cost height；Second is that laser punching, cost
Height, and it is unfavorable for subsequent coating.
Summary of the invention
The object of the present invention is to provide a kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil, energy
The micropore copper foil produced using the preparation method is enough set to have the advantages that thickness is suitable, be unlikely to deform and not cracky；This is micro-
Hole copper foil is coated with suitable for coating machine, and negative electrode material can be made not easily to fall off.
The technical scheme is that should include applied to the preparation method of high capacity lithium ion cells cathode micropore copper foil
Foil rack is equipped with electrolytic cell, has anode plate in the electrolytic cell, gather numerous pin marks on the anode plate, the anode slot
It is connected by the anode of copper bar and power supply, the cathode roll connecting with power cathode, the cathode roll is equipped with above the anode slot
It is the carrier for depositing copper foil.
The Passivation Treatment forms anti-oxidation processing using the chemical deposition of Chrome-free Non-water washing.
Feature of the present invention is different from other hole creating technologies, will not there is any damage to cathode roll.As on cathode roll
Punching, difficulty precision is difficult to realize, and still more titanium roller works in the electrolytic solution can generate oxidation, and cathode roll with holes is come
It says, is to be difficult secondary use.
Production process of the invention includes: that (1) adopts electrolyte using 99.9% tough cathode, is carried out with analytical pure sulfuric acid aerobic
Pure copper-bath is made in reaction, and solution is diluted using RO film plasma water；(2) in electrolyte copper content be 80g/L,
Sulfuric acid content is 120g/L；Electrolyte is heated to 55 degree；(3) when rotated, the pulse power is during pulse plating for cathode roll
Cooperated with cathode roll circulating time period；(4) electric current that the pulse power generates by the anode plates of numerous pin marks that gather into
Row release causes the needle point point close to titanium roller end since current density increases, copper atom deposition resistance due to the point effect of plating
Hinder, causes hole；(5) organic additives such as suitable polyethylene glycol, chloride ion, brightener are added in electrolyte, to guarantee copper
Foil tensile strength (6) rotates out of foil face, is cleaned using copper-bath, prevents foil face from color difference occur；(7) it cleans, uses
Reverse osmosis ejected wash water is cleaned；(8) it is passivated, chemical deposition is carried out using Chrome-free Non-water washing environment-protective process, prevents copper foil from aoxidizing.
Frequency is lower, and peak point current increases, meanwhile, in pulse width time, it will make close to metal ion at cathode
It sharply reduces, since in the short period, matrix metal deposition velocity is very fast, is transported to cathode roll and is embedded in the speed in coating and catch up with
Not upper apposition metal speeds.It, can be according to circumstances wide to pulse power frequency and pulse in order to improve quality of coating and efficiency
Degree is adjusted.
According to plating layer analysis, discovery pulse (peak value) electric current can make metal ion high with high instantaneous current density
It is restored under overpotential, to make sedimentary crystal grains fine；When switch off current, nearby discharge ion is restored to initially again in cathodic region
Concentration, concentration polarization are eliminated, this continues to use high pulse (peak value) current density conducive to the next pulse same period, are simultaneously turned off
In phase also with to the advantageous recrystallization of sedimentary, adsorption desorption phenomena such as
In production, using the anode plate for numerous pin marks that gather, area effectively can be discharged in tip electric current, in the effective impulse time
It is interior, since tip current discharge density is bigger, causes cathode roll in the apex, cause reducing hydrogen ions point excessive, simultaneously
The electrodeposition process of certain points is prevented by obstacle from learning long-pending coating at this on cathode surface, and the coating of surrounding constantly adds
Gap caused by thickness.
Copper powder generation in part can effectively be cleaned using pickling in production, clean foil face.
Passivation Treatment film in production, can environmentally friendly Non-water washing technique, can satisfy the use of high-capacity lithium-ion completely.
Beneficial effects of the present invention: it is used cooperatively by the anode plate of the pulse power and numerous pin marks that gather, produces height
The micropore copper foil of capacity lithium ion battery has the advantages that thickness is suitable, is unlikely to deform and not cracky；The micropore copper foil is applicable in
It is coated in coating machine, negative electrode material can be made not easily to fall off.Porosity 20%, 10 microns of aperture can satisfy market demand completely
Specific embodiment
The preparation method for being applied to high capacity lithium ion cells cathode micropore copper foil includes that foil rack is equipped with electrolysis
Slot has anode plate in the electrolytic cell, and gather numerous pin marks on the anode plate, the anode slot by copper bar and power supply just
Pole connection, the anode slot top are equipped with the cathode roll connecting with power cathode, and the cathode roll is the carrier for depositing copper foil.
Production process of the invention includes: to adopt electrolyte using 99.9% tough cathode, carries out aerobic reaction with analytical pure sulfuric acid
Pure copper-bath is made, solution is diluted using RO film plasma water；Copper content is 80g/L in electrolyte, sulfuric acid contains
Amount is 120g/L；Electrolyte is heated to 55 degree；When rotated, the pulse power revolves during pulse plating with cathode roll cathode roll
Turning the time cycle is cooperated；The electric current that the pulse power generates is discharged by tip anode plate, since the tip of plating is imitated
It answers, causing the pin mark close to titanium roller end, copper atom deposition hinders, and causes hole since current density increases；It is added in electrolyte
The organic additives such as suitable polyethylene glycol, chloride ion, brightener, to guarantee that copper foil tensile strength rotates out of foil face, using sulphur
Sour copper solution is cleaned, and prevents foil face from color difference occur；Cleaning, is cleaned using reverse osmosis ejected wash water；Passivation, using Chrome-free
Non-water washing environment-protective process carries out chemical deposition, prevents copper foil from aoxidizing.
Claims (1)
1. a kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil, which includes foil rack
It is equipped with electrolytic cell, there is anode plate in the electrolytic cell, the anode slot is connected by the anode of copper bar and power supply, the anode
The cathode roll connecting with power cathode is equipped with above slot, it is characterised in that gather numerous pin marks on the anode plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810703557.XA CN109056011A (en) | 2018-07-01 | 2018-07-01 | A kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810703557.XA CN109056011A (en) | 2018-07-01 | 2018-07-01 | A kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109056011A true CN109056011A (en) | 2018-12-21 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201810703557.XA Pending CN109056011A (en) | 2018-07-01 | 2018-07-01 | A kind of preparation method applied to high capacity lithium ion cells cathode micropore copper foil |
Country Status (1)
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| CN (1) | CN109056011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112928280A (en) * | 2021-03-10 | 2021-06-08 | 中国科学院金属研究所 | Patterning method of copper foil for lithium metal negative electrode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201781024U (en) * | 2010-09-06 | 2011-03-30 | 东莞华威铜箔科技有限公司 | Manufacture equipment of copper foil |
| CN203080093U (en) * | 2012-12-20 | 2013-07-24 | 华南理工大学 | Electro-deposition device for manufacturing micro-nano composite porous copper surface structure |
| CN104674313A (en) * | 2015-02-10 | 2015-06-03 | 华南理工大学 | Electroplating method and device for preparing array micro/nanostructure on coated metal surface |
| KR20170090271A (en) * | 2016-01-28 | 2017-08-07 | 삼성전기주식회사 | Electroplating apparatus |
| CN206680598U (en) * | 2017-04-28 | 2017-11-28 | 东莞华威铜箔科技有限公司 | A kind of electrolytic cell for manufacturing flexible, porous copper foil |
-
2018
- 2018-07-01 CN CN201810703557.XA patent/CN109056011A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201781024U (en) * | 2010-09-06 | 2011-03-30 | 东莞华威铜箔科技有限公司 | Manufacture equipment of copper foil |
| CN203080093U (en) * | 2012-12-20 | 2013-07-24 | 华南理工大学 | Electro-deposition device for manufacturing micro-nano composite porous copper surface structure |
| CN104674313A (en) * | 2015-02-10 | 2015-06-03 | 华南理工大学 | Electroplating method and device for preparing array micro/nanostructure on coated metal surface |
| KR20170090271A (en) * | 2016-01-28 | 2017-08-07 | 삼성전기주식회사 | Electroplating apparatus |
| CN206680598U (en) * | 2017-04-28 | 2017-11-28 | 东莞华威铜箔科技有限公司 | A kind of electrolytic cell for manufacturing flexible, porous copper foil |
Non-Patent Citations (2)
| Title |
|---|
| J.E.T. ANDERSEN等: ""Bulk copper electrodeposition on gold imaged by in situ STM:morphology and influence of tip potential"", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》 * |
| U.STIMMING等: ""metal deposition and dissolution monitored by in situ scanning tunneling microscopy"", 《JOURNAL OF POWER SOURCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112928280A (en) * | 2021-03-10 | 2021-06-08 | 中国科学院金属研究所 | Patterning method of copper foil for lithium metal negative electrode |
| CN112928280B (en) * | 2021-03-10 | 2022-06-07 | 中国科学院金属研究所 | Patterning method of copper foil for lithium metal negative electrode |
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Application publication date: 20181221 |