CN108893760A - A kind of production method of lithium ion collector corronil foil - Google Patents

A kind of production method of lithium ion collector corronil foil Download PDF

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Publication number
CN108893760A
CN108893760A CN201810704545.9A CN201810704545A CN108893760A CN 108893760 A CN108893760 A CN 108893760A CN 201810704545 A CN201810704545 A CN 201810704545A CN 108893760 A CN108893760 A CN 108893760A
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CN
China
Prior art keywords
lithium ion
foil
ion collector
electrolyte
corronil
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810704545.9A
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Chinese (zh)
Inventor
刘冰
刘晓
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Qingdao Haoyue Xin Electronic Materials Co Ltd
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Qingdao Haoyue Xin Electronic Materials Co Ltd
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Priority to CN201810704545.9A priority Critical patent/CN108893760A/en
Publication of CN108893760A publication Critical patent/CN108893760A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00Electroforming
    • C25D1/04Wires; Strips; Foils
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/06Filtering particles other than ions
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/12Electroplating: Baths therefor from solutions of nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/661Metal or alloys, e.g. alloy coatings
    • H01M4/662Alloys
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of production methods of lithium ion collector corronil foil, belong to electrolytic copper foil technical field.This method includes being deposited using special anode plate to electrolytic copper foil, and lithium electrolytic copper foil is carried out pickling, is cleaned with RO membrane reverse osmosis water, nickel plating and etc..Due to using above-mentioned process, effective solution lithium ion collector is perishable, in charge and discharge process, there is phenomenon of rupture in collector, lithium ion collector deposited nickel layer texture is closely uniform, distribution is neat, the uniform deviation of thickness is less than 0.01um, and it is excellent using standard, surface solderability that tensile strength and elongation percentage reach lithium ion battery, and electric conductivity is good, high temperature resistant, fine corrosion resistance.

Description

A kind of production method of lithium ion collector corronil foil
Technical field
The invention belongs to electrolytic copper foil production technical field more particularly to a kind of lifes of lithium ion collector corronil foil Production method.
Background technique
In recent years, with the long-time of the promotion of the course continuation mileage of new-energy automobile, model plane, electric tool and electronic toy The development of work requires lithium ion battery that is also higher and higher, but being commercialized at present to the multiplying power discharging property of lithium ion battery Continuous discharge more than 20C multiplying power difficult to realize, the main reason is that battery, in big multiplying power discharging, lithium ion battery fever is tight Weight, battery bulk temperature is excessively high, so that battery is easy thermal runaway, the damage to lithium ion collector, so as to cause battery multiplying power Discharge performance and cycle performance are deteriorated, or even cause the fracture of pole piece, cause battery short circuit.Multiplying power discharging property is good in order to obtain And on the one hand safe and reliable lithium ion battery will avoid lithium ion battery from generating a large amount of heat as far as possible in heavy-current discharge, On the other hand the rate of heat dispation of battery is improved, the former ameliorative way can be from positive and negative pole material, electrolyte and positive and negative electrode pole piece Design is started with, and the latter can improve the rate of heat dispation of battery by optimization battery structure, to improve the safety of battery.
Lithium ion collector is the collection carrier of electron energy transmitting, so improving lithium ion when the big multiplying power discharging of battery The temperature tolerance of battery afflux liquid, and guarantee the transmission of the wide element of electronics.Conventional affluxion body in lithium ion batteries uses common copper foil, It causes damage of the heat to lithium ion collector in electrolyte charge and discharge, since the good corrosion resistance and oxygen-proof property of nickel are high Feature, the strong feature of copper metal electric conductivity, and cupro-nickel copper alloy foil has excellent electric conductivity, conductivity is close to fine copper Conductivity, about 584000 S/cm.Technique to have developed lithium ion collector corronil foil.
When making lithium ion collector corronil foil, only holding electrolytic copper foil is when carrying out deposition nickel, Neng Goujun The two sides of even deposit electrolyte copper foil, is implemented as lithium ion battery, itself is a constant volume reaction unit, such lithium from Collection of the subset fluid corronil foil as lithium ion battery electronics.So the electronics for how allowing collector to be collected into is with safety The mode of property is exported, while being ensured against lithium-ion battery electrolytes and not generated corrosion and lithium ion battery charge and discharge to pole piece Pole piece is broken when electric, is all had certain problems in cost and battery safety.In order to solve the problems, such as it is this kind of exist, examine Consider its parent's profit effect, the processing method for producing lithium ion collector production corronil foil.
The lithium ion collector corronil foil mainly solves for lithium ion battery under high current charge and discharge to pole The problem of insecurity that piece causes pole piece to be broken.Guarantee the guarantee of lithium ion battery security under high current simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of production methods of lithium ion collector corronil foil.
The present invention is realized by following technology technical solution, the method for the cupro-nickel copper alloy foil of the lithium electricity electrolytic copper foil Include the following steps:(1)Electrolytic copper foil is deposited using special anode plate;(2)Iridium is applied as electrolytic anode plate using titanium; (3)Lithium electrolytic copper foil is subjected to pickling, to eliminate the influence of electrolytic copper foil superficial oxidation copper;(4)It is cleaned with RO membrane reverse osmosis water, It is cleaned by atomizer;(5)Electrolyte is stirred and pure sulphur is made using analytical pure sulfuric acid nickel and the pure boric acid of analysis Sour nickel solution, solution are diluted using RO film plasma water;(6)Nickel content is 180g/L in electrolyte, boric acid content is 70g/L;PH range 3.4-3.9;35 degree of temperature;(7)Electrolyte is heated to 35 degree, the organic blending additive of electrolyte addition Including:Organic cooperation additive PPS, TPP and ATPN, which is 20mL/min, after mixing thoroughly, electrolyte Into anode slot;(8)Electrolyte is filtered using fusion-jet type filter;(9)Under electric field action, current density is electrolyte 80A/m2, cation shifts to cathode, and anion shifts to anode, is electrochemically reacted;(10)It is carried out using RO membrane reverse osmosis water Cleaning;(11)It is dried by heating, drying bellows.
It is described in step(2)Middle-jiao yang, function of the spleen and stomach pole plate uses 9mm Titanium board(TC4), metal is coated in titanium plate by electrostatic spraying Iridium 1mm.
It is described in step(3)It is middle that pickling is carried out using content 50g/l dilute sulfuric acid.
It is described in step(6)It is middle that PH adjustment is carried out using nickelous carbonate.
It is described in step(7)The PPS organic additive of 10ppm mass parts is added in middle 1000ml water.
It is described in step(7)30ppmTPp organic additive is added in middle 1000ml water.
It is described in step(7)50ppmATPN organic additive is added in middle 1000ml water.
It is described in step(8)Middle fine filter fusion-jet type filtering accuracy is 1um.
It is found in production practices, in the identical situation of other working conditions, applying iridium anode plate using titanium can be effective Uniform nickel layer is plated in electrolytic copper foil, in addition organic nickel plating mixing intermediate PPS, TPP and ATPN, that is, use organic additive Cooperate with the use of hair side wave crest is flattened with brightener, the nickel layer for keeping nickel finer and smoother, fine and close, bright.
High temperature resistant experiment:It is toasted 120 minutes at a temperature of 500 degree, through detection corronil foil without any oxidative phenomena.
Corrosion-resistant experiment:At room temperature, lithium ion collector corronil foil of the present invention and commercially available ordinary copper Nickel alloy foil sample immerses 48h in 17% hydrochloric acid solution.It is learnt from experimental result, lithium ion collector cupro-nickel of the present invention Alloy foil sample occurs without obvious corrosion phenomenon, and commercially available ordinary copper nickel alloy foil sample etches 15.7%.
Etching experiment:By pressure forming machine, first lithium ion collector corronil foil sample pressure of the present invention For system on dicyandiamide prepreg, press temperature is 160 DEG C, and pressing pressure is 7 MPa, the pressing time is 1 h, obtains cupro-nickel Alloy foil sample.Two pieces of an equal amount of corronil foil samples, the higher etchant of price of one piece of immersion certain temperature In, it is etched in the lower etchant of price of another piece of same temperature of immersion.Experimental result discovery is on substrate without residual Object is stayed, surface is very clean.It can be seen that can choose price lower for lithium ion collector corronil foil of the present invention Etchant be etched, advantageously reduce production cost.
The object of the invention is to use titanium to apply iridium anode plate to carry out deposition nickel surface layer, and using brightener PPS, TPP and ATPN mixing organic additive is produced the optimal lithium ion collector corronil foil of physical property, especially preferably The perishable, easy fracture that solves because of lithium ion battery that there is a phenomenon where collectors under high current.
Beneficial effects of the present invention:Due to using above-mentioned process, effective solution lithium ion collector is perishable, In charge and discharge process, there is phenomenon of rupture in collector, and lithium ion collector deposited nickel layer texture is closely uniform, is distributed whole Together, the uniform deviation of thickness is less than 0.01um, and tensile strength and elongation percentage reach lithium ion battery and use standard, surface solderability Excellent, electric conductivity is good, high temperature resistant, fine corrosion resistance.
Specific embodiment
Lithium ion collector corronil foil applies iridium anode plate using special titanium and deposits to electrolytic copper foil two sides, thus Reach the good nickel layer of each end face even compact to be precipitated.
For lithium ion collector electrolytic copper foil because electrolysis easily causes foil face to aoxidize out, pickling liquid uses RO film reverse osmosis Saturating deionized water and dilute sulfuric acid are matched, and to remove copper oxide surface, while being carried out using RO membrane reverse osmosis water by nozzle Cleaning, to guarantee that lithium ion copper foil of affluxion body is clean, electrolyte preparation is exactly using analytical pure sulfuric acid nickel, analysis boric acid acid and RO Reverse osmosis deionized water is added in agitator tank, in the case where temperature is 35 degree of constant temperature, carries out pH value adjustment using nickelous carbonate 3.5-3.8, finally obtain nickel sulfate solution.When lithium ion collector deposits nickel in production process, electrolyte is all circulation It uses, constantly from precipitating nickel on electrolytic copper foil two sides, so that the nickel in electrolyte is constantly consumed, and by analytical pure sulfuric acid Nickel constantly dissolves the nickel consumed in supplement electrolyte, and the nickel content in electrolyte is made to remain balance.Nickelous carbonate is utilized simultaneously The adjustment of PH value is carried out, not only to guarantee that electrolyte continuously recycles in electrolyte preparation process, it will also be in time according to electricity Solution nickel output adjusts the rate of molten copper and carrys out stability contorting electrolyte composition with this.The ingredient of electrolyte:Nickel sulfate nickel content is 180g/L, boric acid content 70g/L;PH range 3.4-3.9;Electrolyte is heated to 35 degree, organic mixing of electrolyte addition Additive includes:Organic cooperation additive PPS, TPP and ATPN, which is 20mL/min, after mixing thoroughly, Electrolyte enters anode slot;Electrolyte is filtered using fusion-jet type filter, and under electric field action, current density is electrolyte 80A/m2, cation shift to cathode, and anion shifts to anode, are electrochemically reacted, and change nickel original by organic additive The structure electrical migration pattern and link structure of son crystallization, so that one kind is made can be with the electrolytic copper foil of corronil.
Thus the electrolytic copper foil for the corronil foil produced, high-temperature stability is big, corrosion resistance is strong, solderability is high.Through High-end customer is detected using experimental data:The collector produced with the electrolytic copper foil of this corronil foil, as new energy electricity Collect electronics, surface roughness Ra 0.1um, the thickness uniformity deviation 0.01um in pond.Especially high anti-side corrosivity, solves New energy battery charging and discharging causes the technical issues of collector oxidation corrosion and fracture pole piece, while it is anti-that nickel metallic high temperature is utilized Oxidisability and the good electric conductivity of electrolytic copper foil, greatly improve the safety of new energy battery.It avoids in the electrolytic solution There is corrosivity and fracture pole piece, causes new energy battery short circuit, the problems such as charge and discharge are unstable, wherein heat-resisting quantity and anti-side Three corrosivity, electric conductivity indexs have all reached the use standard of new energy battery, which preferably resolves There is the technical bottleneck that corrosion exists and charge and discharge high temperature causes pole piece to be broken in new energy battery afflux liquid pole piece, and has filled up market Blank.

Claims (7)

1. a kind of production method of lithium ion collector corronil foil, it is characterised in that this approach includes the following steps:(1)It adopts Electrolytic copper foil is deposited with special anode plate;(2)Iridium is applied as electrolytic anode plate using titanium;(3)Lithium electrolytic copper foil is carried out Pickling, to eliminate the influence of electrolytic copper foil superficial oxidation copper;(4)It is cleaned with RO membrane reverse osmosis water, is carried out by atomizer Cleaning;(5)Electrolyte is stirred and pure nickel sulfate solution is made using analytical pure sulfuric acid nickel and the pure boric acid of analysis, and solution uses RO film plasma water is diluted;(6)In electrolyte nickel content be 180g/L, boric acid content 70g/L;PH range 3.4-3.9; 35 degree of temperature;(7)Electrolyte is heated to 35 degree, the organic blending additive of electrolyte addition includes:Organic cooperation additive PPS, TPP and ATPN, the organic blending additive flow are 20mL/min, and after mixing thoroughly, electrolyte enters anode slot;(8)Electrolysis Liquid is filtered using fusion-jet type filter;(9)Electrolyte is under electric field action, current density 80A/m2, cation shifts to Cathode, anion shift to anode, are electrochemically reacted;(10)It is cleaned using RO membrane reverse osmosis water;(11)Pass through heating Drying bellows are dried.
2. a kind of production method of lithium ion collector corronil foil as described in claim 1, it is characterised in that in step (2)Middle-jiao yang, function of the spleen and stomach pole plate uses 9mm Titanium board(TC4), metal iridium 1mm is coated in titanium plate by electrostatic spraying.
3. a kind of production method of lithium ion collector corronil foil as described in claim 1, it is characterised in that in step (3)It is middle that pickling is carried out using content 50g/l dilute sulfuric acid.
4. a kind of production method of lithium ion collector corronil foil as described in claim 1, it is characterised in that in step (6)It is middle that PH adjustment is carried out using nickelous carbonate.
5. a kind of production method of lithium ion collector corronil foil as described in claim 1, it is characterised in that in step (7)The PPS organic additive of 10ppm mass parts is added in middle 1000ml water.
6. a kind of production method of lithium ion collector corronil foil as described in claim 1, it is characterised in that in step (7)30ppmTPp organic additive is added in middle 1000ml water.
7. a kind of production method of lithium ion collector corronil foil as described in claim 1, it is characterised in that in step (7)50ppmATPN organic additive is added in middle 1000ml water.
CN201810704545.9A 2018-06-30 2018-06-30 A kind of production method of lithium ion collector corronil foil Pending CN108893760A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109750336A (en) * 2018-08-06 2019-05-14 新疆中亚新材料科技有限公司 A kind of production method of lithium ion collector corronil foil
CN110644025A (en) * 2019-11-12 2020-01-03 长沙理工大学 Ultrathin nickel-copper alloy foil and preparation method thereof
CN112216809A (en) * 2019-07-11 2021-01-12 深圳市比亚迪锂电池有限公司 Lithium metal cathode, preparation method thereof and lithium ion battery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107022778A (en) * 2017-03-12 2017-08-08 山东金盛源电子材料有限公司 The lug that the method and application this method of a kind of four sides nickel plating electrolytic copper foil are produced

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107022778A (en) * 2017-03-12 2017-08-08 山东金盛源电子材料有限公司 The lug that the method and application this method of a kind of four sides nickel plating electrolytic copper foil are produced

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109750336A (en) * 2018-08-06 2019-05-14 新疆中亚新材料科技有限公司 A kind of production method of lithium ion collector corronil foil
CN112216809A (en) * 2019-07-11 2021-01-12 深圳市比亚迪锂电池有限公司 Lithium metal cathode, preparation method thereof and lithium ion battery
CN112216809B (en) * 2019-07-11 2022-03-18 深圳市比亚迪锂电池有限公司 Metal cathode, preparation method thereof and lithium ion battery
CN110644025A (en) * 2019-11-12 2020-01-03 长沙理工大学 Ultrathin nickel-copper alloy foil and preparation method thereof

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