CN110438531A - A kind of extra thin copper foil preparation method and system applied to lithium battery - Google Patents
A kind of extra thin copper foil preparation method and system applied to lithium battery Download PDFInfo
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- CN110438531A CN110438531A CN201910739441.6A CN201910739441A CN110438531A CN 110438531 A CN110438531 A CN 110438531A CN 201910739441 A CN201910739441 A CN 201910739441A CN 110438531 A CN110438531 A CN 110438531A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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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
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said 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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- 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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Abstract
The invention discloses a kind of extra thin copper foil preparation methods and system applied to lithium battery, this method step includes the dissolution of copper material, multistage filtering, electrolysis foil, washing removing and passivation drying, wherein: the specific steps of the electrolysis foil are as follows: plate and cathode roll are dipped in copper electrolyte, additive is added into the copper electrolyte, carries out electrolysis after mixing and in foil obtained on the cathode roll；The additive includes poly- phenyl disulfide sodium sulfonate, N, and N- dimethyl disulfide is for formamide propane sulfonic acid sodium, hydroxyethyl cellulose and collagen.The present invention passes through above-mentioned extra thin copper foil preparation method and system applied to lithium battery, the copper foil for preparing about 4.5 μ m thicks can be stablized by improving and optimizating for technique, enhance the tensile strength of copper foil simultaneously, surface roughness reduces, high temperature oxidation resistance enhancing, copper foil corresponding index performance is also improved when reducing whole copper thickness, is conducive to the batch production of wide cut copper foil.
Description
Technical field
The present invention relates to electrolytic copper foil preparation field, especially a kind of extra thin copper foil preparation method applied to lithium battery and
System.
Background technique
Electrolytic copper foil is the method for producing copper foil by continuous electrolysis method, is suitable for producing wide cut copper foil, and now most
Common copper foil large scale production method.In the manufacturing process of lithium ion battery, need to use copper foil as negative electrode material, and
Copper foil as negative electrode of lithium ion battery often has very harsh requirement, and excellent conduction must be had by not requiring nothing more than copper foil
The performances such as property, corrosion resistance, Gao Changwen elongation percentage, high-tensile and low roughness, simultaneously because electronics industry is gradually to more
Light thinner direction is developed, thus the copper foil in lithium ion battery be also required to it is further lightening.
In the prior art, 6~35 μm are usually maintained in using copper thickness prepared by electrolytic copper foil technique, it is difficult to biography
The electrode copper foil technique of system prepares the copper foil of 6 μm or less thickness；And other methods are used, such as rolled copper foil technique, although can make
Ultra-thin copper foil is obtained, but its process costs is significantly larger than electrolytic copper foil technique, while rolled copper foil technique is also due to process conditions
On limitation, it is difficult to prepare the wide cut copper foil as electrolytic copper foil, and copper foil prepared by other methods also with lithium ion
The performance requirement of cell negative electrode material has larger difference.Therefore need to propose that a kind of new electrolytic copper foil preparation method is used to prepare
Ultra-thin copper foil.
Summary of the invention
The object of the present invention is to provide a kind of extra thin copper foil preparation methods and system applied to lithium battery, for solving
Certainly electrolytic copper foil technique is difficult to prepare extra thin copper foil in the prior art, and copper foil prepared by other methods and lithium ion battery are negative
The larger problem of the demand difference of pole material.
In order to solve the above technical problems, the present invention provides the first solutions: a kind of ultra-thin copper applied to lithium battery
Foil preparation method, step include the dissolution of copper material, multistage filtering, electrolysis foil, washing removing and passivation drying, in which: copper material is molten
Solving step includes: copper material to be placed in acid solution, and compressed air is passed through into acid solution, and copper material is made to dissolve to form copper solution；
It is electrolysed the specific steps of foil are as follows: plate and cathode roll are dipped in copper electrolyte, additive is added into copper electrolyte,
Electrolysis is carried out after mixing and in foil obtained on cathode roll；Additive includes poly- phenyl disulfide sodium sulfonate, N, N- dimethyl
Two thioformamide propane sulfonic acid sodium, hydroxyethyl cellulose and collagen, and the concentration of poly- phenyl disulfide sodium sulfonate be 30~
65mg/L, N, N- dimethyl disulfide are 35~50mg/L, the concentration of hydroxyethyl cellulose for the concentration of formamide propane sulfonic acid sodium
For 25~45mg/L, the concentration of collagen is 120~165mg/L and molecular weight is 2500~3800.
Preferably, in the step of being electrolysed foil, copper ion concentration is 65~85g/L, 110~140g/L of sulfuric acid concentration, chlorine
25~45mg/L of ion concentration；Copper electrolyte temperature is 40~60 DEG C, and current density is 4000~7500A/m2。
Preferably, copper material dissolving step includes: and copper material is placed in acid solution, and be passed through compressed air into acid solution,
Copper material is set to dissolve to form copper solution.
Preferably, acid solution is the sulfuric acid of 110~140g/L of concentration, and the flow velocity of compressed air is 5~20m3/min。
Preferably, multistage filtering step includes: primary filter and secondary filter；Primary filter is filled out using coarse grain diameter diatomite
Material is filtered, and copper solution is obtained to primary filtrate after primary filter；Secondary filter is carried out using fine grain tripolite filling material
Filtering, obtains copper electrolyte for primary filtrate after secondary filter.
Preferably, washing strip step is included: and is rinsed using softening pure water to foil, and rotate cathode roll to flushing
Foil after the completion is removed.
Preferably, softening pure water is obtained deionized water after simultaneously deionization is filtered for multiple times, and softens pure water
Conductivity is less than 30 μ s/cm.
Preferably, passivation baking step includes: the glucose by the chromium trioxide of 0.5~0.7g/L and 2.8~5.4g/L
It is soluble in water, passivating solution is made, the pH value range of passivating solution is 2.3~2.8；Foil is immersed in passivating solution, 20~28
Electroless Plating Procedure and electroplating work procedure are carried out simultaneously at DEG C, and passivation current is 2~3.6A, the time of Electroless Plating Procedure is 6~
20s, the time of electroplating work procedure are 1~5s；Drying winding will be carried out by the copper foil of electroplating work procedure.
In order to solve the above technical problems, the present invention provides the second solutions: a kind of ultra-thin copper applied to lithium battery
Foil preparation system, including copper material dissolution unit, multistage filtering unit, heat exchange unit, electrolysis foil unit, Passivation Treatment unit
With dry rolling unit, in which: copper material dissolution unit is connected to multistage filtering unit, molten for will obtain copper after the dissolution of copper material
Liquid, and it is delivered to multistage filtering unit；Multistage filtering unit is connected to after heat exchange unit with electrolysis foil unit, multistage filtering
Unit is for obtaining copper electrolyte after filtering copper solution, and heat exchange unit is used to adjust the copper for being delivered to electrolysis foil unit
The temperature of electrolyte；Electrolysis foil unit is sent to passivation for being electrolysed obtained foil, and after foil is come into row washing removing
Processing unit；Passivation Treatment unit is used to carry out surface passivating treatment to the foil after washing removing, obtains passivation copper foil,
And passivation copper foil is sent at dry rolling unit, winding is dried；This is applied to the extra thin copper foil preparation system of lithium battery
For executing any extra thin copper foil preparation method applied to lithium battery in aforementioned first solution.
Wherein, electrolysis foil unit is also with the dissolution unit connection of copper material, for the copper electrolyte after electrolysis to be back to copper
In material dissolution unit, and carry out the dissolution of copper material.
The beneficial effects of the present invention are: be in contrast to the prior art, the present invention is by above-mentioned applied to lithium battery
Extra thin copper foil preparation method and system can stablize the copper foil for preparing about 4.5 μ m thicks by improving and optimizating for technique, make simultaneously
The tensile strength enhancing of copper foil, surface roughness reduce, high temperature oxidation resistance enhances, and also improve when reducing whole copper thickness
Copper foil corresponding index performance is conducive to the batch production of wide cut copper foil.
Detailed description of the invention
Fig. 1 is the process flow chart in the present invention applied to one embodiment of extra thin copper foil preparation method of lithium battery；
Fig. 2 is the structural schematic diagram in the present invention applied to one embodiment of extra thin copper foil preparation system of lithium battery.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment belongs to the scope of protection of the invention.
For the first solution proposed in the present invention, referring to Fig. 1, Fig. 1 is to be applied to lithium battery in the present invention
The process flow chart of one embodiment of extra thin copper foil preparation method.It is applied to the extra thin copper foil preparation side of lithium battery in the present invention
Method, step includes copper material dissolution S1, multistage filtering S2, electrolysis foil S3, washing removing S4 and passivation drying S5, below to each
Step is described in detail respectively.
Copper material dissolution S1 step specifically includes: copper material being placed in acid solution, and is passed through compressed air into acid solution, is made
Copper material dissolves to form copper solution；In present embodiment, preferred acid solution is the sulfuric acid of 110~140g/L of concentration, compressed air
Flow velocity be 5~20m3/ min, the purpose that compressed air is passed through into acid solution are, on the one hand supply for oxygen, make copper
Achieve the purpose that copper dissolution after oxidation, be on the other hand to provide stirring action, promote the flowing of acid solution, to improve molten copper speed
Rate.The step of can also carrying out alkali cleaning and washing to copper material before copper material dissolves S1 step, it can remove the greasy dirt on copper material surface,
So that the better copper solution of quality can be obtained when carrying out copper material dissolution S1 step.
Multistage filtering S2 step specifically includes: primary filter and secondary filter；Primary filter is filled out using coarse grain diameter diatomite
Material is filtered, and copper solution is obtained to primary filtrate after primary filter, can filter out cupric filter residue, useless silicon by primary filter
The substances such as diatomaceous earth；Secondary filter is filtered using fine grain tripolite filling material, and primary filtrate is obtained copper after secondary filter
Electrolyte can further filter out cupric filter residue and filter core residue, in other embodiments, accurate mistake by secondary filter
Filter can also filter mode using such as UF membrane, be not limited thereto.In multistage filtering S2 step and electrolysis foil S3 step
Between, heat exchange steps can also be set, so that copper electrolyte can be electrolysed with suitable temperature.
It is electrolysed foil S3 step specifically: plate and cathode roll are dipped in copper electrolyte, added into copper electrolyte
Enter additive, carries out electrolysis after mixing and in foil obtained on cathode roll.In present embodiment, additive includes poly- two sulphur
Sodium hisbenzene sulfonate, N, N- dimethyl disulfide is for formamide propane sulfonic acid sodium, hydroxyethyl cellulose and collagen, and poly- two sulphur two
The concentration of benzene sulfonic acid sodium salt is 30~65mg/L, and N, N- dimethyl disulfide is 35~50mg/ for the concentration of formamide propane sulfonic acid sodium
L, the concentration of hydroxyethyl cellulose are 25~45mg/L, the concentration of collagen be 120~165mg/L and molecular weight be 2500~
3800.Further, each component effect in additive is illustrated respectively.N, N- dimethyl disulfide are for formamide propane sulphur
Sour sodium, as middle low level grain refiner, the copper crystal grain that can be formed to electrolysis is tentatively refined, and the gloss of copper foil can be improved
Degree, ductility and tensile strength；Poly- phenyl disulfide sodium sulfonate can be in N, N- dimethyl disulfide as high-order grain refiner
For further refining on the exposure basis of formamide propane sulfonic acid sodium to copper crystal grain, keep prepared copper foil more smooth, improves
Crystal grain filling capacity, while poly- phenyl disulfide sodium sulfonate and chloride ion synergistic effect can promote the polarization between cathode and anode and make
With to accelerate electrode reaction rate；The effect of hydroxyethyl cellulose is, eliminates copper foil pin hole, improves tensile strength；Collagen
Albumen has the function of auxiliary refinement crystal grain to copper foil, flattens and walk.
Wherein, electrolyte includes copper sulphate, sulfuric acid and hydrochloric acid, and copper ion concentration is 65~85g/L, and sulfuric acid concentration 110~
140g/L, 25~45mg/L of chlorine ion concentration, copper ion is mobile to cathode roll under the function of current, and finally sinks on cathode roll
Product obtains foil；The purpose that hydrochloric acid is added is, due to Cl-With Cu+Interaction can be formed with very little unstable constant
Complex compound CuCl, thus make its equilibrium potential that significant negative shifting occur, enhance activating effect, and then accelerate electrode reaction speed
Degree, but the additional amount of hydrochloric acid needs strict control, if hydrochloric acid additional amount easily causes anodic passivity when excessive, is unfavorable for continuing for electrolysis
It carries out, therefore it is preferred that above-mentioned chlorine ion concentration；Copper electrolyte temperature is 40~60 DEG C, and current density is 4000~7500A/m2, this
Locating copper electrolyte temperature and current density should be adapted with the content ratio of each component in electrolyte, and it is heavy just to can reach optimal copper
Product effect.
Washing removing S4 step includes: to be rinsed using softening pure water to foil, and rotate cathode roll and liquidate and wash into
Foil afterwards is removed.Softening pure water is obtained deionized water after simultaneously deionization is filtered for multiple times, and softens pure water
Conductivity less than 30 μ s/cm；The softening pure water can be filtered for multiple times by tap water and ion exchange after be made, gained softening
The conductivity of pure water needs strict control, it is intended that the softening pure water of relatively low conductivity is easier to that foil surface will be attached to
On copper electrolyte rinse out, the surface treatment of subsequent copper foil is had an impact to avoid the copper electrolyte being attached on copper foil,
And cleaning can also be synchronized while being rinsed to copper foil to the polishing process of cathode roll by softening pure water, to improve copper
Foil successive sedimentation and the quality removed on cathode roll.
Passivation drying S5 step includes: that the glucose of the chromium trioxide of 0.5~0.7g/L and 2.8~5.4g/L is dissolved in water
In, passivating solution is made, the pH value range of passivating solution is 2.3~2.8, and specifically, chromium trioxide is as passivation layer raw material, glucose
As reducing agent, chromium trioxide forms generation hexavalent chromium after being dissolved in water and reacts with glucose, and reaction equation is as follows:
C6H12O6+Cr6+→Cr3++H2O+CO2↑, the deposition raw material plated using trivalent chromic ion as subsequent chemistry, due to needing to keep three
The state of valence chromium ion needs the pH value of strict control passivating solution, and preferable ph range is 2.3~2.8 in present embodiment；It will
Foil is immersed in passivating solution, carries out Electroless Plating Procedure and electroplating work procedure simultaneously at 20~28 DEG C, and passivation current be 2~
3.6A, the time of Electroless Plating Procedure are 6~20s, and the time of electroplating work procedure is 1~5s, when chemical plating is arranged in present embodiment
Between it is longer compared with electroplating time, when will form crome metal and chromium hydroxide mixing when electroplating work procedure and Electroless Plating Procedure carry out simultaneously
The protective layer of composition will continue to form the protection being made of chromium hydroxide when electroplating work procedure terminates and Electroless Plating Procedure still carries out
Layer forms fine and close double shielding layer structure, enhances the inoxidizability of copper foil；It finally will be by the copper foil of electroplating work procedure
Carry out drying winding.Due to easily separated between passivating solution in this step and double shielding layer, therefore present invention process is completed in passivation
Afterwards without being rinsed with water passivating solution, copper foil drying can be directly carried out, process is shortened, reduces preparation cost.
It should be pointed out that every ginseng in the above-mentioned extra thin copper foil preparation method applied to lithium battery in S1~S5 step
Several settings has stronger relevance, blunt in S5 step such as when the concentration proportioning of copper electrolyte in S3 step changes
The concentration proportioning for changing liquid is also required to be adaptively adjusted, and also or is that the parameters of other steps is adaptively adjusted, ability
Make final obtained extra thin copper foil that there is more excellent performance, and for the optimal corresponding scheme number between various process parameters
It measures huge, does not enumerate herein.
For the second solution proposed in the present invention, referring to Fig. 2, Fig. 2 is to be applied to lithium battery in the present invention
The structural schematic diagram of one embodiment of extra thin copper foil preparation system.System is prepared applied to the extra thin copper foil of lithium battery in the present invention
System, including copper material dissolution unit 201, multistage filtering unit 202, heat exchange unit 203, electrolysis foil unit 204, Passivation Treatment
Unit 205 and dry rolling unit 206 should be solved applied to the extra thin copper foil preparation system of lithium battery for executing aforementioned first
Any extra thin copper foil preparation method applied to lithium battery in scheme, is below described in detail each composition mechanism respectively.
Copper material dissolution unit 201 is connected to multistage filtering unit 202, for copper solution will to be obtained after the dissolution of copper material, and it is defeated
It send to multistage filter element 202；In present embodiment, copper material dissolve unit 201 mainly include pot for smelted copper and air compressor, with
It executes copper material in aforementioned first solution and dissolves S1 step, furthermore also settable acid fog absorption tower in copper material dissolution unit 201,
To be absorbed to the acid mist generated during molten copper.
Multistage filtering unit 202 is connected to after heat exchange unit 203 with electrolysis foil unit 204, multistage filtering unit 202
For obtaining copper electrolyte after filtering copper solution, in present embodiment, multistage filtering unit 202 include primary filter and
Precise filtering device, to execute multistage filtering S2 step in aforementioned first solution；Heat exchange unit 203 is for adjusting conveying
To the temperature of the copper electrolyte of electrolysis foil unit, so that copper electrolyte can be electrolysed with suitable temperature, in this implementation
The temperature of copper electrolyte is adjusted using steam heat-exchanger in mode.
Electrolysis foil unit 204 is sent at passivation for being electrolysed obtained foil, and after foil is come into row washing removing
Manage unit 205；In present embodiment, electrolysis foil unit 204 includes anode plate, electrolytic cell, cathode roll and pure water spray head, to hold
Electrolysis foil S3 and washing removing S4 step, are sent to Passivation Treatment for foil after the completion of washing in aforementioned first solution of row
Unit 205.Further, since the solution after electrolysis is strong acid solution, by electrolysis foil unit also with the dissolution unit connection of copper material, use
In being back to the copper electrolyte after electrolysis in copper material dissolution unit, again using dissolution copper material, copper electrolyte is significantly improved
Utilization rate.
Passivation Treatment unit 205 is used to carry out surface passivating treatment to the foil after washing removing, obtains passivation copper
Then it is single to be sent to dry winding to execute passivation drying S5 step in aforementioned first solution by foil for copper foil after passivation
Winding is dried at member 206, thus completes the preparation of extra thin copper foil.
In the following with reference to the drawings and specific embodiments to the borofluoride down-conversion luminescent material and preparation method in the present invention
It is described in further detail.
Embodiment 1
Copper material is placed in sulfuric acid solution, and is passed through compressed air into sulfuric acid solution, copper material is made to dissolve to form copper solution,
Control sulfuric acid concentration is 125g/L, and the flow velocity of compressed air is 15m3/min；By copper solution successively through primary filter, precision
It after filter device and heat-exchange device, is injected with copper electrolyte in the electrolytic cell of electrolysis foil, by regulating and controlling heat-exchange device
Make 60 DEG C of copper electrolyte temperature or so into electrolytic cell；Appropriate hydrochloric acid is added in cupric electrolysis, makes cupric electrolysis in copper electrolyte
Copper ion concentration is 65g/L, sulfuric acid concentration 95g/L, chlorine ion concentration 30mg/L in liquid；Take appropriate poly- phenyl disulfide sodium sulfonate,
N, N- dimethyl disulfide are mixed and made into additive, additive for formamide propane sulfonic acid sodium, hydroxyethyl cellulose and collagen
In the concentration of poly- phenyl disulfide sodium sulfonate be 30mg/L, N, N- dimethyl disulfide is for the concentration of formamide propane sulfonic acid sodium
The concentration of 35mg/L, hydroxyethyl cellulose are 30mg/L, and the concentration of collagen is 125mg/L and molecular weight is 2400, will be matched
The additive set is added in copper electrolyte and is uniformly mixed；Apply DC current between plate and cathode roll and carries out
Copper foil is made in cathode roller surface in electrolysis, and wherein electrolyte temperature is 60 DEG C, current density 7500A/m2；Using 10 μ s/cm
The softening pure water of conductivity is rinsed foil, and rotates the cathode roll foil after the completion of washing that liquidates and removed；It takes appropriate
Chromium trioxide and glucose, which are dissolved in 10L water, is made passivating solution, and the concentration of chromium trioxide is 0.5g/L, the concentration of glucose at this time
For 4g/L, and adjusts passivating solution pH value and be maintained at 2.3~2.8 ranges；Then copper foil is immersed in passivating solution, similarly hereinafter at 25 DEG C
Shi Jinhang Electroless Plating Procedure and electroplating work procedure, Electroless Plating Procedure time are 16s, and the electroplating work procedure time is 4s, institute in electroplating work procedure
The passivation current of application is 2.8A, and the flow for controlling passivating solution is 2.8m3/h；Electroless Plating Procedure and galvanizer will finally be passed through
The copper foil of sequence carries out drying winding by hot-air drying device, obtains extra thin copper foil.
Embodiment 2
Copper material is placed in sulfuric acid solution, and is passed through compressed air into sulfuric acid solution, copper material is made to dissolve to form copper solution,
Control sulfuric acid concentration is 125g/L, and the flow velocity of compressed air is 15m3/min；By copper solution successively through primary filter, precision
It after filter device and heat-exchange device, is injected with copper electrolyte in the electrolytic cell of electrolysis foil, by regulating and controlling heat-exchange device
Make 55 DEG C of copper electrolyte temperature or so into electrolytic cell；Appropriate hydrochloric acid is added in cupric electrolysis, makes cupric electrolysis in copper electrolyte
Copper ion concentration is 80g/L, sulfuric acid concentration 125g/L, chlorine ion concentration 40mg/L in liquid；Take appropriate poly- phenyl disulfide sodium sulfonate,
N, N- dimethyl disulfide are mixed and made into additive, additive for formamide propane sulfonic acid sodium, hydroxyethyl cellulose and collagen
In the concentration of poly- phenyl disulfide sodium sulfonate be 40mg/L, N, N- dimethyl disulfide is for the concentration of formamide propane sulfonic acid sodium
The concentration of 40mg/L, hydroxyethyl cellulose are 40mg/L, and the concentration of collagen is 140mg/L and molecular weight is 2800, will be matched
The additive set is added in copper electrolyte and is uniformly mixed；Apply DC current between plate and cathode roll and carries out
Copper foil is made in cathode roller surface in electrolysis, and wherein electrolyte temperature is 55 DEG C, current density 7500A/m2；Using 10 μ s/cm
The softening pure water of conductivity is rinsed foil, and rotates the cathode roll foil after the completion of washing that liquidates and removed；It takes appropriate
Chromium trioxide and glucose, which are dissolved in 10L water, is made passivating solution, and the concentration of chromium trioxide is 0.6g/L, the concentration of glucose at this time
For 4.2g/L, and adjusts passivating solution pH value and be maintained at 2.3~2.8 ranges；Then copper foil is immersed in passivating solution, at 25 DEG C
Carry out Electroless Plating Procedure and electroplating work procedure simultaneously, the Electroless Plating Procedure time is 16s, and the electroplating work procedure time is 4s, in electroplating work procedure
The passivation current applied is 2.8A, and the flow for controlling passivating solution is 2.8m3/h；Electroless Plating Procedure and plating will finally be passed through
The copper foil of process carries out drying winding by hot-air drying device, obtains extra thin copper foil.
Embodiment 3
Copper material is placed in sulfuric acid solution, and is passed through compressed air into sulfuric acid solution, copper material is made to dissolve to form copper solution,
Control sulfuric acid concentration is 125g/L, and the flow velocity of compressed air is 15m3/min；By copper solution successively through primary filter, precision
It after filter device and heat-exchange device, is injected with copper electrolyte in the electrolytic cell of electrolysis foil, by regulating and controlling heat-exchange device
Make 55 DEG C of copper electrolyte temperature or so into electrolytic cell；Appropriate hydrochloric acid is added in cupric electrolysis, makes cupric electrolysis in copper electrolyte
Copper ion concentration is 85g/L, sulfuric acid concentration 132g/L, chlorine ion concentration 45mg/L in liquid；Take appropriate poly- phenyl disulfide sodium sulfonate,
N, N- dimethyl disulfide are mixed and made into additive, additive for formamide propane sulfonic acid sodium, hydroxyethyl cellulose and collagen
In the concentration of poly- phenyl disulfide sodium sulfonate be 55mg/L, N, N- dimethyl disulfide is for the concentration of formamide propane sulfonic acid sodium
The concentration of 50mg/L, hydroxyethyl cellulose are 45mg/L, and the concentration of collagen is 150mg/L and molecular weight is 3200, will be matched
The additive set is added in copper electrolyte and is uniformly mixed；Apply DC current between plate and cathode roll and carries out
Copper foil is made in cathode roller surface in electrolysis, and wherein electrolyte temperature is 55 DEG C, current density 7500A/m2；Using 10 μ s/cm
The softening pure water of conductivity is rinsed foil, and rotates the cathode roll foil after the completion of washing that liquidates and removed；It takes appropriate
Chromium trioxide and glucose, which are dissolved in 10L water, is made passivating solution, and the concentration of chromium trioxide is 0.7g/L, the concentration of glucose at this time
For 4.8g/L, and adjusts passivating solution pH value and be maintained at 2.3~2.8 ranges；Then copper foil is immersed in passivating solution, at 25 DEG C
Carry out Electroless Plating Procedure and electroplating work procedure simultaneously, the Electroless Plating Procedure time is 16s, and the electroplating work procedure time is 4s, in electroplating work procedure
The passivation current applied is 2.8A, and the flow for controlling passivating solution is 2.8m3/h；Electroless Plating Procedure and plating will finally be passed through
The copper foil of process carries out drying winding by hot-air drying device, obtains extra thin copper foil.
Copper foil obtained in Examples 1 to 3 is respectively designated as sample 1, sample 2 and sample 3, respectively to its thickness,
The many indexs such as tensile strength, elongation percentage, surface roughness are tested；And control sample is set, which is to adopt
Obtained by traditional electrolyte copper foil technique.Table 1 is please referred to, table 1 is copper foil sample and the multinomial survey of control sample in Examples 1 to 3
Try the data comparison table of index, it can be seen that for contrast sample, sample 1~3 all has better tensile strength and extension
Rate, surface roughness is lower, and can stablize and prepare extra thin copper foil of the thickness less than 6 μm, wherein implementation corresponding to sample 2
Example preparation method is optimal process, and 4.5 μm of extra thin copper foil, and sample 1 and sample can be made under the process conditions
Product 3 are also very close with the thickness of sample 2 and other performance parameters aspect, that is, prove aforementioned ultrathin electrolytic copper foil preparation method
Extra thin copper foil of the thickness less than 6 μm can be prepared while guaranteeing that copper foil has preferable tensile strength and flatness, and is had
There is preferable repeatability, is suitable for industrial mass production.
Table 1
It is in contrast to the prior art, the present invention is by the above-mentioned extra thin copper foil preparation method applied to lithium battery and is
System can stablize the copper foil for preparing about 4.5 μ m thicks by improving and optimizating for technique, while enhance the tensile strength of copper foil,
Surface roughness reduces, high temperature oxidation resistance enhances, and also improves copper foil corresponding index performance when reducing whole copper thickness,
Be conducive to the batch production of wide cut copper foil.
It should be noted that the above various embodiments belongs to same inventive concept, the description of each embodiment emphasizes particularly on different fields, In
Not detailed place is described in separate embodiment, can refer to the description in other embodiments.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore it is construed as limiting the scope of the patent.It should be pointed out that for those of ordinary skill in the art, In
Under the premise of not departing from present inventive concept, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.
Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of extra thin copper foil preparation method applied to lithium battery, which is characterized in that step includes the dissolution of copper material, multistage mistake
Filter, electrolysis foil, washing removing and passivation drying, in which:
The copper material dissolving step includes: copper material to be placed in acid solution, and compressed air is passed through into acid solution, makes the copper
Material dissolution forms copper solution；
The specific steps of the electrolysis foil are as follows: plate and cathode roll are dipped in copper electrolyte, Xiang Suoshu copper electrolyte
Middle addition additive carries out electrolysis and in foil obtained on the cathode roll after mixing；
The additive includes poly- phenyl disulfide sodium sulfonate, N, and N- dimethyl disulfide is fine for formamide propane sulfonic acid sodium, ethoxy
Dimension element and collagen, and the concentration of poly- phenyl disulfide sodium sulfonate is 30~65mg/L, N, N- dimethyl disulfide is for formamide third
The concentration of alkyl sulfonic acid sodium is 35~50mg/L, and the concentration of hydroxyethyl cellulose is 25~45mg/L, and the concentration of collagen is 120
~165mg/L and molecular weight are 2500~3800.
2. the extra thin copper foil preparation method according to claim 1 applied to lithium battery, which is characterized in that the electrolysis
In the step of foil, copper ion concentration is 65~85g/L, 110~140g/L of sulfuric acid concentration, 25~45mg/L of chlorine ion concentration；
The copper electrolyte temperature is 40~60 DEG C, and current density is 4000~7500A/m2。
3. the extra thin copper foil preparation method according to claim 1 applied to lithium battery, which is characterized in that the acid is molten
Liquid is the sulfuric acid of 110~140g/L of concentration, and the flow velocity of the compressed air is 5~20m3/min。
4. the extra thin copper foil preparation method according to claim 1 applied to lithium battery, which is characterized in that the multistage
Filtration step includes: primary filter and secondary filter；
The primary filter is filtered using coarse grain diameter tripolite filling material, and the copper solution is obtained after the primary filter
Primary filtrate；
The secondary filter is filtered using fine grain tripolite filling material, by the primary filtrate after the secondary filter
To the copper electrolyte.
5. the extra thin copper foil preparation method according to claim 1 applied to lithium battery, which is characterized in that the washing
Strip step includes: to be rinsed using softening pure water to the foil, and rotate the cathode roll and liquidate the institute after the completion of washing
Foil is stated to be removed.
6. the extra thin copper foil preparation method according to claim 5 applied to lithium battery, which is characterized in that the softening
Pure water is obtained deionized water after simultaneously deionization is filtered for multiple times, and the conductivity of the softening pure water is less than 30 μ s/
cm。
7. the extra thin copper foil preparation method according to claim 1 applied to lithium battery, which is characterized in that the passivation
Baking step includes:
The glucose of the chromium trioxide of 0.5~0.7g/L and 2.8~5.4g/L is soluble in water, passivating solution, the passivation is made
The pH value range of liquid is 2.3~2.8；
The foil is immersed in the passivating solution, carries out Electroless Plating Procedure and electroplating work procedure simultaneously at 20~28 DEG C, and
Passivation current is 2~3.6A, and the time of the Electroless Plating Procedure is 6~20s, and the time of the electroplating work procedure is 1~5s；
Drying winding will be carried out by the copper foil of the electroplating work procedure.
8. a kind of extra thin copper foil preparation system applied to lithium battery, which is characterized in that dissolve unit, multistage filtering including copper material
Unit, heat exchange unit, electrolysis foil unit, Passivation Treatment unit and dry rolling unit, in which:
The copper material dissolution unit is connected to the multistage filtering unit, for will obtain copper solution after the dissolution of copper material, and is conveyed
To the multistage filtering unit；
The multistage filtering unit is connected to after the heat exchange unit with the electrolysis foil unit, the multistage filtering unit
For will obtain the copper electrolyte after copper solution filtering, and the heat exchange unit is delivered to the electrolysis for adjusting
The temperature of the copper electrolyte of foil unit；
The electrolysis foil unit for being electrolysed obtained foil, and the foil come into after row washing removing be sent to it is described blunt
Change processing unit；
The Passivation Treatment unit is used to carry out surface passivating treatment to the foil after washing removing, obtains passivation copper
Foil, and the passivation copper foil is sent at the dry rolling unit, winding is dried；
The extra thin copper foil preparation system applied to lithium battery any described is applied to for what perform claim required in 1~8
The extra thin copper foil preparation method of lithium battery.
9. the extra thin copper foil preparation system according to claim 8 applied to lithium battery, which is characterized in that the electrolysis
Foil unit also with copper material dissolution unit connection, is dissolved for the copper electrolyte after electrolysis to be back to the copper material
In unit, and carry out the dissolution of the copper material.
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| CN111020644A (en) * | 2020-01-03 | 2020-04-17 | 甘肃德福新材料有限公司 | Method for manufacturing electrolytic copper foil for lithium ion secondary battery |
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| CN110923755A (en) * | 2019-12-17 | 2020-03-27 | 九江德福科技股份有限公司 | Surface anti-oxidation process for lithium-ion battery copper foil |
| CN110923755B (en) * | 2019-12-17 | 2021-07-30 | 九江德福科技股份有限公司 | Surface anti-oxidation process for lithium-ion battery copper foil |
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| CN114561673A (en) * | 2022-03-10 | 2022-05-31 | 九江德福科技股份有限公司 | Method for reducing high-temperature high-ductility copper foil surface copper nodules |
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