CN107460498A - The method that copper electrolyzing refining is carried out with carbon nano-tube/composite conducting polymer material minus plate - Google Patents

The method that copper electrolyzing refining is carried out with carbon nano-tube/composite conducting polymer material minus plate Download PDF

Info

Publication number
CN107460498A
CN107460498A CN201710700324.XA CN201710700324A CN107460498A CN 107460498 A CN107460498 A CN 107460498A CN 201710700324 A CN201710700324 A CN 201710700324A CN 107460498 A CN107460498 A CN 107460498A
Authority
CN
China
Prior art keywords
copper
minus plate
resin
cnt
plate
Prior art date
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.)
Granted
Application number
CN201710700324.XA
Other languages
Chinese (zh)
Other versions
CN107460498B (en
Inventor
罗鲲
诸葛祥群
李前进
向利
蓝嘉昕
罗志虹
何雨林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guilin University of Technology
Original Assignee
Guilin University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guilin University of Technology filed Critical Guilin University of Technology
Priority to CN201710700324.XA priority Critical patent/CN107460498B/en
Publication of CN107460498A publication Critical patent/CN107460498A/en
Application granted granted Critical
Publication of CN107460498B publication Critical patent/CN107460498B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention discloses a kind of method that copper electrolyzing refining is carried out with carbon nano-tube/composite conducting polymer material minus plate.Using melt blending or it is stirred in resin and adds multi-walled carbon nanotube, prepare thermoplastic resin or thermosetting resin based conductive composite material minus plate, copper electrolyzing refining is carried out in sulfuric acid system electrolyte.To reduce decomposition voltage, copper is first deposited on cathode plate portion lug, then copper electrolyzing refining is carried out as electric position is connect, until obtaining the cathode copper of dense uniform.After the completion of electrolysis, minus plate is proposed from electrolytic cell, is peeled off after cleaning, electrolytic copper plate is directly obtained after working process.The inventive method preparation technology is simple, and obtained refined copper is easily peelable, minus plate can Reusability, production cost is low, is easy to be extended and applied.

Description

Copper electrolyzing refining is carried out with carbon nano-tube/composite conducting polymer material minus plate Method
Technical field
The present invention relates to a kind of side that copper electrolyzing refining is carried out with carbon nano-tube/composite conducting polymer material minus plate Method.
Background technology
Copper is the non-ferrous metal very close with human relation, is widely used in electric, light industry, machine-building, builds The fields such as industry, national defense industry are built, using more extensive especially in electrical industry, electronics industry, in China YouSe metal material Aluminium is only second in the consumption of material.The purity of copper is very big on the influence of its property, and trace impurity can also produce great to the performance of copper Influence.
Electrorefining is the Main Means of current purifying copper, usually by blister copper（Cupric 99%）Slab conduct is made in advance Anode, fine copper, which is laminated, makees negative electrode, and electrolyte is used as using the mixed liquor of sulfuric acid and copper sulphate.After energization, copper is from anodic solution Into copper ion to movable cathode, obtain electronics after reaching negative electrode and separate out fine copper in negative electrode（Cathode copper）.Sprinkled in blister copper than work in copper Impurity, such as iron and zinc, ion is dissolved as with copper；Because these ions are more difficult to separate out compared with copper ion, so suitable When regulation potential difference can avoid these ions from being separated out on negative electrode.Those are not so good as the impurity that work in copper sprinkle, and such as gold, silver, then deposit In the bottom of electrolytic cell, turn into " earth of positive pole ", the wherein noble metal such as gold, silver can be obtained by successive refinements.
Industrial is to obtain fine copper cathode sheet, usually using negative electrode kind pole plate made of titanium plate or stainless steel plate.Work as kind After the thick copper coins of 2-3 mm are deposited on pole plate, i.e., the fine copper of deposition is stripped down using special equipment, leveling again is made Fine copper cathode sheets, for copper electrolyzing refining.For convenience of stripping, it is necessary to coat polyethylene in advance at kind of a pole plate edge.It is whole to peel off Process is relatively complicated, and operation need to often completely strip copper foil tool and acquire a certain degree of difficulty by specific device.
Conductive filler is uniformly blended into polymeric matrix, is allowed to possess electric conductivity and is used for electrode material.Conductive filler one As include carbon-based material or metal based material powder etc., wherein the former be broadly divided into carbon black, graphite, carbon fiber, CNT and Graphene etc..Compared with metal dust, carbon system powder light specific gravity, cost is low, electric conductivity is poor, but practicality is stronger.Wherein, it is more Wall carbon nano tube is being macroscopically powdered, is easy to effectively scattered in the polymer melt or solution of viscosity；It is more on microcosmic Wall carbon nano tube is 1 dimension material, and it is relatively low to form percolation threshold needed for conductive network after dispersed in polymeric matrix.In recent years Come, multi-walled carbon nanotube scale manufacture its price is significantly declined, possess manufacture conducing composite material it is actual answer Condition.As the matrix of conducing composite material, thermoplastic resin or thermosetting resin can be used.The former can use molten Melt the method for blending, CNT is evenly spread in resin matrix；The latter then can directly by CNT be added to resin, In curing agent or solvent, carbon nano-tube/polymer composite material is made by being stirred.
It is using polymer base conductive composite material as the advantages of copper electrolyzing refining kind pole：（1）Electrode surface is not preferential Nucleating point, it is easy to form homogeneous coating；（2）Copper deposit is moderate with basal body binding force, can be done directly copper electrolyzing refining, raw Output cathode copper, fine copper cathode sheets are prepared without strip operation；（3）It can be recycled for multiple times, production cost is low.Its shortcoming is Electric conductivity easily causes tank voltage to raise, increases electrolysis energy consumption than stainless steel or titanium plate kind extreme difference.It is proposed of the present invention prepares carbon and received Mitron/composite conducting polymer material minus plate, for copper electrolyzing refining, and the control electrolysis energy consumption that takes reasonable measure.The party Method has no report at present.
The content of the invention
It is an object of the invention to provide one kind cupric electrolysis is carried out with carbon nano-tube/composite conducting polymer material minus plate The method of refining, simplify electrolysis procedure, reduce production cost.
The thinking of the present invention：Using melt blending or it is stirred into polymeric matrix and adds multi-walled carbon nanotube, makes Standby thermoplastic resin or thermosetting resin based conductive composite material minus plate, copper electrolyzing refining is carried out in sulfuric acid system electrolyte. To reduce decomposition voltage, copper is first deposited on cathode plate portion lug, then copper electrolyzing refining is carried out as electric position is connect.Electrolysis After the completion of, minus plate is proposed from electrolytic cell, is peeled off after cleaning, electrolytic copper plate is directly produced after working process.
Concretely comprise the following steps：
（1）CNT is scattered in resin matrix：For thermoplastic resin, thermoplastic resin particle is crushed to 60 first The mesh of mesh -300, the CNT for accounting for gross mass 5%-15% is well mixed with thermoplastic resin powder, melted altogether using banbury It is granulated after mixed, CNT/resin composite materials raw material is made；For thermosetting resin, the carbon for accounting for gross mass 5%-15% is received Mitron is added in the organic solvent for accounting for gross mass 10%-15% and stirred, then carries out mixing system with thermosetting resin and curing agent Into CNT/resin composite materials raw material, wherein thermosetting resin and curing agent mass ratio are 100:（20-40）.
（2）The preparation of conducing composite material minus plate：For CNT/resin composite materials made from thermoplastic resin Raw material, CNT/resin composite materials raw material is melted and is rapidly injected in mould in plasticator, conduction is obtained after solidification Composite cathode plate；Or CNT/resin composite materials raw material is first added into single or double screw extruder, melting is made 3D printing silk is deposited, then minus plate is made by increasing material manufacturing method.It is multiple for CNT/resin made from thermosetting resin Condensation material raw material, CNT/resin composite materials raw material is added into mould, heating extrusion forming, obtains conducing composite material Minus plate.
（3）Conducing composite material minus plate is used for copper electrolyzing refining：It is in copper electrolyzing refining groove that conducing composite material is cloudy Pole plate and blister copper anode are separately fixed at relevant position, connect the negative pole and positive pole of D.C. regulated power supply respectively；Addition contains 100-120g/L copper sulphate, 150-180g/L sulfuric acid, 0.01-0.08 g/L hydrochloric acid, 1-80 mg/L gelatin and 1-80 mg/L sulphur The electrolyte of urea, electrolyte are circulated by pump to ensure mass transfer effect, and temperature control is between 60 ~ 65 DEG C；With 100 ~ 300 A/m2Current density be electrolysed, until copper deposits reach required thickness；After the completion of electrolysis, cathode copper will be loaded with Minus plate is proposed from electrolytic cell, is peeled off after cleaning, and electrolytic copper plate is obtained after working process；Conducing composite material minus plate can weigh It is multiple to use.
（4）Electrolytic process saves：To prevent from causing because conducting polymer resistivity is higher cupric electrolysis energy efficiency to decline, electricity Solution preocess is divided into two stages progress.When first stage is electrolysed, cathode plate portion lug is immersed in electrolyte, treats copper deposits Lug is raised to more than liquid level by thickness when reaching 2-3 mm, the copper deposits cleaning on lug is dried, and will connect electric position Drop to and connect herein, start the cupric electrolysis of second stage, until obtaining the cathode copper of appointed thickness.Due to time first stage It is very short, therefore total electrolysis energy consumption will not substantially increase.
The organic solvent is one in the pure acetone of chemistry, toluene, hexone, dichloroethanes and chloroform Kind.
The curing agent is the pure ethylenediamine of chemistry, hexamethylene diamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine, One kind in m-phenylene diamine (MPD), maleic anhydride and phthalic anhydride.
The inventive method preparation technology is simple, and obtained refined copper is easily peelable, minus plate can Reusability, production cost It is low, it is easy to be extended and applied.
Accompanying drawing（Table）Explanation
Fig. 1 is the 3D printing copper electrolyzing refining negative electrode of the embodiment of the present invention 1（1a）And electrolytic cell（1b）.
Fig. 2 is the stripping situation of 1 CNT of the embodiment of the present invention/ABS conducing composite material negative electrode copper deposits: (2a) film；（2b）Thick film.
Fig. 3 is the copper deposits of the embodiment of the present invention 1 and electrode interface combination section SEM photograph.
Fig. 4 is the additive-free copper deposits SEM photograph of electrolyte of the present invention.
Fig. 5 is the copper deposits SEM photograph that electrolyte of the present invention adds 1 mg/L gelatin.
Fig. 6 is the copper deposits SEM photograph that the electrolyte of the embodiment of the present invention 1 adds 1 mg/L gelatin and 2 mg/L thiocarbamides.
Embodiment
Embodiment 1：
（1）CNT is scattered in resin matrix：Engineering plastics ABS resin is selected, first by engineering plastics ABS resin tree Fat particle is crushed to 80 mesh, and the multi-walled carbon nanotube purchased in market for accounting for gross mass 10% is mixed with engineering plastics ABS resin powder Uniformly, it is granulated after 80 DEG C of oven dryings use banbury melt blending after 12 hours, CNT/resin composite materials is made Raw material.
（2）The preparation of conducing composite material minus plate：By step（1）Obtained CNT/resin composite materials raw material Double screw extruder is added, fusion sediment 3D printing silk is made.During extrusion, the r/min of control twin-screw rotating speed 15~25, charging Mouth pressure is 40~50 MPa, and discharging opening pressure is 20~40 MPa, and each section of extrusion temperature is as shown in table 1：
Table 1：Prepare CNT/ABS fusion sediment 3D printing consumptive material double screw extruder temperature setting parameters
Heating region 1 section 2 sections 3 sections 4 sections 5 sections 6 sections 7 sections
Temperature/DEG C 190 195 210 210 215 220 225
（3）Conducing composite material minus plate is used for copper electrolyzing refining：Minus plate and supporting electrolytic cell are designed using mapping software, its Middle cell dimension is the mm of the mm of 50 mm × 40 × 40, and negative electrode current-carrying part size is the mm of the mm of 35 mm × 24 × 3, anode and cathode Spacing is 35 mm, and is come out with fusion sediment type 3D printer, refers to Fig. 1.By conducing composite material in copper electrolyzing refining groove Minus plate and blister copper anode are separately fixed at relevant position, connect the negative pole and positive pole of D.C. regulated power supply respectively；Addition contains 113 g/L copper sulphate, 165 g/L sulfuric acid, 0.07 g/L hydrochloric acid, the electrolyte of 1 mg/L gelatin and 2 mg/L thiocarbamides, using outer Add the mode of peristaltic pump electrolyte is constantly circulated, temperature control is at 60 DEG C.With 200 A/m2Current density be electrolysed, Until copper deposits reach required thickness.After the completion of electrolysis, the minus plate for being loaded with cathode copper is proposed from electrolytic cell, after cleaning Peel off, electrolytic copper plate is obtained after working process.Conducing composite material minus plate can be reused.Fig. 2 is in conducing composite material The refined copper of electrode surface deposition, it can be seen that thin, the thick equal dense uniform of deposit, copper deposit are combined with composite electrode Power is moderate, is easy to from composite electrode sur-face peeling；Fig. 3 is copper deposits and electrode interface combination section SEM photograph, can be with Find out that sedimentary relies primarily on interfacial mechanical " pinning " and is combined together with composite electrode.Fig. 4, Fig. 5 and Fig. 6 are additive Influence to copper deposits structure, it can find that deposit compact structure can be made by adding appropriate amounts of gelatin and thiocarbamide.
（4）Electrolytic process saves：To prevent from causing because conducting polymer resistivity is higher cupric electrolysis energy efficiency to decline, electricity Solution preocess is divided into two stages progress.When first stage is electrolysed, cathode plate portion lug is immersed in electrolyte, treats copper deposits Lug is raised to more than liquid level by thickness when reaching 2 mm, and the copper deposits cleaning on lug is dried, and will connect under electric position It is down to and connects herein, start the cupric electrolysis of second stage, until obtains the cathode copper of appointed thickness.Due to time first stage very It is short, therefore total electrolysis energy consumption will not substantially increase.
Embodiment 2：
（1）CNT is scattered in resin matrix：Engineering plastics ABS resin is selected, first by engineering plastics ABS resin Grain is crushed to 60 mesh, and the multi-walled carbon nanotube purchased in market for accounting for gross mass 10% is well mixed with engineering plastics ABS toner, 80 DEG C of oven dryings are granulated after using banbury melt blending after 12 hours, and CNT/resin composite materials raw material is made.
（2）The preparation of conducing composite material minus plate：By step（1）Gained CNT/resin composite materials raw material is again It is secondary to be ground into 60 mesh powder, it is filled in cathode plate mould；Above-mentioned mould is placed on hot press, 15 are preheated at 205 DEG C Minute, then suppressed 15 minutes under 10.5 MPa pressure, then pressurize is cooled down to room temperature, conducing composite material negative electrode is made Plate.
（3）Conducing composite material minus plate is used for copper electrolyzing refining：It is in copper electrolyzing refining groove that conducing composite material is cloudy Pole plate and blister copper anode are separately fixed at relevant position, connect the negative pole and positive pole of D.C. regulated power supply respectively；Addition contains 113 G/L copper sulphate, 165 g/L sulfuric acid, 0.07 g/L hydrochloric acid, the electrolyte of 1 mg/L gelatin and 2 mg/L thiocarbamides, using being followed outside pump Ring mode improves electrolyte mass transfer, and solution temperature is controlled at 65 DEG C.With 190 A/m2Current density be electrolysed, until copper Sedimentary reaches required thickness.After the completion of electrolysis, the minus plate for being loaded with cathode copper is proposed from electrolytic cell, peeled off after cleaning, Electrolytic copper plate is obtained after working process.Conducing composite material minus plate can be reused.
（4）Electrolytic process saves：To prevent from causing because conducting polymer resistivity is higher cupric electrolysis energy efficiency to decline, electricity Solution preocess is divided into two stages progress.When first stage is electrolysed, cathode plate portion lug is immersed in electrolyte, treats copper deposits Lug is raised to more than liquid level by thickness when reaching 3 mm, and the copper deposits cleaning on lug is dried, and will connect under electric position It is down to and connects herein, start the cupric electrolysis of second stage, until obtains the cathode copper of appointed thickness.Due to time first stage very It is short, therefore total electrolysis energy consumption will not substantially increase.
Embodiment 3：
（1）CNT is scattered in resin matrix：Select bisphenol A epoxide resin（EP）, by EP and curing agent mass ratio 100:35 weigh the pure hexamethylene diamine curing agent of chemistry.The multi-walled carbon nanotube purchased in market for accounting for composite gross mass 12% is disperseed first In the solution chemical pure acetone of composite gross mass 10%, then add the pure hexamethylene diamine curing agent of chemistry and be well mixed, then add Enter EP to be sufficiently stirred at room temperature, after being well mixed, be placed in vacuum drying oven drying degassing 15 minutes or so, to not having substantially Untill bubble.
（2）The preparation of conducing composite material minus plate：By step（1）Resin compound cast after obtained drying degassing Into mould.After the complete mold filling of resin, gas outlet and air inlet are clamped, is solidified 24 hours at room temperature, then at 80 DEG C admittedly It is stripped after changing 15 hours, conducing composite material battery lead plate is made.
（3）Conducing composite material minus plate is used for copper electrolyzing refining：It is in copper electrolyzing refining groove that conducing composite material is cloudy Pole plate and blister copper anode are separately fixed at relevant position, connect the negative pole and positive pole of D.C. regulated power supply respectively；Addition contains 113 G/L copper sulphate, 165 g/L sulfuric acid, 0.07 g/L hydrochloric acid, the electrolyte of 1 mg/L gelatin and 2 mg/L thiocarbamides, using being followed outside pump Ring mode improves electrolyte mass transfer, and solution temperature is controlled at 60 DEG C.With 210 A/m2Current density be electrolysed, until copper Sedimentary reaches required thickness.After the completion of electrolysis, the minus plate for being loaded with cathode copper is proposed from electrolytic cell, peeled off after cleaning, Electrolytic copper plate is obtained after working process.Conducing composite material minus plate can be reused.
（4）Electrolytic process saves：To prevent from causing because conducting polymer resistivity is higher cupric electrolysis energy efficiency to decline, electricity Solution preocess is divided into two stages progress.When first stage is electrolysed, cathode plate portion lug is immersed in electrolyte, treats copper deposits Lug is raised to more than liquid level by thickness when reaching 3 mm, and the copper deposits cleaning on lug is dried, and will connect under electric position It is down to and connects herein, start the cupric electrolysis of second stage, until obtains the cathode copper of appointed thickness.Due to time first stage very It is short, therefore total electrolysis energy consumption will not substantially increase.

Claims (1)

  1. A kind of 1. method that copper electrolyzing refining is carried out with carbon nano-tube/composite conducting polymer material minus plate, it is characterised in that Concretely comprise the following steps：
    （1）CNT is scattered in resin matrix：For thermoplastic resin, thermoplastic resin particle is crushed to 60 first The mesh of mesh -300, the CNT for accounting for gross mass 5%-15% is well mixed with thermoplastic resin powder, melted altogether using banbury It is granulated after mixed, CNT/resin composite materials raw material is made；For thermosetting resin, the carbon for accounting for gross mass 5%-15% is received Mitron is added in the organic solvent for accounting for gross mass 10%-15% and stirred, then carries out mixing system with thermosetting resin and curing agent Into CNT/resin composite materials raw material, wherein thermosetting resin and curing agent mass ratio are 100:（20-40）；
    （2）The preparation of conducing composite material minus plate：It is former for CNT made from thermoplastic resin/resin composite materials Material, CNT/resin composite materials raw material is melted and is rapidly injected in mould in plasticator, is obtained after solidification conductive multiple Condensation material minus plate；Or CNT/resin composite materials raw material is first added into single or double screw extruder, it is heavy that melting is made Product 3D printing silk, then minus plate is made by increasing material manufacturing method；For CNT/resin compounded made from thermosetting resin Material feedstock, CNT/resin composite materials raw material is added into mould, heating extrusion forming, obtains conducing composite material the moon Pole plate；
    （3）Conducing composite material minus plate is used for copper electrolyzing refining：By conducing composite material minus plate in copper electrolyzing refining groove Relevant position is separately fixed at blister copper anode, connects the negative pole and positive pole of D.C. regulated power supply respectively；Addition contains 100- 120g/L copper sulphate, 150-180g/L sulfuric acid, 0.01-0.08 g/L hydrochloric acid, 1-80 mg/L gelatin and 1-80 mg/L thiocarbamides Electrolyte, electrolyte are circulated by pump to ensure mass transfer effect, and temperature control is between 60 ~ 65 DEG C；With 100 ~ 300 A/ m2Current density be electrolysed, until copper deposits reach required thickness；After the completion of electrolysis, the minus plate of cathode copper will be loaded with It is proposed from electrolytic cell, peeled off after cleaning, electrolytic copper plate is obtained after working process；Conducing composite material minus plate can repeat to make With；
    （4）Electrolytic process saves：To prevent from causing because conducting polymer resistivity is higher cupric electrolysis energy efficiency to decline, it was electrolysed Journey is divided into two stages progress；When first stage is electrolysed, cathode plate portion lug is immersed in electrolyte, treats copper deposits thickness Lug is raised to more than liquid level when reaching 2-3 mm, the copper deposits cleaning on lug dried, and electric position decline will be connect To connecting herein, start the cupric electrolysis of second stage, until obtaining the cathode copper of appointed thickness；Due to time first stage very It is short, therefore total electrolysis energy consumption will not substantially increase；
    The organic solvent is one kind in the pure acetone of chemistry, toluene, hexone, dichloroethanes and chloroform；
    The curing agent is the pure ethylenediamine of chemistry, hexamethylene diamine, diethylenetriamine, triethylene tetramine, diethylaminopropylamine, isophthalic One kind in diamines, maleic anhydride and phthalic anhydride.
CN201710700324.XA 2017-08-16 2017-08-16 The method for carrying out copper electrolyzing refining with carbon nano-tube/composite conducting polymer material cathode plate Active CN107460498B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710700324.XA CN107460498B (en) 2017-08-16 2017-08-16 The method for carrying out copper electrolyzing refining with carbon nano-tube/composite conducting polymer material cathode plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710700324.XA CN107460498B (en) 2017-08-16 2017-08-16 The method for carrying out copper electrolyzing refining with carbon nano-tube/composite conducting polymer material cathode plate

Publications (2)

Publication Number Publication Date
CN107460498A true CN107460498A (en) 2017-12-12
CN107460498B CN107460498B (en) 2019-04-12

Family

ID=60549828

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710700324.XA Active CN107460498B (en) 2017-08-16 2017-08-16 The method for carrying out copper electrolyzing refining with carbon nano-tube/composite conducting polymer material cathode plate

Country Status (1)

Country Link
CN (1) CN107460498B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110219018A (en) * 2019-05-28 2019-09-10 西北矿冶研究院 Device and method for industrially implementing magnetized copper electrolysis
CN114525549A (en) * 2022-01-24 2022-05-24 先导薄膜材料（广东）有限公司 Preparation method of high-purity copper

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749464A (en) * 1986-04-28 1988-06-07 Technical Plastic T-R Ltd. Non conductive edge strip for use on an electrolytic metal refining cathode
CN102839390A (en) * 2012-08-17 2012-12-26 致远控股集团有限公司 Low-grade black scrap copper electrolysis process
CN105542377A (en) * 2015-12-19 2016-05-04 桂林理工大学 Preparation method of conductive 3D printing supplies by using double screw extruder
CN105885267A (en) * 2016-05-21 2016-08-24 桂林理工大学 Preparation method for conductive 3D printing consumables

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749464A (en) * 1986-04-28 1988-06-07 Technical Plastic T-R Ltd. Non conductive edge strip for use on an electrolytic metal refining cathode
CN102839390A (en) * 2012-08-17 2012-12-26 致远控股集团有限公司 Low-grade black scrap copper electrolysis process
CN105542377A (en) * 2015-12-19 2016-05-04 桂林理工大学 Preparation method of conductive 3D printing supplies by using double screw extruder
CN105885267A (en) * 2016-05-21 2016-08-24 桂林理工大学 Preparation method for conductive 3D printing consumables

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110219018A (en) * 2019-05-28 2019-09-10 西北矿冶研究院 Device and method for industrially implementing magnetized copper electrolysis
CN114525549A (en) * 2022-01-24 2022-05-24 先导薄膜材料（广东）有限公司 Preparation method of high-purity copper

Also Published As

Publication number Publication date
CN107460498B (en) 2019-04-12

Similar Documents

Publication Publication Date Title
CA1129807A (en) Organic polymer mandrel for electroforming
CN107460498B (en) The method for carrying out copper electrolyzing refining with carbon nano-tube/composite conducting polymer material cathode plate
CN102473930B (en) Method for producing a fuel cell separator
TW200400281A (en) Method for making electrode
JP5551161B2 (en) Conductive solid composite material and method for obtaining the same
CN108396168A (en) A kind of preparation method of high-strength highly-conductive creep resistant graphene enhancing aluminum alloy materials
CN108728876A (en) A kind of preparation method of FeCoNiCuMo high-entropy alloys film
CN1302056C (en) Zinc polymer thick film composition
CN107610803A (en) A kind of 3D printing composite conducting wire rod and preparation method thereof
CN100585917C (en) Preparatin method of high conductivity double polar plates for vanadium battery
JP2019512842A (en) Electrode solution and electrochemical cell and battery using the same
CN1307733C (en) Preparation method of electrode for all-vanadium ion flow battery
JP4421556B2 (en) Metal particle and method for producing the same
CN102615804B (en) Preparing-molding method and performance testing method of zinc-bromine flow battery polar plate
JP2006057129A (en) Composite metal body, method for producing the same, metal grain and method for producing the same
CN107785545A (en) A kind of preparation method of lithium ion battery cathode slurry
CN102212845B (en) Method for preparing TiB2 cathode coating for aluminium electrolysis
CN113666367B (en) Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation
CN104409699A (en) Preparation method of graphene coated cuprous phosphide composite material
CN106854768B (en) electrodeposition preparation method of superfine copper powder
CN105463504A (en) Method for electrolytic separation of copper and soldering tin mixture
JP4259994B2 (en) Method for producing polymerized gold sheet
CN1557700A (en) Preparation of nano-graphite carbon sol by anode graphite electrode oxidation method
CN108264683A (en) A kind of graphene-PP composite material and preparation method thereof
JP2005320579A (en) Lumpy granule, linear granule and method for producing granule

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant