CN105350054A - Method for modifying nano-carbon material on surface of secondary battery diaphragm through electrophoretic deposition - Google Patents

Method for modifying nano-carbon material on surface of secondary battery diaphragm through electrophoretic deposition Download PDF

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CN105350054A
CN105350054A CN201510829714.8A CN201510829714A CN105350054A CN 105350054 A CN105350054 A CN 105350054A CN 201510829714 A CN201510829714 A CN 201510829714A CN 105350054 A CN105350054 A CN 105350054A
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nano
carbon material
electrophoresis
electrophoretic deposition
secondary battery
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CN105350054B (en
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方海涛
李霏
王慧鑫
苗成成
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Harbin Institute of Technology
Shanghai Institute of Space Power Sources
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Harbin Institute of Technology
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00Electrophoretic coating characterised by the process
    • C25D13/02Electrophoretic coating characterised by the process with inorganic material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00Electrophoretic coating characterised by the process
    • C25D13/22Servicing or operating apparatus or multistep processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403Manufacturing processes of separators, membranes or diaphragms
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/431Inorganic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/449Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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 provides a method for modifying a nano-carbon material on the surface of a secondary battery diaphragm through electrophoretic deposition and relates to the method for modifying the nano-carbon material on the surface of the secondary battery diaphragm. The method aims at solving the problems that a bottom layer of a diaphragm is exposed when an ultra-thin nano-carbon layer modified diaphragm is manufactured through an existing coating method and the surface distribution of a nano-carbon layer is uneven when the thin nano-carbon layer modified diaphragm is manufactured through an existing spraying method. The method includes the steps that firstly, stable nano-carbon material dispersion liquid is prepared; secondly, electrophoretic deposition is performed; and thirdly, pressing is performed, so that the surface modified diaphragm of the nano-carbon material is obtained. By the adoption of the method, controllability is high, the quantity of the nano-carbon material deposited on the diaphragm in unit area can be accurately adjusted and controlled, the problems that the bottom layer of the diaphragm is exposed and the nano-carbon layer is uneven can be effectively solved, the technological process is simple, and production cost is low.

Description

A kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition
Technical field
The present invention relates to secondary cell field, particularly relate to a kind of method to the nano-carbon material modification of secondary battery membrane surface.
Background technology
The barrier film of surface deposition nano-carbon material is used for secondary cell, namely carries out after nano-carbon material surface modification, for secondary cell, the charge-discharge performance of secondary cell can being improved to barrier film.Such as, there is scientific and technical literature to report, adopted the barrier film of graphenic surface modification to substitute unmodified barrier film for lithium ion battery and lithium-sulfur cell, the specific storage of these two kinds of batteries can not only be improved, cycle performance and battery high rate performance can also be improved.
Normal paint-on technique and the spraying technology of adopting prepares nano-sized carbon surface modification barrier film at present.First nano-carbon material and solvent are mixed with slurry by cladding process, then by the method for blade coating, slurry are coated in membrane surface, obtain the barrier film of nano-sized carbon surface modification after dry compacting.Because of the restriction of slurry rheological property matter, cladding process not easily realizes the even coating of ultrathin nanometer carbon-coating at membrane surface, easily occurs the problem that barrier film bottom exposes during actually operating.Spraying method is that nano-sized carbon dispersion liquid is sprayed on battery diaphragm surface with the state of small droplets, after dispersion liquid solvent seasoning, and the barrier film of obtained nano-sized carbon surface modification.But the volatile dry of small droplets solvent needs the time, in drying process, can assemble for large drop between small droplets, the nano carbon particle after dry in large drop or nanometer carbon plate overlap reunion mutually.When this phenomenon can cause spraying thin nano-carbon layer on barrier film, occur that nano-sized carbon is in membrane surface problem pockety.
Summary of the invention
The object of the invention is to solve existing cladding process barrier film bottom when preparing ultrathin nanometer carbon-coating modified diaphragm to expose, and the existing spraying method problem that nano-carbon layer surface arrangement is uneven when preparing thin nano-carbon layer modified diaphragm, and a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition is provided.
A kind of method realizing the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition of the present invention is carried out according to the following steps:
One, prepare stabilized nanoscale carbon material dispersion liquid: by nano-carbon material ultrasonic disperse in solvent, the concentration obtaining nano-carbon material is the stabilized nanoscale carbon material dispersion liquid of 0.01mg/mL ~ 40mg/mL;
Two, electrophoretic deposition: stabilized nanoscale carbon material dispersion liquid step one obtained is as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 0.2cm ~ 20cm, secondary battery membrane is placed between electrophoresis positive pole and electrophoresis negative pole, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be lower electrophoretic deposition 0.1min ~ 600min under the condition of 1.0V ~ 1000.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits nano-carbon material, described electrophoresis is inert metal sheet or graphite flake just very, and described electrophoresis negative pole is inert metal sheet or graphite flake,
Three, suppress: the barrier film that one side step 2 obtained deposits nano-carbon material is suppressed under compacting pressure is the condition of 0.1MPa ~ 500MPa, complete the nano-carbon material modification of secondary battery membrane surface, obtain nano-carbon material surface modification barrier film.
Beneficial effect of the present invention
(1) the invention provides a kind of method of by electrophoretic deposition nano-carbon material realization nano-carbon material, various secondary battery membrane being carried out to surface modification.Adopt electrophoretic technique, realize at membrane surface depositing nano carbon material, by the amount of depositing nano carbon material on nano-sized carbon concentration in change electrophoretic voltage, electrophoresis time, nano-sized carbon dispersion liquid and interelectrode distance accuracy controlling unit surface barrier film, the advantage that controllability is strong can be had.
(2) electrophoretic technique is adopted to realize the preparation of nano-sized carbon surface modification barrier film, the problem that when can effectively avoid preparing thin nano-carbon layer modified diaphragm, barrier film bottom exposes and nano-carbon layer is uneven.
(3) preparation method of the present invention, technological process is simple, and production cost is low.
Accompanying drawing explanation
Fig. 1 is test one and tests the continuous electrophoresis deposition apparatus schematic diagram used in two; Wherein the direction of arrow is barrier film working direction, and a represents two iontophoretic electrodes;
Fig. 2 is the discontinuous electrophoretic deposition set schematic diagram that test three and experiment four use; Wherein a represents constant voltage power supply, b represents two iontophoretic electrodes, c and represent barrier film;
Fig. 3 is the stereoscan photograph of the aminated redox graphene surface modification lithium ion battery separator that test one obtains;
Fig. 4 is macroscopical digital photograph of the aminated redox graphene surface modification lithium ion battery separator that test one obtains;
Fig. 5 is the stereoscan photograph that test two obtains intercalated graphite alkene surface modification lithium-sulfur cell barrier film;
Fig. 6 is macroscopical digital photograph that test two obtains intercalated graphite alkene surface modification lithium-sulfur cell barrier film.
Embodiment
Embodiment one: a kind of method realizing the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition of present embodiment is carried out according to the following steps:
One, prepare stabilized nanoscale carbon material dispersion liquid: by nano-carbon material ultrasonic disperse in solvent, the concentration obtaining nano-carbon material is the stabilized nanoscale carbon material dispersion liquid of 0.01mg/mL ~ 40mg/mL;
Two, electrophoretic deposition: stabilized nanoscale carbon material dispersion liquid step one obtained is as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 0.2cm ~ 20cm, secondary battery membrane is placed between electrophoresis positive pole and electrophoresis negative pole, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be electrophoretic deposition 0.1min ~ 600min under the condition of 1.0V ~ 1000.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits nano-carbon material, described electrophoresis is inert metal sheet or graphite flake just very, and described electrophoresis negative pole is inert metal sheet or graphite flake,
Three, suppress: the barrier film that one side step 2 obtained deposits nano-carbon material is suppressed under compacting pressure is the condition of 0.1MPa ~ 500MPa, complete the nano-carbon material modification of secondary battery membrane surface, obtain nano-carbon material surface modification barrier film.
Embodiment two: present embodiment and embodiment one unlike: the nano-carbon material described in step one is a kind of or wherein several mixture in Graphene, carbon nanotube, gac, nanoporous carbon, gas-phase grown nanometer carbon fibre, graphitized carbon black, nano-graphite and carbonaceous molecular sieve.Other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the solvent described in step one is a kind of or wherein several mixture in ethanol, Virahol, acetone, N-methyl pyrrole network alkane ketone, dioctyl phthalate (DOP), tetrahydrofuran (THF) and dimethyl formamide.Other steps and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the inert metal sheet described in step 2 is Ti sheet, Pd sheet, Au sheet, Pt sheet, Pb sheet or stainless steel substrates.Other steps and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the secondary battery membrane described in step 2 is lithium ion battery separator, sodium-ion battery barrier film, Magnesium ion battery barrier film, aluminum ion battery diaphragm or lithium-sulfur cell barrier film.Other steps and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: in step 2 during electrophoretic deposition nano-carbon material, when in stabilized nanoscale carbon material dispersion liquid, the Zeta potential of nano-carbon material is positive, the distance between the pole-face of secondary battery membrane and electrophoresis negative pole is greater than zero.Other steps and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to five unlike: in step 2 during electrophoretic deposition nano-carbon material, when in stabilized nanoscale carbon material dispersion liquid, the Zeta potential of nano-carbon material is negative value, the distance between the pole-face of secondary battery membrane and electrophoresis positive pole is greater than zero.Other steps and parameter identical with one of embodiment one to five.
Following test is adopted to verify beneficial effect of the present invention
A kind of method realizing the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition of test one, (Fig. 1) this test is carried out according to the following steps:
One, aminated redox graphene-alcohol dispersion liquid is stablized in preparation: by aminated redox graphene ultrasonic disperse in ethanol, ultrasonic power is 100W, ultrasonic time is 30min, the concentration obtaining aminated redox graphene be 1mg/mL stablize aminated redox graphene-alcohol dispersion liquid;
Two, electrophoretic deposition: what step one obtained stablizes aminated redox graphene-alcohol dispersion liquid as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 2cm, lithium ion battery separator is placed in electrophoresis positive pole and electrophoresis negative pole middle, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be electrophoretic deposition 10min under the condition of 20.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits aminated redox graphene, described electrophoresis is Ti sheet just very, and described electrophoresis negative pole is Ti sheet,
Three, suppress: the barrier film that one side step 2 obtained deposits aminated redox graphene is suppressed under the condition of compacting pressure 120MPa, complete lithium ion battery separator surperficial with aminated redox graphene modification, obtain aminated redox graphene surface modification barrier film.
Be prepared described aminated redox graphene before aminated redox graphene-alcohol dispersion liquid is stablized in this testing sequence one preparation, preparation process is:
1. disperseed in 150mL deionized water for ultrasonic by graphene oxide standby for 0.15gHummers legal system, ultrasonic power is 427W, and ultrasonic time is 1h, obtains graphene oxide dispersion A;
2. 1.35g Ursol D is dissolved in 150mL dimethyl formamide and obtains solution B, after graphene oxide dispersion A step 1. obtained and solution B mix, back flow reaction 24h at temperature is 90 DEG C, then acetone eccentric cleaning is used three times, take out again and wash once with acetone filtering, obtain pre-treatment, obtain aminated redox graphene.
The amount aminated its unit surface barrier film of redox graphene surface modification barrier film of this test depositing aminated redox graphene is 0.017mg/cm 2.
This test adopts the mode of continuous electrophoresis deposition.As shown in Figure 1, this device is primarily of unreeling device, stepper motor driven coiler, electrolyzer, iontophoretic electrode composition for continuous electrophoresis deposition apparatus schematic diagram used.First being placed in by the barrier film of rolling before carrying out continuous electrophoresis unreels on device, and barrier film initiating terminal is fixed on coiler by the direction of advancing according to barrier film.During continuous electrophoresis, connect constant voltage power supply and apply voltage to iontophoretic electrode; Stepper-motor drives barrier film on coiler to rotate, and under a stretching force, and drive unreels device synergic rotation.This device integrates electrophoretic deposition and unwinding winding, is applicable to the nano-carbon material modified diaphragm of continuous production overlength.
A kind of method realizing the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition of test two, (Fig. 1) this test is carried out according to the following steps:
One, intercalated graphite alkene-alcohol dispersion liquid is stablized in preparation: by intercalated graphite alkene ultrasonic disperse in ethanol, ultrasonic power is 200W, and ultrasonic time is 60min, and the concentration obtaining intercalated graphite alkene is the stable intercalated graphite alkene-alcohol dispersion liquid of 0.2mg/mL;
Two, electrophoretic deposition: stable intercalated graphite alkene-alcohol dispersion liquid step one obtained is as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 2cm, lithium-sulfur cell barrier film is placed in electrophoresis positive pole and electrophoresis negative pole middle, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be electrophoretic deposition 20min under the condition of 200.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits intercalated graphite alkene, described electrophoresis is Ti sheet just very, and described electrophoresis negative pole is Ti sheet,
Three, suppress: the barrier film that one side step 2 obtained deposits intercalated graphite alkene is suppressed under the condition of compacting pressure 120MPa, completes the modification of lithium-sulfur cell membrane surface intercalated graphite alkene, obtains intercalated graphite alkene surface modification barrier film.
Carry out pre-treatment to described intercalated graphite alkene before intercalated graphite alkene-alcohol dispersion liquid is stablized in this testing sequence one preparation, described preprocessing process is:
1. commercialization intercalated graphite alkene prepared by 0.1g " intercalation-expansion-stripping method " is joined in the aqueous solution of the 500mL of the sodium lignosulfonate being dissolved with 1g, carry out ultrasonic disperse, ultrasonic power is 300W, and ultrasonic time is 1h, obtains the aqueous dispersions A of intercalated graphite alkene;
The aqueous dispersions A vacuum filtration of the intercalated graphite alkene 2. 1. step obtained, clean with deionized water during suction filtration, add deionized water after draining again to clean, clean 3 times, then the mixture adding deionized water and ethanol carries out suction filtration, complete pre-treatment, obtain the intercalated graphite alkene powder of ethanol wet.
The amount its unit surface barrier film of intercalated graphite alkene surface modification barrier film of this test depositing intercalated graphite alkene is 0.1mg/cm 2.
The mode that this test adopts the continuous electrophoresis identical with experiment one to deposit.
A kind of method realizing the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition of test three, (Fig. 2) this test is carried out according to the following steps:
One, prepare graphene oxide-Virahol dispersion liquid: by graphene oxide ultrasonic disperse in Virahol, ultrasonic power is 400W, and ultrasonic time is 60min, and the concentration obtaining graphene oxide is the Stable Oxygen functionalized graphene-Virahol dispersion liquid of 10mg/mL;
Two, electrophoretic deposition: Stable Oxygen functionalized graphene-Virahol dispersion liquid step one obtained is as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 15cm, lithium-sulfur cell barrier film is placed between electrophoresis positive pole and electrophoresis negative pole, keep in touch with electrophoresis positive pole, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be electrophoretic deposition 2min under the condition of 800.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits graphene oxide, described electrophoresis is Pt sheet just very, and described electrophoresis negative pole is Pt sheet,
Three, suppress: the barrier film that one side step 2 obtained deposits graphene oxide is suppressed under the condition of compacting pressure 50MPa, completes the modification of lithium-sulfur cell membrane surface graphene oxide, obtains surface of graphene oxide modified diaphragm.
Graphene oxide described in this test is the standby graphene oxide of Hummers legal system.
On its unit surface barrier film of the surface of graphene oxide modified diaphragm of this test, the amount of deposited oxide Graphene is 0.6mg/cm 2.
This test adopts the mode of discontinuous electrophoretic deposition, and as shown in Figure 2, be placed in by barrier film between positive and negative iontophoretic electrode, nano-carbon material is deposited on barrier film discontinuous electrophoretic deposition set schematic diagram used under the effect of electrical forces.
A kind of method realizing the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition of test four, (Fig. 2) this test is carried out according to the following steps:
One, prepare stable carbon nano-tube-tetrahydrofuran (THF) dispersion liquid: by carbon nanotube ultrasonic disperse in tetrahydrofuran (THF), ultrasonic power is 200W, and ultrasonic time is 60min, and the concentration obtaining carbon nanotube is the stable carbon nano-tube of 0.02mg/mL-tetrahydrofuran (THF) dispersion liquid;
Two, electrophoretic deposition: stable carbon nano-tube step one obtained-tetrahydrofuran (THF) dispersion liquid is as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 0.5cm, sodium-ion battery barrier film is placed in distance electrophoresis positive pole 0.2cm place, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be electrophoretic deposition 300min under the condition of 15.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits carbon nanotube, described electrophoresis just very graphite flake, described electrophoresis negative pole is graphite flake,
Three, suppress: the barrier film that one side step 2 obtained deposits carbon nanotube is suppressed under the condition of compacting pressure 20MPa, completes sodium-ion battery membrane surface carbon nano-tube modification, obtains surface modification of carbon nanotube barrier film.
This testing sequence one carries out pre-treatment to described carbon nanotube before preparing stable carbon nano-tube-acetone dispersion liquor, and described preprocessing process is:
1. joined by 0.01g carbon nanotube in the 500mL aqueous solution of the sodium lignosulfonate being dissolved with 1g, ultrasonic disperse, ultrasonic power is 300W, and ultrasonic time is 1h, obtains the aqueous dispersions of carbon nanotube;
The aqueous dispersions vacuum filtration of the carbon nanotube 2. step 1. obtained, cleans with deionized water during suction filtration, adds deionized water again and clean after draining, clean 3 times, then the mixture adding deionized water and acetone carries out suction filtration, completes pre-treatment, obtains the carbon nanotube that acetone is wetting.
On its unit surface barrier film of the surface modification of carbon nanotube barrier film of this test, the amount of deposition of carbon nanotubes is 0.07mg/cm 2.
This test adopts the mode of the discontinuous electrophoretic deposition identical with experiment three.。
(1) microcosmic scanning electron microscopic observation and macroscopical visual inspection are carried out to the aminated redox graphene surface modification lithium ion battery separator that test one obtains, obtain the stereoscan photograph of aminated redox graphene surface modification lithium ion battery separator as shown in Figure 3 and the macroscopical digital photograph shown in Fig. 4, can find out that membrane surface deposits graphene layer.Realizing membrane surface deposition 0.017mg/cm 2while the thin graphene layer of areal density, graphene layer macroscopic view is evenly distributed, and does not occur the problem that macroscopical localized clusters and white barrier film bottom expose.
(2) microscopic examination of microcosmic scanning electron microscope and naked eyes macroscopic observation are carried out to the intercalated graphite alkene surface modification lithium-sulfur cell barrier film that test two obtains, obtain macroscopical digital photograph shown in the stereoscan photograph of intercalated graphite alkene surface modification lithium-sulfur cell barrier film as shown in Figure 5 and Fig. 6, can find out that membrane surface deposits graphene layer, not occur the problem that macroscopical localized clusters and white barrier film bottom expose.

Claims (7)

1. realized a method for secondary battery membrane surface nano-carbon material modification by electrophoretic deposition, it is characterized in that the method is carried out according to the following steps:
One, prepare stabilized nanoscale carbon material dispersion liquid: by nano-carbon material ultrasonic disperse in solvent, the concentration obtaining nano-carbon material is the stabilized nanoscale carbon material dispersion liquid of 0.01mg/mL ~ 40mg/mL;
Two, electrophoretic deposition: stabilized nanoscale carbon material dispersion liquid step one obtained is as electrophoresis liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole is 0.2cm ~ 20cm, secondary battery membrane is placed between electrophoresis positive pole and electrophoresis negative pole, and make barrier film face parallel with the pole-face of electrophoresis positive pole, be electrophoretic deposition 0.1min ~ 600min under the condition of 1.0V ~ 1000.0V at electrophoretic deposition voltage, complete electrophoretic deposition, dry after taking out, obtain the barrier film that one side deposits nano-carbon material, described electrophoresis is inert metal sheet or graphite flake just very, and described electrophoresis negative pole is inert metal sheet or graphite flake,
Three, suppress: the barrier film that one side step 2 obtained deposits nano-carbon material is suppressed under compacting pressure is the condition of 0.1MPa ~ 500MPa, complete the nano-carbon material modification of secondary battery membrane surface, obtain nano-carbon material surface modification barrier film.
2. a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition according to claim 1, is characterized in that the nano-carbon material described in step one is a kind of or wherein several mixture in Graphene, carbon nanotube, gac, nanoporous carbon, gas-phase grown nanometer carbon fibre, graphitized carbon black, nano-graphite or carbonaceous molecular sieve.
3. a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition according to claim 1, is characterized in that the solvent described in step one is a kind of or wherein several mixture in ethanol, Virahol, acetone, N-methyl pyrrole network alkane ketone, dioctyl phthalate (DOP), tetrahydrofuran (THF) and dimethyl formamide.
4. a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition according to claim 1, is characterized in that the inert metal sheet described in step 2 is Ti sheet, Pd sheet, Au sheet, Pt sheet, Pb sheet or stainless steel substrates.
5. a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition according to claim 1, is characterized in that the secondary battery membrane described in step 2 is lithium ion battery separator, sodium-ion battery barrier film, Magnesium ion battery barrier film, aluminum ion battery diaphragm or lithium-sulfur cell barrier film.
6. a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition according to claim 1, when it is characterized in that electrophoretic deposition nano-carbon material in step 2, when in stabilized nanoscale carbon material dispersion liquid, the Zeta potential of nano-carbon material is positive, the distance between secondary battery membrane and electrophoresis negative pole is greater than zero.
7. a kind of method being realized the nano-carbon material modification of secondary battery membrane surface by electrophoretic deposition according to claim 1, when it is characterized in that electrophoretic deposition nano-carbon material in step 2, when in stabilized nanoscale carbon material dispersion liquid, the Zeta potential of nano-carbon material is negative value, the distance between secondary battery membrane and electrophoresis positive pole is greater than zero.
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CN112705056A (en) * 2020-12-23 2021-04-27 华南理工大学 Method for rapidly preparing two-dimensional zeolite molecular sieve membrane by electrophoretic deposition and two-dimensional zeolite molecular sieve membrane prepared by method
CN112831819A (en) * 2021-01-29 2021-05-25 广东墨睿科技有限公司 Electrophoretic deposition method for preparing reduced graphene oxide film
CN114522543A (en) * 2022-01-19 2022-05-24 华南理工大学 Ultrathin two-dimensional Cu-TCPP film and preparation method thereof

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