CN105350054B - A kind of method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition - Google Patents
A kind of method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition Download PDFInfo
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- CN105350054B CN105350054B CN201510829714.8A CN201510829714A CN105350054B CN 105350054 B CN105350054 B CN 105350054B CN 201510829714 A CN201510829714 A CN 201510829714A CN 105350054 B CN105350054 B CN 105350054B
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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
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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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
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition.The present invention relates to a kind of method being modified to secondary battery membrane surface with nano-carbon material.The invention aims to solve existing cladding process to expose after film bottom preparing ultrathin nanometer carbon-coating modified diaphragm, and existing spraying process the problem of nano-carbon layer surface distributed is uneven when preparing thin nano-carbon layer modified diaphragm.The step of the inventive method is：First, stable nano-carbon material dispersion liquid is prepared；2nd, electrophoretic deposition；3rd, suppress, obtain nano-carbon material surface modified diaphragm.The method controllability of the present invention is strong, the problem of can depositing the amount of nano-carbon material on accuracy controlling unit area barrier film, while can effectively avoid the exposure of barrier film bottom and uneven nano-carbon layer.Technical process is simple, and production cost is low.
Description
Technical field
The present invention relates to secondary cell field, more particularly to a kind of secondary battery membrane surface is modified with nano-carbon material
Method.
Background technology
The barrier film of surface deposition nano-carbon material is used for secondary cell, i.e., nano-carbon material surface modification is carried out to barrier film
It is used for secondary cell afterwards, the charge-discharge performance of secondary cell can be improved.For example had scientific and technical literature report, using graphite
The barrier film that alkene surface is modified substitutes unmodified barrier film and is used for lithium ion battery and lithium-sulfur cell, can not only improve both batteries
Specific capacity, additionally it is possible to improve cycle performance and battery high rate performance.
At present nanometer carbon surface modified diaphragm is prepared frequently with paint-on technique and spraying technology.Cladding process is first by nano-sized carbon
Material is hybridly prepared into slurry with solvent, and slurry then is coated in into membrane surface with the method for blade coating, obtained after drying compacting
The barrier film that nanometer carbon surface is modified.Because of the limitation of slurry rheological property matter, cladding process is not easy to realize ultrathin nanometer carbon-coating in barrier film table
The uniform coating in face, easily occurs the problem of barrier film bottom exposure during practical operation.Spraying process is with small by nano-sized carbon dispersion liquid
The state of drop is sprayed on battery diaphragm surface, and after dispersion liquid solvent seasoning, the barrier film that nanometer carbon surface is modified is made.However,
The volatile dry of droplet solvent needs the time, in the drying process, big drop can be collected as between droplet, big liquid after drying
Nano carbon particle or nanometer carbon plate in drop mutually overlap reunion.This phenomenon can cause to spray thin nano-carbon layer on barrier film
When, there is nano-sized carbon the membrane surface skewness the problem of.
The content of the invention
The invention aims to solve existing cladding process to prepare ultrathin nanometer carbon-coating modified diaphragm sudden and violent after film bottom
Dew, and existing spraying process the problem of nano-carbon layer surface distributed is uneven when preparing thin nano-carbon layer modified diaphragm, and carry
For a kind of method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition.
The present invention it is a kind of by electrophoretic deposition realize method that secondary battery membrane surface nano-carbon material is modified by
Following steps are carried out：
First, stable nano-carbon material dispersion liquid is prepared：By nano-carbon material ultrasonic disperse in solvent, nano carbon material is obtained
The concentration of material is 0.01mg/mL~40mg/mL stable nano-carbon material dispersion liquid；
2nd, electrophoretic deposition：Using the stable nano-carbon material dispersion liquid that step 1 obtains as electrophoresis liquid, then by electrophoresis just
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 electricity
Swimming the distance between positive pole and electrophoresis negative pole are 0.2cm~20cm, and secondary battery membrane is placed in into electrophoresis positive pole and electrophoresis negative pole
Between, and make barrier film face parallel with the pole-face of electrophoresis positive pole, the lower electricity under conditions of electrophoretic deposition voltage is 1.0V~1000.0V
Swimming deposition 0.1min~600min, completes electrophoretic deposition, is dried after taking-up, and obtaining one side deposition has the barrier film of nano-carbon material；
Just extremely inert metal piece or graphite flake, described electrophoresis negative pole are inert metal piece or graphite flake to described electrophoresis；
3rd, suppress：By one side that step 2 obtains deposition have the barrier film of nano-carbon material compacting pressure be 0.1MPa~
Suppressed under conditions of 500MPa, complete to be modified secondary battery membrane surface with nano-carbon material, obtain nano-carbon material
Surface modified diaphragm.
Beneficial effect of the present invention
(1) present invention provides one kind by electrophoretic deposition nano-carbon material realization nano-carbon material to various secondary cells
The method that barrier film carries out surface modification.Using electrophoretic techniques, realize and deposit nano-carbon material in membrane surface, change can be passed through
Sunk in electrophoretic voltage, electrophoresis time, nano-sized carbon dispersion liquid on nanometer concentration of carbon and electrode spacing accuracy controlling unit area barrier film
The amount of product nano-carbon material, has the advantages of controllability is strong.
(2) preparation of nanometer carbon surface modified diaphragm is realized using electrophoretic techniques, can effectively avoid preparing thin nano-carbon layer
Modified diaphragm exposes the problem of uneven with nano-carbon layer after film bottom.
(3) preparation method of the invention, technical process is simple, and production cost is low.
Brief description of the drawings
Fig. 1 is the continuous electrophoresis precipitation equipment schematic diagram used in experiment one and experiment two；Wherein the direction of arrow is barrier film
Direction of advance, a represent two iontophoretic electrodes；
Fig. 2 is the discontinuous electrophoretic deposition set schematic diagram that experiment three and experiment four use；Wherein a represents constant voltage source, b
Represent two iontophoretic electrodes, c and represent barrier film；
Fig. 3 is the ESEM for the aminated redox graphene surface modification lithium-ion battery barrier film that experiment one obtains
Photo；
Fig. 4 is that the macroscopic view for the aminated redox graphene surface modification lithium-ion battery barrier film that experiment one obtains is digital
Photo；
Fig. 5 is that experiment two obtains the stereoscan photograph that intercalated graphite alkene surface is modified lithium-sulfur cell barrier film；
Fig. 6 is that experiment two obtains macroscopical digital photograph that intercalated graphite alkene surface is modified lithium-sulfur cell barrier film.
Embodiment
Embodiment one：One kind of present embodiment realizes secondary battery membrane surface nanometer by electrophoretic deposition
The method that carbon material is modified is carried out according to the following steps：
First, stable nano-carbon material dispersion liquid is prepared：By nano-carbon material ultrasonic disperse in solvent, nano carbon material is obtained
The concentration of material is 0.01mg/mL~40mg/mL stable nano-carbon material dispersion liquid；
2nd, electrophoretic deposition：Using the stable nano-carbon material dispersion liquid that step 1 obtains as electrophoresis liquid, then by electrophoresis just
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 electricity
Swimming the distance between positive pole and electrophoresis negative pole are 0.2cm~20cm, and secondary battery membrane is placed in into electrophoresis positive pole and electrophoresis negative pole
Between, and make barrier film face parallel with the pole-face of electrophoresis positive pole, the electrophoresis under conditions of electrophoretic deposition voltage is 1.0V~1000.0V
0.1min~600min is deposited, completes electrophoretic deposition, is dried after taking-up, obtaining one side deposition has the barrier film of nano-carbon material；Institute
Just extremely inert metal piece or graphite flake, described electrophoresis negative pole are inert metal piece or graphite flake to the electrophoresis stated；
3rd, suppress：By one side that step 2 obtains deposition have the barrier film of nano-carbon material compacting pressure be 0.1MPa~
Suppressed under conditions of 500MPa, complete to be modified secondary battery membrane surface with nano-carbon material, obtain nano-carbon material
Surface modified diaphragm.
Embodiment two：Present embodiment is unlike embodiment one：Nanometer described in step 1
Carbon material is graphene, CNT, activated carbon, nano-pore carbon, gas-phase grown nanometer carbon fibre, conductive black, nano-graphite
With a kind of or wherein several mixture in carbon molecular sieve.Other steps and parameter are identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one or two：Described in step 1
Solvent is ethanol, isopropanol, acetone, N- methyl pyrrole networks alkanone, dioctyl phthalate, tetrahydrofuran and dimethylformamide
In a kind of or wherein several mixture.Other steps and parameter are identical with embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Institute in step 2
The inert metal piece stated is Ti pieces, Pd pieces, Au pieces, Pt pieces, Pb pieces or stainless steel substrates.Other steps and parameter and specific embodiment party
One of formula one to three is identical.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Institute in step 2
The secondary battery membrane stated is lithium ion battery separator, sodium-ion battery barrier film, Magnesium ion battery barrier film, aluminium ion battery diaphragm
Or lithium-sulfur cell barrier film.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six：Unlike one of present embodiment and embodiment one to five：It is electric in step 2
During swimming deposition nano-carbon material, when the Zeta potential for stablizing nano-carbon material in nano-carbon material dispersion liquid is positive, two
The distance between pole-face of primary cell barrier film and electrophoresis negative pole is more than zero.Other steps and parameter and embodiment one to five
One of it is identical.
Embodiment seven：Unlike one of present embodiment and embodiment one to five：It is electric in step 2
During swimming deposition nano-carbon material, when the Zeta potential for stablizing nano-carbon material in nano-carbon material dispersion liquid is negative value, two
The distance between pole-face of primary cell barrier film and electrophoresis positive pole is more than zero.Other steps and parameter and embodiment one to five
One of it is identical.
Beneficial effects of the present invention are verified using tests below
Experiment one, one kind of (Fig. 1) this experiment realize secondary battery membrane surface nano-carbon material by electrophoretic deposition
Modified method is carried out according to the following steps：
First, prepare and stablize aminated redox graphene-alcohol dispersion liquid：By aminated redox graphene ultrasound
It is scattered in ethanol, ultrasonic power 100W, ultrasonic time 30min, the concentration for obtaining aminated redox graphene is
1mg/mL's stablizes aminated redox graphene-alcohol dispersion liquid；
2nd, electrophoretic deposition：Stablize aminated redox graphene-alcohol dispersion liquid as electrophoresis using what step 1 obtained
Liquid, then electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensure that the pole-face of the pole-face and electrophoresis negative pole of electrophoresis positive pole is put down
Row is staggered relatively, and the distance between electrophoresis positive pole and electrophoresis negative pole be 2cm, by lithium ion battery separator be placed in electrophoresis positive pole with
Electrophoresis negative pole middle, and make barrier film face parallel with the pole-face of electrophoresis positive pole, the electricity under conditions of electrophoretic deposition voltage is 20.0V
Swimming deposition 10min, completes electrophoretic deposition, is dried after taking-up, and obtaining one side deposition has the barrier film of aminated redox graphene；
Just extremely Ti pieces, described electrophoresis negative pole are Ti pieces to described electrophoresis；
3rd, suppress：The one side deposition that step 2 obtains there is into the barrier film of aminated redox graphene in compacting pressure
Suppressed under conditions of 120MPa, complete to be modified lithium ion battery separator surface with aminated redox graphene, obtain
To aminated redox graphene surface modified diaphragm.
This test procedure one prepare stablize before aminated redox graphene-alcohol dispersion liquid to it is described it is aminated also
Prepared by former graphene oxide, preparation process is：
1. graphene oxide prepared by 0.15g Hummers methods ultrasonic disperse, ultrasonic power in 150mL deionized waters
For 427W, ultrasonic time 1h, graphene oxide dispersion A is obtained；
2. 1.35g p-phenylenediamine is dissolved in 150mL dimethylformamides and obtains solution B, 1. oxygen that step is obtained
After graphite alkene dispersion liquid A and solution B mix, back flow reaction 24h at being 90 DEG C in temperature, then with acetone eccentric cleaning three
It is secondary, then take out and washed once with acetone filtering, obtain completing pretreatment, obtain aminated redox graphene.
Aminated go back is deposited on its unit area barrier film of the aminated redox graphene surface modified diaphragm of this experiment
The amount of former graphene oxide is 0.017mg/cm2。
This experiment is by the way of continuous electrophoresis deposition.Continuous electrophoresis precipitation equipment schematic diagram used is as shown in figure 1, the dress
Put and mainly formed by unreeling device, stepper motor driven coiler, electrolytic cell, iontophoretic electrode.Carrying out first will be into before continuous electrophoresis
The barrier film of volume, which is placed in, to be unreeled on device, and barrier film initiating terminal is fixed on coiler by the direction advanced according to barrier film.During continuous electrophoresis,
Connect constant voltage source and apply voltage to iontophoretic electrode；Stepper motor drives coiler upper diaphragm to rotate, and under a stretching force, and drives
Unreel device synergic rotation.The present apparatus integrates electrophoretic deposition and unwinding winding, is adapted to the continuous nano-carbon material for preparing overlength
Modified diaphragm.
Experiment two, one kind of (Fig. 1) this experiment realize secondary battery membrane surface nano-carbon material by electrophoretic deposition
Modified method is carried out according to the following steps：
First, stable intercalated graphite alkene-alcohol dispersion liquid is prepared：By intercalated graphite alkene ultrasonic disperse in ethanol, ultrasonic work(
Rate is 200W, ultrasonic time 60min, and the concentration for obtaining intercalated graphite alkene is 0.2mg/mL stable intercalated graphite alkene-ethanol
Dispersion liquid；
2nd, electrophoretic deposition：Using stable intercalated graphite alkene-alcohol dispersion liquid that step 1 obtains as electrophoresis liquid, then will
Electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, are ensured that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole and are put relatively
Put, and the distance between electrophoresis positive pole and electrophoresis negative pole are 2cm, and lithium-sulfur cell barrier film is being placed in into electrophoresis positive pole and electrophoresis negative pole just
Centre, and make barrier film face parallel with the pole-face of electrophoresis positive pole, the electrophoretic deposition under conditions of electrophoretic deposition voltage is 200.0V
20min, electrophoretic deposition is completed, dried after taking-up, obtaining one side deposition has the barrier film of intercalated graphite alkene；Described electrophoresis is just extremely
Ti pieces, described electrophoresis negative pole are Ti pieces；
3rd, suppress：The one side deposition that step 2 obtains is had to bar of the barrier film in compacting pressure 120MPa of intercalated graphite alkene
Suppressed under part, complete to lithium-sulfur cell membrane surface intercalated graphite alkene be modified, obtain the surface modification of intercalated graphite alkene every
Film.
This test procedure one is located in advance before preparing stable intercalated graphite alkene-alcohol dispersion liquid to described intercalated graphite alkene
Reason, described preprocessing process are：
1. 0.1g " intercalation-expansion-stripping method " the commercialization intercalated graphite alkene prepared is added to dissolved with the wooden of 1g
In the 500mL of the plain sodium sulfonate aqueous solution, ultrasonic disperse is carried out, ultrasonic power 300W, ultrasonic time 1h, obtains intercalation stone
The aqueous dispersions A of black alkene；
2. the aqueous dispersions A vacuum filtrations of 1. intercalated graphite alkene that step is obtained, are carried out clearly with deionized water during suction filtration
Wash, add deionized water to be cleaned again after draining, clean 3 times, then add deionized water and the mixture of ethanol is filtered,
Pretreatment is completed, obtains the intercalated graphite alkene powder of ethanol wet.
The amount that intercalated graphite alkene is deposited on its unit area barrier film of the intercalated graphite alkene surface modified diaphragm of this experiment is 0.1
mg/cm2。
This experiment with one identical continuous electrophoresis of experiment by the way of depositing.
Experiment three, one kind of (Fig. 2) this experiment realize secondary battery membrane surface nano-carbon material by electrophoretic deposition
Modified method is carried out according to the following steps：
First, graphene oxide-isopropanol dispersion liquid is prepared：By graphene oxide ultrasonic disperse in isopropanol, ultrasonic work(
Rate is 400W, ultrasonic time 60min, and the concentration for obtaining graphene oxide is 10mg/mL stable graphene oxide-isopropanol
Dispersion liquid；
2nd, electrophoretic deposition：Using stable graphene oxide-isopropanol dispersion liquid that step 1 obtains as electrophoresis liquid, then
Electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensures that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole and puts relatively
Put, and the distance between electrophoresis positive pole and electrophoresis negative pole are 15cm, and lithium-sulfur cell barrier film is placed in into electrophoresis positive pole and electrophoresis negative pole
Between, keep contacting with electrophoresis positive pole, and make barrier film face parallel with the pole-face of electrophoresis positive pole, it is in electrophoretic deposition voltage
Electrophoretic deposition 2min under conditions of 800.0V, electrophoretic deposition is completed, dried after taking-up, obtaining one side deposition has graphene oxide
Barrier film；Just extremely Pt pieces, described electrophoresis negative pole are Pt pieces to described electrophoresis；
3rd, suppress：The one side deposition that step 2 obtains is had to condition of the barrier film in compacting pressure 50MPa of graphene oxide
Under suppressed, complete to be modified lithium-sulfur cell membrane surface with graphene oxide, obtain surface of graphene oxide modified diaphragm.
The described graphene oxide of this experiment is graphene oxide prepared by Hummers methods.
The amount of deposited oxide graphene is 0.6 on its unit area barrier film of the surface of graphene oxide modified diaphragm of this experiment
mg/cm2。
This experiment by the way of discontinuous electrophoretic deposition, discontinuous electrophoretic deposition set schematic diagram used as shown in Fig. 2
Between barrier film is placed in into positive and negative iontophoretic electrode, nano-carbon material is deposited on barrier film in the presence of electric field force.
Experiment four, one kind of (Fig. 2) this experiment realize secondary battery membrane surface nano-carbon material by electrophoretic deposition
Modified method is carried out according to the following steps：
First, stable carbon nano-tube-tetrahydrofuran dispersion liquid is prepared：By CNT ultrasonic disperse in tetrahydrofuran, surpass
Acoustical power is 200W, ultrasonic time 60min, and the concentration for obtaining CNT is 0.02mg/mL stable carbon nano-tube-four
Hydrogen furans dispersion liquid；
2nd, electrophoretic deposition：The stable carbon nano-tube that step 1 is obtained-tetrahydrofuran dispersion liquid is as electrophoresis liquid, then
Electrophoresis positive pole and electrophoresis negative pole are placed in electrophoresis liquid, ensures that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole and puts relatively
Put, and the distance between electrophoresis positive pole and electrophoresis negative pole are 0.5cm, and sodium-ion battery barrier film is placed in apart from electrophoresis positive pole
At 0.2cm, and make barrier film face parallel with the pole-face of electrophoresis positive pole, the electrophoretic deposition under conditions of electrophoretic deposition voltage is 15.0V
300min, electrophoretic deposition is completed, dried after taking-up, obtaining one side deposition has the barrier film of CNT；Described electrophoresis is just extremely
Graphite flake, described electrophoresis negative pole are graphite flake；
3rd, suppress：The one side deposition that step 2 obtains there is into the barrier film of CNT under conditions of pressure 20MPa is suppressed
Suppressed, complete, to sodium-ion battery membrane surface carbon nano-tube modification, to obtain surface modification of carbon nanotube barrier film.
This test procedure one pre-processes before preparing stable carbon nano-tube-acetone dispersion liquor to described CNT,
Described preprocessing process is：
1. 0.01g CNTs are added in the 500mL aqueous solution of the sodium lignin sulfonate dissolved with 1g, ultrasound point
Dissipate, ultrasonic power 300W, ultrasonic time 1h, obtain the aqueous dispersions of CNT；
2. the aqueous dispersions vacuum filtration of 1. CNT that step is obtained, is cleaned with deionized water during suction filtration,
Add deionized water to be cleaned again after draining, clean 3 times, then add deionized water and the mixture of acetone is filtered, it is complete
Into pretreatment, the CNT of acetone wetting is obtained.
The amount of deposition of carbon nanotubes is 0.07 on its unit area barrier film of the surface modification of carbon nanotube barrier film of this experiment
mg/cm2。
This experiment using with experiment the discontinuous electrophoretic deposition of three identicals by the way of.
(1) the aminated redox graphene surface modification lithium-ion battery barrier film that experiment one obtains is carried out microcosmic
Scanning electron microscopic observation and macroscopic view visually observe, and obtain aminated redox graphene surface modification lithium-ion as shown in Figure 3
Macroscopical digital photograph shown in the stereoscan photograph and Fig. 4 of battery diaphragm, it can be seen that membrane surface deposition has graphene layer.
Realizing membrane surface deposition 0.017mg/cm2While areal density thin graphene layer, graphene layer macroscopic view is evenly distributed, and does not have
The problem of occurring macroscopical localized clusters and the exposure of white barrier film bottom.
(2) it is micro- that the microcosmic ESEM of lithium-sulfur cell barrier film progress is modified to the intercalated graphite alkene surface that experiment two obtains
Observation and naked eyes macroscopic observation, obtain the ESEM photograph that intercalated graphite alkene surface as shown in Figure 5 is modified lithium-sulfur cell barrier film
Macroscopical digital photograph shown in piece and Fig. 6, it can be seen that membrane surface deposition has graphene layer, do not occur macroscopical localized clusters and
The problem of white barrier film bottom exposure.
Claims (7)
- A kind of 1. method that the nano-carbon material modification of secondary battery membrane surface is realized by electrophoretic deposition, it is characterised in that should Method is carried out according to the following steps：First, stable nano-carbon material dispersion liquid is prepared：By nano-carbon material ultrasonic disperse in solvent, nano-carbon material is obtained Concentration is 0.01mg/mL~40mg/mL stable nano-carbon material dispersion liquid；2nd, electrophoretic deposition：Using the stable nano-carbon material dispersion liquid that step 1 obtains as electrophoresis liquid, then by electrophoresis positive pole and Electrophoresis negative pole is placed in electrophoresis liquid, ensures that the pole-face of electrophoresis positive pole is parallel with the pole-face of electrophoresis negative pole staggered relatively, and electrophoresis is just The distance between pole and electrophoresis negative pole are 0.2cm~20cm, and 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, the electrophoretic deposition under conditions of electrophoretic deposition voltage is 1.0V~1000.0V 0.1min~600min, electrophoretic deposition is completed, dried after taking-up, obtaining one side deposition has the barrier film of nano-carbon material；Described Just extremely inert metal piece or graphite flake, described electrophoresis negative pole are inert metal piece or graphite flake to electrophoresis；3rd, suppress：By one side that step 2 obtains deposition have the barrier film of nano-carbon material compacting pressure be 0.1MPa~ Suppressed under conditions of 500MPa, complete to be modified secondary battery membrane surface with nano-carbon material, obtain nano-carbon material Surface modified diaphragm.
- 2. one kind according to claim 1 realizes that secondary battery membrane surface is modified with nano-carbon material by electrophoretic deposition Method, it is characterised in that nano-carbon material described in step 1 is graphene, CNT, activated carbon, nano-pore carbon, gas A kind of or wherein several mixture in phase growing nano carbon fiber, conductive black, nano-graphite or carbon molecular sieve.
- 3. one kind according to claim 1 realizes that secondary battery membrane surface is modified with nano-carbon material by electrophoretic deposition Method, it is characterised in that solvent described in step 1 is ethanol, isopropanol, acetone, 1-METHYLPYRROLIDONE, adjacent benzene two A kind of or wherein several mixture in formic acid dioctyl ester, tetrahydrofuran and dimethylformamide.
- 4. one kind according to claim 1 realizes that secondary battery membrane surface is modified with nano-carbon material by electrophoretic deposition Method, it is characterised in that the inert metal piece described in step 2 is Ti pieces, Pd pieces, Au pieces, Pt pieces, Pb pieces or stainless steel Piece.
- 5. one kind according to claim 1 realizes that secondary battery membrane surface is modified with nano-carbon material by electrophoretic deposition Method, it is characterised in that secondary battery membrane described in step 2 is lithium ion battery separator, sodium-ion battery barrier film, magnesium Ion battery barrier film, aluminium ion battery diaphragm or lithium-sulfur cell barrier film.
- 6. one kind according to claim 1 realizes that secondary battery membrane surface is modified with nano-carbon material by electrophoretic deposition Method, it is characterised in that in step 2 during electrophoretic deposition nano-carbon material, when stablizing nano-sized carbon in nano-carbon material dispersion liquid When the Zeta potential of material is positive, the distance between secondary battery membrane and electrophoresis negative pole are more than zero.
- 7. one kind according to claim 1 realizes that secondary battery membrane surface is modified with nano-carbon material by electrophoretic deposition Method, it is characterised in that in step 2 during electrophoretic deposition nano-carbon material, when stablizing nano-sized carbon in nano-carbon material dispersion liquid When the Zeta potential of material is negative value, the distance between secondary battery membrane and electrophoresis positive pole are more than zero.
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| WO2018045226A1 (en) * | 2016-08-31 | 2018-03-08 | William Marsh Rice University | Anodes, cathodes, and separators for batteries and methods to make and use same |
| CN107785524B (en) * | 2016-08-31 | 2019-12-03 | 清华大学 | The preparation method of lithium-sulfur cell diaphragm |
| CN107785523B (en) * | 2016-08-31 | 2019-12-03 | 清华大学 | Lithium-sulfur cell diaphragm and lithium-sulfur cell |
| KR102159364B1 (en) * | 2016-11-29 | 2020-09-23 | 주식회사 엘지화학 | A laser-induced graphene layered separator and a Li-S battery comprising the same |
| KR102244909B1 (en) * | 2017-10-26 | 2021-04-26 | 주식회사 엘지화학 | Seperator and lithium sulfur battery comprising the same |
| CN110057897B (en) * | 2018-01-19 | 2020-10-09 | 中国科学院化学研究所 | Carbon fiber electrode modified by electrophoretic deposition carbon nano tube and application thereof in detection of living ascorbic acid |
| US11380939B2 (en) | 2018-05-18 | 2022-07-05 | GM Global Technology Operations LLC | Hybrid lithium ion capacitor battery having a carbon coated separate layer and method of making the same |
| CN112614977B (en) * | 2020-12-17 | 2022-02-18 | 上海交通大学 | Lithium ion battery optimization method based on graphene/artificial graphite composite material |
| CN112705056B (en) * | 2020-12-23 | 2022-07-26 | 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 |
| CN112831819B (en) * | 2021-01-29 | 2022-04-15 | 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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| US7662265B2 (en) * | 2000-10-20 | 2010-02-16 | Massachusetts Institute Of Technology | Electrophoretic assembly of electrochemical devices |
| US6887361B1 (en) * | 2001-03-22 | 2005-05-03 | The Regents Of The University Of California | Method for making thin-film ceramic membrane on non-shrinking continuous or porous substrates by electrophoretic deposition |
| US7252749B2 (en) * | 2001-11-30 | 2007-08-07 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
| FR2982086B1 (en) * | 2011-11-02 | 2013-11-22 | Fabien Gaben | METHOD FOR MANUFACTURING MICRO-BATTERIES IN THIN LITHIUM ION LAYERS, AND MICRO-BATTERIES OBTAINED THEREBY |
| FR2982083B1 (en) * | 2011-11-02 | 2014-06-27 | Fabien Gaben | METHOD FOR PRODUCING SOLID ELECTROLYTE THIN FILMS FOR LITHIUM ION BATTERIES |
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