CN106229464A - A kind of conductive polymer membrane and use the film modified anode pole piece of this conducting polymer - Google Patents
A kind of conductive polymer membrane and use the film modified anode pole piece of this conducting polymer Download PDFInfo
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- CN106229464A CN106229464A CN201610599725.6A CN201610599725A CN106229464A CN 106229464 A CN106229464 A CN 106229464A CN 201610599725 A CN201610599725 A CN 201610599725A CN 106229464 A CN106229464 A CN 106229464A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
The invention discloses a kind of conductive polymer membrane and use the film modified anode pole piece of this conducting polymer, this conductive polymer membrane is to be prepared by the method comprised the following steps: 1) coating initiator in film forming substrate, the film forming substrate being coated with initiator is placed in the hermetic container filling conducting polymer monomer；2) control hermetic container vacuum condition, make conducting polymer monomer evaporate, in-situ polymerization film forming in the film forming substrate be coated with initiator, after be drying to obtain.The conductive polymer membrane of the present invention, uses vacuum evaporation coating membrane process to prepare, therefore in polymerization process, it is not necessary to complicated exacting terms controls, and can form the conductive polymer membrane that thickness is homogeneous；Gained conducting polymer film thickness is uniform, is placed between positive pole and barrier film, the side reaction between suppression electrode material and electrolyte, improves structural stability and the heat stability of positive electrode in battery charge and discharge process, thus improves the chemical property of material.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of conductive polymer membrane, also relate to one
Use the anode pole piece that this conducting polymer is film modified.
Background technology
Specific energy is high, capacity is big, voltage is high, self discharge is little, cyclicity is good, lightweight, volume because having for lithium ion battery
The outstanding advantages such as little, length in service life and become the ideal source of the portable electric appts such as mobile phone, notebook computer.Closely
Nian Lai, in order to protect environment, it is achieved sustainable development, countries in the world competitively Development of EV industry, to finally taking completely
For conventional fuel oil automobile.And restrict ev industry development it is crucial that develop the electrokinetic cell of function admirable.Meet
Electrokinetic cell is in the requirement of the aspects such as energy density, safety, price and life-span, and positive electrode seems particularly urgent and closes
Key.
In recent years, the LiFePO of height ratio capacity4(170mAh/g), ternary material (< 180mAh/g), lithium-rich positive pole material
Material (> 200mAh/g) and new sulfur positive pole (> 1675mAh/g) etc. cause the extensive concern of people it is considered to be have most and send out
The power lithium-ion battery positive electrode of exhibition prospect.LiFePO4Middle source of iron has rich reserves, environmental friendliness, cyclical stability
The plurality of advantages such as excellence；Ternary material, combines LiCoO2、LiNiO2And LiMnO2The advantage of three kinds of materials, has played three's
Synergism, and relative inexpensiveness；Lithium-rich structure positive electrode Li1+xA1-xO2(A is Ti, Cr, Fe, Co, Ni, Mn
Combination in various metals atom) and novel active sulfur positive electrode there is higher theoretical specific capacity, promise to be most and send out
The positive electrode of exhibition high-energy-density (more than 300Wh/kg) lithium ion battery.
Though anode material for lithium-ion batteries has many advantages, but there is also a lot of problem in actual charge and discharge process, to electricity
What the performance in pond made a significant impact has: (1) part positive electrode electric conductivity is poor；(2) some in electrolyte become branch with
Positive electrode generation side reaction, destroys the normal configuration of material, and by-product moving structure, electric conductivity and the lithium ion of electrode
Shifting has a negative impact；(3), in charge and discharge process, the reaction of part positive electrode expands and shrinks, and causes electrode overall structure to break
Bad and electric conductivity deteriorates.
At present, from the point of view of progress, the Main Means overcoming the problem above that positive electrode exists is doping (transition gold
Belong to ion, rare earth element etc.) and cladding (metal-oxide, Graphene, nano-sized carbon etc.).Above method is all to close from battery material
The angle become solves problem, there is the drawbacks such as complex process, cost is high, large-scale production difficulty is big, achievements conversion is difficult, mesh
Before mostly be experimentation use.
Conducting polymer, is that a class has the polymerization of special electricity, optics and electrochemical properties because of conjugated pi electron system
Thing material, has more research in recent years in terms of the high rate performance improving low conductivity material and cyclical stability, is to improve
Positive electrode chemical property and a kind of feasible method of performance of lithium ion battery.
In prior art, conducting polymer is used to be modified positive electrode generally using solution situ aggregation method, should
Polymer monomer, initiator and the material being wrapped by mainly are disperseed in a solvent by method, carry out in-situ polymerization thus obtain
The material of conducting polymer cladding.Solution situ aggregation method is primarily present following shortcoming: 1. during in-situ polymerization, polymer list
Body, initiator and the material being wrapped by are collectively reside in solution, owing to the concentration of monomer is big, cause the speed of polymerization to be exceedingly fast,
Easily cause polymerization uneven, cause ultimately forming material surface conducting polymer clad thickness and differ, affect the electrification of material
Learn performance；In order to overcome these problems, during cladding, need exacting terms, as strict control system temperature less than 0 DEG C, strongly
Stirrings etc., reaction condition is difficult to control to, and is difficult to realize industrialized production；The most common solution in-situ polymerization, is to lithium-ion electric
After the positive electrode cladding of pond, then make slurry and coat on a current collector, after coated with conductive polymer, positive electrode size
And character can occur a certain degree of change, when application and actual production, original coating processes must adjust, as closed slurry raw material
Proportioning, dispersion condition, and original technique such as coated conditions, drying condition and film-making process is no longer desirable for the positive pole after cladding
Material；3. solution in-situ polymerization cladding is to be coated with positive pole material powder granule, and the granule being wrapped by is in follow-up slurrying
In coating procedure, easily cause the destruction of clad；Conducting polymer is relative to carbonaceous conductive material simultaneously, and poorly conductive is the most right
After particles coat, the conductive contact between granule is deteriorated, and the resistance inevitably resulting in molding pole piece becomes big.The most above-mentioned many
The existence of problem, causes existing conducting polymer modified positive electrode and positive plate preparation section complexity, chemical property not
Good, limit the development of conducting polymer modified positive electrode.
Summary of the invention
It is an object of the invention to provide a kind of conductive polymer membrane, solve to use conducting polymer modified anode pole piece system
The problem that standby complex procedures, chemical property are the best.
Second object of the present invention is to provide a kind of anode pole piece using above-mentioned conducting polymer film modified.
In order to realize object above, the technical solution adopted in the present invention is:
A kind of conductive polymer membrane, is to be prepared by the method comprised the following steps:
1) in film forming substrate, coat initiator, be coated with the film forming substrate of initiator and be placed in and fill conducting polymer list
In the hermetic container of body；
2) control hermetic container vacuum condition, make conducting polymer monomer evaporate, be coated with the film forming substrate of initiator
Upper in-situ polymerization film forming, is dried afterwards, to obtain final product.
Step 1) in, described conducting polymer monomer is pyrroles, thiophene or aniline.Described conducting polymer monomer is at room temperature
It it is liquid under normal pressure.
Conducting polymer in described conductive polymer membrane be polypyrrole (PPy), polythiophene (PTh), polyaniline (PAN) and
One in its derivant poly-N-hydroxyethylaniline.
Step 1) in, described initiator is oxidizing agent solution, in described oxidizing agent solution containing concentration be 0.1～
The oxidant of 1.0mol/L.
Described oxidant is (NH4)2S2O8、(NH4)2Ce(NO3)6、K2Cr2O7、Ce(SO4)2.2(NH4)2SO4、FeCl3、
KMnO4、H2O2In any one or combination.
Possibly together with the Bronsted acid that concentration is 0.07～0.3mol/L in described oxidizing agent solution.Bronsted acid is provided that reactant
PH value needed for system and the H required for proton exchange+。
Described Bronsted acid includes inorganic proton acid and organic proton acid.Described inorganic proton acid includes H2SO4、HCl、HNO3、
H3PO4、HCO3-、NH4+.Organic proton acid includes CH3COOH, sulfonic group compound, benzenephosphonic acid, benzoic acid and derivant bigcatkin willow thereof
Acid.
Described Bronsted acid is H2SO4、HCl、HNO3、H3PO4、HCO3-、NH4+、CH3COOH, sulfonic group compound, benzenephosphonic acid,
Any one in benzoic acid and derivant salicylic acid thereof.
Described sulfonic group compound is camphorsulfonic acid (CSA) or DBSA (DBSA).
Solvent used by described oxidizing agent solution be water, ethanol, acetonitrile, oxolane, chloroform, N-Methyl pyrrolidone,
Any one or the mixture of two kinds in metacresol.
When the mixture that described solvent is two kinds of organic solvents, the volume ratio of two kinds of organic solvents is 1～3:1～3.
Step 2) in, described vacuum condition is: vacuum is 0.001～0.09Mpa.The size of the vacuum of hermetic container
The amount of noble gas can be passed through by control to control.Described noble gas is nitrogen or argon.
Step 2) in, the temperature of described in-situ polymerization is 20～60 DEG C.Described temperature is provided by water bath device；Described water-bath
Device is constant temperature water bath.Depending on temperature can be according to the volatilization temperature of different conducting polymer monomers and polymerization temperature.
Step 2) in, the time of described in-situ polymerization is 0.1～70h.Preferably, the time of in-situ polymerization is 1～24h.
It is further preferred that the time of in-situ polymerization is 10～18h.
A kind of anode pole piece, is just formed including by collector and the positive electrode material layer being attached to collector one or both sides
Pole plate, described positive plate is also attached with outside positive electrode material layer above-mentioned conductive polymer membrane.
Above-mentioned anode pole piece, is to be prepared by the method comprised the following steps:
A) take positive plate, at the positive electrode material layer surface-coated initiator of positive plate, be coated with the positive plate of initiator
It is placed in the hermetic container filling conducting polymer monomer；
B) control hermetic container vacuum condition, make conducting polymer monomer evaporate, on the positive plate being coated with initiator
In-situ polymerization film forming, is dried afterwards, to obtain final product.
Described positive plate is prepared by following methods: take positive active material, conductive agent and binding agent mix homogeneously, system
Form slurry, is evenly coated in gained slurry on collector, is drying to obtain.
Described positive active material is polyanion olivine-type LiFePO4、LiFePO4/ C positive electrode material be (carbon cladding
LiFePO4Positive electrode), LiMn2O4Or S/C composite positive pole (sulfur carbon composite anode material).
Described collector is aluminium foil.
In step b), described in be dried before also the positive plate after in-situ polymerization film forming is washed；Described washing
It is positive plate to be immersed in the water or organic solvent 1～60s is carried out, or any with in water, ethanol, acetone, chloroform
A kind of flushing.The purpose of washing is to be removed by the foreign metal ion introduced on conductive polymer membrane, and makes positive plate reply acid
Alkali is neutral, plays activation and protects the effect of final material.
In step b), described being dried is to be vacuum dried 8～36h under the conditions of 60 DEG C.
A kind of lithium ion battery, including positive pole, negative pole and barrier film, described positive pole uses above-mentioned anode pole piece.
The conductive polymer membrane of the present invention, mode of appearance is granule, and inside is web frame.The particle diameter of described granule be 1～
200nm.Preferably, the particle diameter of described granule is 20～100nm.The thickness of described conductive polymer membrane is 10～500nm.
Conducting polymer in described conductive polymer membrane is presented in single or multiple lift conductive carbon structure.This conduction
Polymeric film is coated on the surface of positive electrode material layer, between positive electrode active materials and electrolyte, had both served cushion and has made
With serving again the effect of conduction, increase electron transport ability and promote the diffusion of lithium ion.
The conductive polymer membrane of the present invention, is coating initiator in film forming substrate, uses vacuum evaporation coating membrane process, make
Conducting polymer monomer evaporates, and in the film forming substrate be coated with initiator, in-situ polymerization prepares, this vacuum vapor plating work
Skill is separate due to monomer and initiator, and the monomer vapor contact suprabasil initiator of film forming just causes polymerization, is therefore polymerized
Speed is controlled by monomer vapor diffusion, and monomer vapor is low relative to strength of fluid simultaneously, with contacting of film forming substrate and initiator
Evenly, therefore in polymerization process, it is not necessary to complicated exacting terms controls, and can form the conductive polymer membrane that thickness is homogeneous；
Gained conducting polymer film thickness is uniform, is placed between positive pole and barrier film, and the pair between suppression electrode material and electrolyte is anti-
Should, improve structural stability and the heat stability of positive electrode in battery charge and discharge process, thus improve the electrochemistry of material
Energy.
The anode pole piece of the present invention, positive plate is also attached with outside positive electrode material layer above-mentioned conductive polymer membrane,
Conducting polymer film thickness is uniform, forms cladding on positive electrode material layer surface, and during work, this conductive polymer membrane is positioned at positive pole material
Between the bed of material and barrier film, the side reaction between electrode material and electrolyte can be suppressed, improve positive pole material in battery charge and discharge process
The structural stability of material and heat stability, thus improve the chemical property of material.
The preparation method of the anode pole piece of the present invention, is the positive electrode material layer surface-coated initiator at positive plate, uses
Vacuum evaporation coating membrane process, makes conducting polymer monomer evaporate, on the positive electrode material layer surface of the positive plate being coated with initiator
In-situ polymerization becomes conductive polymer membrane, compared with existing solution in-situ polymerization, has a following clear superiority:
1. this preparation method due to monomer and initiator be separate, the monomer vapor contact suprabasil initiator of film forming is
Causing polymerization, therefore polymerization speed is controlled by monomer vapor diffusion, and monomer vapor is low relative to strength of fluid simultaneously, with film forming base
The end, contacts evenly, therefore in polymerization process with initiator, it is not necessary to complicated exacting terms controls, and can form thickness homogeneous
Conductive polymer membrane；
2. this preparation method is coating initiator on the positive plate of molding, contacts initiation polymerization with monomer vapor, can be straight
Scooping out for former positive plate production line, the coating of original positive plate forms the preparation work of the most former positive plate of technique of positive electrode material layer
Skill is without adjusting；
3. this preparation method is to form one layer of uniform conducting polymer on the positive electrode material layer surface of the positive plate of molding
Film, is coated with the positive electrode material layer on positive plate, in stabilized electrodes structure, while improving chemical property, inconspicuous
Increase the impedance of positive plate.
4. this preparation method improves the positive electrode conductance as the important bottleneck existence of suppression lithium ion battery development
The problem that rate is low, specific capacity is low, cycle performance is poor with high rate performance, coulombic efficiency is low, simple for process, it is not necessary to template, behaviour
Facilitating, condition is easily controllable, and degree of being practical is high, is suitable for large-scale industrial production.
The conductive polymer membrane of the present invention in the preparation, the volatility of liquid polymer monomer and the temperature of system and pressure
Closely related, control the thermometer vacuum of system, the vapour pressure of liquid polymer monomer can be regulated.The steaming of polymer monomer
Gas contacts initiation in-situ polymerization with the molding positive plate of the most coated initiator, and the conductive polymer membrane of formation is formed positive pole
The clad of material layer.By controlling polymerization time, thermometer vacuum, it is achieved thick to final conductive polymer membrane (clad)
The regulation and control of degree.Vacuum and thermal source that the present invention provides make the conducting polymer liquid monomer of container bottom evaporate, and are formed certain
The monomer vapor of concentration, initiator on this steam and positive plate (oxidant, or the mixing of oxidant and Bronsted acid) contacts
Raw reaction, in-situ polymerization thing becomes conductive polymer membrane.
Accompanying drawing explanation
Fig. 1 is the structural representation of the vacuum evaporation film coating device of embodiment 1；
Fig. 2 is that embodiment 1 gained conductive polymer membrane one side modifies pure LiFePO4Positive plate and the pure LiFePO of unmodified4Just
The discharge and recharge comparison diagram of the button cell of pole plate；
Fig. 3 is that embodiment 1 gained conductive polymer membrane one side modifies pure LiFePO4Positive plate and the pure LiFePO of unmodified4Just
The cycle performance comparison diagram of the button cell of pole plate；
Fig. 4 is the embodiment 2 gained pure LiFePO of conductive polymer membrane double measure4Positive plate and the pure LiFePO of unmodified4Just
The discharge and recharge comparison diagram of pole plate；
Fig. 5 is the embodiment 2 gained pure LiFePO of conductive polymer membrane double measure4Positive plate and the pure LiFePO of unmodified4Just
The cycle performance comparison diagram of pole plate；
Fig. 6 is the charge and discharge that embodiment 3 gained conductive polymer membrane one side modifies S/C positive plate and unmodified S/C positive plate
Electricity comparison diagram；
Fig. 7 is the charge and discharge that embodiment 3 gained conductive polymer membrane one side modifies S/C positive plate and unmodified S/C positive plate
Electricity comparison diagram.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
Embodiment 1
The anode pole piece of the present embodiment, is just formed including by collector and the positive electrode material layer being attached to collector side
Pole plate, described positive plate is also attached with outside positive electrode material layer conductive polymer membrane.
The preparation method of the anode pole piece of the present embodiment, comprises the following steps:
A) positive plate is prepared: with the pure LiFePO of olivine-type4It is conductive agent, polytetrafluoro for positive active material, acetylene black
Ethylene is binding agent, mixs homogeneously with the ratio that mass ratio is 80:10:10 of binding agent according to positive active material, conductive agent,
Add appropriate NMP and make slurry as solvent, this slurry is evenly coated in aluminium foil (collector thickness is a 0.02mm) side surface
On, coating thickness is 0.02mm, is vacuum dried 12h under the conditions of 120 DEG C, aluminium foil is formed positive electrode material layer, obtains positive plate；
B) the positive electrode material layer surface in step a) gained positive plate uniformly coats one layer of initiator, and described initiator is for containing
(the NH having concentration to be 0.4mol/L4)2S2O8(NH with 0.1mol/L4)2Ce(NO3)6And the HCl's that concentration is 0.5mol/L is molten
The liquid mixed solvent that volume ratio is 9:1 of water and ethanol (solvent be)；
The vacuum evaporation film coating device of the present embodiment is as it is shown in figure 1, hermetic container 2 is horizontally placed in constant temperature water bath 1, permanent
Warm water bath 1 is placed with thermometer 9, is used for reading bath temperature；Connect on described hermetic container 2 and have for being passed through indifferent gas
The vent line 7 of body and the exhaust pipe 8 for evacuation, described vent line is provided with breather valve 10, exhaust pipe sets
There is extraction valve 11, for controlling the vacuum of hermetic container；Hermetic container 2 inner bottom part is placed with the conducting polymer monomer 3 of excess
(the present embodiment is aniline monomer), is also placed with the support 6 for placing positive plate in hermetic container 2；During use, it is coated with drawing
The positive plate 4 sending out agent is placed on the support 6 in hermetic container 2, and positive plate 4 does not contacts with the conducting polymer monomer 3 of liquid；
C) controlling constant temperature water bath temperature is 60 DEG C, and in control hermetic container, vacuum is 0.08MPa so that hermetic container
The aniline monomer evaporation of bottom, forms certain density aniline steam, this steam and the oxidation on positive plate in hermetic container
Agent (NH4)2S2O8(NH4)2Ce(NO3)6And Bronsted acid HCl contact, there is proton exchange and home position polymerization reaction, just after 24h
The positive electrode material layer surface of pole plate forms the Polyaniline Film 5 (as shown in Figure 1) that thickness is 100nm, takes out this positive plate, uses
After water rinses surface, under the conditions of 80 DEG C, it is vacuum dried 24h, obtains conductive polymer membrane one side and modify LiFePO4Positive plate.
Above-mentioned gained conductive polymer membrane one side is modified LiFePO4Positive plate is cut into the disk of a diameter of 1.4cm, pressure
Sheet, as positive pole；With metal lithium sheet as negative pole, with Celgard 2400 as barrier film, add appropriate electrolyte, group in glove box
Dress up battery.By this battery LAND battery test system carry out discharge and recharge and cycle performance test, result as shown in Figure 2,3,
Discharge and recharge blanking voltage is 2.7～4.2V, and gained battery specific discharge capacity compared with unmodified material is greatly improved, discharge and recharge
Platform voltage is brought up to 3.4V and steadily by 3.3V, and cycle performance is obviously improved.
Embodiment 2
The anode pole piece of the present embodiment, is just formed including by collector and the positive electrode material layer being attached to collector both sides
Pole plate, described positive plate is also attached with outside positive electrode material layer conductive polymer membrane.
The preparation method of the anode pole piece of the present embodiment, comprises the following steps:
A) positive plate is prepared: with the pure LiFePO of olivine-type4It is conductive agent, poly-inclined fluorine for positive active material, acetylene black
Ethylene is binding agent, mixs homogeneously with the ratio that mass ratio is 89:7:4 of binding agent according to positive active material, conductive agent, with
NMP is that slurry made by solvent, uses coating machine that this slurry is evenly coated in aluminium foil (collector thickness is 0.02mm) tow sides
On, coating thickness is 0.02mm, is vacuum dried 12h under the conditions of 120 DEG C, and aluminium foil tow sides are respectively formed on positive electrode material layer,
Obtain positive plate；
B) divide bar in step a) gained positive plate, and uniformly coat initiator, described initiator on positive electrode material layer surface
For being (the NH of 0.6mol/L containing concentration4)2S2O8(solvent is the body of water and ethanol with the solution of the HCl that concentration is 0.5mol/L
Long-pending than the mixed solvent for 7:3)；
The vacuum evaporation film coating device of the present embodiment is placed in airtight appearance with embodiment 1, the positive plate being coated with initiator
In device, described hermetic container is horizontally placed in constant temperature water bath, and hermetic container inner bottom part is placed with the aniline monomer of excess；
C) controlling constant temperature water bath temperature is 50 DEG C, and in control hermetic container, vacuum is 0.06MPa so that hermetic container
The aniline monomer evaporation of bottom, forms certain density aniline steam, this steam and the oxidation on positive plate in hermetic container
Agent (NH4)2S2O8Contact with Bronsted acid HCl, proton exchange and home position polymerization reaction occur, at the positive electrode of positive plate after 48h
It is the Polyaniline Film of 150nm that layer surface forms thickness, takes out this positive plate, quickly immerses in alcohol water mixed solvent, afterwards
Quickly remove, the impurity that such three times wash away excess surface, under the conditions of 80 DEG C, be vacuum dried 24h, obtain conductive polymer membrane
Double measure LiFePO4Positive plate.
By above-mentioned gained conductive polymer membrane double measure LiFePO4Positive plate coupling graphite cathode, with Celgard
2400 is barrier film, is assembled into cylindrical battery.This battery is carried out partial volume, test at battery test system, as shown in Figure 4,5, fills
Discharge cut-off voltage is 2.0～3.65V, and gained battery specific discharge capacity compared with unmodified material is greatly improved, discharge and recharge
Platform voltage improves and steady.
Embodiment 3
The anode pole piece of the present embodiment, is just formed including by collector and the positive electrode material layer being attached to collector side
Pole plate, described positive plate is also attached with outside positive electrode material layer conductive polymer membrane.
The preparation method of the anode pole piece of the present embodiment, comprises the following steps:
A) prepare positive plate: with S/C composite positive pole as positive active material, politef as water-based binder,
Superconduction carbon black is conductive agent, mixes all with the ratio that mass ratio is 7:3:1 of conductive agent according to positive active material, binding agent
Even, add appropriate NMP and make slurry as solvent, this slurry is evenly coated on aluminium foil, be vacuum dried under the conditions of 60 DEG C
12h, aluminium foil is formed positive electrode material layer, obtains positive plate；
B) in step 1) the positive electrode material layer surface of gained positive plate uniformly coats one layer of initiator, and described initiator is for containing
The H having concentration to be 0.35mol/L2O2It is the CH of 0.3mol/L with concentration3The aqueous solution of COOH；
The vacuum evaporation film coating device of the present embodiment is placed in airtight appearance with embodiment 1, the positive plate being coated with initiator
In device, described hermetic container is horizontally placed in constant temperature water bath, and hermetic container inner bottom part is placed with the pyrrole monomer of excess；
C) controlling constant temperature water bath temperature is 20 DEG C, and in control hermetic container, vacuum is 0.09MPa so that hermetic container
The pyrrole monomer evaporation of bottom, forms certain density pyrroles's steam, this steam and the oxidation on positive plate in hermetic container
Agent H2O2Contact with Bronsted acid acetic acid, proton exchange and home position polymerization reaction occur, at the positive electrode material layer table of positive plate after 70h
Face forms the electric polypyrrole film that thickness is 20nm, takes out this positive plate, and after rinsing surface with water, under the conditions of 60 DEG C, vacuum is done
Dry 36h, obtains the S/C positive plate that conducting polymer is film modified.
By S/C positive plate cutting film modified for above-mentioned gained conducting polymer, tabletting, as working electrode；With lithium metal
For negative pole, add appropriate electrolyte, be assembled into lithium-sulfur rechargeable battery.This battery is carried out discharge and recharge at LAND battery test system
Testing with cycle performance, as shown in Figure 6,7, discharge and recharge blanking voltage is 1～3V (vs.Li/Li to result+), gained battery with not
Decorative material is compared and is had extended cycle life and have preferable cyclical stability.
Claims (9)
1. a conductive polymer membrane, it is characterised in that: be to be prepared by the method comprised the following steps:
1) in film forming substrate, coat initiator, be coated with the film forming substrate of initiator and be placed in and fill conducting polymer monomer
In hermetic container；
2) control hermetic container vacuum condition, make conducting polymer monomer evaporate, former in the film forming substrate be coated with initiator
Position polymerization film formation, is dried afterwards, to obtain final product.
Conductive polymer membrane the most according to claim 1, it is characterised in that: step 1) in, described conducting polymer monomer
For pyrroles, thiophene or aniline.
Conductive polymer membrane the most according to claim 1 and 2, it is characterised in that: step 1) in, described initiator is oxidation
Agent solution, containing the oxidant that concentration is 0.1～1.0mol/L in described oxidizing agent solution.
Conductive polymer membrane the most according to claim 3, it is characterised in that: described oxidant is (NH4)2S2O8、(NH4)2Ce(NO3)6、K2Cr2O7、Ce(SO4)2·2(NH4)2SO4、FeCl3、H2O2In any one or combination.
Conductive polymer membrane the most according to claim 3, it is characterised in that: described oxidizing agent solution possibly together with concentration is
The Bronsted acid of 0.07～0.3mol/L.
Conductive polymer membrane the most according to claim 5, it is characterised in that: described Bronsted acid is H2SO4、HCl、HNO3、
H3PO4、HCO3-、NH4+、CH3Any one in COOH, sulfonic group compound, benzenephosphonic acid, benzoic acid and derivant salicylic acid thereof
Kind.
Conductive polymer membrane the most according to claim 1, it is characterised in that: step 2) in, described vacuum condition is: vacuum
Degree is 0.001～0.09Mpa.
8. use the anode pole piece that conducting polymer as claimed in claim 1 is film modified, including by collector and attachment
The positive plate that positive electrode material layer in collector one or both sides is formed, it is characterised in that: at positive electrode on described positive plate
Described conductive polymer membrane also it is attached with outside Ceng.
Anode pole piece the most according to claim 8, it is characterised in that: this anode pole piece is by the method comprised the following steps
Preparation:
A) taking positive plate, at the positive electrode material layer surface-coated initiator of positive plate, the positive plate being coated with initiator is placed in
Fill in the hermetic container of conducting polymer monomer；
B) control hermetic container vacuum condition, make conducting polymer monomer evaporate, on the positive plate be coated with initiator in situ
Polymerization film formation, is dried afterwards, to obtain final product.
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| CN117117089A (en) * | 2023-10-23 | 2023-11-24 | 浙江帕瓦新能源股份有限公司 | Positive electrode of sodium ion battery, preparation method of positive electrode and sodium ion battery |
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