CN108390016A - A kind of preparation method of high resiliency porous electrode - Google Patents
A kind of preparation method of high resiliency porous electrode Download PDFInfo
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- CN108390016A CN108390016A CN201810149089.6A CN201810149089A CN108390016A CN 108390016 A CN108390016 A CN 108390016A CN 201810149089 A CN201810149089 A CN 201810149089A CN 108390016 A CN108390016 A CN 108390016A
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- Prior art keywords
- high resiliency
- porous electrode
- preparation
- conductive
- mixture
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of preparation methods for the high resiliency porous electrode for belonging to electrochemical energy storage technical field.The method includes：Active material, high resiliency binder, conductive agent, additive are subjected to mixing dispersion, to form mixture；Roll-in is carried out to the mixture, to form active material highly elastic film；Conducting resinl is applied and forms conductive adhesive coating on a current collector；The collector progress hot pressing that high resiliency active matter plasma membrane and surface are formed to conductive adhesive coating is compound, obtains high resiliency porous electrode.The present invention can be used for the production of super-capacitor pole piece, the production of electrodes of lithium-ion batteries, in the production process of the contour elastic electrode of production of fuel cell pole piece.It can be mass produced, and solvent-free volatilization causes environmental pollution in production process, greatly reduces cost, speed of production is fast, and manufacturing cost is low.
Description
Technical field
The invention belongs to electrochemical energy storage technical field, more particularly to a kind of preparation method of high resiliency porous electrode.
Background technology
Electrochemical power source has received extensive use as energy storage component, with the hair of China's electrical source of power industry
Exhibition, it is increasing to the demand of electrochemical power source, it is higher and higher to its performance requirement.Electrode is the core of electrochmical power source, electricity
Pole performance parameter determines the performance of power supply itself, and active material, which is easy to fall off, when high resiliency electrode solves power supply processing causes
The disadvantage that self discharge is big, consistency is poor.High resiliency electrode solves the shortcomings of part is easy in power supply winding process simultaneously.It is high-elastic
Property electrode solves active material active material caused by volume change in charge and discharge process and falls off Problem of Failure.High resiliency electricity
Pole and preparation method thereof can be widely applied in the electrochemical power sources such as lithium ion battery, ultracapacitor.
Invention content
The object of the present invention is to provide a kind of preparation methods of high resiliency porous electrode, which is characterized in that the high resiliency
The preparation of electrode includes：
1）Active material, high resiliency binder, conductive agent, additive are first subjected to mixing dispersion, to form mixture；It is described mixed
The gross mass for closing object includes 1 wt %-20 wt % of high resiliency binder, 0.5 wt %-30 wt % of conductive agent, active material
50 wt %-98 wt %, 0.5 wt %-1 wt % of additive；
2）Mixture after disperseing to mixing carries out multiple roll-in, to form active material highly elastic film；
3）Conducting resinl is coated in collection liquid surface, forms conductive adhesive coating；
4）The collector progress hot pressing that high resiliency active matter plasma membrane and surface are formed to conductive adhesive coating is compound, obtains high resiliency
Porous electrode.
The active material be 0.1 to 2 μm of diameter of particle range, and choose activated carbon, aeroge charcoal, carbon nanotube,
Modified Activated Carbon nano-tube material, graphene, modified graphene material, activated carbon and graphene composite material, activated carbon and charcoal nanometer
Pipe composite material, carbonaceous mesophase spherules, natural graphite, modified graphite, coated graphite, artificial graphite, coke, silica flour, silicon line lithium
The cathode powder material containing elemental lithium that the positive pole powder material containing elemental lithium, the negative electrode of lithium ion battery that ion battery uses use
One or more kinds of mixtures of material.
The high resiliency binder is solid or powder, and molecular weight is 10 ten thousand to 100 ten thousand binder, and chooses
Ethylene propylene diene rubber, acrylic resin, polytetrafluoroethylene (PTFE), Kynoar, butadiene-styrene rubber, nitrile rubber demethyl sodium cellulosate
One or more mixture.
The conductive agent be powder, acetylene black, Ketjen black, conductive fiber, electrically conductive graphite, wire one kind or one kind with
On mixture.
The additive is rubber or plastic processing additives；And choose reinforcing agent, antiaging agent, vulcanizing agent, plasticizer
One or more mixture.
The step 1）Mixing dispersing mode disperseed using open double rods mixing dispersion, the sealed mixing of single screw rod,
The sealed mixing dispersion of twin-screw, the sealed mixing dispersion of multiscrew, double planetary mixing dispersion, the mixing dispersion of ball milling formula；It is mixed
It is 5 to 360 minutes to close jitter time.
The step 2）Mixture carry out roll-in use Hot-rolling process；Roll temperature is 120 DEG C -200 DEG C；To mixture
Multiple hot-rolling pressure is carried out, to form continuous high resiliency active matter plasma membrane.
It is described to be selected from copper foil, aluminium foil or sticking conductive polymer film for collector.
The conducting resinl is glued by one or more of conductive black, electrically conductive graphite, graphene, carbon nanotube with water system
Either oil system binder is tuned into paste and is formed in collection liquid surface by intaglio plate coating or bar rubbing method solid-state like for knot agent
Conductive adhesive coating.
The beneficial effects of the invention are as follows the production that can be used for super-capacitor pole piece, the production of electrodes of lithium-ion batteries,
In the production process of the contour elastic electrode of production of fuel cell pole piece.It can be mass produced, and in production process
Solvent-free volatilization causes environmental pollution, greatly reduces cost, speed of production is fast, and manufacturing cost is low.
Description of the drawings
Fig. 1 is the flow diagram for preparing high resiliency electrode.
Fig. 2 is the pole piece scanning electron microscope (SEM) photograph of embodiment 1.
Fig. 3 is the pole piece scanning electron microscope (SEM) photograph of embodiment 2.
Fig. 4 is the pole piece scanning electron microscope (SEM) photograph of embodiment 3.
Specific implementation mode
The present invention provides a kind of preparation method of high resiliency porous electrode, is explained below in conjunction with the accompanying drawings to the present invention.
Fig. 1 show the flow diagram for preparing high resiliency electrode.The preparation method of the high resiliency electrode includes step
It is as follows：
1）Active material, high resiliency binder, conductive agent, additive are first subjected to mixing dispersion, to form mixture；It is described mixed
The gross mass for closing object includes 1 wt %-20 wt % of high resiliency binder, 0.5 wt %-30 wt % of conductive agent, active material
50 wt %-98 wt %, 0.5 wt %-1 wt % of additive；
2）Mixture after disperseing to mixing carries out roll-in, and mixing dispersion process carries out about 5 to 360 minutes, roll temperature 120
℃-200℃；Multiple hot-rolling pressure is carried out to mixed material, to form continuous high resiliency active matter plasma membrane.
3）Conducting resinl is coated in collection liquid surface and forms conductive adhesive coating；
4）The collector progress hot pressing that high resiliency active matter plasma membrane and surface are formed to conductive adhesive coating is compound, obtains high resiliency
Porous electrode.
" high resiliency electrode " of the present invention means to be piled by little particle and sticks in one piece by high resiliency binder and have
The electrode of high resiliency performance, in favor of adapting to the variation of material volume dilation in device assembling and reaction process.In electrode plus
A small amount of additive is added during work, the processing performance of high electrode can be led to, improve the flexibility of electrode, improve the resistance to ring of electrode
Border performance.
" conductive agent " means to ensure that electrode has good charge-discharge performance, is usually added into when pole piece makes
A certain amount of conductive materials play the role of collected current, to subtract between active material, between active material and collector
The contact resistance of small electrode accelerates the transfer rate of electronics, adsorbs more electrolyte, effectively improves ion in electrode material
Migration rate, to improve the efficiency for charge-discharge of electrode.
" conducting resinl " has the adhesive of certain conducting function at a certain temperature after meaning solidification or drying.
" collector " means that the structure or part for collecting electric current, function mainly produce electroactive substance
Raw electric current collects to form larger current versus output.In example scheme, the active material is powder shape
Formula.
The active material that can be used in the present invention includes but not limited to that activated carbon, aeroge charcoal, carbon nanotube, Modified Activated Carbon are received
Nanotube material, graphene, modified graphene material, activated carbon and graphene composite material, activated carbon and carbon nanotube composite wood
Material, carbonaceous mesophase spherules, natural graphite, modified graphite, coated graphite, artificial graphite, coke, silica flour, silicon line lithium ion battery
It is a kind of in the cathode powder body material containing elemental lithium that the positive pole powder material containing elemental lithium, the negative electrode of lithium ion battery used uses
Or several mixture.
The high resiliency binder that can be used in the present invention is solid or powder, and preferred molecular weight is 10 ten thousand to 100
Ten thousand binder, and it is described include but not limited to ethylene propylene diene rubber, acrylic resin, polytetrafluoroethylene (PTFE), Kynoar,
One or more of mixture in butadiene-styrene rubber, nitrile rubber demethyl sodium cellulosate.
The conductive agent that can be used in the present invention is powder；Including but not limited to acetylene black, Ketjen black, conductive fiber, conduction
One or more of mixture in graphite, wire.
The mixing dispersing mode that can be used in the present invention includes but not limited to open double rod mixing dispersions, single screw rod sealing
Formula mixing dispersion, the sealed mixing dispersion of twin-screw, the sealed mixing dispersion of multiscrew, double planetary mixing dispersion, ball milling formula
Mixing dispersion.
The collector that can be used in the present invention includes but not limited to that copper foil, aluminium foil or sticking conducting polymer are thin
Film.And solid-state like conductive adhesive coating is formed in collection liquid surface by intaglio plate coating or bar rubbing method.
With reference to the accompanying drawings, the present invention is explained in detail by following embodiment.
Embodiment 1
Using the activated carbon that PCT companies of South Korea produce as active material, specific surface area is 1850 to 2150 ㎡/g, and D50 is
1-2μm。
The carbonaceous mesophase spherules produced using Shanghai China fir China fir, specific discharge capacity 330mAh/g, irreversible specific capacity are
20mAh/g。
The lithium titanate produced using Shenzhen City Beiterui New Energy Materials Co., Ltd, 1C specific capacities are about
165mAh/g, 99% or more purity.
Using the ethylene propylene diene rubber particle that Dow produces as binder, D50 is 0.25 μm.
Using the Super P of Changzhou Te Migao companies as conductive agent.
Using the SN-307R that auspicious father-in-law produces as conducting resinl.
The ethylene propylene diene rubber particle of the activated carbon (active material) of PCT companies of South Korea production, Dow production is (viscous
Tie agent), the SP (conductive agent) of Changzhou Te Migao companies production weighs by quality, its mass ratio of plastic processing additives is 85：10:
4.5:0.5, the above substance carries out ball milling dispersion using ball-milling dispersion machine, and dispersion process carries out 60 minutes, and the dispersion for obtaining 1kg is mixed
Close object；Hot press roll-in, 180 DEG C of roller temperature, 3 formation active matter plasma membranes of roll-in are carried out to being formed by mixture；Made with aluminium foil
For collector, waterborne conductive glue SN-307R is coated on aluminium foil using gravure coating process, to form conductive coating；It will obtain
Active matter plasma membrane and formation conductive coating copper foil carry out it is compound, wait for that the solvent in active matter plasma membrane and conducting resinl is evaporated completely
Finish, that is, forms dry high resiliency porous electrode.Such as the scanning electron microscope (SEM) photograph that Fig. 2 is obtained high resiliency porous electrode pole piece.
Embodiment 2
The carbonaceous mesophase spherules of Shanghai China fir China fir production, the ethylene propylene diene rubber particle of Dow production, Changzhou Te Migao companies
The SP of production weighs by quality, plastic processing additives；Its mass ratio is 90：7.5:2:0.5, the above substance uses ball-milling dispersion machine
Ball milling dispersion is carried out, dispersion process carries out 120 minutes, obtains the dispersed mixture of 1kg；Hot pressing is carried out to being formed by mixture
Machine roll-in, 160 DEG C of roller temperature, roll-in 4 times form active matter plasma membrane；It, will be aqueous using gravure coating process using copper foil as collector
Conducting resinl SN-307R is coated on aluminium foil, to form conductive coating；By the conductive coating of obtained active matter plasma membrane and formation
Copper foil progress is compound, waits for that the volatilization of the solvent in active matter plasma membrane and conducting resinl finishes, that is, forms dry high resiliency porous electrode.
The scanning electron microscope (SEM) photograph of obtained high resiliency porous electrode pole piece as shown in Figure 3.
Embodiment 3
Lithium titanate, the ethylene propylene diene rubber of Dow production of Shenzhen City Beiterui New Energy Materials Co., Ltd are micro-
The SP of grain, the production of Changzhou Te Migao companies weighs by quality, plastic processing additives；Its mass ratio is 89.5：8:2:0.5, it is above
Substance carries out ball milling dispersion using ball-milling dispersion machine, and dispersion process carries out 240 minutes, obtains the dispersed mixture of 1kg；To institute's shape
At mixture carry out hot press roll-in, 190 DEG C of roller temperature, roll-in 3 times, formed active matter plasma membrane；Using aluminium foil as collector, adopt
Waterborne conductive glue SN-307R is coated on aluminium foil with gravure coating process, to form conductive coating；The active matter plasma membrane that will be obtained
It is compound with the copper foil progress of the conductive coating of formation, it waits for that the volatilization of the solvent in active matter plasma membrane and conducting resinl finishes, that is, is formed dry
Dry high resiliency porous electrode.Such as the scanning electron microscope (SEM) photograph that Fig. 4 is obtained high resiliency porous electrode pole piece.
Claims (9)
1. a kind of preparation method of high resiliency porous electrode, which is characterized in that the preparation of the high resiliency electrode includes：
1）Active material, high resiliency binder, conductive agent, additive are first subjected to mixing dispersion, to form mixture；It is described mixed
The gross mass for closing object includes 1 wt %-20 wt % of high resiliency binder, 0.5 wt %-30 wt % of conductive agent, active material
50 wt %-98 wt %, 0.5 wt %-1 wt % of additive；
2）Multiple roll-in is carried out to the mixture, to form active material highly elastic film；
3）Conducting resinl is applied into collection liquid surface, forms conductive adhesive coating；
4）The collector progress hot pressing that high resiliency active matter plasma membrane and surface are formed to conductive adhesive coating is compound, obtains high resiliency
Porous electrode.
2. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the active material is
0.1 μm to 2 μm of diameter of particle range, and choose activated carbon, aeroge charcoal, carbon nanotube, Modified Activated Carbon nano-tube material, graphite
Alkene, modified graphene material, activated carbon and graphene composite material, activated carbon and carbon nanotube composite material, mesocarbon are micro-
What ball, natural graphite, modified graphite, coated graphite, artificial graphite, coke, silica flour, silicon line lithium ion battery used contains elemental lithium
Positive pole powder material, the one or more of the cathode powder body material containing elemental lithium that use of negative electrode of lithium ion battery it is mixed
Close object.
3. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the high resiliency bonds
Agent is solid or powder, and molecular weight is 10 ten thousand to 100 ten thousand binder, and it is of heap of stone to choose ethylene propylene diene rubber, acrylic acid
The one or more of resin, polytetrafluoroethylene (PTFE), Kynoar, butadiene-styrene rubber, nitrile rubber demethyl sodium cellulosate
Mixture.
4. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the conductive agent is powder
Body, acetylene black, the one or more of Ketjen black, conductive fiber, electrically conductive graphite, wire mixture.
5. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the additive is rubber
Glue or plastic processing additives；And choose the mixing of the one or more of reinforcing agent, antiaging agent, vulcanizing agent, plasticizer
Object.
6. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the step 1）It is mixed
Conjunction dispersing mode is disperseed using open double rods mixing dispersions, the sealed mixing dispersion of single screw rod, the sealed mixing of twin-screw, is more
Segment hub seal formula mixing dispersion, double planetary mixing dispersion, the mixing dispersion of ball milling formula；It is 5 to 360 minutes to mix jitter time.
7. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the step 2）It is mixed
It closes object and carries out roll-in using Hot-rolling process；Roll temperature is 120 DEG C -200 DEG C；Multiple hot-rolling pressure is carried out to mixture, to
Form continuous high resiliency active matter plasma membrane.
8. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that described to be selected for collector
From copper foil, aluminium foil or sticking conductive polymer film.
9. a kind of preparation method of high resiliency porous electrode according to claim 1, which is characterized in that the conducting resinl is by leading
One or more of electric carbon black, electrically conductive graphite, graphene, carbon nanotube are tuned into water-based binder or oil system binder
Paste, and solid-state like conductive adhesive coating is formed in collection liquid surface by intaglio plate coating or bar rubbing method.
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| CN201810149089.6A CN108390016A (en) | 2018-02-13 | 2018-02-13 | A kind of preparation method of high resiliency porous electrode |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112038576A (en) * | 2020-09-28 | 2020-12-04 | 合肥国轩高科动力能源有限公司 | Electrode, manufacturing method thereof and lithium ion battery comprising electrode |
| CN112993212A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Three-dimensional porous elastic electrode and preparation and application thereof |
| CN114407263A (en) * | 2022-01-17 | 2022-04-29 | 中汽创智科技有限公司 | Carbon-coated current collector, preparation method thereof and electrochemical device |
| CN114824177A (en) * | 2022-03-24 | 2022-07-29 | 合肥国轩高科动力能源有限公司 | Preparation method of silicon negative electrode composite pole piece |
| CN115332539A (en) * | 2022-10-17 | 2022-11-11 | 天津普兰能源科技有限公司 | Composite material for preparing electrode, preparation method of composite material, electrode and preparation method of electrode |
| WO2023150691A1 (en) * | 2022-02-03 | 2023-08-10 | Global Graphene Group, Inc. | Elastomer-protected anode and lithium battery |
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