CN104916809B - A kind of integrated flexible electrode - Google Patents
A kind of integrated flexible electrode Download PDFInfo
- Publication number
- CN104916809B CN104916809B CN201410091409.9A CN201410091409A CN104916809B CN 104916809 B CN104916809 B CN 104916809B CN 201410091409 A CN201410091409 A CN 201410091409A CN 104916809 B CN104916809 B CN 104916809B
- Authority
- CN
- China
- Prior art keywords
- lithium
- flexible electrode
- layer
- graphene
- integrated flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of integrated flexible electrode, belong to electrochemical cell art field.Integrated flexible electrode is followed successively by polymeric layer, graphene layer and active material layer by up of three layers, realizes multicomponent integrated design.Graphene layer is dispersed through by Graphene, coated on polymeric layer, and active material layer is coated on graphene layer by slurry, and integrated flexible electrode material is obtained after drying.Integrated flexible electrode material of the invention has excellent flexibility and tensile strength, is suitable for flexible battery, and its preparation method is simple, easily-controllable, is capable of achieving a large amount of, low cost and prepares, and various types of electrodes material is can be applied to, with potential application value.
Description
Technical field
The present invention relates to energy storage device and associated materials technical field, and in particular to a kind of integrated flexible electrode.
Background technology
As people are frivolous for various, the demand of flexibility/foldable electronic, for development of small-scale, light and have
There are high-energy-density, power density and the flexible serondary lithium battery with bending stability to propose requirement higher.Flexible electrical
Pole is one of key factor of high-performance flexible secondary cell development.The positive electrode storage lithium machine of current commodity serondary lithium battery
Reason is insertion reaction mechanism, electron number is shifted in electrochemical process and is respectively less than an electronics, therefore use these electrode materials
It is assembled into the mass-energy density metric density generally below 200Wh/kg of serondary lithium battery, its performance has reached or close to materials theory
The limit of capacity, therefore positive electrode has turned into the bottleneck that serondary lithium battery performance is further improved.Serondary lithium battery assembles work
Skill is coated in metal collector after mixing electrode material, conductive agent and binding agent, because metal collector density is big and right
Do not contributed in capacity, thus greatly reduce the energy density of lithium battery.Simultaneously because metal surface smoother, makes metal
Collector is not enough with the adhesion strength of active material, causes active material relatively low with collector interface bond strength, in discharge and recharge
During can depart from, be continuously increased the internal resistance of cell, reduce cycle life.Generally will be in bending for flexible electronic battery
Under the conditions of use, active material is easier to be occurred and the break-off of metal collector.Therefore R and D high power capacity, length are followed
Ring life-span, the positive electrode without metal collector of high active substance content, are the important research directions in the field.
The structure composition of business lithium battery is including positive pole, negative pole, membrane for polymer, electrolyte and its packaging etc..Positive pole material
Material and negative material are separated by barrier film, are respectively charged into battery, seldom consider to combine to form one with barrier film by electrode material
Body, on the one hand reduces the contact resistance of material and barrier film, on the other hand can make full use of and improve electrode material every film strength
Intensity.For flexible electrode material, common material flexible carbon nano-tube film or graphene film.Preparation process master
The method to use suction filtration, self assembly or spraying, preparation process is relatively complicated.Contacted with active material border in collector
On, surface etch or coating conductive carbon layer are carried out to metal collector can increase surface roughness, so as to improve it with active material
The contact area of material, but due to metal collector nature, it is not suitable for the flexible battery of multiple bending.Lithium-sulfur cell is asked
The solution of topic also focuses primarily upon electrode material design and electrolyte optimization, seldom goes out to send preparation high-performance from structure design soft
Property lithium sulphur battery electrode material.In flexible electrode design, material is integrated on barrier film can also dramatically increase the stretching of material
Intensity and pliability.
The content of the invention
It is an object of the invention to provide integrated flexible electrode.The present invention is by key components in lithium battery：Every
Film, collector and active material carry out integrated design, realize three parts and organically combine, and form a kind of MULTILAYER COMPOSITE electricity
Pole structure.Electrode plates have good pliability and energy density higher, can be used for high-energy flexibility secondary cell, improve
The combination property of battery.
The technical scheme is that：
A kind of integrated flexible electrode, the flexible electrode is composited by three layers, is followed successively by polymeric layer, graphene layer
And active material layer, wherein：Polymeric layer described in integrated flexible electrode is the poly- of 10~1000nm for pore size distribution range
Propylene microcellular barrier film, polyethylene micropore barrier film, Kynoar（PVDF）Barrier film or cellulose composite membrane barrier film；The Graphene
Layer is with (90~99) by graphene film and binding agent:Disperse 0.5-2h in a solvent after the part by weight mixing of (1~10), apply
Overlay on and obtained after being dried on membrane for polymer；The active material layer is with (4~8) by active material, conductive agent and binding agent:
(1~5):It is coated on graphene layer after 1 part by weight mixing and is obtained, integrated flexible electric is obtained after trilaminate material is dried
Pole.
The graphene layer thickness is 5~50 μm, and electrical conductivity is 600~2000S/cm；The thickness of the active material layer
It is 5~100 μm.
The number of plies of the graphene film is below 10 layers, lateral dimension more than 1 micron, carbon-to-oxygen ratio is more than 20；It is preferred that
Scope be：5~50 microns of 3~8 layers of the number of plies of graphene film, lateral dimension, carbon-to-oxygen ratio 20~120.
The solvent for dispersed graphite alkene piece is alcohols, ketone, aldehydes, organic acid, 1-METHYLPYRROLIDONE, diformazan
Base formamide, dimethylacetylamide, chlorobenzene or dichloro-benzenes etc., graphene film content in a solvent are 1~5mg/mL.
For dispersed graphite alkene piece method for ultrasonic disperse, high speed shear dispersion, be stirred vigorously and emulsify in one kind
Or it is several.
Active material in the active material layer is anode material for lithium-ion batteries, negative material or lithium-sulphur cell positive electrode
Material.The anode material for lithium-ion batteries includes LiFePO4, cobalt acid lithium, LiMn2O4, lithium manganese phosphate, phosphoric acid vanadium lithium, nickel manganese
One or several combinations in sour lithium and nickel-cobalt-manganese ternary material；The lithium ion battery negative material include native graphite,
Delanium, lithium metal, silicon-base alloy, silicon-base oxide, kamash alloy, tin-based oxide, lithium titanate, titanium dioxide, oxidation
One or several combinations in tin, iron oxide and cobalt oxide；The lithium sulfur battery anode material include elemental sulfur, the sulphur of lithium two or
Lithium sulfide.
The conductive agent（That is conductive carbon material）It is conductive black, mesoporous carbon, micropore carbon ball, level hole carbon, activated carbon, sky
Heart carbon ball, CNT, carbon fiber, fullerene or Graphene；The binding agent is polyvinylidene fluoride（PVDF）, polytetrafluoroethyl-ne
Alkene (PTFE), sodium carboxymethylcellulose (CMC), polyvinyl alcohol (PVA) or modified styrene butadiene rubber (SBR), by active material, conduction
The mode of agent and binding agent mixing is mechanical mixture, ball milling or ultrasonic mixing.
In above-mentioned integrated flexible electrode material, Graphene content be 10~15wt%, activity substance content be 55~
70wt%, conductive carbon material and binder content are 5~10wt%, and remaining is polymer.
Compared with prior art, the integrated flexible electric that the present invention is provided has following characteristics：
Lithium battery multicomponent is carried out into integrated design design and reduce constituent element realizing flexible electrode material to get an electric shock indirectly
Hinder to lift the performance of lithium battery.Graphene film layer can effectively reduce collector in battery when this is designed for flexible lithium battery
Weight（Improve the mass energy density and volume energy density of electrode plates）And it is effective with active electrode material to improve collector
Contact, enhances interface binding intensity between the two, is effectively increased electronics and ion transmission, reduces the internal resistance of cell.For lithium sulphur
Graphene layer is alternatively arranged as the barrier layer of polysulfide when in battery, strongly limit the shuttle of many sulphions.Graphene layer pair
Sulphur and many sulphur products also have adsorption capacity, and film is formed by Sheet Graphite alkene stacking, can be one in electrochemical reaction process
Determine degree and suppress the work that volumetric expansion and polysulfide of the elemental sulfur in electrochemical reaction process are dissolved in electrolyte and cause
Property material be lost in, improve battery cycle life and security.The good heat dissipation characteristics of Graphene can be by electrode plates in big electricity
The heat produced during stream discharge and recharge is derived in time, further improves the security performance of battery.Integrated flexible electrode of the invention
Material has excellent flexibility and intensity, in the flexible battery needed for being suitable for flexible electronic device, its preparation method is simple,
It is easily-controllable, it is capable of achieving a large amount of, low cost and prepares, various types of electrodes material is can be applied to, with application value.
The present invention has the beneficial effect that：
1st, the present invention proposes a kind of integrated flexible electrode, and the flexible electrode is by polymeric layer, graphene layer and active material
Three layers of the bed of material is composited, and realizes lithium battery multicomponent integrated design, and three independences are divided into different from conventional batteries assembling
Anabolic process, such as active material are coated in metal collector, and along with the three-decker of polymer, this design can reduce each
Partial contact resistance.
2nd, integrated flexible electrode material of the invention has excellent flexibility and tensile strength, is suitable for flexible electronic
In various flexible batteries needed for device.
3rd, the weight of inert matter metal collector in lithium ion battery and lithium-sulfur cell can be effectively reduced, is greatly improved
Battery energy density.
4th, in lithium ion battery, graphene layer has been effectively reduced the weight of metal collector in battery simultaneously in the present invention
The contact area of collector and active material is increased, the interface bond strength between collector and active material is increased, and
Significantly reduce battery contact internal resistance.
5th, in lithium-sulfur cell, graphene film has an adsorption capacity in lithium-sulfur cell to sulphur and many sulphur products, film by
Sheet Graphite alkene stacking is formed, can be in suppression elemental sulfur to a certain degree in electrochemical reaction process in electrochemical reaction process
Volumetric expansion and the polysulfide active material that is dissolved in electrolyte and causes be lost in, lithium-sulfur cell specific volume can be increased substantially
Amount, cycle characteristics and high rate performance.
Brief description of the drawings
Fig. 1 is the structural representation of the integrated flexible electrode prepared by the present invention, wherein：1- polymer；2- Graphenes
Layer；3- active material layers.
Fig. 2 is the photo that straight polymer and present invention gained graphene layer are coated in polymer surfaces.
Fig. 3 is integrated flexible electrode photo of the present invention；Wherein：A () is the photo of polymer and Graphene；B () is one
The photo of body polarizing electrode.
Fig. 4 is the stereoscan photograph of present invention gained integrated flexible electrode cross section.
Fig. 5 is the interface bond strength pair of present invention gained integrated flexible electrode material and polymer-coated active material
Than.Line 1 is integrated flexible electrode material interface bond strength test curve prepared by the embodiment of the present invention 1；Line 2 is polymer
Coating sulphur active material border bond strength test curve.
Fig. 6 is that the integrated flexible electrode material prepared by the embodiment of the present invention 1 and the polymer prepared by comparative example 1 are applied
Sulphur positive pole is covered in 1500mAg-1Charging and discharging curve and polarization potential difference comparison diagram under current density.
Fig. 7 is that the integrated flexible electrode material prepared by the embodiment of the present invention 1 and the polymer prepared by comparative example 1 are applied
Cover sulphur positive pole high rate performance cyclic curve comparison diagram under different current densities.
Fig. 8 is that the integrated flexible electrode material prepared by the embodiment of the present invention 1 and the polymer prepared by comparative example 1 are applied
Sulphur positive pole is covered in 1500mAg-1Charge-discharge magnification under 200 cycle charge-discharge curves and coulombic efficiency contrast.
Fig. 9 is that the integrated flexible electrode material prepared by the embodiment of the present invention 1 is flexible soft with what flexible lithium paper tinsel was assembled into
Wrap the LED that full battery lights parallel connection in the bent state.
Specific embodiment
For a further understanding of the present invention, below in conjunction with the accompanying drawings and embodiment carries out detailed complete description to the present invention.
These descriptions are only explanation the features and advantages of the present invention, rather than limiting to the claimed invention.
As shown in figure 1, a kind of integrated flexible electrode of the invention is constituted by three layers, including polymeric layer 1, graphene layer 2
With active material layer 3, the thickness of the polymeric layer 1 is 15~25 μm；The thickness of the graphene layer 2 is 5~50 μm；It is described
The thickness of active material layer 3 is 5~100 μm.It is barrier film that its middle polymeric layer 1 is played a role, graphene layer 2 play collector and
The effect on barrier layer.Graphene layer is with (90~99) by graphene film with a small amount of binding agent:The part by weight of (1~10) is mixed
Conjunction disperses 0.5-2h in a solvent, is then coated with being dried on polymeric layer, you can obtain graphene layer coating as shown in Figure 2
Material.The graphene layer coating material has good electric conductivity and pliability：Using four-point probe methods test graphene layer
Electric conductivity, its electrical conductivity is 600~2000S/cm；The collector can bend repeatedly, and its geomery can be according to actual needs
Cut.Active material layer is with (4~8) by active material, conductive carbon material and binding agent:(1~5):1 part by weight
It is coated on graphene layer after mixing composition, sulphur positive pole integration as shown in Figure 3 is can obtain after this trilaminate material is dried
Flexible electrode.
The present invention is described in detail with reference to specific embodiment.
Embodiment 1
Uniform ultrasound 0.5h disperses during Graphene 700mg is added to 1-METHYLPYRROLIDONE with 300mg polyvinylidene fluoride
Afterwards（Graphene content is 1mg/mL in dispersion liquid）Blade coating can obtain graphite on microporous polypropylene membrane after drying removal solvent
Alkene coating material such as Fig. 3 (a), the thickness of graphene layer is 30 μm.On the surface of graphene layer sulphur：Conductive black：Binding agent
（Polyvinylidene fluoride）With 7：2：The slurry smear that 1 part by weight is mixed to form, carbon/sulphur active matter is formed on graphene layer surface
Matter layer, is vacuum dried at 70 DEG C, and the dry time is 12h, obtains material and sees Fig. 3 (b).Gained sulphur positive pole integrated flexible electric
The cross sectional Scanning Electron microscope figure of pole is shown in Fig. 4, it can be seen that graphene film stacked structure layer by layer.Carbon/sulphur active material layer
Middle sulphur, conductive black and binding agent uniform coating are close on the surface of graphene layer, and the thickness of carbon/sulphur active material layer is big
About 30-40 microns.
To the coating sulphur positive pole prepared by the sulphur positive pole integrated flexible electrode material and comparative example 1 prepared by embodiment 1
Interface bond strength performance test is carried out, the interface bond strength of described sulphur positive pole integrated flexible electrode material is that barrier film is applied
6 times of sulphur positive pole are covered, such as Fig. 5, show its excellent interface bond strength.
The charging and discharging curve that button half-cell is carried out under different multiplying is assembled into after electrode plates obtained above are cut
And cycle performance test.Fig. 6 is prepared by sulphur positive pole integrated flexible electrode material and comparative example 1 prepared by embodiment 1
Coating sulphur positive pole（Active material（Sulphur simple substance）：Conductive black：Weight of binder ratio is 7：2：1）First charge-discharge curve,
Can be seen that two obvious discharge platforms correspond to from sulphur to high-order lithium polysulfide and high-order lithium polysulfide to low order lithium
The transition process of polysulfide.In 1500mAg-1Current density under, discharge capacity is up to 1032mAhg first-1, polarization
Electrical potential difference only has 258mV.Discharge capacity under each current density is shown in Fig. 7, in 6000mAg-1Current density transfers electric capacity
Amount is more than 690mAhg-1, show superior high rate performance.In 1500mAg-1Hold after circulating 200 times under current density
Amount is still close to 800mAhg-1, coulombic efficiency illustrates that the electrode has extraordinary cyclical stability still more than 95%,
As shown in Figure 8.
The sulphur positive pole integrated flexible electrode material and flexible lithium paper tinsel negative pole prepared using above-described embodiment 1, with 14cm ×
The aluminium plastic material of 8cm sizes is assembled into flexible full battery as encapsulating material in glove box, and its gross thickness is about 1.5cm.Should
Full battery is not only frivolous and with good flexibility, can under conditions of repeating to bend holding structure it is constant, and can be in bending
Electric current output is carried out under state, the LED of parallel connection, such as Fig. 9 is lighted.
Comparative example 1
Difference from Example 1 is：Only with microporous polypropylene membrane, there is no graphene layer.The electrode material exists
1500mA·g-1Current density under, such as Fig. 6, first discharge capacity be 720mAhg-1, hence it is evident that less than the sulphur under identical multiplying power
The specific discharge capacity of positive pole integrated flexible electrode material, and can be seen that its polarization potential difference apparently higher than sulphur just by contrast
Pole integrated electrode material, polarization potential difference is up to 537mV, shows the resistance of the resistance significantly lower than comparative example 1 of embodiment 1.
Discharge capacity under each current density is shown in Fig. 7, and with the increase of multiplying power, its capacity is decayed rapidly, in 6000mAg-1Electricity
Current density discharge capacity is almost 0, and specific capacity under each multiplying power is below sulphur positive pole integrated electrode.
1500mA·g-1Capacity is down to 260mAhg after circulating 200 times under current density-1, coulombic efficiency is down to 80%（See Fig. 8）.
Comparative example 2
Difference from Example 1 is：Select the metal aluminum foil of commercialized 25 microns of thickness as collector, selection is poly-
Propylene microcellular film.In aluminium foil surface sulphur：Conductive black：Binding agent（Polyvinylidene fluoride）With 7：2：1 part by weight mixes shape
Into slurry and smear formation carbon/sulphur active material layer, it is vacuum dried at 70 DEG C, the dry time is 12h, obtains aluminium foil afflux
Body lithium sulfur battery anode material.The electrode material is in 1500mAg-1Current density under, first discharge capacity be 550mAh
g-1, in 3000mAg-1Current density discharge capacity is only 170mAhg-1, in 4500mAg-1Almost do not have under current density
There is capacity.
Comparative example 3
Using pure graphene film as a comparison, section carries out lithium-sulfur cell chemical property after drying 12h at 70 DEG C
Test, in 1500mAg-1Current density under, its first charge-discharge capacity is in 10mAhg-1Hereinafter, Posterior circle is almost
There is no capacity.
Embodiment 2
By commercialized LiFePO4 powder, conductive black, binding agent PVDF according to 8:1:1 mass ratio is in solvent NMP
Middle stirring mixing, is made uniform active electrode slurry, is put after the slurry is scratched on microporous polypropylene membrane and graphene layer
Enter drying to obtain iron phosphate lithium positive pole integrated flexible electrode in 60 DEG C of baking ovens.Electrode plates obtained above are cut rear group
The charge and discharge cycles test that button half-cell is carried out under different multiplying is dressed up, finds the electrode in 170mAg-1Electric current it is close
Under degree, discharge capacity is up to 140mAhg-1, in 1700mAg-1High current density under, the discharge capacity of LiFePO4 is
90mAh·g-1。
Comparative example 4
Difference with embodiment 2 is：The metal aluminum foil of commercialized 25 microns of thickness is selected as collector.By business
LiFePO4 powder, conductive black, the binding agent PVDF of industry are according to 8:1:1 mass ratio stirs mixing in solvent NMP, system
Into uniform active electrode slurry, it is coated in aluminum foil current collector with scraper, is vacuum dried at 90 DEG C, that is, obtains aluminium foil afflux
Body-iron phosphate lithium positive pole pole piece.The electrode material is in 170mAg-1Current density under, discharge capacity is 130mAhg-1,
With the increase of multiplying power, its specific capacity declines rapidly, in 1700mAg-1Almost without capacity, its high rate performance under current density
Compared compared with embodiment 2, there is very big gap.
Embodiment 3
By commercialized LiMn2O4 powder, conductive black, binding agent PVDF according to 85:7:8 mass ratio is in solvent NMP
Stirring mixing, is made uniform active electrode slurry, is put into after the slurry is scratched on microporous polypropylene membrane and graphene layer
Drying to obtain lithium manganate cathode integrated flexible electrode in 60 DEG C of baking ovens.Half-cell performance test is carried out to it, can obtain with
The similar multiplying power of embodiment 2 and cycle performance, and result better than under the same terms aluminum foil current collector-lithium manganate cathode it is cell performance
Energy.
Embodiment 4
Difference from Example 2 is：LiFePO4 in embodiment 2 is replaced with into cobalt acid lithium, is separated into NMP
After uniform sizing material, drying to obtain cobalt in being put into 60 DEG C of baking ovens after the slurry is scratched on microporous polypropylene membrane and graphene layer
Sour lithium positive pole integrated flexible electrode.Half-cell performance test is carried out to it, its result better than aluminum foil current collector under the same terms-
The battery performance of lithium cobaltate cathode.
Embodiment 5
By commercialized titanium dioxide powder, conductive black, binding agent PVDF according to 8:1:1 mass ratio is in solvent NMP
Middle stirring mixing, is made uniform active electrode slurry, is put after the slurry is scratched on microporous polypropylene membrane and graphene layer
Enter drying to obtain titanium dioxide cathode integrated flexible electrode in 60 DEG C of baking ovens.Half-cell performance test is carried out to it, can be obtained
Multiplying power and cycle performance similar to Example 2, and result are obtained better than aluminum foil current collector-titanium dioxide cathode under the same terms
Battery performance.
Embodiment 6
Difference from Example 5 is：Titanium dioxide in embodiment 5 is replaced with into commercialized native graphite,
After being separated into uniform sizing material in NMP, it is put into 60 DEG C of baking ovens after the slurry is scratched on microporous polypropylene membrane and graphene layer
Drying to obtain graphite cathode integrated flexible electrode.Half-cell performance test is carried out to it, its result is better than under the same terms
The battery performance of copper foil current collector-graphite cathode.
Electrochemical property test：
Make after the disk that above example and comparative example composite construction electrode section compressing tablet are struck out diameter 19mm respectively
It is lithium battery anode or negative material.All electrode slices are assembled into 2025 type button cells, metal in inert-atmosphere glove box
Lithium piece is that, to electrode, lithium-sulfur cell electrolyte is 1mol/L LiTFSI/DOL+DME (wherein, the volume ratios 1 of DOL and DME：1,
LiTFSI is bis trifluoromethyl sulfonic acid imide li, and DOL is DOX, and DME is glycol dimethyl ether)；In lithium ion
Electrolyte is that electrolyte is 1mol/LLiPF in battery6/ EC+EMC+DMC (wherein, the volume ratios 1 of EC, EMC, DMC：1：1, EC
It is ethylene carbonate, EMC is methyl ethyl carbonate, and DMC is dimethyl carbonate)；Barrier film used is polypropylene
（Celgard2400）.Electrochemical property test is surveyed in Wuhan Lan electricity companies Land BT-1 type testers to battery performance
Examination.Be referred to as telescopiny of the lithium ion in active material in active material-lithium half-cell to charge by the present invention, and lithium ion exists
Deintercalation process in active material is referred to as electric discharge.
Above test result shows that a kind of integrated flexible electrode material of the invention can be effectively increased collector with activity
The conductive contact area of electrode material, the interface binding intensity between active material and collector, relative to existing metal collection
Fluid electrode pole piece has a more preferable high rate performance, lower internal resistance, energy density higher, and special with good bending
Property.The present invention is used in lithium-sulfur cell, effectively reduces the weight of metal collector in lithium-sulfur cell, and preparation process is simply high
Effect.Graphene film also has adsorption capacity to sulphur and many sulphur products, can to a certain degree suppress single in electrochemical reaction process
The matter sulphur active material that polysulfide is dissolved in electrolyte and causes in electrochemical reaction process is lost in.Graphene layer is used as afflux
Body and barrier layer, effectively increase electronics and the ion transmission of barrier film, and largely limit the shuttle of many sulphions, therefore
Integrated flexible electrode material of the present invention has specific capacity high, and excellent cyclical stability and high rate performance are expected in high energy
Applied in metric density, the flexible lithium battery of high power density.
Claims (6)
1. a kind of integrated flexible electrode, it is characterised in that：The flexible electrode is composited by three layers, is followed successively by polymer
Layer, graphene layer and active material layer, wherein：The polymeric layer is micro- for the polypropylene that pore size distribution range is 10~1000nm
Hole barrier film, polyethylene micropore barrier film, Kynoar barrier film or cellulose composite membrane barrier film；The graphene layer is by Graphene
Piece is with binding agent with (90~99):The part by weight mixing of (1~10) disperses 0.5-2h in a solvent, is coated on polymeric layer
Obtained after drying；The active material layer is with (4~8) by active material, conductive agent and binding agent:(1~5):1 weight ratio
It is coated in after example mixing on graphene layer and is obtained, integrated flexible electrode is obtained after trilaminate material is dried；
The graphene layer thickness is 5~50 μm, and electrical conductivity is 600~2000S/cm；The thickness of the active material layer be 5~
100μm；The number of plies of the graphene film is below 10 layers, lateral dimension more than 1 micron, carbon-to-oxygen ratio is more than 20；For dividing
The solvent for dissipating graphene film is alcohols, ketone, aldehydes, organic acid, dimethylformamide, dimethylacetylamide, chlorobenzene or dichloro
Benzene, graphene film content in a solvent is 1~5mg/mL；Method for dispersed graphite alkene piece includes ultrasonic disperse, high speed
Shearing dispersion, be stirred vigorously and emulsify in one or more.
2. integrated flexible electrode according to claim 1, it is characterised in that：3~8 layers of the number of plies of the graphene film,
5~50 microns of lateral dimension, carbon-to-oxygen ratio 20~120.
3. integrated flexible electrode according to claim 1, it is characterised in that：Active material in the active material layer
It is anode material for lithium-ion batteries, negative material or lithium sulfur battery anode material.
4. integrated flexible electrode according to claim 3, it is characterised in that：The anode material for lithium-ion batteries includes
One kind in LiFePO4, cobalt acid lithium, LiMn2O4, lithium manganese phosphate, phosphoric acid vanadium lithium, nickel ion doped and nickel-cobalt-manganese ternary material or
Several combinations；The lithium ion battery negative material includes native graphite, Delanium, lithium metal, silicon-base alloy, silicon substrate oxidation
One or several combinations in thing, kamash alloy, tin-based oxide, lithium titanate, titanium dioxide, iron oxide and cobalt oxide；Institute
Stating lithium sulfur battery anode material includes elemental sulfur or lithium sulfide.
5. integrated flexible electrode according to claim 1, it is characterised in that：The conductive agent is conductive black, mesopore
Carbon, micropore carbon ball, level hole carbon, activated carbon, hollow carbon sphere, CNT, carbon fiber, fullerene or Graphene；The bonding
Agent is polyvinylidene fluoride, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, polyvinyl alcohol or modified styrene butadiene rubber；By active material,
Conductive agent and the mode of binding agent mixing are mechanical mixture, ball milling or ultrasonic mixing.
6. integrated flexible electrode according to claim 1, it is characterised in that：In the integrated flexible electrode, graphite
Alkene content is 10~15wt%, and activity substance content is 55~70wt%, and conductive agent and binder content are 5~10wt%, its
Remaining is polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410091409.9A CN104916809B (en) | 2014-03-12 | 2014-03-12 | A kind of integrated flexible electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410091409.9A CN104916809B (en) | 2014-03-12 | 2014-03-12 | A kind of integrated flexible electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104916809A CN104916809A (en) | 2015-09-16 |
| CN104916809B true CN104916809B (en) | 2017-06-09 |
Family
ID=54085665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410091409.9A Active CN104916809B (en) | 2014-03-12 | 2014-03-12 | A kind of integrated flexible electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104916809B (en) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140523A (en) * | 2015-09-17 | 2015-12-09 | 上海大学 | Flexible thin film electrode material for lithium ion battery and preparing method of flexible thin film electrode material |
| CN107026269B (en) * | 2016-02-02 | 2019-08-27 | 中国科学院金属研究所 | A kind of collector, electrode and diaphragm integral structure and semi liquid state lithium-sulfur cell |
| CN107056086A (en) * | 2016-02-05 | 2017-08-18 | 新材料与产业技术北京研究院 | A kind of duplicature and preparation method thereof |
| CN105742567A (en) * | 2016-04-27 | 2016-07-06 | 长沙矿冶研究院有限责任公司 | Composite positive electrode of lithium sulfur battery, preparation method of composite positive electrode and lithium sulfur battery |
| CN106024420A (en) * | 2016-05-03 | 2016-10-12 | 常州工程职业技术学院 | Preparation method of graphene-containing energy storage polymer electrode sheet |
| CN109690839B (en) * | 2016-07-22 | 2022-06-03 | 魁北克电力公司 | Flexible electrode-separator element and method for the production thereof |
| CN106207095A (en) * | 2016-07-30 | 2016-12-07 | 肖丽芳 | A kind of lithium-sulfur cell and preparation method thereof |
| WO2018023218A1 (en) * | 2016-07-30 | 2018-02-08 | 肖丽芳 | Lithium-sulfur battery and preparation method therefor |
| CN106058150A (en) * | 2016-08-15 | 2016-10-26 | 柔电（武汉）科技有限公司 | Electrode of lithium sulfur battery and preparation method thereof |
| CN107887572B (en) * | 2016-09-29 | 2020-07-21 | 华为技术有限公司 | Lithium ion battery negative pole piece, preparation method thereof and lithium ion secondary battery |
| CN106159197A (en) * | 2016-09-30 | 2016-11-23 | 上海空间电源研究所 | A kind of integrated flexible membrane electrode and preparation method thereof |
| CN107910489A (en) * | 2017-11-28 | 2018-04-13 | 广东省肇庆市质量计量监督检测所 | A kind of lithium ion battery negative material and preparation method thereof |
| CN109873166B (en) * | 2017-12-05 | 2021-06-29 | 宁德时代新能源科技股份有限公司 | Current collector, pole piece thereof and electrochemical device |
| CN108281608A (en) * | 2018-02-07 | 2018-07-13 | 深圳前海优容科技有限公司 | Electrode slice, battery and battery |
| CN110323392A (en) * | 2018-03-30 | 2019-10-11 | 北京国能电池科技股份有限公司 | Rechargeable battery and preparation method thereof and electrical equipment |
| CN110323483A (en) * | 2018-03-30 | 2019-10-11 | 北京国能电池科技股份有限公司 | Secondary cell and preparation method thereof with include its power device |
| CN109728228A (en) * | 2018-12-11 | 2019-05-07 | 溧阳天目先导电池材料科技有限公司 | A kind of film and preparation method thereof and secondary cell |
| CN110098374B (en) * | 2019-04-26 | 2021-05-07 | 中国航发北京航空材料研究院 | Flexible electrode film and preparation method and application thereof |
| CN112349910B (en) * | 2019-04-28 | 2022-03-08 | 宁德时代新能源科技股份有限公司 | Negative current collector, negative pole piece, electrochemical device, electric automobile and consumer electronics |
| CN110350147A (en) * | 2019-06-06 | 2019-10-18 | 西安交通大学 | A kind of integrated-type tunica fibrosa battery component |
| WO2021163892A1 (en) * | 2020-02-18 | 2021-08-26 | 深圳先进技术研究院 | Flexible battery negative electrode and preparation method therefor, and flexible battery |
| CN111916850B (en) * | 2020-08-04 | 2022-10-18 | 太仓中科赛诺新能源科技有限公司 | Preparation method and structure of water system quasi-solid sodium ion battery |
| CN112185715B (en) * | 2020-10-12 | 2021-10-26 | 广西大学 | Zinc-cobalt bimetal oxide sandwich structure flexible thin film electrode and preparation method thereof |
| CN112563443B (en) * | 2020-11-20 | 2022-08-12 | 扬州大学 | Flexible battery electrode and manufacturing process thereof |
| CN114520335B (en) * | 2020-11-20 | 2023-08-29 | 中国科学院金属研究所 | Carbon-based flexible integrated electrode of lithium ion battery and preparation method thereof |
| CN114643186B (en) * | 2020-12-18 | 2024-02-20 | 晨柔点智能科技(北京)有限公司 | High-barrier flexible packaging material and manufacturing method thereof |
| CN113161511B (en) * | 2021-04-20 | 2022-04-29 | 太仓中科赛诺新能源科技有限公司 | Plastic electrode and preparation method thereof, and aqueous sodium ion battery and preparation method thereof |
| CN113265538B (en) * | 2021-05-21 | 2022-09-30 | 中南大学 | Preparation method of high-conductivity porous electrode for lithium extraction in salt lake |
| CN115411218A (en) * | 2021-05-26 | 2022-11-29 | 比亚迪股份有限公司 | Test pole piece, lithium battery and preparation method |
| CN115051112A (en) * | 2022-07-12 | 2022-09-13 | 远景动力技术(江苏)有限公司 | Composite diaphragm and application thereof |
| CN115566137B (en) * | 2022-11-09 | 2023-05-26 | 楚能新能源股份有限公司 | High-energy-density pole piece, preparation method thereof and battery cell |
| CN116487522A (en) * | 2023-06-21 | 2023-07-25 | 南京邮电大学 | Flexible stretchable electrode and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593464A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Current collector and preparation method thereof |
| CN103000939A (en) * | 2012-12-12 | 2013-03-27 | 涂健 | Lithium ion battery with graphene composite membrane as current collector and preparation method thereof |
| CN103022505A (en) * | 2012-12-12 | 2013-04-03 | 涂健 | Lithium ion battery with graphene dialysis membrane as current collector and preparation method thereof |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN103427087A (en) * | 2012-05-17 | 2013-12-04 | 清华大学 | Current collector, electrochemical cell electrode, and electrochemical cell |
| CN103579633A (en) * | 2012-08-09 | 2014-02-12 | 清华大学 | Anode and lithium ion battery |
| CN103579583A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Manufacturing method of lithium-sulfur battery anode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
-
2014
- 2014-03-12 CN CN201410091409.9A patent/CN104916809B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593464A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Current collector and preparation method thereof |
| CN103427087A (en) * | 2012-05-17 | 2013-12-04 | 清华大学 | Current collector, electrochemical cell electrode, and electrochemical cell |
| CN103579583A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Manufacturing method of lithium-sulfur battery anode |
| CN103579633A (en) * | 2012-08-09 | 2014-02-12 | 清华大学 | Anode and lithium ion battery |
| CN103000939A (en) * | 2012-12-12 | 2013-03-27 | 涂健 | Lithium ion battery with graphene composite membrane as current collector and preparation method thereof |
| CN103022505A (en) * | 2012-12-12 | 2013-04-03 | 涂健 | Lithium ion battery with graphene dialysis membrane as current collector and preparation method thereof |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| "A Graphene-Pure-Sulfur Sandwich Struture for Ultrafast Long-Life Lithium-Sulfur Batteries";G.M.Zhou,等;《Advanced Materials》;20131104;第26卷(第4期);第625页右栏倒数第1段、第626页左栏第1段、第626页右栏第2段、第627页左栏第1段至右栏第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104916809A (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104916809B (en) | A kind of integrated flexible electrode | |
| JP5167703B2 (en) | Battery electrode | |
| CN103972467B (en) | A kind of lithium-sulfur cell MULTILAYER COMPOSITE positive pole and preparation method thereof | |
| JP5888012B2 (en) | Non-aqueous electrolyte secondary battery and manufacturing method thereof | |
| CN103904291B (en) | Aquo-lithium ion battery electrode and preparation method thereof, aquo-lithium ion battery | |
| JP5935405B2 (en) | Laminated battery | |
| KR101670580B1 (en) | Separator for secondary battery, method of fabricating the same, and lithium secondary battery comprising the same | |
| JP4426154B2 (en) | Method for producing electrode film and battery element including the electrode film | |
| CN104347881A (en) | Preparation method and applications of battery graphene-base current collector | |
| CN104810504A (en) | Flexible graphene current collector and active material integrated electrode pole piece and preparation method thereof | |
| CN104103791A (en) | Composite diaphragm for battery and preparation method thereof | |
| CN103918108A (en) | Lithium metal doped electrodes for lithium-ion rechargeable chemistry | |
| JP5601361B2 (en) | Battery electrode | |
| CN106159197A (en) | A kind of integrated flexible membrane electrode and preparation method thereof | |
| CN101154750A (en) | High power gel polymer lithium ion power cell and method of producing the same | |
| CN103155229B (en) | Secondary cell | |
| CN102332558A (en) | Lithium ion battery and anode pole piece thereof | |
| KR20140016180A (en) | Laminate structural cell | |
| JP6973244B2 (en) | Non-aqueous electrolyte secondary battery and method for manufacturing non-aqueous electrolyte secondary battery | |
| JP2013127845A (en) | Electric device | |
| JP2014216250A (en) | Method for manufacturing slurry composition for positive electrode of lithium ion battery | |
| CN105934845B (en) | Electrical part | |
| KR101586536B1 (en) | Manufacturing method of carbon fiber sheet current collector for all solid state rechargeable thin film lithium secondary battery, and all solid state rechargeable thin film lithium secondary battery comprising carbon fiber sheet current collector | |
| CN109148840A (en) | PEO-PVA based adhesive for lithium-sulfur cell | |
| JP2007280806A (en) | Electrode for battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |