CN104916809A - Integrated flexible electrode - Google Patents
Integrated flexible electrode Download PDFInfo
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- CN104916809A CN104916809A CN201410091409.9A CN201410091409A CN104916809A CN 104916809 A CN104916809 A CN 104916809A CN 201410091409 A CN201410091409 A CN 201410091409A CN 104916809 A CN104916809 A CN 104916809A
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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
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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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- 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 an integrated flexible electrode and belongs to the technical field of electrochemical cells. The integrated flexible electrode is composed of three layers which are successively a polymer layer, a graphene layer and an active material layer. According to the invention, the multi-component integrated design is realized. The graphene layer is formed by dispersing and coating graphene onto the polymer layer. The active material layer is formed by coating slurry onto the graphene layer. After drying, the integrated flexible electrode material is obtained. The integrated flexible electrode material has excellent flexibility and tensile strength and is applicable to flexible cells. A preparation method of the integrated flexible electrode is simple and easy to control, can be applied to various electrode materials and has potential application value. Mass and low-cost preparation can be realized.
Description
Technical field
The present invention relates to energy storage device and associated materials technical field, be specifically related to a kind of integrated flexible electrode.
Background technology
Along with people are for various frivolous, the demand of flexibility/foldable electronic, for development of small-scale, light and there is high-energy-density, power density and have bending stability flexible serondary lithium battery have higher requirement.Flexible electrode is one of key factor of high-performance flexible secondary cell development.The positive electrode storage lithium mechanism of current commodity serondary lithium battery is insertion reaction mechanism, shift electron number in electrochemical process and be all less than an electronics, therefore these electrode materials are used to be assembled into the mass-energy density metric density of serondary lithium battery generally lower than 200Wh/kg, its performance has reached or close to the limit of materials theory capacity, therefore positive electrode has become the bottleneck that serondary lithium battery performance improves further.Serondary lithium battery packaging technology is coated in metal collector after electrode material, conductive agent and binding agent being mixed, and because metal collector density is large, and do not contribute for capacity, thus greatly reduce the energy density of lithium battery.Simultaneously due to metal surface smoother, make the adhesion strength of metal collector and active material not enough, cause active material and collector interface bond strength lower, can depart from charge and discharge process, the internal resistance of cell is constantly increased, reduction cycle life.Usually will use under bending condition for flexible electronic battery, more easily there is the break-off with metal collector in active material.Therefore the positive electrode without metal collector of R and D high power capacity, long circulation life, high active substance content is the important research direction in this field.
The structure composition of business lithium battery comprises positive pole, negative pole, membrane for polymer, electrolyte and packaging thereof etc.Positive electrode and negative material are separated by barrier film, be respectively charged in battery, electrode material combines with barrier film and forms one by little consideration, reduces on the one hand material and the contact resistance of barrier film, can make full use of the intensity every film strength raising electrode material on the other hand.For flexible electrode material, common material has flexible carbon nano-tube film or graphene film.Preparation process mainly adopts suction filtration, the method for self assembly or spraying, and preparation process is relatively complicated.Contact with active material border at collector, surface etch is carried out to metal collector or coated with conductive carbon-coating can increase surface roughness, thus improve the contact area of itself and active material, but due to metal collector nature, be not suitable for the flexible battery repeatedly bent.Electrode material design and electrolyte optimization are also mainly concentrated on to the solution of lithium-sulfur cell problem, seldom goes out to send to prepare high-performance flexible lithium sulphur battery electrode material from structural design.In flexible electrode design, material is integrated in hot strength and the pliability that barrier film also significantly can increase material.
Summary of the invention
The object of the present invention is to provide integrated flexible electrode.The present invention is by key components in lithium battery: barrier film, collector and active material carry out integrated design, achieves three parts and organically combines, define a kind of multi-layer composite electrode structure.Electrode plates has good pliability and higher energy density, can be used for the flexible secondary cell of high-energy, improves the combination property of battery.
Technical scheme of the present invention is:
A kind of integrated flexible electrode, this flexible electrode is composited by three layers, be followed successively by polymeric layer, graphene layer and active material layer, wherein: the polypropylene micropore diaphragm of to be pore size distribution range the be 10 ~ 1000nm of polymeric layer described in integrated flexible electrode, polyethylene micropore barrier film, Kynoar (PVDF) barrier film or cellulose composite membrane barrier film; Described graphene layer be by graphene film with binding agent with (90 ~ 99): disperse 0.5-2h in a solvent after the part by weight of (1 ~ 10) mixes, be coated in dry on membrane for polymer after obtain; Described active material layer be by active material, conductive agent and binding agent with (4 ~ 8): (1 ~ 5): be coated on graphene layer and obtain after the part by weight mixing of 1, obtain integrated flexible electrode by after trilaminate material drying.
Described graphene layer thickness is 5 ~ 50 μm, and conductivity is 600 ~ 2000S/cm; The thickness of described active material layer is 5 ~ 100 μm.
The number of plies of described graphene film below 10 layers, lateral dimension more than 1 micron, carbon-to-oxygen ratio is more than 20; Preferred scope is: the number of plies 3 ~ 8 layers of graphene film, lateral dimension 5 ~ 50 microns, carbon-to-oxygen ratio 20 ~ 120.
Described solvent for dispersed graphite alkene sheet is alcohols, ketone, aldehydes, organic acid, 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, chlorobenzene or dichloro-benzenes etc., and graphene film content is in a solvent 1 ~ 5mg/mL.
Method for dispersed graphite alkene sheet is one or more in ultrasonic disperse, high speed shear dispersion, vigorous stirring and emulsification.
Active material in described active material layer is anode material for lithium-ion batteries, negative material or lithium sulfur battery anode material.Described anode material for lithium-ion batteries comprises one or several combinations in LiFePO4, cobalt acid lithium, LiMn2O4, lithium manganese phosphate, phosphoric acid vanadium lithium, nickel ion doped and nickel-cobalt-manganese ternary material; Described lithium ion battery negative material comprises one or several combinations in native graphite, Delanium, lithium metal, silicon-base alloy, silicon-base oxide, kamash alloy, tin-based oxide, lithium titanate, titanium dioxide, tin oxide, iron oxide and cobalt oxide; Described lithium sulfur battery anode material comprises elemental sulfur, lithium two sulphur or lithium sulfide.
Described conductive agent (i.e. conductive carbon material) is conductive black, mesoporous carbon, microporous carbon ball, level hole carbon, activated carbon, hollow carbon sphere, carbon nano-tube, carbon fiber, fullerene or Graphene; Described binding agent is polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), polyvinyl alcohol (PVA) or modified styrene butadiene rubber (SBR), and mode active material, conductive agent and binding agent mixed is mechanical mixture, ball milling or ultrasonic mixing.
In above-mentioned integrated flexible electrode material, Graphene content is 10 ~ 15wt%, and activity substance content is 55 ~ 70wt%, and conductive carbon material and binder content are 5 ~ 10wt%, and all the other are polymer.
Compared with prior art, integrated flexible electric provided by the invention has following characteristics:
Lithium battery multicomponent is carried out integrated design design to realize flexible electrode material and reduce constituent element Contact resistance to promote the performance of lithium battery.When this is designed for flexible lithium battery, graphene film layer effectively can reduce collector weight in battery (improving mass energy density and the volume energy density of electrode plates) and improve collector and effectively contacts with active electrode material, enhance interface binding intensity between the two, effective increase electronics and ion transfer, reduce the internal resistance of cell.For in lithium-sulfur cell time graphene layer also can be used as the barrier layer of polysulfide, strongly limit shuttling back and forth of many sulphions.Graphene layer also has adsorption capacity to sulphur and many sulphur product, film forms by Sheet Graphite alkene is stacking, the active material that can be dissolved in electrolyte in the volumetric expansion to a certain degree suppressing elemental sulfur in electrochemical reaction process and polysulfide and cause in electrochemical reaction process runs off, and improves cycle life and the fail safe of battery.The heat that electrode plates can produce when high current charge-discharge by the good heat dissipation characteristics of Graphene is derived in time, improves the security performance of battery further.Integrated flexible electrode material of the present invention has excellent flexibility and intensity, be suitable in the flexible battery needed for flexible electronic device, its preparation method simply, is easily controlled, and can realize a large amount of, low cost preparation, can be applicable to various types of electrodes material, there is using value.
Beneficial effect of the present invention is as follows:
1, the present invention proposes a kind of integrated flexible electrode, this flexible electrode is composited by polymeric layer, graphene layer and active material layer three layers, achieve the integrated design of lithium battery multicomponent, be different from conventional batteries assembling and be divided into three independent anabolic processes, as active material is coated in metal collector, add the three-decker of polymer, this design can reduce the contact resistance of various piece.
2, integrated flexible electrode material of the present invention has excellent flexibility and hot strength, is suitable in the various flexible batteries needed for flexible electronic device.
3, effectively can reduce the weight of inert matter metal collector in lithium ion battery and lithium-sulfur cell, greatly improve battery energy density.
4, in lithium ion battery, in the present invention, graphene layer can effectively reduce the weight of metal collector in battery and add the contact area of collector and active material, add the interface bond strength between collector and active material, and significantly reduce battery terminal contact internal resistance.
5, in lithium-sulfur cell, graphene film has adsorption capacity to sulphur and many sulphur product in lithium-sulfur cell, film forms by Sheet Graphite alkene is stacking, the active material that can be dissolved in electrolyte in the volumetric expansion to a certain degree suppressing elemental sulfur in electrochemical reaction process and polysulfide and cause in electrochemical reaction process runs off, lithium-sulfur cell specific capacity can be increased substantially, cycle characteristics and high rate performance.
Accompanying drawing explanation
The structural representation of the integrated flexible electrode of Fig. 1 prepared by the present invention, wherein: 1-polymer; 2-graphene layer; 3-active material layer.
Fig. 2 is the photo that straight polymer and gained graphene layer of the present invention are coated in polymer surfaces.
Fig. 3 is integrated flexible electrode photo of the present invention; Wherein: the photo that (a) is polymer and Graphene; The photo of (b) integrated electrode.
Fig. 4 is the stereoscan photograph of gained integrated flexible electrode cross section of the present invention.
Fig. 5 is the interface bond strength contrast of gained integrated flexible electrode material of the present invention and polymer-coated active material.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-coated sulphur active material border bond strength test curve.
The integrated flexible electrode material of Fig. 6 prepared by the embodiment of the present invention 1 and the polymer-coated sulphur positive pole prepared by comparative example 1 are at 1500mAg
-1charging and discharging curve under current density and polarization potential difference comparison diagram.
The integrated flexible electrode material of Fig. 7 prepared by the embodiment of the present invention 1 and the polymer-coated sulphur positive pole prepared by comparative example 1 high rate performance cyclic curve comparison diagram under different current density.
The integrated flexible electrode material of Fig. 8 prepared by the embodiment of the present invention 1 and the polymer-coated sulphur positive pole prepared by comparative example 1 are at 1500mAg
-1charge-discharge magnification under 200 cycle charge-discharge curves and coulombic efficiency contrast.
LED in parallel lighted in the bent state by the full battery of flexible Soft Roll that the integrated flexible electrode material of Fig. 9 prepared by the embodiment of the present invention 1 and flexible lithium paper tinsel are assembled into.
Embodiment
In order to understand the present invention further, below in conjunction with drawings and Examples, detailed complete description is carried out to the present invention.These descriptions are only explanation the features and advantages of the present invention, instead of limiting to the claimed invention.
As shown in Figure 1, a kind of integrated flexible electrode of the present invention is formed by three layers, and comprise polymeric layer 1, graphene layer 2 and active material layer 3, the thickness of described polymeric layer 1 is 15 ~ 25 μm; The thickness of described graphene layer 2 is 5 ~ 50 μm; The thickness of described active material layer 3 is 5 ~ 100 μm.Wherein polymeric layer 1 plays a role is barrier film, and graphene layer 2 plays the effect on collector and barrier layer.Graphene layer be by graphene film with a small amount of binding agent with (90 ~ 99): the part by weight of (1 ~ 10) mixes and disperses 0.5-2h in a solvent, then be coated on polymeric layer dry, graphene layer coating material as shown in Figure 2 can be obtained.This graphene layer coating material has good conductivity and pliability: the electric conductivity adopting four-point probe methods test graphene layer, and its conductivity is 600 ~ 2000S/cm; This collector can bend repeatedly, and its geomery can carry out cutting according to actual needs.Active material layer be by active material, conductive carbon material and binding agent with (4 ~ 8): (1 ~ 5): 1 part by weight mixing composition after be coated on graphene layer, will can obtain sulphur positive pole integrated flexible electrode as shown in Figure 3 after this trilaminate material drying.
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Graphene 700mg and 300mg polyvinylidene fluoride join even ultrasonic 0.5h in 1-METHYLPYRROLIDONE and disperse rear (in dispersion liquid, Graphene content is 1mg/mL) blade coating on microporous polypropylene membrane, can obtain Graphene coating material as Fig. 3 (a) after dry removal solvent, the thickness of graphene layer is 30 μm.On the surface of graphene layer sulphur: conductive black: the slurry smear that binding agent (polyvinylidene fluoride) is mixed to form with 7:2:1 part by weight, carbon/sulphur active material layer is formed on graphene layer surface, vacuumize at 70 DEG C, the dry time is 12h, obtains material and sees Fig. 3 (b).The cross sectional Scanning Electron microscope figure of gained sulphur positive pole integrated flexible electrode is shown in Fig. 4, can find out graphene film stacked structure layer by layer.In carbon/sulphur active material layer, sulphur, conductive black and binding agent uniform coating closely cover the surface of graphene layer, the about 30-40 micron of thickness of carbon/sulphur active material layer.
Interface bond strength performance test is carried out to the sulphur positive pole integrated flexible electrode material prepared by embodiment 1 and the coating sulphur positive pole prepared by comparative example 1, the interface bond strength of described sulphur positive pole integrated flexible electrode material is 6 times of barrier film coating sulphur positive pole, as Fig. 5, demonstrate the interface bond strength of its excellence.
Be assembled into button half-cell after being cut by above-mentioned obtained electrode plates and carry out charging and discharging curve under different multiplying and cycle performance test.The first charge-discharge curve of the sulphur positive pole integrated flexible electrode material of Fig. 6 prepared by embodiment 1 and the coating sulphur positive pole prepared by comparative example 1 (active material (sulphur simple substance): conductive black: weight of binder ratio is 7:2:1), can find out that two obvious discharge platforms correspond to from sulphur to high-order lithium polysulfide and high-order lithium polysulfide to the transition process of low order lithium polysulfide.At 1500mAg
-1current density under, discharge capacity can reach 1032mAhg first
-1, polarization potential difference only has 258mV.Discharge capacity under each current density is shown in Fig. 7, at 6000mAg
-1current density discharge capacity is more than 690mAhg
-1, show superior high rate performance.At 1500mAg
-1the capacity that to circulate under current density after 200 times is still close to 800mAhg
-1, coulombic efficiency, still more than 95%, illustrates that this electrode has extraordinary cyclical stability, as shown in Figure 8.
The sulphur positive pole integrated flexible electrode material adopting above-described embodiment 1 to prepare and flexible lithium paper tinsel negative pole, using the aluminium plastic material of 14cm × 8cm size as encapsulating material, in glove box, be assembled into flexible full battery, its gross thickness is about 1.5cm.This full battery is not only frivolous and have good flexibility, to repeat holding structure under the condition bent constant, and can carry out electric current output under bending state, light LED in parallel, as Fig. 9.
Comparative example 1
Difference from Example 1 is: only adopt microporous polypropylene membrane, does not have graphene layer.This electrode material is at 1500mAg
-1current density under, as Fig. 6, discharge capacity is 720mAhg first
-1be starkly lower than the specific discharge capacity of the sulphur positive pole integrated flexible electrode material under identical multiplying power, and can find out that its polarization potential difference is apparently higher than sulphur positive pole integrated electrode material by contrast, polarization potential difference, up to 537mV, shows that the resistance of embodiment 1 is starkly lower than the resistance of comparative example 1.Discharge capacity under each current density is shown in Fig. 7, and along with the increase of multiplying power, its capacity is decayed rapidly, at 6000mAg
-1current density discharge capacity is almost 0, and the specific capacity under each multiplying power is all lower than sulphur positive pole integrated electrode.At 1500mAg
-1the capacity after 200 times that circulates under current density is down to 260mAhg
-1, coulombic efficiency is down to 80%(and is seen Fig. 8).
Comparative example 2
Difference from Example 1 is: select the metal aluminum foil of business-like 25 micron thickness as collector, selects microporous polypropylene membrane.At aluminium foil surface sulphur: conductive black: binding agent (polyvinylidene fluoride) is mixed to form slurry with 7:2:1 part by weight and smear forms carbon/sulphur active material layer, vacuumize at 70 DEG C, the dry time is 12h, obtains aluminum foil current collector lithium sulfur battery anode material.This electrode material is at 1500mAg
-1current density under, discharge capacity is 550mAhg first
-1, at 3000mAg
-1current density discharge capacity is only 170mAhg
-1, at 4500mAg
-1almost capacity is not had under current density.
Comparative example 3
Adopt pure graphene film as a comparison, dry 12h at 70 DEG C after, section carries out lithium-sulfur cell electrochemical property test, at 1500mAg
-1current density under, its first charge-discharge capacity is all at 10mAhg
-1below, Posterior circle does not almost have capacity.
Embodiment 2
Business-like LiFePO4 powder, conductive black, binding agent PVDF are uniformly mixed in solvent NMP according to the mass ratio of 8:1:1, making uniform active electrode slurry, being drying to obtain iron phosphate lithium positive pole integrated flexible electrode by putting into 60 DEG C of baking ovens after this slurry blade coating is on microporous polypropylene membrane and graphene layer.Be assembled into the charge and discharge cycles test that button half-cell carries out under different multiplying after being cut by above-mentioned obtained electrode plates, find that this electrode is at 170mAg
-1current density under, discharge capacity can reach 140mAhg
-1, at 1700mAg
-1high current density under, the discharge capacity of LiFePO4 is 90mAhg
-1.
Comparative example 4
Be with the difference of embodiment 2: select the metal aluminum foil of business-like 25 micron thickness as collector.Business-like LiFePO4 powder, conductive black, binding agent PVDF are uniformly mixed in solvent NMP according to the mass ratio of 8:1:1, make uniform active electrode slurry, be coated in aluminum foil current collector with scraper, vacuumize at 90 DEG C, namely obtains aluminum foil current collector-iron phosphate lithium positive pole pole piece.This electrode material is at 170mAg
-1current density under, discharge capacity is 130mAhg
-1, along with the increase of multiplying power, its specific capacity declines rapidly, at 1700mAg
-1almost do not have capacity under current density, its high rate performance comparatively embodiment 2 is compared, and has very large gap.
Embodiment 3
Business-like LiMn2O4 powder, conductive black, binding agent PVDF are uniformly mixed in solvent NMP according to the mass ratio of 85:7:8, making uniform active electrode slurry, being drying to obtain lithium manganate cathode integrated flexible electrode by putting into 60 DEG C of baking ovens after this slurry blade coating is on microporous polypropylene membrane and graphene layer.Half-cell performance test is carried out to it, the multiplying power similar to embodiment 2 and cycle performance can be obtained, and result is better than the battery performance of aluminum foil current collector-lithium manganate cathode under the same terms.
Embodiment 4
Difference from Example 2 is: the LiFePO4 in embodiment 2 is replaced with cobalt acid lithium, be separated into uniform sizing material in NMP after, be drying to obtain lithium cobaltate cathode integrated flexible electrode by putting into 60 DEG C of baking ovens after this slurry blade coating is on microporous polypropylene membrane and graphene layer.Carry out half-cell performance test to it, its result is better than the battery performance of aluminum foil current collector-lithium cobaltate cathode under the same terms.
Embodiment 5
Business-like titanium dioxide powder, conductive black, binding agent PVDF are uniformly mixed in solvent NMP according to the mass ratio of 8:1:1, making uniform active electrode slurry, being drying to obtain titanium dioxide cathode integrated flexible electrode by putting into 60 DEG C of baking ovens after this slurry blade coating is on microporous polypropylene membrane and graphene layer.Half-cell performance test is carried out to it, the multiplying power similar to embodiment 2 and cycle performance can be obtained, and result is better than the battery performance of aluminum foil current collector-titanium dioxide cathode under the same terms.
Embodiment 6
Difference from Example 5 is: the titanium dioxide in embodiment 5 is replaced with business-like native graphite, be separated into uniform sizing material in NMP after, be drying to obtain graphite cathode integrated flexible electrode by putting into 60 DEG C of baking ovens after this slurry blade coating is on microporous polypropylene membrane and graphene layer.Carry out half-cell performance test to it, its result is better than the battery performance of copper foil current collector-graphite cathode under the same terms.
Electrochemical property test:
Respectively above embodiment and comparative example composite construction electrode section compressing tablet are struck out after the disk of diameter 19mm as lithium battery anode or negative material.All electrode slices are assembled into 2025 type button cells in inert-atmosphere glove box, metal lithium sheet is to electrode, lithium-sulfur cell electrolyte be 1mol/L LiTFSI/DOL+DME (wherein, the volume ratio 1:1 of DOL and DME, LiTFSI is bis trifluoromethyl sulfonic acid imide li, DOL is DOX, and DME is glycol dimethyl ether); In lithium ion battery, electrolyte is electrolyte is 1mol/LLiPF
6/ EC+EMC+DMC (wherein, the volume ratio 1:1:1 of EC, EMC, DMC, EC are ethylene carbonate, and EMC is methyl ethyl carbonate, and DMC is dimethyl carbonate); Barrier film used is polypropylene (Celgard2400).Electrochemical property test is tested battery performance at Wuhan Lan electricity company Land BT-1 type tester.The telescopiny of lithium ion in active material in active material-lithium half-cell is called charging by the present invention, and the deintercalation process of lithium ion in active material is called electric discharge.
Above test result shows, a kind of integrated flexible electrode of the present invention material, effectively can increase the conductive contact area of collector and active electrode material, interface binding intensity between active material and collector, relative to existing metal collector electrode plates, there is better high rate performance, lower internal resistance, higher energy density, and there is good bending characteristic.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 efficient.Graphene film also has adsorption capacity to sulphur and many sulphur product, and the active material that can cause to a certain degree suppressing elemental sulfur polysulfide in electrochemical reaction process to be dissolved in electrolyte in electrochemical reaction process runs off.Graphene layer is as collector and barrier layer, effectively increase electronics and the ion transfer of barrier film, and largely limit shuttling back and forth of many sulphions, therefore integrated flexible electrode material of the present invention has high specific capacity, excellent cyclical stability and high rate performance, be expected to obtain application in the flexible lithium battery of high-energy-density, high power density.
Claims (10)
1. an integrated flexible electrode, it is characterized in that: this flexible electrode is composited by three layers, be followed successively by polymeric layer, graphene layer and active material layer, wherein: the polypropylene micropore diaphragm of described polymeric layer to be pore size distribution range be 10 ~ 1000nm, polyethylene micropore barrier film, Kynoar barrier film or cellulose composite membrane barrier film; Described graphene layer be by graphene film with binding agent with (90 ~ 99): the part by weight of (1 ~ 10) mixes and disperses 0.5-2h in a solvent, to be coated on membrane for polymer dry after obtain; Described active material layer be by active material, conductive agent and binding agent with (4 ~ 8): (1 ~ 5): be coated on graphene layer and obtain after the part by weight mixing of 1, obtain integrated flexible electrode by after trilaminate material drying.
2. integrated flexible electrode according to claim 1, is characterized in that: described graphene layer thickness is 5 ~ 50 μm, and conductivity is 600 ~ 2000S/cm; The thickness of described active material layer is 5 ~ 100 μm.
3. integrated flexible electrode according to claim 1, is characterized in that: the number of plies of described graphene film below 10 layers, lateral dimension more than 1 micron, carbon-to-oxygen ratio is more than 20.
4. integrated flexible electrode according to claim 3, is characterized in that: the number of plies 3 ~ 8 layers of described graphene film, lateral dimension 5 ~ 50 microns, carbon-to-oxygen ratio 20 ~ 120.
5. integrated flexible electrode according to claim 1, it is characterized in that: the solvent for dispersed graphite alkene sheet is alcohols, ketone, aldehydes, organic acid, 1-METHYLPYRROLIDONE, dimethyl formamide, dimethylacetylamide, chlorobenzene or dichloro-benzenes etc., and graphene film content is in a solvent 1 ~ 5mg/mL.
6. integrated flexible electrode according to claim 1, is characterized in that: the method for dispersed graphite alkene sheet comprises one or more in ultrasonic disperse, high speed shear dispersion, vigorous stirring and emulsification.
7. integrated flexible electrode according to claim 1, is characterized in that: the active material in described active material layer is anode material for lithium-ion batteries, negative material or lithium sulfur battery anode material.
8. integrated flexible electrode according to claim 7, is characterized in that: described anode material for lithium-ion batteries comprises one or several combinations in LiFePO4, cobalt acid lithium, LiMn2O4, lithium manganese phosphate, phosphoric acid vanadium lithium, nickel ion doped and nickel-cobalt-manganese ternary material; Described lithium ion battery negative material comprises one or several combinations in native graphite, Delanium, lithium metal, silicon-base alloy, silicon-base oxide, kamash alloy, tin-based oxide, lithium titanate, titanium dioxide, tin oxide, iron oxide and cobalt oxide; Described lithium sulfur battery anode material comprises elemental sulfur, lithium two sulphur or lithium sulfide.
9. integrated flexible electrode according to claim 1, is characterized in that: described conductive agent is conductive black, mesoporous carbon, microporous carbon ball, level hole carbon, activated carbon, hollow carbon sphere, carbon nano-tube, carbon fiber, fullerene or Graphene; Described binding agent is polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, polyvinyl alcohol or modified styrene butadiene rubber; Mode active material, conductive agent and binding agent mixed is mechanical mixture, ball milling or ultrasonic mixing.
10. integrated flexible electrode according to claim 1, it is characterized in that: in described integrated flexible electrode, Graphene content is 10 ~ 15wt%, and activity substance content is 55 ~ 70wt%, conductive carbon material and binder content are 5 ~ 10wt%, and all the other are polymer.
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| CN (1) | CN104916809B (en) |
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