CN107293751A - A kind of flexible self-supporting polymer overmold carbon interlayer, preparation method and applications - Google Patents
A kind of flexible self-supporting polymer overmold carbon interlayer, preparation method and applications Download PDFInfo
- Publication number
- CN107293751A CN107293751A CN201710452431.5A CN201710452431A CN107293751A CN 107293751 A CN107293751 A CN 107293751A CN 201710452431 A CN201710452431 A CN 201710452431A CN 107293751 A CN107293751 A CN 107293751A
- Authority
- CN
- China
- Prior art keywords
- interlayer
- carbon
- flexible self
- polymer overmold
- supporting polymer
- 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.)
- Granted
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to a kind of flexible self-supporting polymer overmold carbon interlayer, preparation method and application, belong to battery material technical field.In the interlayer, poly-dopamine cladding carbon material weave in is in network pilotaxitic texture, and binding agent is coated on the outside of network pilotaxitic texture with film forming agent.At room temperature, carbon material is added and be dissolved with the cushioning liquid of Dopamine hydrochloride, 4~24h of stirring is mixed, and filters to obtain powder;Powder, binding agent and film forming agent are mixed into obtain slurry;Slurry is applied in substrate, 4~24h is dried, goes the removal of impurity with solvent washing, come off from substrate, obtain the interlayer.The interlayer can improve the utilization rate of active material sulphur with self-supporting and with flexibility, while can effectively suppress the dissolving of polysulfide, improve the cycle life of lithium-sulfur cell, reduce lithium-sulfur cell impedance, be particularly suitable for application as the interlayer of lithium-sulfur cell;Preparation method is simple, with low cost, environmental protection, it is easy to accomplish produce in enormous quantities.
Description
Technical field
The present invention relates to a kind of flexible self-supporting polymer overmold carbon interlayer, preparation method and application, belong to battery material
Technical field.
Background technology
Due to the rapidly growth to high-energy-density device requirement, people research and develop various energy storage devices.Lithium-sulfur cell
With up to 1675m Ahg-1Theoretical capacity and 2600Whkg-1Energy density, far above conventional lithium ion electricity
Pond.Although there is these significant advantages, the practical of lithium-sulfur cell still faces many problems and challenge.Subject matter is:
First, the poorly conductive of sulphur, causes the utilization rate of sulphur in lithium-sulfur cell low;2nd, during charge and discharge cycles, many vulcanizations of generation
Thing is easily soluble in electrolyte, and between both positive and negative polarity continuous " shuttle ", causes the coulombic efficiency of lithium-sulfur cell low and circulation is steady
Qualitative difference.
The described problem existed for lithium-sulfur cell, there has been proposed a variety of improving countermeasures, including improvement positive pole, bears
Pole and electrolyte etc..It is existing studies have reported that in, by finding suitable positive electrode and electrolyte system, lithium-sulfur cell can be made
Performance be effectively improved.Barrier film is as one of important component in lithium battery system, and the quality of its performance is to battery
Performance equally has important influence.Barrier film be located at both positive and negative polarity between, during charge and discharge cycles, prevent both positive and negative polarity contact and
Generation short circuit, and allow lithium ion to carry out free migration.
Battery sandwich is inserted into the material between positive electrode and barrier film.Battery sandwich eliminates the material processing of complexity
Problem, with the difunctional effect as upper strata collector and storage polysulfide.Carbon material possesses layer upon layer of, cranky
Pore passage structure, polysulfide can be adsorbed, the distance that increase polysulfide infiltration is lost in, is the interlayer material as lithium-sulfur cell
The ideal material of material.Porous carbon particle, CNT (CNT), graphene (GO), carbon microfibre paper and carbon nano-fiber are used for lithium
Sulphur battery sandwich can improve the coulombic efficiency and cycle performance of lithium-sulfur cell.Lai Yanqing seminars of Central South University pass through vacuum
Filtering and heat treatment prepare independent hollow carbon nano-fiber/redox graphene interlayers (Wang Zhang Z, Wang G,
Lai Y,et al.A freestanding hollow carbon nanofiber/reduced graphene oxide
interlayer for high-performance lithium–sulfur batteries[J].Journal of Alloys
and Compounds,2016,663:501-506.), but document procedure is cumbersome, it is necessary to use the dangerous gas of reproducibility
Body and dangerous liquid, and vacuum environment is needed, it is unfavorable for extensive preparation.
The content of the invention
For defect present in prior art, an object of the present invention is to provide a kind of flexible self-supporting polymer
Carbon interlayer is coated, the interlayer composition structure is:The network pilotaxitic texture of polymer overmold carbon material weave in formation, glues
Knot agent is coated on the outside of the network pilotaxitic texture again with film forming agent, and the interlayer has flexible and is independent self-supporting structure.
The second object of the present invention is to provide a kind of preparation method of flexible self-supporting polymer overmold carbon interlayer, passed through
It is well mixed, is applied in substrate by polymer overmold carbon material, and with binding agent and film forming agent, with solvent washing, you can obtain
The interlayer, methods described is simple, can be mass-produced.
The third object of the present invention is to provide a kind of application of flexible self-supporting polymer overmold carbon interlayer, the application
Be using the interlayer be as lithium-sulfur cell interlayer, shuttle effect can be suppressed.
To realize the purpose of the present invention, there is provided following technical scheme.
A kind of flexible self-supporting polymer overmold carbon interlayer, the composition structure of the interlayer is as follows:Polymer overmold carbon materials
Expect weave in formation network pilotaxitic texture, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
Wherein, the polymer is poly-dopamine;
Carbon material is preferably one or more of porous carbon particle, graphene oxide, carbon nano-fiber and CNT;
It is preferred that the thickness of interlayer is 10 μm~70 μm.
A kind of preparation method of flexible self-supporting polymer overmold carbon interlayer of the present invention, methods described step is as follows:
At room temperature, carbon material is added and be dissolved with the cushioning liquid of polymer monomer, stirring 4h~24h mixing is equal
Even, filtering obtains powder;Powder, binding agent and film forming agent are well mixed, slurry is obtained;Slurry is applied in substrate, dried
4h~24h, the removal of impurity is gone with solvent washing, is come off from substrate and be can obtain a kind of flexible self-supporting polymerization of the present invention
Thing coats carbon interlayer.
Wherein, the carbon material is preferably one in porous carbon particle, graphene oxide, carbon nano-fiber and CNT
More than kind.
Polymer monomer is Dopamine hydrochloride;
The mass ratio of carbon material and polymer monomer is 10:1~1:10, preferably 1:1.
Cushioning liquid is three (methylol) aminomethane-hydrochloric acid (Tris-HCl) cushioning liquid that pH value is 7.5~10.
Binding agent is the polyethylene dioxythiophene (PEDOT that polystyrolsulfon acid adulterates:PSS).
Film forming agent is phenmethylol, Lauryl Alcohol ester, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propane diols fourth
Ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether or dimethyl sulfoxide (DMSO);Preferably dimethyl sulfoxide (DMSO) (DMSO).
Powder and PEDOT:PSS mass ratio is 1:9~9:1, preferably 3:2~4:1.
PEDOT:PSS and DMSO volume ratio is preferably 25:1~5:1.
Substrate is preferably silicon plate or glass plate.
Slurry is applied in substrate, and coating thickness is 1 μm~500 μm.
Solvent is water or acetone.
It is preferred that the purity of water is more than deionized water purity.
A kind of application of flexible self-supporting polymer overmold carbon material of the present invention, the application is to make the interlayer
For the interlayer of lithium-sulfur cell.
Beneficial effect
1. the present invention relates to a kind of flexible self-supporting polymer overmold carbon interlayer, the interlayer can be with self-supporting and with soft
Property, the utilization rate of active material sulphur can be improved, while can effectively suppress the dissolving of polysulfide, following for lithium-sulfur cell is improved
In the ring life-span, reduce lithium-sulfur cell impedance.
2. the invention provides a kind of preparation method of flexible self-supporting polymer overmold carbon interlayer, methods described is simple,
It is with low cost, environmental protection, it is easy to accomplish produce in enormous quantities.
3. the present invention relates to a kind of application of flexible self-supporting polymer overmold carbon interlayer, the material can with self-supporting and
With flexibility, the interlayer as lithium-sulfur cell is applicable, shuttle effect can be suppressed.
Brief description of the drawings
Fig. 1 is the pictorial diagram of flexible self-supporting polymer overmold carbon interlayer made from embodiment 1.
Fig. 2 is SEM (SEM) figure of flexible self-supporting polymer overmold carbon interlayer made from embodiment 1.
Fig. 3 is transmission electron microscope (TEM) figure of flexible self-supporting polymer overmold carbon interlayer made from embodiment 1.
Fig. 4 is containing the lithium-sulfur cell of flexible self-supporting polymer overmold carbon interlayer made from embodiment 1 and without described
The impedance behavior figure of the lithium-sulfur cell of interlayer.
Embodiment
With reference to specific embodiment, the invention will be further elaborated, but the present invention is not limited to following examples.
In following examples:
Miillpore filter is purchased from Beijing North dawn membrane separation technique Co., Ltd;
PEDOT:PSS is purchased from Nichem, 1000ml.
To flexible self-supporting polymer overmold carbon interlayer made from following examples and the lithium-sulfur cell containing the interlayer
Carry out testing as follows respectively:
(1) SEM (SEM) is tested:The INSTRUMENT MODEL of SEM is SUPRA55, Germany;Survey
Test agent and preparation method:Sample will be made after flexible self-supporting polymer overmold carbon interlayer drying made from embodiment, carries out
SEM test;
(2) transmission electron microscope (TEM) is tested:The model JEM-2100F, 200kV, day of transmission electron microscope
This;Test sample and preparation method:Flexible self-supporting polymer overmold carbon interlayer made from embodiment is scattered in absolute ethyl alcohol
In, drop in the micro-grid of transmission electron microscope and dry, carry out TEM tests;
(3) assembling of the lithium-sulfur cell containing the interlayer:A strata aniline system is coated again by conductive black and sulphur are compound
Standby material is used as negative pole as positive pole, lithium piece;In electrolyte, solute is 1mol/L bis trifluoromethyl sulfonic acid imide lis
(LiTFSI), 0.4mol/L lithium nitrates (LiNO3), solvent is that volume ratio is 1:1 glycol dimethyl ether (DME) and 1,3- dioxies
Penta ring (DOL);Barrier film uses model Celgard2325 microporous polypropylene membrane;Flexible self-supporting made from embodiment is gathered
Compound cladding carbon interlayer is positioned between positive pole and barrier film, the lithium-sulfur cell of composition S/ interlayers/barrier film/lithium piece structure;
The assembling of the lithium-sulfur cell of the interlayer is not contained:Positive pole, negative pole, electrolyte and barrier film and its assembling are with containing
The lithium-sulfur cell for stating interlayer is identical, does not place flexible self-supporting polymer overmold phacolith made from embodiment between positive pole and barrier film
Layer.
(4) lithium-sulfur cell performance test:
Lithium-sulfur cell impedance behavior is tested:The use of INSTRUMENT MODEL is CHI660 electrochemical workstations, Shanghai Chen Hua instrument has
Limit company;Test parameter:Frequency range 0.1Hz~1MHz, constant voltage is battery open circuit voltage.
Embodiment 1
At room temperature, it is 8.5 100ml 0.2g CNTs to be added to and be dissolved with the pH value of 0.2g Dopamine hydrochlorides
Mix, magnetic agitation 8h is well mixed, with the miillpore filter suction filtration that average pore size is 0.22 μm, obtain in Tris-HCl cushioning liquid
To powder;By powder, PEDOT:PSS and DMSO grind 30min in mortar and are well mixed, and obtain slurry;Slurry is applied to silicon
On plate, coating thickness is 150 μm, and 24h is dried at normal temperatures, impurity is washed off with deionized water, is come off from substrate, obtained
A kind of flexible self-supporting polymer overmold carbon interlayer of the present invention, photo pictorial diagram is as shown in Figure 1.
Wherein, powder and PEDOT:PSS mass ratio is 4:1, PEDOT:PSS and DMSO volume ratio is 25:3.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is as shown in Fig. 2 as shown in Figure 2, the thickness of the interlayer is 15.1 μm.
(2) transmission electron microscope is tested:
Test result is as shown in Figure 3, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
Lithium-sulfur cell containing the interlayer and the lithium-sulfur cell for not containing the interlayer are tested respectively, as a result such as
Shown in Fig. 4, it is known that add after the interlayer, add after interlayer, impedance is reduced to 27 Ω by 67 Ω.The significant reduction of positive electrode resistance,
Illustrate to add the conduction for promoting ion after interlayer, battery conductive, which improves, means the good utilization of active material, it is suppressed that
Shuttle effect.
Embodiment 2
At room temperature, 1g CNTs and 0.1g graphene oxides are added to the pH value for being dissolved with 0.2g Dopamine hydrochlorides
To be mixed in 8.5 100ml Tris-HCl cushioning liquid, magnetic agitation 8h is well mixed, micro- for 0.22 μm with average pore size
Hole filter membrane suction filtration, obtains powder;By powder, PEDOT:PSS and DMSO grind 30min in mortar and are well mixed, and obtain slurry;
Slurry is applied on silicon plate, coating thickness is 500 μm, and 24h is dried at normal temperatures, impurity is washed off with deionized water, from base
Come off on bottom, obtain a kind of flexible self-supporting polymer overmold carbon interlayer of the present invention, photo pictorial diagram is similar with Fig. 1.
Wherein, powder and PEDOT:PSS mass ratio is 1:9, PEDOT:PSS and DMSO volume ratio is 5:1.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is similar with Fig. 2 results, it is known that the thickness of the flexible self-supporting polymer overmold carbon interlayer is 67 μm.
(2) transmission electron microscope is tested:
Test result is similar with Fig. 3, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
To the lithium-sulfur cell containing the interlayer and do not contain the lithium-sulfur cell of the interlayer and test respectively, as a result with
Fig. 4 is similar, it is known that add after the interlayer, the impedance of lithium-sulfur cell is greatly reduced, it is meant that promote the conduction of ion, battery
Electric conductivity improves, and active material is well utilized, it is suppressed that shuttle effect.
Embodiment 3
At room temperature, it is 7.5 100ml 0.2g CNTs to be added to and be dissolved with the pH value of 2g Dopamine hydrochlorides
Mix, magnetic agitation 8h is well mixed, with the miillpore filter suction filtration that average pore size is 0.22 μm, obtain in Tris-HCl cushioning liquid
To powder;By powder, PEDOT:PSS and DMSO grind 30min in mortar and are well mixed, and obtain slurry;Slurry is applied to silicon
On plate, coating thickness is 1 μm, and 24h is dried at normal temperatures, impurity is washed off with deionized water, is come off from substrate, obtains this
A kind of described flexible self-supporting polymer overmold carbon interlayer of invention, photo pictorial diagram is similar with Fig. 1.
Wherein, powder and PEDOT:PSS mass ratio is 1:9, PEDOT:PSS and DMSO volume ratio is 25:1.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is similar with Fig. 2, it is known that the thickness of the flexible self-supporting polymer overmold carbon interlayer is 55 μm.
(2) transmission electron microscope is tested:
Test result is similar with Fig. 3, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
To the lithium-sulfur cell containing the interlayer and do not contain the lithium-sulfur cell of the interlayer and test respectively, as a result with
Fig. 4 is similar, it is known that add after the interlayer, the impedance of lithium-sulfur cell is greatly reduced, it is meant that promote the conduction of ion, battery
Electric conductivity improves, and active material is well utilized, it is suppressed that shuttle effect.
Embodiment 4
At room temperature, it is 10 100ml 0.2g graphene oxides to be added to and be dissolved with the pH value of 1.2g Dopamine hydrochlorides
Mix, magnetic agitation 8h is well mixed, with the miillpore filter suction filtration that average pore size is 0.22 μm, obtain in Tris-HCl cushioning liquid
To powder;By powder, PEDOT:PSS and DMSO grind 30min in mortar and are well mixed, and obtain slurry;Slurry is applied to silicon
On plate, coating thickness is 150 μm, and 24h is dried at normal temperatures, impurity is washed off with deionized water, is come off from substrate, obtained
A kind of flexible self-supporting polymer overmold carbon interlayer of the present invention, photo pictorial diagram is similar with Fig. 1.
Wherein, powder and PEDOT:PSS mass ratio is 9:1, PEDOT:PSS and DMSO volume ratio is 5:1.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is similar with Fig. 2, it is known that the thickness of the flexible self-supporting polymer overmold carbon interlayer is 34 μm.
(2) transmission electron microscope is tested:
Test result is similar with Fig. 3, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
To the lithium-sulfur cell containing the interlayer and do not contain the lithium-sulfur cell of the interlayer and test respectively, as a result with
Fig. 4 is similar, it is known that add after the interlayer, the impedance of lithium-sulfur cell is greatly reduced, it is meant that promote the conduction of ion, battery
Electric conductivity improves, and active material is well utilized, it is suppressed that shuttle effect.
Embodiment 5
At room temperature, it is 10 100ml 0.2g CNTs to be added to and be dissolved with the pH value of 1.2g Dopamine hydrochlorides
Mixed in Tris-HCl cushioning liquid, magnetic agitation 24h is well mixed, be 0.22 μm of miillpore filter suction filtration with average pore size,
Obtain powder;By powder, PEDOT:PSS and DMSO grind 30min in mortar and are well mixed, and obtain slurry;Slurry is applied to
On silicon plate, coating thickness is 150 μm, and 24h is dried at normal temperatures, the removal of impurity is gone with acetone rinsing, is come off from substrate, obtains this
A kind of described flexible self-supporting polymer overmold carbon interlayer of invention, photo pictorial diagram is similar with Fig. 1.
Wherein, powder and PEDOT:PSS mass ratio is 9:1, PEDOT:PSS and DMSO volume ratio is 5:1.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is similar with Fig. 2, it is known that the thickness of the flexible self-supporting polymer overmold carbon interlayer is 35 μm.
(2) transmission electron microscope is tested:
Test result such as Fig. 3 is similar, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
To the lithium-sulfur cell containing the interlayer and do not contain the lithium-sulfur cell of the interlayer and test respectively, as a result with
Fig. 4 is similar, it is known that add after the interlayer, the impedance of lithium-sulfur cell is greatly reduced, it is meant that promote the conduction of ion, battery
Electric conductivity improves, and active material is well utilized, it is suppressed that shuttle effect.
Embodiment 6
At room temperature, it is 7.5 100ml 0.2g CNTs to be added to and be dissolved with the pH value of 0.2g Dopamine hydrochlorides
Mix, magnetic agitation 4h is well mixed, with the miillpore filter suction filtration that average pore size is 0.22 μm, obtain in Tris-HCl cushioning liquid
To powder;By powder, PEDOT:PSS and DMSO grind 30min in mortar and are well mixed, and obtain slurry, slurry is applied into glass
In glass plate, coating thickness is 150 μm, and 24h is dried at normal temperatures, impurity is washed off with deionized water, is come off from substrate, obtained
To a kind of flexible self-supporting polymer overmold carbon interlayer of the present invention, photo pictorial diagram is similar with Fig. 1.
Wherein, powder and PEDOT:PSS mass ratio is 3:2, PEDOT:PSS and DMSO volume ratio is 5:1.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is similar with Fig. 2, it is known that the thickness of the flexible self-supporting polymer overmold carbon interlayer is 35 μm.
(2) transmission electron microscope is tested:
Test result such as Fig. 3 is similar, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
To the lithium-sulfur cell containing the interlayer and do not contain the lithium-sulfur cell of the interlayer and test respectively, as a result with
Fig. 4 is similar, it is known that add after the interlayer, the impedance of lithium-sulfur cell is greatly reduced, it is meant that promote the conduction of ion, battery
Electric conductivity improves, and active material is well utilized, it is suppressed that shuttle effect.
Embodiment 7
At room temperature, it is 0.05g CNTs, 0.05g graphene oxides and 0.05g carbon nano-fibers and 0.05g is porous
Carbon particle is added to the pH value dissolved with 0.2g Dopamine hydrochlorides to be mixed in 10 100ml Tris-HCl cushioning liquid, and magnetic force is stirred
Mix 8h to be well mixed, with the miillpore filter suction filtration that average pore size is 0.22 μm, obtain powder;By powder, PEDOT:PSS and
DMSO grinds 30min in mortar and is well mixed, and obtains slurry;Slurry is applied on glass plate, coating thickness is 150 μm,
24h is dried under normal temperature, impurity is washed off with deionized water, is come off from substrate, a kind of flexibility of the present invention is obtained certainly
Support polymer coats carbon interlayer, and photo pictorial diagram is similar with Fig. 1.
Wherein, powder and PEDOT:PSS mass ratio is 4:1, PEDOT:PSS and DMSO volume ratio is 5:1.
Flexible self-supporting polymer overmold carbon interlayer made from the present embodiment is tested, it is as a result as follows:
(1) scanning electron microscope test:
Test result is similar with Fig. 2, it is known that the thickness of the flexible self-supporting polymer overmold carbon interlayer is 40 μm.
(2) transmission electron microscope is tested:
Test result is similar with Fig. 3, it is known that poly-dopamine is coated with the network single fisherman's knot of carbon material weave in formation
Structure, binding agent is coated on the outside of the network pilotaxitic texture with film forming agent.
(3) lithium-sulfur cell performance test
To the lithium-sulfur cell containing the interlayer and do not contain the lithium-sulfur cell of the interlayer and test respectively, as a result with
Fig. 4 is similar, it is known that add after the interlayer, the impedance of lithium-sulfur cell is greatly reduced, it is meant that promote the conduction of ion, battery
Electric conductivity improves, and active material is well utilized, it is suppressed that shuttle effect.
Claims (9)
1. a kind of flexible self-supporting polymer overmold carbon interlayer, it is characterised in that:The composition structure of the interlayer is as follows:Poly- DOPA
Amine cladding carbon material weave in formation network pilotaxitic texture, binding agent is coated on the network pilotaxitic texture with film forming agent
Outside.
2. a kind of flexible self-supporting polymer overmold carbon interlayer according to claim 1, it is characterised in that:Carbon material is porous
One or more of carbon particle, graphene oxide, carbon nano-fiber and CNT.
3. a kind of flexible self-supporting polymer overmold carbon interlayer according to claim 1, it is characterised in that:The thickness of interlayer
For 5 μm~70 μm.
4. a kind of flexible self-supporting polymer overmold carbon interlayer according to claim 1, it is characterised in that:Carbon material is porous
One or more of carbon particle, graphene oxide, carbon nano-fiber and CNT;The thickness of interlayer is 1 μm~70 μm.
5. a kind of preparation method of flexible self-supporting polymer overmold carbon interlayer as described in Claims 1 to 4, its feature exists
In:Methods described step is as follows:
At room temperature, carbon material is added and be dissolved with the cushioning liquid of Dopamine hydrochloride, stirring 4h~24h is well mixed, mistake
Filter, obtains powder;Powder, binding agent and film forming agent are well mixed, slurry is obtained;Slurry is applied in substrate, dry 4h~
24h, the removal of impurity is gone with solvent washing, is come off from substrate, obtains a kind of described flexible self-supporting polymer overmold carbon interlayer;
The mass ratio of carbon material and Dopamine hydrochloride is 10:1~1:10;
Cushioning liquid is the Tris-HCl cushioning liquid that pH value is 7.5~10;
Binding agent is PEDOT:PSS;
Film forming agent is phenmethylol, Lauryl Alcohol ester, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propandiol butyl ether, two
Propylene glycol monomethyl ether, dipropylene glycol monopropyl ether or dimethyl sulfoxide (DMSO);
Powder and PEDOT:PSS mass ratio is 1:9~9:1;
Slurry is applied in substrate, and coating thickness is 1 μm~500 μm;
Solvent is water or acetone.
6. a kind of preparation method of flexible self-supporting polymer overmold carbon interlayer according to claim 5, it is characterised in that:
The mass ratio of carbon material and Dopamine hydrochloride is 1:1;Powder and PEDOT:PSS mass ratio is 3:2~4:1;PEDOT:PSS with
The volume ratio of dimethyl sulfoxide (DMSO) is 25:1~5:1.
7. a kind of preparation method of flexible self-supporting polymer overmold carbon interlayer according to claim 5, it is characterised in that:
Film forming agent is dimethyl sulfoxide (DMSO);Substrate is silicon plate or glass plate.
8. a kind of preparation method of flexible self-supporting polymer overmold carbon interlayer according to claim 5, it is characterised in that:
The mass ratio of carbon material and Dopamine hydrochloride is 1:1;Powder and PEDOT:PSS mass ratio is 3:2~4:1;PEDOT:PSS with
The volume ratio of dimethyl sulfoxide (DMSO) is 25:1~5:1;Film forming agent is dimethyl sulfoxide (DMSO);Substrate is silicon plate or glass plate;The purity of water
More than deionized water purity.
9. a kind of application of flexible self-supporting polymer overmold carbon interlayer as described in Claims 1 to 4, it is characterised in that:Will
The interlayer as lithium-sulfur cell interlayer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710452431.5A CN107293751B (en) | 2017-06-15 | 2017-06-15 | Flexible self-supporting polymer coated carbon interlayer, preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710452431.5A CN107293751B (en) | 2017-06-15 | 2017-06-15 | Flexible self-supporting polymer coated carbon interlayer, preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107293751A true CN107293751A (en) | 2017-10-24 |
CN107293751B CN107293751B (en) | 2020-04-14 |
Family
ID=60097067
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710452431.5A Active CN107293751B (en) | 2017-06-15 | 2017-06-15 | Flexible self-supporting polymer coated carbon interlayer, preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107293751B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109244455A (en) * | 2018-09-04 | 2019-01-18 | 复旦大学 | A kind of lithium-sulfur cell loads the preparation method of positive electrode with self-supporting high-sulfur |
CN109449425A (en) * | 2018-11-20 | 2019-03-08 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium-sulfur cell composite material and the application of the composite material |
CN117316526A (en) * | 2023-09-14 | 2023-12-29 | 河北大学 | Method for preparing self-supporting nano carbon-based conductive macroscopic body and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104022267A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Sandwich-structure sulfur-graphene-conductive polymer composite material, preparation and application |
CN104617327A (en) * | 2014-12-31 | 2015-05-13 | 北京理工大学 | Anode material of lithium-sulfur battery, lithium-sulfur battery and method for preparing anode material |
CN104900856A (en) * | 2015-04-29 | 2015-09-09 | 中南大学 | Nanometer sulfur-based positive electrode composite material for lithium sulfur batteries, and preparation method thereof |
-
2017
- 2017-06-15 CN CN201710452431.5A patent/CN107293751B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104022267A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Sandwich-structure sulfur-graphene-conductive polymer composite material, preparation and application |
CN104617327A (en) * | 2014-12-31 | 2015-05-13 | 北京理工大学 | Anode material of lithium-sulfur battery, lithium-sulfur battery and method for preparing anode material |
CN104900856A (en) * | 2015-04-29 | 2015-09-09 | 中南大学 | Nanometer sulfur-based positive electrode composite material for lithium sulfur batteries, and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
FENG WU等: ""A polypyrrole-supported carbon paper acting as a polysulfide trap for lithium–sulfur batteries"", 《RSC ADVANCES》 * |
JOO HYUN KIM等: ""Synergistic Ultrathin Functional Polymer-Coated Carbon Nanotube Interlayer for High Performance Lithium–Sulfur Batteries"", 《ACS APPL. MATER. INTERFACES》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109244455A (en) * | 2018-09-04 | 2019-01-18 | 复旦大学 | A kind of lithium-sulfur cell loads the preparation method of positive electrode with self-supporting high-sulfur |
CN109244455B (en) * | 2018-09-04 | 2021-04-30 | 复旦大学 | Preparation method of self-supporting high-sulfur-loading positive electrode material for lithium-sulfur battery |
CN109449425A (en) * | 2018-11-20 | 2019-03-08 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium-sulfur cell composite material and the application of the composite material |
CN117316526A (en) * | 2023-09-14 | 2023-12-29 | 河北大学 | Method for preparing self-supporting nano carbon-based conductive macroscopic body and application thereof |
CN117316526B (en) * | 2023-09-14 | 2024-05-03 | 河北大学 | Method for preparing self-supporting nano carbon-based conductive macroscopic body and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN107293751B (en) | 2020-04-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Xu et al. | Gel polymer electrolyte based on PVDF-HFP matrix composited with rGO-PEG-NH2 for high-performance lithium ion battery | |
Yang et al. | PIM-1 as an artificial solid electrolyte interphase for stable lithium metal anode in high-performance batteries | |
Zhang et al. | Water-soluble polyacrylic acid as a binder for sulfur cathode in lithium-sulfur battery | |
Zhou et al. | NiCo 2 O 4 nanosheet supported hierarchical core–shell arrays for high-performance supercapacitors | |
Gao et al. | Lithiated Nafion-garnet ceramic composite electrolyte membrane for solid-state lithium metal battery | |
CN105098233B (en) | The preparation method of semi-interpenetrating network polymer gel electrolyte membrane | |
Cui et al. | Rational construction of a 3D hierarchical NiCo 2 O 4/PANI/MF composite foam as a high-performance electrode for asymmetric supercapacitors | |
Huang et al. | Composite nanofiber membranes of bacterial cellulose/halloysite nanotubes as lithium ion battery separators | |
CN104466134B (en) | The preparation method of self-supporting graphene/carbon nano-tube hybrid foam support amino anthraquinones base polymer | |
US10665893B2 (en) | Anode material including graphite phase carbon material and functionalized graphene, method thereof, and lithium ion battery | |
CN107221454B (en) | A kind of all-solid-state flexible supercapacitor and preparation method thereof based on porous carbon fiber cloth | |
CN107959049A (en) | Preparation method, gel electrolyte and the lithium ion battery of gel electrolyte | |
Kong et al. | A Janus nanofiber-based separator for trapping polysulfides and facilitating ion-transport in lithium–sulfur batteries | |
CN109256583A (en) | A kind of organo-mineral complexing all solid state electrolyte and its preparation method and application | |
CN104466168A (en) | Preparation method of cobaltosic oxide-carbon porous nanofiber and application of cobaltosic oxide-carbon porous nanofiber to preparation of lithium ion battery | |
CN104934610A (en) | Preparation method of self-supporting flexible composite electrode material used by lithium ion battery | |
CN107221660A (en) | A kind of flexible lithium sulfur battery anode material | |
CN109075324A (en) | Cathode and the method for being used to prepare cathode | |
CN111430716B (en) | Water-based soy protein-based supermolecule sulfur positive electrode binder and preparation method and application thereof | |
CN103972584A (en) | Electrolyte carrier membrane, electrolyte, preparation method of two and lithium ion battery | |
Yue et al. | A heat resistant and flame-retardant polysulfonamide/polypropylene composite nonwoven for high performance lithium ion battery separator | |
Tsao et al. | Ionic conducting and surface active binder of poly (ethylene oxide)-block-poly (acrylonitrile) for high power lithium-ion battery | |
CN110534711B (en) | Preparation method of polyimide composite material and application of polyimide composite material in battery | |
CN107293751A (en) | A kind of flexible self-supporting polymer overmold carbon interlayer, preparation method and applications | |
CN106450474A (en) | Gelled polymer electrolyte membrane and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |