CN106997947A - A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell - Google Patents
A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell Download PDFInfo
- Publication number
- CN106997947A CN106997947A CN201710350489.9A CN201710350489A CN106997947A CN 106997947 A CN106997947 A CN 106997947A CN 201710350489 A CN201710350489 A CN 201710350489A CN 106997947 A CN106997947 A CN 106997947A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- self assembly
- porous material
- lithium
- polyimide porous
- 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.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell, using aromatic dianhydride and diamines as raw material, the porous polyimide particle for being self-assembly of layering of molecule is utilized in single organic solvent, pass through high temperature cabonization again, rush sulphur process, obtain self assembly polyimide porous material；Polyimide porous material is assembled by polyimides lamella, and each lamellar spacing is 20 40nm, and there is 50 200nm hole between lamella.Self assembly polyimide porous material is used to prepare lithium sulfur battery anode material.Beneficial effects of the present invention are simple to operate, and reaction condition is gentle；It is that can control its pattern only by the control of reaction time and reactant concentration；Synthesized carbon material contains nitrogen in itself, has certain depression effect for the shuttle of the polysulfide of lithium-sulfur cell；Size is larger, can reduce contact resistance, beneficial to discharge and recharge under big multiplying power.
Description
Technical field
The invention belongs to lithium-sulfur cell field, and in particular to the polyimide particles that a kind of utilization self-assembling method is obtained,
And as the presoma of porous carbon, it is used as the positive pole carbon material of lithium-sulfur cell.
Background technology
With increase of the people for heavy-duty battery demand, existing lithium rechargeable battery system, due to traditional
The limitation of transition metal oxide base anode material theory lithium storage content, the raising of lithium-inserting amount encounters bottleneck.
Compared with conventional lithium ion battery, lithium-sulfur cell is up to 1675mAh/g, theoretical specific energy with its theoretical specific capacity
2600Wh/Kg, elemental sulfur nature rich reserves, hypotoxicity, it is cheap the advantages of, it is latent as secondary cell of new generation
Power army.
However, following problem hampers the commercialization of lithium-sulfur cell：1. sulphur and discharging product lithium sulfide (Li2S) it is
The non-conductor of electronics.2. about 80% Volume Changes can be produced in charge and discharge process, it is likely that anode structure can be caused
Cave in.3. " the shuttle effect " of intermediate product polysulfide can reduce the utilization rate of active material, the coulombic efficiency of battery is caused
Relatively low, capacity declines very fast.
For problem above, vast scholar's research is proved, the design of positive electrode can solve three above well and ask
Topic.Carbon material is the good stability for modifying performance of control and skeleton structure with its excellent electric conductivity, extensive
Applied in lithium sulfur battery anode material.But it is existing comparatively laborious with template progress synthesis carbon material post processing；Utilize
The carbon material of self-assembling method synthesis is generally two kinds of solvents, and influence factor is more.
The content of the invention
The problem of existing for prior art, the present invention by single solvent be self-assembled into lithium sulfur battery anode material there is provided
A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell.
The technical scheme is that：
A kind of self assembly polyimide porous material, the self assembly polyimide porous material is with aromatic dianhydride and diamines
For raw material, with the method for solvent heat self assembly, the porous poly- of layering is self-assembly of using molecule in single organic solvent
Acid imide particle, then pass through high temperature cabonization, rush sulphur process, obtain self assembly polyimide porous material.Described polyimides
Porous material is assembled by polyimides lamella, and each lamellar spacing is to have 50-200nm's between 20-40nm, and lamella
Hole.Later stage completion is rushed after sulphur process, and sulphur simple substance is present between the hole of polyimide porous material, and is attached to self assembly
On the lamella of polyimide porous material.The expansion issues of volume, can also when sulphur simple substance reaction is not only alleviated in the space of piece interlayer
Beneficial to the transmission of lithium ion in course of reaction；The lamella of interconnection shortens the distance of electric transmission, for smoothly entering for reaction
Row, which is provided, to be ensured.The material also has N, and O elements can adsorb polysulfide by physics and chemical action, necessarily simultaneously
The shuttle of polysulfide is inhibited in degree, the utilization rate of sulphur is improved, while piece interlayer has abundant hole, can be accommodated
Sulphur, and provide space for the volumetric expansion during lithiumation.
The preparation method of above-mentioned self assembly polyimide porous material, comprises the following steps：
The first step, prepares performed polymer A
At room temperature, diamines is dissolved in solvent, is equipped with concentration 0.15-0.20mol/L diamine solutions, is stirred vigorously down in batches
Secondary addition and the polyvinylpyrrolidone (PVB) of the quality such as diamines in solution, rub after being added after its dissolving with diamines in solution etc.
Your dianhydride, prepolymerization 8-10h, obtains the polyamic acid solution of yellow at room temperature.The diamines is 4,4- diaminodiphenyl ethers
(ODA)；The dianhydride is 3,3'4,4'- benzophenone tetracarboxylic dianhydrides (BTDA) or 1,4,5,8 naphthalenetetracarboxylic acid acid anhydride (NTCDA)；
The solvent is 1-Methyl-2-Pyrrolidone (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide
(DMAC)。
Second step, prepares stephanoporate polyamide granulates B
Above-mentioned polyamic acid solution is transferred in polytetrafluoroethylene bushing, by reactor as in baking oven, 170-200 DEG C
Lower reaction 6-10h, is cooled to after room temperature, filters, washs, dries, obtains stephanoporate polyamide granulates B；
3rd step, prepares porous polyimide particle C and is carbonized
Under inert gas shielding, the solid porous polyamic acid particle B that second step is obtained is high at 350 DEG C -400 DEG C
Temperature calcining 1 hour, carries out dehydration closed-loop, forms polyimide particles C.The inert gas is nitrogen or argon gas；Described
Heating rate is 3-5 DEG C/min.
4th step, prepares porous carbon ball D
Under inert gas shielding, the polyimide particles C that the 3rd step is obtained is maintained in 800-1000 DEG C of high-temperature calcination
1-3h, obtains porous carbon ball D.The inert gas is nitrogen or argon gas；Described heating rate is 3-5 DEG C/min.
5th step, prepares carbon sulphur composite
Sublimed sulfur is completely dissolved in solvent, then adds porous carbon ball D in a solvent, stirs complete to solution evaporation at room temperature
Quan Hou, carries out obtaining carbon sulphur composite C/S after melting fills sulphur 10-12 hours, as self assembly polyimides is more at 155 DEG C
Porous materials.Described solvent is carbon disulfide (CS2), toluene.
Above-mentioned self assembly polyimide porous material is applied to lithium-sulfur cell field, for preparing lithium-sulphur cell positive electrode material
Material.Prepare concretely comprising the following steps for lithium sulfur battery anode material：Kynoar PVDF is dissolved in appropriate NMP, then will be certainly
Assemble polyimide porous material and superconduction carbon black super P and be scattered in PVDF nmp solution, and stir 6h and be well mixed
Anode sizing agent is made afterwards, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h use tablet press machine
Diameter 12mm disk is struck out, anode pole piece is obtained.Described self assembly polyimide porous material, superconduction carbon black (super
P), the mass ratio of Kynoar (PVDF) is 8:1:1.
Assembling lithium-sulfur cell the step of be：By lithium sulfur battery anode material, polypropylene micropore diaphragm, negative pole lithium piece in order
It is assembled into battery and appropriate electrolyte is added dropwise.The double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3It is dissolved in 1,
Electrolyte, DOX and ethylene glycol are obtained in the mixed solution of 3- dioxolanes (DOL)/glycol dimethyl ether (DME)
Volume ratio be 1:1.
The present invention has following beneficial effect：
1) it is simple to operate, compared to template, it is not necessary to perform etching the process for removing template.2) reaction condition is gentle,
Harsh reaction condition is not needed.3) it is that can control its pattern only by the control of reaction time and reactant concentration.4)
Synthesized carbon material contains nitrogen in itself, has certain depression effect for the shuttle of the polysulfide of lithium-sulfur cell.5)
Size is larger, reduces contact resistance, beneficial to discharge and recharge under big multiplying power.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 (a is Local map, and b is single carbon ball)；
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 4 (a is Local map, and b is overall diagram)；
Fig. 3 is first charge-discharge curve of the embodiment 1 under 0.1C；
Fig. 4 is the thermal gravimetric analysis curve of the carbon sulphur compound of embodiment 1.
Embodiment
The preparation method and property of sulphur carbon composite of the present invention are further described below by way of embodiment
Can, but any limitation of the invention is not constituted.
Embodiment 1
At room temperature, by 0.200g4,4- diaminodiphenyl ethers (ODA) and the PVB of quality is waited to be added to 6.5ml DMF solutions
In, being stirred vigorously makes it be uniformly dispersed, and 0.266g1 is added in batches, and 4,5,8- naphthalenetetracarbacidic acidic acid anhydrides are stirred at room temperature 10 small
When.
Above-mentioned solution is transferred in polytetrafluoroethylene bushing, and reactor is reacted into 10h as in baking oven at 180 DEG C,
Room temperature is cooled to, through filtering, washing, dries, obtains stephanoporate polyamide granulates.
Obtained polyimides granulates are placed in tube furnace, in N2400 DEG C, dimension are warming up to 3 DEG C/min under atmosphere
1h is held, polyimide particles are obtained；Continue to be warming up to 900 DEG C with 3 DEG C/min, maintain 1h, obtain porous carbon ball.
0.19g elemental sulfurs are dissolved in 40ml toluene, the above-mentioned carbon materials of 0.08g are weighed, and by the toluene solution and carbon of sulphur
Material is mixed, and is stirred at room temperature to solution evaporation completely, and maintain 12h to obtain carbon sulphur composite C/S at 155 DEG C.
Lithium sulfur battery anode material prepared by this example is used to prepare lithium-sulfur cell, and its concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.22g, super P 0.0268g, PVDF 0.0268g are taken, the PVDF claimed is dissolved in
In appropriate NMP, then by positive electrode and super P and it is scattered in PVDF nmp solution and grinds 30min and be well mixed
Anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h use tablet machine drift
Diameter 12mm disk is pressed into, anode pole piece is obtained；
B:The preparation of lithium-sulfur cell：
Anode pole piece, polypropylene micropore diaphragm, negative pole lithium piece made from step A are subsequently assembled into battery and are added dropwise suitable
Measure electrolyte：Electrolyte is the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3It is dissolved in 1,3- dioxolanes
(DOL) (volume ratio is 1 to/glycol dimethyl ether (DME):1).
Embodiment 2
At room temperature, by 0.4234g4,4- diaminodiphenyl ethers (ODA) and the PVB of quality is waited to be added to 13.2mlDMF solution
In, being stirred vigorously makes to be uniformly dispersed, and 0.6460g1 is added in batches, and 4,5,8- naphthalenetetracarbacidic acidic acid anhydrides are stirred at room temperature 9 hours.
Above-mentioned solution is transferred in polytetrafluoroethylene bushing, and reactor is reacted into 10h as in baking oven at 180 DEG C,
Room temperature is cooled to, and filters, wash, drying, stephanoporate polyamide granulates are obtained.
Obtained polyimides granulates are placed in tube furnace, 350 DEG C, dimension are warming up to 3 DEG C/min under n 2 atmosphere
1h is held, polyimide particles are obtained；Continue to be warming up to 800 DEG C with 3 DEG C/min, maintain 1h, obtain porous carbon ball.
0.3g elemental sulfurs are dissolved in 60ml toluene, the above-mentioned carbon materials of 0.3g are weighed, and by the toluene solution and carbon materials of sulphur
Material is mixed, and is stirred at room temperature to solution evaporation completely, and maintain 12h to obtain carbon sulphur composite C/S at 155 DEG C.
Lithium sulfur battery anode material prepared by this example is used to prepare lithium-sulfur cell, and its concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.2804g, super P0.0349g, PVDF0.0349g are taken, the PVDF claimed is dissolved in
In appropriate NMP, then by positive electrode and super P and it is scattered in PVDF nmp solution and grinds 30min and be well mixed
Anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h use tablet machine drift
Diameter 12mm disk is pressed into, anode pole piece is obtained；
B:The preparation of lithium-sulfur cell：
Anode pole piece, polypropylene diaphragm, negative pole lithium piece made from step A are subsequently assembled into battery and electrolysis is added dropwise
Liquid：Electrolyte is the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3It is 1 to be dissolved in volume ratio:1 1,3-
In dioxolanes (DOL)/glycol dimethyl ether (DME) solution.
Embodiment 3
At room temperature, by 0.445g4,4- diaminodiphenyl ethers (ODA) and the PVB of quality is waited to be added to 13ml1- methyl -2-
In pyrrolidones (NMP) solution, being stirred vigorously makes to be uniformly dispersed, and 0.530g1 is added in batches, and 4,5,8- naphthalenetetracarbacidic acidic acid anhydrides are added
In above-mentioned solution, being stirred vigorously makes to be uniformly dispersed, and is stirred at room temperature 10 hours.
Above-mentioned solution is transferred in polytetrafluoroethylene bushing, and reactor is reacted into 10h as in baking oven at 180 DEG C,
Room temperature is cooled to, and filters, wash, drying, stephanoporate polyamide granulates are obtained.
Obtained polyimides granulates are placed in tube furnace, 350 DEG C, dimension are warming up to 3 DEG C/min under n 2 atmosphere
1h is held, polyimide particles are obtained；Continue to be warming up to 900 DEG C with 3 DEG C/min, maintain 3h, obtain porous carbon ball.
0.19g elemental sulfurs are dissolved in 40ml toluene, the above-mentioned carbon materials of 0.08g are weighed, and by the toluene solution and carbon of sulphur
Material is mixed, and is stirred at room temperature to solution evaporation completely, and maintain 12h to obtain carbon sulphur composite C/S at 155 DEG C.
Lithium sulfur battery anode material prepared by this example is used to prepare lithium-sulfur cell, and its concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.22g, superconduction carbon black 0.0268g, PVDF0.0268g are taken, the PVDF claimed is dissolved in
In appropriate NMP, then by positive electrode and super P and it is scattered in PVDF nmp solution and grinds 30min and be well mixed
Anode sizing agent is made, anode sizing agent is coated in aluminum foil current collector with coating machine, 60 DEG C of vacuum drying 12h use tablet machine drift
Diameter 12mm disk is pressed into, anode pole piece is obtained；
B:The preparation of lithium-sulfur cell：
Anode pole piece, polypropylene micropore diaphragm, negative pole lithium piece made from step A are subsequently assembled into battery and electricity is added dropwise
Solve liquid：Electrolyte is the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3It is dissolved in 1,3- dioxolanes
(DOL) (volume ratio is 1 to/glycol dimethyl ether (DME):1).
Embodiment 4
At room temperature, by 0.2067g4,4- diaminodiphenyl ethers (ODA) and the PVB of quality is waited to be added to 6.5mlDMF solution
In, being stirred vigorously makes to be uniformly dispersed, the polyvinylpyrrolidone (PVP) of the quality such as addition, and the 3,3' of 0.3230g is added in batches
4,4'- benzophenone tetracarboxylic dianhydrides (BTDA) are added in above-mentioned solution, and being stirred vigorously makes to be uniformly dispersed, and is stirred at room temperature
10 hours.
Above-mentioned solution is transferred in polytetrafluoroethylene bushing, and reactor is reacted into 10h as in baking oven at 180 DEG C,
Room temperature is cooled to, and filters, wash, drying, stephanoporate polyamide granulates are obtained.
Obtained polyimides granulates are placed in tube furnace, 350 DEG C, dimension are warming up to 3 DEG C/min under n 2 atmosphere
1h is held, polyimide particles are obtained；Continue to be warming up to 900 DEG C with 3 DEG C/min, maintain 3h, obtain porous carbon ball.
0.0518g elemental sulfurs are dissolved in 20ml toluene, the above-mentioned carbon materials of 0.1220g are weighed, and by the toluene solution of sulphur
Mixed, stirred at room temperature to solution evaporation completely, and maintain 12h to obtain carbon sulphur composite at 155 DEG C with carbon material
C/S。
Lithium sulfur battery anode material prepared by this example is used to prepare lithium-sulfur cell, and its concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned cell positive material 0.1192g, superconduction carbon black 0.0145g, PVDF0.0140g are taken, the PVDF claimed is molten
In appropriate NMP, anode sizing agent is coated in aluminium foil afflux by the well mixed obtained anode sizing agents of grinding 30min with coating machine
On body, 60 DEG C of vacuum drying 12h are pressed into diameter 12mm disk with tablet machine drift, obtain anode pole piece；
B:The preparation of lithium-sulfur cell：
Anode pole piece, polypropylene micropore diaphragm, negative pole lithium piece made from step A are subsequently assembled into battery and electricity is added dropwise
Solve liquid：Electrolyte is the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3It is dissolved in 1,3- dioxolanes
(DOL) (volume ratio is 1 to/glycol dimethyl ether (DME):1).
Embodiment 5
At room temperature, by 0.4140g4,4- diaminodiphenyl ethers (ODA) and the PVB of quality is waited to be added to 13.3mlDMF solution
In, being stirred vigorously makes to be uniformly dispersed, and adds equimolar 0.413g polyvinylpyrrolidone, and the 3 of 0.6460g is added in batches,
3'4,4'- benzophenone tetracarboxylic dianhydride (BTDA) are added in above-mentioned solution, and being stirred vigorously makes to be uniformly dispersed, and stirs at room temperature
Mix 10 hours.
Above-mentioned solution is transferred in polytetrafluoroethylene bushing, and reactor is reacted into 10h as in baking oven at 180 DEG C,
Room temperature is cooled to, and filters, wash, drying, stephanoporate polyamide granulates are obtained.
Obtained polyimides granulates are placed in tube furnace, 350 DEG C, dimension are warming up to 3 DEG C/min under n 2 atmosphere
1h is held, polyimide particles are obtained；Continue to be warming up to 1000 DEG C with 3 DEG C/min, maintain 3h, obtain porous carbon.
0.1485g elemental sulfurs are dissolved in 40ml toluene, the above-mentioned carbon materials of 0.0636g are weighed, and by the toluene solution of sulphur
Mixed with carbon material, stir at room temperature to solution evaporation completely, maintain 12h to obtain carbon sulphur composite C/ at 155 DEG C
S。
Lithium sulfur battery anode material prepared by this example is used to prepare lithium-sulfur cell, and its concrete operation step is：
A：The preparation of anode pole piece：
Above-mentioned material 0.1394g, superconduction carbon black 0.0170g, PVDF0.0172g are taken, the PVDF claimed is dissolved in appropriate
In NMP, then by positive electrode and super P and it is scattered in PVDF nmp solution and stirs 12h slurry is made, with coating
Anode sizing agent is coated in aluminum foil current collector by machine, 60 DEG C of vacuum drying 12h, and diameter 12mm disk is pressed into tablet machine drift,
Obtain anode pole piece；
B:The preparation of lithium-sulfur cell：
Anode pole piece, polypropylene micropore diaphragm, negative pole lithium piece made from step A are subsequently assembled into battery and electricity is added dropwise
Solve liquid：Electrolyte is the double trifluoromethanesulfonimide lithiums (LiTFSI) of 1M and 0.2M LiNO3It is dissolved in 1,3- dioxolanes
(DOL) (volume ratio is 1 to/glycol dimethyl ether (DME):1).
Claims (7)
1. a kind of self assembly polyimide porous material, it is characterised in that the self assembly polyimide porous material is with aromatic series
Dianhydride and diamines are raw material, using the porous polyimide particle for being self-assembly of layering of molecule in single organic solvent,
Pass through high temperature cabonization again, rush sulphur process, obtain self assembly polyimide porous material；Described self assembly polyimide foraminous material
Material is assembled by polyimides lamella, and each lamellar spacing is the hole that there is 50-200nm between 20-40nm, and lamella；
Rush after sulphur process, sulphur simple substance is present between the hole of self assembly polyimide porous material, and be attached to self assembly and gather
On the lamella of acid imide porous material.
2. the preparation method of the self assembly polyimide porous material described in claim 1, it is characterised in that following steps：
The first step, prepares performed polymer A
At room temperature, diamines is dissolved in solvent, is equipped with concentration 0.15-0.20mol/L diamine solution, is stirred vigorously down in batches
The polyvinylpyrrolidone PVB of the quality such as diamines in addition and solution, it is equimolar with diamines in solution after being added after its dissolving
Dianhydride；Prepolymerization 8-10h, obtains the polyamic acid solution of yellow at room temperature；
The diamines is 4,4- diaminodiphenyl ethers；The dianhydride be 3,3'4,4'- benzophenone tetracarboxylic dianhydrides or 1,4,5,
8- naphthalenetetracarbacidic acidic acid anhydrides；
Second step, prepares stephanoporate polyamide granulates B
Above-mentioned polyamic acid solution is transferred in polytetrafluoroethylene bushing, it is anti-at 170-200 DEG C by reactor as in baking oven
6-10h is answered, is cooled to after room temperature, filters, wash, dry, obtain stephanoporate polyamide granulates B；
3rd step, prepares porous polyimide particle C and is carbonized
Under inert gas shielding, the solid porous polyamic acid particle B that second step is obtained high temperature at 350 DEG C -400 DEG C is forged
Burn 1 hour, carry out dehydration closed-loop, form polyimide particles C；
4th step, prepares porous carbon ball D
Under inert gas shielding, the polyimide particles C that the 3rd step is obtained maintains 1-3h in 800-1000 DEG C of high-temperature calcination,
Obtain porous carbon ball D；
5th step, prepares carbon sulphur composite
Sublimed sulfur is completely dissolved in solvent B, then porous carbon ball D is added in solvent B, stirs to solution and volatilizees completely at room temperature
Afterwards, carry out obtaining carbon sulphur composite C/S, as self assembly polyimide foraminous after melting fills sulphur 10-12 hours at 155 DEG C
Material.
3. the preparation method of self assembly polyimide porous material according to claim 2, it is characterised in that in the first step
Described solvent B is carbon disulfide, toluene.
4. the preparation method of the self assembly polyimide porous material according to Claims 2 or 3, it is characterised in that first
Solvent orange 2 A described in step is 1-Methyl-2-Pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.
5. the preparation method of the self assembly polyimide porous material according to Claims 2 or 3, it is characterised in that second
Inert gas described in step, the 3rd step and the 4th step is nitrogen or argon gas；Described heating rate is 3-5 DEG C/min.
6. the preparation method of self assembly polyimide porous material according to claim 4, it is characterised in that second step,
Inert gas described in 3rd step and the 4th step is nitrogen or argon gas；Described heating rate is 3-5 DEG C/min.
7. the self assembly polyimide porous material described in claim 1 is applied to lithium-sulfur cell field, for preparing lithium sulphur electricity
Pond positive electrode.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710350489.9A CN106997947A (en) | 2017-05-22 | 2017-05-22 | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell |
| PCT/CN2018/087659 WO2018214844A1 (en) | 2017-05-22 | 2018-05-21 | Self-assembled polyimide porous material, preparation method therefor and use thereof in lithium sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710350489.9A CN106997947A (en) | 2017-05-22 | 2017-05-22 | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106997947A true CN106997947A (en) | 2017-08-01 |
Family
ID=59435351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710350489.9A Pending CN106997947A (en) | 2017-05-22 | 2017-05-22 | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106997947A (en) |
| WO (1) | WO2018214844A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107640766A (en) * | 2017-10-27 | 2018-01-30 | 哈尔滨工业大学 | A kind of method that three-dimensional variable density porous material is made based on amylofermentation principle |
| CN108442114A (en) * | 2018-02-07 | 2018-08-24 | 东华大学 | A kind of poly-triphenylamine-carbon nano-fiber composite material and its preparation and application |
| WO2018214844A1 (en) * | 2017-05-22 | 2018-11-29 | 大连理工大学 | Self-assembled polyimide porous material, preparation method therefor and use thereof in lithium sulfur battery |
| CN109728279A (en) * | 2018-12-29 | 2019-05-07 | 桂林电器科学研究院有限公司 | The surface treatment method and product and battery of a kind of nickelic tertiary cathode material |
| CN111085179A (en) * | 2019-11-29 | 2020-05-01 | 宁波海关技术中心 | Application of sulfur-containing polyimide resin as silver adsorbent |
| CN111498827A (en) * | 2020-04-12 | 2020-08-07 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
| CN112670515A (en) * | 2021-01-11 | 2021-04-16 | 大连理工大学 | Preparation method of iron/iron carbide high-filling-rate carbon nanotube lithium-sulfur battery positive electrode material |
| CN112981615A (en) * | 2021-02-26 | 2021-06-18 | 南方科技大学 | Nano carbon fiber and preparation method and application thereof |
| CN113660999A (en) * | 2019-03-22 | 2021-11-16 | 思攀气凝胶公司 | Carbon aerogel-based cathode for lithium sulfur battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230136A (en) * | 2007-01-22 | 2008-07-30 | 东丽纤维研究所（中国）有限公司 | Polyimide microparticle and preparation method thereof |
| CN106159205A (en) * | 2015-04-10 | 2016-11-23 | 中国科学院青岛生物能源与过程研究所 | A kind of carbon sulfur composite of the loose structure of amino functional and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105336930B (en) * | 2015-10-16 | 2018-09-25 | 浙江理工大学 | A kind of lithium-sulfur cell with rich nitrogen it is carbon-based/sulphur composite positive pole and preparation method thereof |
| CN106340632B (en) * | 2016-08-29 | 2019-08-20 | 温州大学 | Nano carbon balls/sulphur composite material and preparation method and application |
| CN106997947A (en) * | 2017-05-22 | 2017-08-01 | 大连理工大学 | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell |
-
2017
- 2017-05-22 CN CN201710350489.9A patent/CN106997947A/en active Pending
-
2018
- 2018-05-21 WO PCT/CN2018/087659 patent/WO2018214844A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230136A (en) * | 2007-01-22 | 2008-07-30 | 东丽纤维研究所（中国）有限公司 | Polyimide microparticle and preparation method thereof |
| CN106159205A (en) * | 2015-04-10 | 2016-11-23 | 中国科学院青岛生物能源与过程研究所 | A kind of carbon sulfur composite of the loose structure of amino functional and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| ZHIXIAO XU，ET AL.: "Nitrogen-Doped Porous Carbon Superstructures Derived from Hierarchical Assembly of Polyimide Nanosheets", 《ADVANCED MATERIALS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018214844A1 (en) * | 2017-05-22 | 2018-11-29 | 大连理工大学 | Self-assembled polyimide porous material, preparation method therefor and use thereof in lithium sulfur battery |
| CN107640766A (en) * | 2017-10-27 | 2018-01-30 | 哈尔滨工业大学 | A kind of method that three-dimensional variable density porous material is made based on amylofermentation principle |
| CN108442114A (en) * | 2018-02-07 | 2018-08-24 | 东华大学 | A kind of poly-triphenylamine-carbon nano-fiber composite material and its preparation and application |
| CN109728279A (en) * | 2018-12-29 | 2019-05-07 | 桂林电器科学研究院有限公司 | The surface treatment method and product and battery of a kind of nickelic tertiary cathode material |
| CN113660999A (en) * | 2019-03-22 | 2021-11-16 | 思攀气凝胶公司 | Carbon aerogel-based cathode for lithium sulfur battery |
| CN111085179A (en) * | 2019-11-29 | 2020-05-01 | 宁波海关技术中心 | Application of sulfur-containing polyimide resin as silver adsorbent |
| CN111498827A (en) * | 2020-04-12 | 2020-08-07 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
| CN111498827B (en) * | 2020-04-12 | 2022-12-30 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
| CN112670515A (en) * | 2021-01-11 | 2021-04-16 | 大连理工大学 | Preparation method of iron/iron carbide high-filling-rate carbon nanotube lithium-sulfur battery positive electrode material |
| CN112981615A (en) * | 2021-02-26 | 2021-06-18 | 南方科技大学 | Nano carbon fiber and preparation method and application thereof |
| CN112981615B (en) * | 2021-02-26 | 2023-02-21 | 南方科技大学 | Nano carbon fiber and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018214844A1 (en) | 2018-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106997947A (en) | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell | |
| JP6445585B2 (en) | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery | |
| Wu et al. | Preparation of mesohollow and microporous carbon nanofiber and its application in cathode material for lithium–sulfur batteries | |
| CN103456929B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN102208608B (en) | Preparation method of carbon-sulfur composite material for lithium ion battery carbon cathode material | |
| CN103219517B (en) | Preparation method for nitrogen-doped porous carbon sphere-sulfur composite positive material | |
| CN103500819B (en) | Carbon fiber/sulphur composite positive pole of a kind of finishing cellular carbon structure and preparation method thereof | |
| CN106602063B (en) | Preparation method of graphene flower and application of graphene flower in lithium-sulfur battery | |
| Chen et al. | Labyrinth-inspired nitrogen-sulfur co-doped reduced holey graphene oxide/carbonized cellulose paper: A permselective and multifunctional interlayer for high-performance lithium-sulfur batteries | |
| CN103390752B (en) | Graphene-based matrix material, its preparation method and the application in lithium-sulfur cell thereof | |
| CN104362294B (en) | A kind of porous sulphur positive pole for lithium-sulfur cell, its preparation method and lithium-sulfur cell | |
| CN105762360A (en) | Graphene-silicon-coated composite negative electrode material and preparing method and application thereof | |
| CN112670507B (en) | Preparation method of lithium-sulfur battery intermediate layer of metal selenide-loaded carbon nanofiber and lithium-sulfur battery | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN107808955B (en) | Activated carbon material with spherical structure and preparation method and application thereof | |
| CN107331839A (en) | A kind of preparation method of carbon nanotube loaded nano titanium oxide | |
| CN111446414B (en) | Covalent organic framework material, preparation method and application thereof | |
| CN114204218B (en) | Loaded hollow Co 3 O 4 Preparation method of positive electrode side interlayer for cubic lithium-sulfur battery | |
| CN110148739A (en) | A kind of carbon@allyl sulfides itrile group polymer composite anode active material, anode and its preparation and the application in lithium-sulfur cell | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN106898746A (en) | Hierarchical porous structure nano-sized carbon/sulphur composite and the application in lithium-sulfur cell are prepared by raw material of Hawaii shell | |
| CN110600713A (en) | Porous carbon doped anode material, preparation method thereof and alkali metal ion battery | |
| CN105742597A (en) | Preparation method for novel negative electrode material of lithium ion battery | |
| CN105161690B (en) | The method that molybdenum disulfide charge and discharge cycles ability is improved by doped graphene and titanium dioxide | |
| CN109755542B (en) | Sodium-sulfur battery positive electrode material 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170801 |
|
| WD01 | Invention patent application deemed withdrawn after publication |