CN106935771A - A kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms - Google Patents
A kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms Download PDFInfo
- Publication number
- CN106935771A CN106935771A CN201710225961.6A CN201710225961A CN106935771A CN 106935771 A CN106935771 A CN 106935771A CN 201710225961 A CN201710225961 A CN 201710225961A CN 106935771 A CN106935771 A CN 106935771A
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- Prior art keywords
- polyacrylonitrile
- graphene oxide
- fluorinated graphene
- fluorinated
- celgard
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- 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.)
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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
- H01M50/411—Organic material
-
- 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
- H01M50/44—Fibrous material
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
-
- 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 present invention provides a kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms, polyacrylonitrile including commercial Celgard barrier films and its surface/Fluorinated graphene oxide layer composition, the thickness of described polyacrylonitrile/Fluorinated graphene oxide layer is 1~10 μm, and polyacrylonitrile and the mass ratio of Fluorinated graphene oxide are 0.2 1 in described polyacrylonitrile/Fluorinated graphene oxide layer：1, the mass fraction of oxygen is 1% 20% in described Fluorinated graphene oxide, and the mass fraction of fluorine is 1% 20% in described Fluorinated graphene oxide.The itrile group on polyacrylonitrile in polyacrylonitrile/Fluorinated graphene oxide layer, oxygen, fluorine with Fluorinated graphene oxide surface are highly polar group, strong chemisorbed can be formed to the polysulfide formed in charge and discharge process, polysulfide can be effectively prevented to reach negative pole through barrier film, the generation of shuttle effect is reduced, the life-span of lithium-sulfur cell is improved.
Description
Technical field
The present invention relates to lithium-sulfur cell field, more particularly to a kind of lithium-sulfur cell barrier film.
Background technology
Lithium-sulfur cell is that, with lithium metal as negative pole, elemental sulfur is the battery system of positive pole.Lithium-sulfur cell is put with two
Level platform（About 2.4 V and 2.1 V）, but its electrochemical reaction mechanism is more complicated.Lithium-sulfur cell has specific energy high
（2600 Wh/kg）, specific capacity it is high（1675 mAh/g）, low cost and other advantages, it is considered to be very promising a new generation's electricity
Pond.But the problems such as there is low active material utilization, low cycle life and poor security at present, this seriously governs lithium
The development of sulphur battery.Causing the main cause of above mentioned problem has the following aspects：（1）Elemental sulfur is electronics and ion insulation
Body, room-temperature conductivity is low（5×10-30S·cm-1）, it is because the sulphur without ionic state is present thus tired as positive electrode activation
It is difficult；（2）The many lithium sulfide Li of high poly- state produced in electrode process2Sn（8 ＞ n >=4）It is soluble in electrolyte, positive and negative
Concentration difference is formed between pole, negative pole is moved in the presence of concentration gradient, the poly- many lithium sulfides of state high are reduced into low by lithium metal
The poly- many lithium sulfides of state.The carrying out of reaction more than, the oligomeric many lithium sulfides of state are assembled in negative pole, are finally formed between electrodes
Concentration difference, moves to positive pole and is oxidized to many lithium sulfides of poly- state high again.This phenomenon is referred to as shuttle effect, reduces sulphur activity
The utilization rate of material.While insoluble Li2S and Li2S2Cathode of lithium surface is deposited on, lithium-sulfur cell is further degrading
Performance；（3）Reaction final product Li2S is equally electronic body, can be deposited on sulfur electrode, and lithium ion vulcanizes in solid-state
Migration velocity is slow in lithium, makes electrochemical reaction kinetic rate slack-off；（4）Sulphur and final product Li2The density of S is different, works as sulphur
Rear volumetric expansion about 79% is lithiated, Li is easily caused2The efflorescence of S, causes the safety problem of lithium-sulfur cell.Above-mentioned not enough restriction
The development of lithium-sulfur cell, this is also the Important Problems that current lithium-sulfur cell research needs to solve.
The content of the invention
The technical problem to be solved in the present invention be to provide a kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard it is compound every
Film, including commercial Celgard barrier films and its surface polyacrylonitrile/Fluorinated graphene oxide layer composition, described polyacrylonitrile/
The thickness of Fluorinated graphene oxide layer is 1~10 μm, polyacrylonitrile and fluorine in described polyacrylonitrile/Fluorinated graphene oxide layer
The mass ratio for changing graphene oxide is 0.2-1：1, the mass fraction of oxygen is 1%-20% in described Fluorinated graphene oxide, described
Fluorinated graphene oxide in fluorine mass fraction be 1%-20%.
It is as follows that the present invention provides a kind of preparation method of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms：
（1）Graphite oxide is put into heating response in Muffle furnace, reaction atmosphere is the mixed gas of nitrogen and fluorine gas, and reaction is completed
Natural cooling, obtains fluorinated graphite afterwards；
（2）By in fluorinated graphite addition organic solvent, ultrasonic disperse forms suspension；
（3）Commercial polyacrylonitrile powder is added in organic solvent, after swelling 24 hours, heating stirring reaction obtains poly- third
Alkene nitrile solution；
（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction, obtains polyacrylonitrile/fluorinated graphite
Spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard and is combined
Barrier film.
Step（1）The temperature of middle heating response be 50-200 DEG C, reaction time 10-60 minute, reaction atmosphere be nitrogen with
Volume ratio shared by the mixed gas of fluorine gas, wherein fluorine gas is 5%-10%;
Step（2）Middle fluorinated graphite is 1 with the mass ratio of organic solvent：10-100, organic solvent is N- crassitudes
Ketone, dimethyl sulfoxide (DMSO), DMF, one or more in ethanol, ultrasonic time 0.5-5 hours;
Step（3）Middle polyacrylonitrile powder is 1 with the mass ratio of organic solvent：10-100, polyacrylonitrile powder and fluorinated
The mass ratio of Graphene is 0.2-1：1, organic solvent is 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), DMF,
One or more in ethanol, heating response temperature is 50-80 DEG C, 0.5-5 hours heating stirring reaction time;
Step（4）Middle mechanic whirl-nett reaction time 1-5 hour, electrospinning conditions are：Temperature is 20~50 DEG C, and spinning voltage is
8-22kV, flow velocity is 0.01-10mL/h, and it is 8~16cm that spinning receives distance, syringe needle walking speed 20-50cm/min back and forth, during spinning
Between 12-48h.
The present invention has the advantages that：The itrile group on polyacrylonitrile in polyacrylonitrile/Fluorinated graphene oxide layer,
Oxygen, fluorine with Fluorinated graphene oxide surface are highly polar group, and the polysulfide that formed in charge and discharge process can be formed
Strong chemisorbed, can effectively prevent polysulfide from reaching negative pole through barrier film, reduce the generation of shuttle effect, improve lithium
The life-span of sulphur battery.
Brief description of the drawings
Fig. 1 is composite separator structure schematic diagram of the invention.
Fig. 2 is composite diaphragm preparation flow figure of the invention.
Fig. 3 is the cycle life figure of composite diaphragm of the invention.
Wherein, 1 is polyacrylonitrile/Fluorinated graphene oxide layer, and 2 is Celgard barrier films.
Specific embodiment
Below in conjunction with the accompanying drawings, preferably embodiment of the invention is described in further detail：
Embodiment 1
（1）Graphite oxide is put into Muffle furnace be heated to 50 DEG C react 60 minutes, reaction atmosphere is the nitrogen fluorine containing 5% fluorine gas
Mixed gas, natural cooling after the completion of reaction obtains fluorinated graphite；
（2）By in 10g fluorinateds graphite addition 100g 1-METHYLPYRROLIDONEs, ultrasonic disperse 5 hours forms suspension；
（3）2g commercialization polyacrylonitrile powders are added in 20g 1-METHYLPYRROLIDONEs, after swelling 24 hours, 50 is heated to
DEG C, stirring reaction 5 hours obtains polyacrylonitrile solution；
（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction 1 hour obtains polyacrylonitrile/fluorinated
Graphite spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard
Composite diaphragm.
Embodiment 2
（1）Graphite oxide is put into Muffle furnace be heated to 200 DEG C react 10 minutes, reaction atmosphere is the nitrogen containing 10% fluorine gas
Fluorine mixed gas body, natural cooling after the completion of reaction obtains fluorinated graphite；
（2）By in 10g fluorinateds graphite addition 1000g dimethyl sulfoxide (DMSO)s, ultrasonic disperse 0.5 hour forms suspension；
（3）10g commercialization polyacrylonitrile powders are added in 1000g dimethyl sulfoxide (DMSO)s, after swelling 24 hours, 50 DEG C is heated to,
Stirring reaction 0.5 hour, obtains polyacrylonitrile solution；
（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction 5 hours obtains polyacrylonitrile/fluorinated
Graphite spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard
Composite diaphragm.
Embodiment 3
（1）Graphite oxide is put into Muffle furnace be heated to 100 DEG C react 30 minutes, reaction atmosphere is the nitrogen fluorine containing 7% fluorine gas
Mixed gas, natural cooling after the completion of reaction obtains fluorinated graphite；
（2）By in 10g fluorinateds graphite addition 500g DMFs, ultrasonic disperse 3 hours forms suspension；
（3）5g commercialization polyacrylonitrile powders are added in 250g DMFs, after swelling 24 hours, are heated to
65 DEG C, stirring reaction 2.5 hours obtains polyacrylonitrile solution；
（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction 3 hours obtains polyacrylonitrile/fluorinated
Graphite spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard
Composite diaphragm.
Embodiment 4
（1）Graphite oxide is put into Muffle furnace be heated to 150 DEG C react 40 minutes, reaction atmosphere is the nitrogen fluorine containing 6% fluorine gas
Mixed gas, natural cooling after the completion of reaction obtains fluorinated graphite；
（2）By in 10g fluorinateds graphite addition 800g ethanol, ultrasonic disperse 4 hours forms suspension；
（3）8g commercialization polyacrylonitrile powders are added in 250g ethanol, after swelling 24 hours, 70 DEG C, stirring reaction is heated to
25 hours, obtain polyacrylonitrile solution；
（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction 2 hours obtains polyacrylonitrile/fluorinated
Graphite spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard
Composite diaphragm.
Embodiment 5
（1）Graphite oxide is put into Muffle furnace be heated to 120 DEG C react 50 minutes, reaction atmosphere is the nitrogen fluorine containing 8% fluorine gas
Mixed gas, natural cooling after the completion of reaction obtains fluorinated graphite；
（2）By in 10g fluorinateds graphite addition 600g N- methyl pyrrolidones, ultrasonic disperse 2 hours forms suspension；
（3）4g commercialization polyacrylonitrile powders are added in 300g 1-METHYLPYRROLIDONEs, after swelling 24 hours, 60 is heated to
DEG C, stirring reaction 4 hours obtains polyacrylonitrile solution；
（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction 4 hours obtains polyacrylonitrile/fluorinated
Graphite spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard
Composite diaphragm.
The preparation and performance test of lithium-sulfur cell；By sulphur simple substance material, acetylene black and PVDF in mass ratio 70：20：10
Mix in NMP, be coated on aluminium foil as electrode film, metal lithium sheet be to electrode, composite diaphragm prepared by embodiment 1 as every
Film, the LiTFSI/DOL-DME (volume ratios 1 of 1mol/L:1) it is electrolyte, the LiNO3 of 1mol/L is additive, full of Ar hands
Button cell is assembled into casing, constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope is
1-3V, current density is 0.5C.
It is lithium-sulfur cell barrier film that comparative example uses Celgard barrier films, and other conditions are same as described above.
Fig. 3 is the cycle life figure that composite diaphragm prepared by the embodiment of the present invention 1 is assembled into lithium-sulfur cell.As can be seen from the figure
Capacity still possesses the 71% of initial capacity after composite diaphragm prepared by the present invention carries out 400 discharge and recharges, and comparative example is used
Celgard barrier films are assembled into lithium-sulfur cell, and to enter be the 40% of initial capacity to capacity after carrying out 200 circulations, illustrates the composite diaphragm
Shuttle effect can effectively be suppressed, the life-span of sulphur battery is improved.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert
Specific implementation of the invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should be all considered as belonging to of the invention
Protection domain.
Claims (6)
1. a kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms, including commercial Celgard barrier films and its surface
Polyacrylonitrile/Fluorinated graphene oxide layer composition, the thickness of described polyacrylonitrile/Fluorinated graphene oxide layer is 1~10 μ
M, polyacrylonitrile and the mass ratio of Fluorinated graphene oxide are 0.2-1 in described polyacrylonitrile/Fluorinated graphene oxide layer：1,
The mass fraction of oxygen is 1%-20%, the mass fraction of fluorine in described Fluorinated graphene oxide in described Fluorinated graphene oxide
It is 1%-20%.
2. a kind of preparation method of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms as claimed in claim 1,
It is characterised in that it includes following steps：
Step（1）Graphite oxide is put into heating response in Muffle furnace, reaction atmosphere is the mixed gas of nitrogen and fluorine gas, reaction
After the completion of natural cooling, obtain fluorinated graphite；
Step（2）By in fluorinated graphite addition organic solvent, ultrasonic disperse forms suspension；
Step（3）Commercial polyacrylonitrile powder is added in organic solvent, after swelling 24 hours, heating stirring reaction is obtained
Polyacrylonitrile solution；
Step（4）Suspension is slowly added in polyacrylonitrile solution, mechanic whirl-nett reaction, obtains polyacrylonitrile/fluorinated
Graphite spinning solution, carries out electrostatic spinning on Celgard barrier films, obtains polyacrylonitrile/Fluorinated graphene oxide/Celgard
Composite diaphragm.
3. method as claimed in claim 2, it is characterised in that the step（1）The temperature of middle heating response is 50-200 DEG C,
Reaction time 10-60 minutes, reaction atmosphere was the mixed gas of nitrogen and fluorine gas, and wherein the volume ratio shared by fluorine gas is 5%-
10%。
4. method as claimed in claim 2, it is characterised in that the step（2）Middle fluorinated graphite and organic solvent
Mass ratio is 1：10-100, organic solvent is 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), DMF, in ethanol
One or more, ultrasonic time 0.5-5 hours.
5. method as claimed in claim 2, it is characterised in that the step（3）Middle polyacrylonitrile powder and organic solvent
Mass ratio is 1：10-100, polyacrylonitrile powder is 0.2-1 with the mass ratio of Fluorinated graphene oxide：1, organic solvent is N- first
Base pyrrolidones, dimethyl sulfoxide (DMSO), DMF, one or more in ethanol, heating response temperature is 50-80
DEG C, 0.5-5 hours heating stirring reaction time.
6. method as claimed in claim 2, it is characterised in that the step（4）Middle mechanic whirl-nett reaction time 1-5 hour,
Electrospinning conditions are：Temperature is 20~50 DEG C, and spinning voltage is 8-22kV, and flow velocity is 0.01-10mL/h, and spinning receives distance
It is 8~16cm, syringe needle walking speed 20-50cm/min, spinning time 12-48h back and forth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710225961.6A CN106935771A (en) | 2017-04-08 | 2017-04-08 | A kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710225961.6A CN106935771A (en) | 2017-04-08 | 2017-04-08 | A kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms |
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| CN106935771A true CN106935771A (en) | 2017-07-07 |
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| CN201710225961.6A Pending CN106935771A (en) | 2017-04-08 | 2017-04-08 | A kind of polyacrylonitrile/Fluorinated graphene oxide/Celgard composite diaphragms |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786619A (en) * | 2017-11-13 | 2019-05-21 | 北京碳阳科技有限公司 | A kind of battery diaphragm and preparation method thereof |
| EP3667768A4 (en) * | 2017-10-26 | 2020-07-22 | LG Chem, Ltd. | Separation membrane and lithium secondary battery comprising same |
| CN113113620A (en) * | 2021-04-16 | 2021-07-13 | 龙泉市强宏环保科技有限公司 | Preparation method of alkaline zinc-iron flow battery |
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| CN102532890A (en) * | 2010-12-30 | 2012-07-04 | 海洋王照明科技股份有限公司 | Fluorinated and oxidized grapheme/polyaniline composite material and preparation method thereof |
| CN104393349A (en) * | 2014-11-17 | 2015-03-04 | 陕西煤业化工技术研究院有限责任公司 | Protective layer for lithium sulphur battery, preparation method thereof and lithium sulphur battery using protective layer |
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2017
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| CN102532890A (en) * | 2010-12-30 | 2012-07-04 | 海洋王照明科技股份有限公司 | Fluorinated and oxidized grapheme/polyaniline composite material and preparation method thereof |
| CN104393349A (en) * | 2014-11-17 | 2015-03-04 | 陕西煤业化工技术研究院有限责任公司 | Protective layer for lithium sulphur battery, preparation method thereof and lithium sulphur battery using protective layer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3667768A4 (en) * | 2017-10-26 | 2020-07-22 | LG Chem, Ltd. | Separation membrane and lithium secondary battery comprising same |
| CN109786619A (en) * | 2017-11-13 | 2019-05-21 | 北京碳阳科技有限公司 | A kind of battery diaphragm and preparation method thereof |
| CN109786619B (en) * | 2017-11-13 | 2022-04-08 | 新材料与产业技术北京研究院 | Battery diaphragm and preparation method thereof |
| CN113113620A (en) * | 2021-04-16 | 2021-07-13 | 龙泉市强宏环保科技有限公司 | Preparation method of alkaline zinc-iron flow battery |
| CN113113620B (en) * | 2021-04-16 | 2022-11-11 | 峰特(浙江)新材料有限公司 | Preparation method of alkaline zinc-iron flow battery |
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Application publication date: 20170707 |