CN110197898A - A kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure - Google Patents
A kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure Download PDFInfo
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- CN110197898A CN110197898A CN201910528200.7A CN201910528200A CN110197898A CN 110197898 A CN110197898 A CN 110197898A CN 201910528200 A CN201910528200 A CN 201910528200A CN 110197898 A CN110197898 A CN 110197898A
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- sulphur
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000005864 Sulphur Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 19
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 17
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 229910052760 oxygen Inorganic materials 0.000 claims description 6
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 229910007552 Li2Sn Inorganic materials 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 21
- 230000009514 concussion Effects 0.000 abstract description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
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- 230000008595 infiltration Effects 0.000 description 3
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- 229920001021 polysulfide Polymers 0.000 description 3
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- 150000008117 polysulfides Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 241000219146 Gossypium Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 229910001216 Li2S Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 238000010410 dusting Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A kind of preparation method of carbon-based flexible lithium sulphur battery anode, belongs to the lithium-sulfur cell technical field of material for electrochemical energy storage.It is made annealing treatment first with carbon fiber by oxidizing atmosphere, prepare three-dimensional conductive carbon network, using three-dimensional conductive carbon fiber network as collector, the three-dimensional conductive carbon fiber network is immersed again in the carbon disulfide of sulphur, ultrasonic wave or mechanical concussion make sulphur solution impregnation carbon fiber hole configurations and are evaporated under vacuum, and sulphur is further diffused into the more tiny gap of carbon fiber using high temperature gas phase diffusion and forms sulphur equally distributed carbon-based flexible lithium sulphur battery anode in three-dimensional conductive carbon fiber network.The flexible battery of the self-supporting electrode assembling can keep high and stable charge/discharge capacity under different folding angles.The preparation method of this self-supporting flexible electrode in the present invention is easy to operate, is easy to be mass produced, and can be widely applied in energy storage and flexible wearable equipment, has good practical value.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field of material, and in particular to a kind of carbon-based flexible lithium sulphur electricity of porous structure
The preparation method of pond positive electrode.
Background technique
With the raising of people's material and cultural needs and the rapid development of science and technology, facilitate light and handy portable wearable
Electronic product has obtained people and has greatly liked, including the display that flexible folds, Electronic Paper, flexible battery etc..Cause
This, portable wearable flexible, light energy storage device will have the huge market demand and space, peace high as energy density
Quan Xingqiang, lithium ion battery easy to carry have very big development space.Currently, cobalt acid lithium, LiMn2O4, LiFePO4, ternary
The energy density of the conventional lithium ion batteries such as NCM/NCA has been difficult to the use demand for meeting electronic equipment to energy density, therefore
The new secondary battery for developing higher energy density is imperative.In addition, the geometry of lithium ion battery is fairly simple at present,
Shapes and sizes are usually fixed, the battery of this fixation limits electronic product in the hair of portable wearable application aspect
Exhibition.Especially exist, many small-sized wearable smart machines and a variety of miniature organism implant devices are required to function device one
It can be used in the case of fixed deformation, and traditional hard lithium ion cell electrode is not able to satisfy these conditions generally.Therefore exist
The fields such as wearable device, flexible electronic, microbiosensor need to develop matched flexible high-energy density storage
It can device.Flexible carbon-based lithium-sulfur cell, has close to 1675mAh g-1Theoretical specific capacity and 2600Wh kg-1Specific energy,
It is environmental-friendly, cheap, the advantages that capable of crimping, fold in a certain range, stretching, squeezing, and becomes and solve above-mentioned lance
The primary scheme of shield.
Up to the present, the research of lithium-sulfur cell is concentrated mainly on both at home and abroad and solves the problems, such as the following aspects: (1)
The electronic conductivity of sulphur and its discharging product lithium sulfide is low；(2) elemental sulfur (S in charge and discharge process8, density is 2.03g cm-3)
With lithium sulfide (Li2S, density are 1.66g cm-3) between when mutually converting, due to the difference of the two structure and density, can generate
About 80% volume change, Volumetric expansion are easy to cause electrode dusting, and volume change is obvious, and electrode is easy powder of detached；
(3) the electric discharge more lithium sulfides of intermediate product are soluble in electrolyte, cause " shuttle effect ", so cause a series of performance degradation and
Safety problem.
Summary of the invention
The purpose of the present invention is to solve traditional lithium-sulfur cells can not folded bent, sulphur active material poorly conductive, sulphur
More lithium sulfide intermediate products that volume sharply generates in dilatancy and discharge process after the embedding lithium of electrode are soluble in electrolyte
Problem provides a kind of preparation method of carbon-based flexible lithium sulphur battery positive electrode of porous structure.
Present invention selection has the carbon-based conducting fibrous web network of three-dimensional of some strength, as flexible lithium sulphur battery positive electrode
Carrier and conductive network, sulphur active material is evenly dispersed in by the conduction by the method for dissolving-recrystallization and High temperature diffusion
In the porous structure of network of fibers, solve the problems, such as that conventional lithium sulfur battery anode material can not bending fold.In charge and discharge
The conductive fiber network can provide more efficient electron propagation ducts and slow down the volume expansion of sulphur, porous cabin effect in journey
The load capacity that sulphur active material can also be increased slows down the dissolution diffusion velocity of polysulfide.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure, specific step is as follows for the method:
Step 1: it using three-dimensional carbon-based conducting fibrous web network as collector, immerses in the solution containing sulphur active material；Or
Person is first immersed in solvent using three-dimensional carbon-based conducting fibrous web network as collector, then mixed with the solution containing sulphur active material
It closes；
Step 2: under vacuum or condition of high voltage, make the solution impregnation containing sulphur active material to three-dimensional carbon by oscillation
In the pore structure of base conductive fiber network, it is living to obtain sulfur loaded for the pressure condition and Stirring solvent evaporated maintained like
Property substance the carbon-based conducting fibrous web network of three-dimensional；
Step 3: in closed autoclave, under vacuum or inert atmosphere, make sulphur in three-dimensional carbon using High temperature diffusion
It further being spread in base conductive fiber network, sulphur is uniformly distributed in three-dimensional carbon-based conducting fibrous web network, it then cools to room temperature,
Obtain carbon-based flexible lithium sulphur battery positive electrode；The temperature of the High temperature diffusion is 400~600 DEG C, the heat-insulation pressure keeping time
For 1~5h.
The beneficial effect of the present invention compared with the existing technology is:
(1) present invention selects highly conductive carbon-based fibrous material, the gas-phase oxidization process preparation that use is at low cost, homogeneity is high
Three-dimensional conductive network structure material porous out and with some strength, it is as the carrier of lithium sulfur battery anode material that sulphur is active
Substance is evenly dispersed in the hole configurations of the conductive network, can be increased material to the load of sulphur active material and be improved it
The electron transport ability in charge and discharge process.
(2) present invention is in such a way that solvent dissolution, vacuum/negative pressure environment, Ultrasonic/Mechanical oscillating phase combine by sulphur activity
Substance solution is evenly dispersed in carbon-based material surface and the inside with multiple hole structure, has than tradition dissolution hybrid mode
Better operability and homogeneity.
(3) present invention disperses molten sulfur using long-time melt oscillation, then high-temperature part sublimed sulfur permeates tiny microcellular structure
Mode gaseous state is dispersed in the inside of carbon-based material multiple hole structure, which can in charge and discharge process
Slow down the dissolution diffusion of polysulfide.The loss for reducing active material, improves the stable circulation performance of material.
(4) preparation method of the invention, the cost of raw material is cheap, simple process strong operability, pollution-free generation, process
It is controllable to be conducive to large-scale production, there is biggish commercial applications prospect.
Detailed description of the invention
Fig. 1 is the specific surface area BET test result figure of three-dimensional porous carbon-based conductive network in the present invention；
Fig. 2 is the pore-size distribution test result figure of three-dimensional porous carbon-based conductive network in the present invention；
Fig. 3 is SEM the and EDS specimen page figure of the flexible positive electrode of high load sulphur in the present invention；
Fig. 4 is the charge-discharge performance curve graph of the flexible lithium sulphur battery that assembles in the present invention at 1C.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is done below in conjunction with drawings and examples and more comprehensively, is meticulously described,
But protection scope of the present invention is not limited to following specific embodiments.Unless otherwise defined, all professions used hereinafter
It is identical that term with those skilled in the art is generally understood meaning.It is specific that technical term used in the present invention is intended merely to description
The purpose of embodiment can not be used to limit the scope of the invention.Unless otherwise defined, the former material used in the present invention
Material, solvent, instrument and equipment etc. can be commercially available by market or can be prepared by existing straightforward procedure.
The present invention uses the three-dimensional conductive carbon fiber network carbon skeleton with multiple hole structure as electrode current collecting body, by sulphur
Active material is infiltrated by solvent, and the method for High temperature diffusion is dispersed in this three-dimensional porous conducting matrix grain, forms sulphur active material
In the lithium sulphur battery electrode structure of the evenly dispersed load of three-dimensional conductive carbon fiber network internal and surface, high-sulfur load is realized
Measuring electrode material has high conductivity.Network porous carbon structure is conducive to what inhibition elemental sulfur occurred in charge and discharge process simultaneously
The cabin blanketing effect of volume change and the porous structure is conducive to slow down the problems of dissolution of polysulfide in the electrolytic solution.
In addition, the three-dimensional porous conductive carbon fibre by specially treated also has certain intensity and flexibility, the height to sulphur is realized
Load uniformly wraps up, and obtains good chemical property.
Specific embodiment 1: present embodiment record is a kind of carbon-based flexible lithium sulphur battery positive electrode of porous structure
Preparation method, specific step is as follows for the method:
Step 1: it using three-dimensional carbon-based conducting fibrous web network as collector, immerses in the solution containing sulphur active material；Or
Person is first immersed in solvent using three-dimensional carbon-based conducting fibrous web network as collector, then mixed with the solution containing sulphur active material
It closes；The concentration of the solution containing sulphur active material is 0.05~1.5g/mL, and the environment temperature of the step is 5~45 DEG C；
Step 2: under closed vacuum or condition of high voltage, arrive the solution impregnation containing sulphur active material by oscillation
In the pore structure of three-dimensional carbon-based conducting fibrous web network, the pressure condition and Stirring solvent evaporated maintained like is born
Carry the carbon-based conducting fibrous web network of three-dimensional of sulphur active material；The oscillation is supersonic oscillations, the mechanical higher-order of oscillation, mechanical low
Frequency vibration one of is swung or a variety of is used cooperatively；The vacuum degree of the vacuum is -1~-95Kpa；
Step 3: in closed autoclave, under vacuum or inert atmosphere, make sulphur in three-dimensional carbon using High temperature diffusion
It is further spread in base conductive fiber network, sulphur is uniformly distributed in three-dimensional carbon-based conducting fibrous web network, is then naturally cooled to
Room temperature to get arrive carbon-based flexible lithium sulphur battery positive electrode；The temperature of the High temperature diffusion is 400~600 DEG C, heat-insulation pressure keeping
Time is 1~5h.
Specific embodiment 2: a kind of carbon-based flexible lithium sulphur battery anode material of porous structure described in specific embodiment one
The preparation method of material, the carbon-based conducting fibrous web network of three-dimensional have pore structure abundant such as BET test result institute in Fig. 1,2
Show, including micropore, mesoporous and macropore, pore structure are mainly distributed in the micropore and macropore range of 0.5~3.5nm.
Specific embodiment 3: a kind of carbon-based flexible lithium sulphur battery anode material of porous structure described in specific embodiment one
The preparation method of material, in step 1, the carbon-based conducting fibrous web network of three-dimensional is prepared in accordance with the following methods:
The materials of high conductivity carbon based fibers is capable of forming as raw material, 250~610 using carbon fiber or by carbonization
DEG C, it is handled in the atmosphere that oxidation volumetric concentration is 1%~80%, makes carbon material partial oxidation, obtain the ratio with some strength
The carbon-based conducting fibrous web network of controllable, highly conductive, the flexible three-dimensional of surface area；The treatment temperature is 250~610 DEG C, carrier of oxygen
Product concentration is 1%~80%.
It is raw material by carbon that three-dimensional carbon-based conducting fibrous web network, which can be using native cellulose fibres such as bamboo, flax, cotton yarns,
With the carbon based fibers of certain electric conductivity and intensity made of change；It is also possible to polyacrylonitrile (PAN), mud blueness base carbon based fibers
(HPCF), the artificial synthetic fibers such as viscose fiber are raw material, prepared by carbonization treatment with high conductivity and intensity
Carbon based fibers.Low temperature (250~610 DEG C) hollow annealing, oxide etch form active position to carbon fiber needs in air
The three-dimensional conductive carbon base body of point and micro-nano hole configurations.
Specific embodiment 4: a kind of carbon-based flexible lithium sulphur battery of porous structure described in specific embodiment one or three is just
The specific surface area of the preparation method of pole material, the carbon-based conducting fibrous web network of three-dimensional is 100~1200m2g-1, fiber element
Diameter be 1~100 micron.
Specific embodiment 5: a kind of carbon-based flexible lithium sulphur battery anode material of porous structure described in specific embodiment three
The preparation method of material, the atmosphere are the atmosphere containing oxidation effectiveness.As the air of different partial pressures, oxygen, oxygen with
The gas that inert gas (such as nitrogen, argon gas) is mutually mixed, one of the above or a variety of mixed forms have oxygen at 250~610 DEG C
Change the oxidizing gas of function.
Specific embodiment 6: a kind of carbon-based flexible lithium sulphur battery anode material of porous structure described in specific embodiment one
The preparation method of material, the concentration of the solution containing sulphur active material are 10~600mg ml-1, can be by adjusting sulphur in solution
In concentration regulate and control the loading of sulphur, the mass surface density of the sulphur active material is 0.1mg cm-2~40mg cm-2, can
The infiltration degree of sulphur solution is adjusted by ultrasonic wave under negative pressure or mechanical concussion processing.
Specific embodiment 7: a kind of carbon-based flexible lithium sulphur battery of porous structure described in specific embodiment one or six is just
The preparation method of pole material, the solvent of the solution containing sulphur active material are carbon disulfide, carbon tetrachloride, toluene, hexamethylene
Alkane, normal octane, dimethyl sulfoxide, acetone, dimethylbenzene, ethyl alcohol, ethylene glycol, N-Methyl pyrrolidone, glycerol, chloroform, glacial acetic acid, carbon
Acid propylene ester, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, 1,2- dimethoxy-ethane, acetonitrile are one or more to be mixed
It closes in object and thermokalite or critical state carbon dioxide.
Specific embodiment 8: a kind of carbon-based flexible lithium sulphur battery of porous structure described in specific embodiment one or six is just
The preparation method of pole material, the sulphur active material are soluble elemental sulfur and sulfur-based compound；The elemental sulfur be rhombic sulfur,
One of amorphous sulphur, sublimed sulfur or high purity sulphur or a variety of mixtures；The sulfur-based compound be organic sulfur compound,
Li2Sn, at least one of n >=1, carbon-sulfur polymer.
Embodiment 1:
A kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure, specific step is as follows for the method:
Step 1: using three-dimensional carbon-based conducting fibrous web network as collector, and immersing in the carbon disulfide solution of sulphur, described
The concentration of the carbon disulfide solution of sulphur is 25g mL-1；
Step 2: under vacuum (- 5 arrive -95Kpa) environment, pass through supersonic oscillations (power: 500W, frequency: 40KHz)
Make the solution impregnation containing elemental sulfur into the pore structure of three-dimensional carbon-based conducting fibrous web network, the pressure and ultrasound that maintain like
Condition, and Stirring solvent evaporated, elemental sulfur meeting uniform enrichment obtain sulfur loaded in three-dimensional carbon-based conducting fibrous web network
Three-dimensional carbon-based conducting fibrous web network；Set pressure condition is conducive to removal and remains in inside three-dimensional carbon-based conducting fibrous web network
It is more thorough to be combined exclusion air, while being conducive to sulphur solution impregnation and arriving by the air in hole for ultrasonic wave or mechanical concussion
In the internal void of three-dimensional carbon-based conducting fibrous web network, disperse sulphur more uniformly；The step is according to similar compatibility principle
The active material of the sulfur-bearings such as the compound of sulphur can be dissolved in the one or more pairs of sulphur such as carbon disulfide with larger solubility
Solvent in, in a solvent by above-mentioned three-dimensional porous conductive carbon fibre infiltration, and using infiltration environmental pressure and shake is varied multiple times
The air reduced inside porous carbon sill of sheet the methods of is swung, makes the solution impregnation containing active material to the hole of carbon-based material as far as possible
In the structure of hole；By adjusting active material concentration in the solution, and regulate and control using the means such as recrystallizing the loading of sulphur；
Step 3: the carbon-based conducting fibrous web network of three-dimensional for having loaded sulphur that step 2 is obtained is put into vacuum or inert atmosphere
In pressure vessel in environment, and temperature is controlled between 115~440 DEG C, 1~30h of time；Make sulphur in the melting compared with low viscosity
State deeply penetrates into the hole configurations of carbon material.Temperature is controlled at 400~600 DEG C after this process, 1~5h is kept, makes portion
Sulphur is divided to gasify in the hole configurations of carbon fiber and uniformly spread, it is last cooling rapidly, be conducive to penetrate into carbon fiber hole
Sulphur homogeneous condensation, obtain a kind of carbon-based flexible lithium sulphur battery positive electrode of porous structure as shown in Figure 3.
By the flexible current-collecting bodies such as carbon-based flexible lithium sulphur battery anode obtained above and flexible copper clad or foam copper and every
Film, lithium piece/lithium film assemble after obtaining naked battery core, and soldering polar ear enters shell/enter bag, baking, fluid injection, standing, chemical conversion, shaping
Obtain the flexible finished product electrochemical energy storage cell of high-energy density.
Embodiment 2:
A kind of preparation method of the carbon-based conducting fibrous web network of three-dimensional of the invention: it will be cut with a thickness of the carbon cloth fiber of 0.3mm
At the pieces of cloth of 10x 10cm, then this carbon cloth piece is fixed and erect and is placed in corundum crucible, and is put into Muffle furnace with 5 DEG C/min
Heating rate from room temperature to 400 DEG C, keep the temperature 3h after cooled to room temperature, obtain with some strength and have it is porous
The specific surface area test of the carbon-based conducting fibrous web network of three-dimensional of hole structure, the structure is as shown in Figure 1, 2.
Embodiment 3:
A kind of preparation method of the carbon-based conducting fibrous web network of three-dimensional of the invention, which includes that electrostatic spinning technique preparation is artificial, closes
At carbon fiber precursor finally aoxidize to be formed by environment of high temperature gas using carbon based fibers obtained from high temperature cabonization
The highly conductive carbon-based fibrillar meshwork structure of multiple hole structure.One of is typically the synthesis of raw material with polyacrylonitrile (PAN)
Method is as follows, comprising the following steps:
(1) firstly, 1g PAN is added in the DMF solution of 10mL, 12h is stirred at 50 DEG C.Finally, acquired solution adds
Note is in the syringe of 10mL, the stainless steel syringe needle of model 20 in placement, loads onto electrostatic spinning machine and carries out spinning.Spinning accelerates
Voltage is set as 13~14kV, and syringe needle and receiving body distance are set as 14cm, and injecting rate is 1.2mLh-1, obtained after the completion of spinning
PNA base spinning presoma-fiber cloth.
(2) by PNA base spinning presoma-fiber cloth of above-mentioned preparation in argon hydrogen (Ar/H2) lower 150 DEG C of mixed atmosphere pre- places
1h is managed, be then carbonized at 1000 DEG C and in identical atmospheric condition 2h, obtains the flexible 3 D conductive carbon fibre cloth based on PAN.
(3) carbon cloth for obtaining (2) obtains the flexible, porous three-dimensional carbon based on PAN according to the method in embodiment 2
Base conductive fiber network.
Embodiment 4:
A kind of preparation method of the carbon-based conducting fibrous web network of three-dimensional of the invention includes natural fine with bamboo, flax, cotton yarn etc.
Cellulose fiber is raw material by having the carbon base fiber of certain electric conductivity and intensity made of carbonization；It is one of typical sub-
Flaxen fiber cloth is as follows for the synthetic method of raw material, comprising the following steps:
(1) with ethyl alcohol and deionized water repeatedly, alternately cleaning flax fiber/fiber cloth to remove its surface and oil contaminant, it
Afterwards in argon hydrogen (Ar/H2) the lower 150 DEG C of pretreatments 1h of mixed atmosphere, be then carbonized at 1000 DEG C and in identical atmospheric condition 2h,
Obtain the flexible 3 D conductive carbon fibre cloth based on flax fiber.
(2) the flexible 3 D conductive carbon fibre cloth based on flax fiber for obtaining (2) is according to the method in embodiment 2,
Obtain the flexible, porous three-dimensional conductive carbon fiber network based on flax fiber.
Embodiment 5:
A kind of three-dimensional porous conductive carbon fibre network of the invention is not limited only to following illustrated to the carrying method of sulphur
Embodiment substance, also comprising the carbon-based three-dimensional with high load amount that is prepared using method used in the following example
Conductive fiber comprising the following steps:
(1) it will obtain that there is some strength in above-described embodiment 2 and there is the carbon cloth 1.5g of multiple hole structure to immerse
Concentration is in the carbon disulfide solution of 0.25g/mL sulphur, in the item of supersonic oscillations (power 1Kw) and negative pressure of vacuum (- 95Kpa)
It is iteratively repeated operation under part, when the crystallization of obvious sulphur occur in container bottom or carbon cloth surfaces, carbon cloth fiber is taken out and is dried in 60 DEG C
Dry, it is 1.26g (12.6mg cm that load capacity, which is prepared,-2) carbon cloth sulfur loaded electrode slice.
(2) the porous carbon fiber cloth of step (1) back loading sulphur is transferred in rotatable equipment at 155 DEG C to heat melts 12
Hour, wherein mechanical whirling vibration rotation speed is 0.1min rod-1After cool down, obtaining molten sulfur, to be dispersed in three-dimensional more
Composite material in the hole mechanism of hole carbon fiber.
(3) composite material obtained after step (2) is put into enclosed high pressure reaction kettle, with 5 DEG C of min-1Speed heating
To 400 DEG C, heat-insulation pressure keeping 10 hours, after with 100 DEG C of min-1Rate be rapidly cooled to room temperature, obtain load capacity be 10.6mg
cm-2Flexible lithium sulphur battery positive electrode.By the flexible lithium sulphur battery anode material for the high load amount being prepared in the present embodiment
Material and soldering polar ear after aluminium foil bonding, and it is assembled into the naked battery core of lithium-sulfur cell lamination with plating lithium copper foil cathode, diaphragm, aluminum plastic film,
Finished product flexibility Soft Roll lithium-sulfur cell is prepared after filling electrolyte.The lithium-sulfur cell being prepared is subjected to charge and discharge, circulation
The test such as performance.
Embodiment 6:
A kind of carbon-based conducting fibrous web network of three-dimensional of the invention is not limited only to following illustrated to the carrying method of sulphur
Embodiment substance, also the three-dimensional with high load amount comprising being prepared using method used in the following example is carbon-based leads
Electric network of fibers, comprising the following steps:
(1) carbon cloth obtained in above-described embodiment 2 with some strength and with multiple hole structure is distilled
Water, acetone and alcohol are dried in vacuo spare after alternately cleaning.
(2) 10g porous active carbon material is taken, is placed in corundum crucible, and is put into Muffle furnace with 5 DEG C of min-1Heating rate
From room temperature to 300 DEG C, Temperature fall is cooling after keeping the temperature 3h, obtains the porous active carbon materials of the partial oxidation under oxidizing atmosphere
Material.
(3) the 5g porous active Carbon Materials after above-mentioned oxidation are mixed and stirred for uniformly with 200mL carbon disulfide solution, then
It is fitted into 500mL rotary evaporation bottle, adds the carbon disulfide solution 50mL dissolved with 5g sulphur, be warming up to 30 DEG C and be aided with
It is operated repeatedly under conditions of supersonic oscillations (power 1Kw) and negative pressure of vacuum (- 95Kpa), finally obtains uniform load 5g sulphur
Porous carbon active material.
(4) the porous active Carbon Materials for obtaining (3), after being sufficiently stirred with conductive agent, binder, solvent (insoluble sulphur)
Active material slurry is obtained, is coated on obtains having some strength and the carbon with multiple hole structure in embodiment 2 later
Fiber cloth surface, or be coated in and obtain the flexible lithium sulphur battery anode that load capacity further increases in embodiment 5 (3).
(5) flexible lithium sulphur battery anode obtained in (4) is successively finally obtained according to (2), (3) step in embodiment 5
Load capacity is 39mg cm-2Flexible lithium sulphur battery positive electrode.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to above-mentioned specific embodiment, all those skilled in the art exist
Made any conspicuous improvement, replacement or modification all belong to the scope of protection of the present invention on the basis of the present invention.This
Outside, although using some specific terms in this specification, these terms are merely for convenience of description, not to the present invention
Constitute any restrictions.
Claims (8)
1. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure, it is characterised in that: the method is specific
Steps are as follows:
Step 1: it using three-dimensional carbon-based conducting fibrous web network as collector, immerses in the solution containing sulphur active material；Or first
It is immersed in solvent using three-dimensional carbon-based conducting fibrous web network as collector, then is mixed with the solution containing sulphur active material；
Step 2: under vacuum or condition of high voltage, lead the solution impregnation containing sulphur active material to three-dimensional is carbon-based by oscillation
In the pore structure of electric network of fibers, the pressure condition and Stirring solvent evaporated maintained like obtains sulfur loaded active matter
The carbon-based conducting fibrous web network of three-dimensional of matter；
Step 3: in closed autoclave, under vacuum or inert atmosphere, lead sulphur carbon-based three-dimensional using High temperature diffusion
It further being spread in electric network of fibers, sulphur is uniformly distributed in three-dimensional carbon-based conducting fibrous web network, then cooled to room temperature,
Obtain carbon-based flexible lithium sulphur battery positive electrode；The temperature of the High temperature diffusion is 400~600 DEG C, the heat-insulation pressure keeping time
For 1~5h.
2. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 1, special
Sign is: the described carbon-based conducting fibrous web network of three-dimensional includes micropore, mesoporous and macropore.
3. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 1, special
Sign is: in step 1, the carbon-based conducting fibrous web network of three-dimensional is prepared in accordance with the following methods:
The materials of high conductivity carbon based fibers is capable of forming as raw material using carbon fiber or by carbonization, at 250~610 DEG C, oxygen
Change and handled in the atmosphere that volumetric concentration is 1%~80%, make carbon material partial oxidation, obtains three-dimensional carbon-based conducting fibrous web network；
The treatment temperature is 250~610 DEG C, and oxygen volumetric concentration is 1%~80%.
4. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 1 or 3,
Be characterized in that: the specific surface area of the carbon-based conducting fibrous web network of three-dimensional is 100~1200m2 g-1, the diameter of fiber element
It is 1~100 micron.
5. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 3, special
Sign is: the atmosphere is the atmosphere containing oxidation effectiveness.
6. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 1, special
Sign is: the concentration of the solution containing sulphur active material is 10~600mg ml-1, the mass surface of the sulphur active material is close
Degree is 0.1mg cm-2~40mg cm-2。
7. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 1 or 6,
Be characterized in that: the solvent of the solution containing sulphur active material is carbon disulfide, carbon tetrachloride, toluene, hexamethylene, just pungent
Alkane, dimethyl sulfoxide, acetone, dimethylbenzene, ethyl alcohol, ethylene glycol, N-Methyl pyrrolidone, glycerol, chloroform, glacial acetic acid, propylene carbonate
The one or more mixture of ester, methyl ethyl carbonate, methyl propyl carbonate, dimethyl carbonate, 1,2- dimethoxy-ethane, acetonitrile,
And in thermokalite or critical state carbon dioxide.
8. a kind of preparation method of the carbon-based flexible lithium sulphur battery positive electrode of porous structure according to claim 1 or 6,
Be characterized in that: the sulphur active material is soluble elemental sulfur and sulfur-based compound；The elemental sulfur is rhombic sulfur, amorphous
One of sulphur, sublimed sulfur or high purity sulphur or a variety of mixtures；The sulfur-based compound is organic sulfur compound, Li2Sn, n >=1,
At least one of carbon-sulfur polymer.
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Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai CosMX Battery Co.,Ltd. Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
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