CN109449008A - A kind of preparation method of the hollow core-shell structure electrode material of self-supporting and its application in lithium-sulfur cell and supercapacitor - Google Patents
A kind of preparation method of the hollow core-shell structure electrode material of self-supporting and its application in lithium-sulfur cell and supercapacitor Download PDFInfo
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- CN109449008A CN109449008A CN201811339232.4A CN201811339232A CN109449008A CN 109449008 A CN109449008 A CN 109449008A CN 201811339232 A CN201811339232 A CN 201811339232A CN 109449008 A CN109449008 A CN 109449008A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 78
- 239000011258 core-shell material Substances 0.000 title claims abstract description 65
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000012545 processing Methods 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 19
- 230000004048 modification Effects 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002134 carbon nanofiber Substances 0.000 claims description 15
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002121 nanofiber Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004494 ethyl ester group Chemical group 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 42
- 239000005864 Sulphur Substances 0.000 abstract description 34
- 238000004146 energy storage Methods 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- 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
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of preparation method of the hollow core-shell structure electrode material of self-supporting and its applications in lithium-sulfur cell and supercapacitor.The preparation method of the hollow core-shell structure electrode material of the self-supporting includes: that precursor solution is carried out electrostatic spinning, carbonization treatment, Surface Oxidation Modification processing, coated with silica modification, phenolic resin coating modification, carbonization treatment, etching silicon dioxide.The preparation method of the hollow core-shell structure electrode material of self-supporting provided by the invention is allowed to combine with sulphur, can directly improve the electric conductivity of sulphur and prevent the diffusion and transfer of sulphur by constructing the carbon-based material of multilayered structure；Meanwhile the titanium dioxide on electrode material can be combined with element sulphur, formed chemical bonding between the two, be can be further improved the stability of sulphur anode, thus the captured sulfur result of electrode material can be improved, optimize the energy-storage property of lithium-sulfur cell.
Description
Technical field
The invention belongs to electrode material fields, and in particular to a kind of preparation side of the hollow core-shell structure electrode material of self-supporting
Method and its application in lithium-sulfur cell and supercapacitor.
Background technique
Currently in the case where the historical background for greatly developing clean energy resource is advocated in the whole world, energy density is higher for exploitation, cycle life
It is longer, system cost is lower, the better energy storage technology of security performance has become an important research direction.Lithium-sulfur cell be with
Element sulphur is as anode, a kind of lithium battery of the lithium metal as cathode.Elemental sulfur rich reserves in the earth have price
The features such as cheap, environmental-friendly.Using sulphur as the lithium-sulfur cell of positive electrode, materials theory specific capacity and battery theory ratio
Energy is higher, respectively reaches 1675mAh/g and 2600Wh/kg, the reason of significantly larger than commercial widely applied cobalt acid lithium battery
By specific capacity (< 150mAh/g).Meanwhile sulphur is a kind of environment amenable element, is not polluted substantially to environment, it is comprehensive next
It sees, lithium-sulfur cell is a kind of very promising lithium battery.
The application of lithium-sulfur cell still remains a series of problems at present, specifically includes that sulphur is non-conductive, the dissolution of polysulfide
Lead to structural instability etc. with sulphur volume expansion in shuttle effect and charge and discharge process, factors above is likely to lead to battery
Damage, to limit the development of lithium-sulfur cell.Therefore, key component of the sulphur anode as lithium-sulfur cell, is largely fixed
The basic performance of lithium-sulfur cell.
Notification number is that the Chinese patent of CN106449159B discloses a kind of capacitor of carbon fiber package metal oxide
It is that the intracavitary package metal oxide nano of carbon nano-fiber is prepared using electrostatic spinning technique with flexible electrode and preparation method
Particle flexible membrane, volume change when being worked using carbon nano-fiber for metal oxide nanoparticles are provided cushion space, subtracted
The bulk effect of small metal oxide.Captured sulfur result of the electrode material when being applied to lithium-sulfur cell is poor, is unfavorable for lithium sulphur
The raising of battery high rate performance and cycle performance.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of the hollow core-shell structure electrode material of self-supporting, existing to solve
There is the problem of the captured sulfur result difference of lithium-sulfur cell.
Second object of the present invention is to provide a kind of application of above-mentioned electrode material in lithium-sulfur cell, existing to solve
There is the problem of high rate performance and poor circulation of lithium-sulfur cell.
Third object of the present invention is to provide a kind of application of above-mentioned electrode material in supercapacitor, to solve
The problem of the energy storage capacity difference of existing supercapacitor.
To achieve the above object, the technical solution of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention
It is:
A kind of preparation method of the hollow core-shell structure electrode material of self-supporting, comprising the following steps:
1) titanium tetrachloride, polyacrylonitrile are dissolved in solvent, obtain precursor solution, precursor solution is subjected to Static Spinning
Silk, obtains polyacrylonitrile nanofiber cloth；
2) polyacrylonitrile nanofiber cloth is subjected under protective atmosphere carbonization treatment, obtains carbon nano-fiber/titanium dioxide
Titanium composite material；
3) carbon nano-fiber/composite titania material is subjected to Surface Oxidation Modification processing, it is compound obtains surface modification
Fiber；
4) it using surface modified composite fiber as active template, is immersed in alcohols solvent, ammonium hydroxide, water, just is then added
Silester is reacted, and coated with silica modified composite fiber is obtained；
5) coated with silica modified composite fiber is immersed in alcohols solvent, ammonium hydroxide, water, resorcinol is then added
It is reacted with formalin, obtains phenolic resin coating modification composite fibre；
6) phenolic resin coating modification composite fibre is subjected to carbonization treatment under protective atmosphere, it then will be after carbonization treatment
Obtained product immerses in hydrofluoric acid, etch away coated with silica layer to get.
The preparation method of the hollow core-shell structure electrode material of self-supporting provided by the invention passes through building multilayered structure
Carbon-based material is allowed to combine with sulphur, can directly improve the electric conductivity of sulphur and prevent the diffusion and transfer of sulphur；Meanwhile electrode
Titanium dioxide on material can be combined with element sulphur, form chemical bonding between the two, can be further improved sulphur anode
Stability, thus the captured sulfur result of electrode material can be improved, optimize the energy-storage property of lithium-sulfur cell.In addition, side made above
Method also has the characteristics that preparation process is simple, process is short, device dependence is low, is suitable for industrialization large-scale production.
In step 1), to further increase carbon, titanium dioxide and the synergy of sulphur, optimize the ratio of carbon and titanium dioxide
Example, it is preferred that the additional amount that every gram of polyacrylonitrile corresponds to titanium tetrachloride is 0.1-1ml.
In step 2), carbonization treatment, which can satisfy presoma, can accordingly be converted into carbon-based material and metal oxide nano
Particle, on this basis, to improve carbonization treatment efficiency, it is preferred that the temperature of the carbonization treatment is 900-1100 DEG C,
The time of carbonization treatment is 1h.
In step 3), being handled by Surface Oxidation Modification can be improved the active site of material and improves wellability, Jin Eryou
Conducive to the progress of subsequent step, from taking into account modification efficiency and modified effect aspect, it is preferred that at the Surface Oxidation Modification
Reason is to immerse carbon nano-fiber/composite titania material in concentrated nitric acid to carry out immersion treatment.
Step 4) is the coating modification process of silica, for the being evenly coated property for improving silicon dioxide layer, it is preferred that every
The dosage that gram polyacrylonitrile corresponds to ethyl orthosilicate is 1-5ml.
Step 5) is the coating modification process of phenolic resin, for the being evenly coated property for improving novolac resin layer, it is preferred that every
The dosage that gram polyacrylonitrile corresponds to resorcinol is 0.1-0.5g, and the dosage of corresponding formalin is 0.15-0.75ml, the first
The mass concentration of aldehyde solution is 35-40%.
Step 6) is the carbonisation of phenolic resin, to improve carbonization treatment efficiency, it is preferred that the temperature of the carbonization treatment
Degree is 700-900 DEG C, and the time of carbonization treatment is 1h.In the step, by hf etching, it can be obtained in self-supporting
The electrode material of empty core-shell structure characteristic, the electrode material have excellent three-dimensional conductive network and overlength 1-dimention nano knot
Structure is conducive to the quick collection and transfer of electronics.In addition, the electrode material for preparing in this way while also having interconnects
Three-dimensional porous structure and hollow core-shell structure feature, can greatly shorten ion dilation angle, be conducive in electrolyte from
The quick transmission of son.
Further to prepare multilayer hollow core-shell structure electrode material, Hierarchical porosity gap structure is constructed, higher ratio is provided
Surface area, and more active sites are provided for ionic adsorption, it is preferred that it is repeated in and carries out step 4) and step 5), then
Step 6) is carried out again.
The electrode material prepared using the above method, since it is with good self-supporting characteristic, electrode production process
In do not need collector, conductive agent and binder etc., furthermore continuous electronic conduction access is also advantageous to the fast of electronics
Speed is collected and transfer, promotes the raising of high rate performance；Simultaneously the electrode material can directly as flexible substrate, it is convenient and other
Dissimilar materials is compound, and then is conducive to the assembling of high performance electrode material.This three-dimensional porous structure can promote electrolyte to
Electrode interior is quickly spread, and improves the ion diffusion rates of electrode material.
The technical solution of the application of above-mentioned electrode material of the invention in lithium-sulfur cell is:
Electrode material made from a kind of preparation method using the hollow core-shell structure electrode material of above-mentioned self-supporting is in lithium sulphur
Application in battery.
Using the lithium-sulfur cell of above-mentioned electrode material, ideal captured sulfur result is may be implemented in the positive electrode of lithium-sulfur cell,
The problems such as sulphur volume expansion and dissolution can not only be inhibited, it also can effectively avoid sulphur shuttle effect.With electrode material preparation
Lithium-sulfur cell, the face load capacity and mass fraction of sulphur can respectively reach 6mg/cm2With 90% or more, and still there is good electricity
Capacity and service life cycle show good electrochemical energy storage property.
The technical solution of the application of above-mentioned electrode material of the invention in supercapacitor is:
Electrode material made from a kind of preparation method using the hollow core-shell structure electrode material of above-mentioned self-supporting is super
Application in capacitor.
Had good using the supercapacitor of above-mentioned electrode material using the hollow core-shell structure electrode material of self-supporting
Good three-dimensional continuous conduction channel can promote the quick collection of electronics and transfer, Hierarchical porosity gap structure are conducive to the quick of ion
Diffusion has many advantages, such as that specific capacitance is high, stability is good, further improves the energy storage effect of supercapacitor.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method embodiment 1 of the hollow core-shell structure electrode material of self-supporting of the present invention；
Fig. 2 is the 1 the electrode obtained material of preparation method embodiment of the hollow core-shell structure electrode material of self-supporting of the present invention
Optical photograph；
Fig. 3 is the 1 the electrode obtained material of preparation method embodiment of the hollow core-shell structure electrode material of self-supporting of the present invention
SEM figure；
Fig. 4 is the 20 the electrode obtained material of preparation method embodiment of the hollow core-shell structure electrode material of self-supporting of the present invention
SEM figure；
Fig. 5 is the forthright again of the lithium-sulfur cell that the Application Example 1 of electrode material of the invention in lithium-sulfur cell is related to
It can curve；
Fig. 6 is the cyclicity for the lithium-sulfur cell that the Application Example 1 of electrode material of the invention in lithium-sulfur cell is related to
It can curve；
Fig. 7 is the electricity for the supercapacitor that the Application Example 1 of electrode material of the invention in supercapacitor is related to
Stream-voltage curve；
Fig. 8 is the electricity for the supercapacitor that the Application Example 1 of electrode material of the invention in supercapacitor is related to
Pressure-discharge time curve.
Specific embodiment
The present invention constructs a kind of carbon substrate with multilayered structure mainly from the design angle of electrode material
Material, is allowed to combine with sulphur, the electric conductivity of Lai Tigao sulphur and the diffusion and transfer for preventing sulphur.In addition, the multivalence gold such as titanium dioxide
Chemical bonding can also be formed between the two, may further improve the stability of sulphur anode in conjunction with element sulphur by belonging to oxide.Its
In, the Surface Oxidation Modification step of carbon nano-fiber, the soaking time in concentrated nitric acid is suitable in 48h or more；Surface oxidation changes
Property after prepare coated with silica layer, the dosage that every gram of polyacrylonitrile correspond to ammonium hydroxide can be for 1-3ml, and the dosage of correspondence water can be with
For 2-6ml, the reaction time is suitable in 4h or more, with being advisable with a thickness of 20-40nm for silicon dioxide layer；Prepare novolac resin layer
Step, the dosage that every gram of polyacrylonitrile corresponds to ammonium hydroxide can be 1-3ml, and the dosage of corresponding water can be 2-6ml, and the reaction time is suitable
Preferably in 12h or more, with being advisable with a thickness of 10-20nm for novolac resin layer.
Embodiments of the present invention are described further combined with specific embodiments below.Involved in following embodiment
Reagent is commercially available customary commercial, and the mass concentration of concentrated nitric acid is 67-69%, and the mass concentration of ammonium hydroxide is 24-26%, and formaldehyde is molten
The mass concentration of liquid is 35-40%.
The number-average molecular weight of polyacrylonitrile is 150000 (Mike woods reagents).
The embodiment 1 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, flow chart such as Fig. 1 institute
Show, prepared using following steps:
1) 0.5ml titanium tetrachloride and 1g polyacrylonitrile are successively dissolved into 10ml n,N-Dimethylformamide, stirring is extremely
Clarification, obtains precursor solution.
2) electrostatic spinning technique is utilized, 2ml precursor solution is poured into injector for medical purpose every time (syringe volume is
10ml；The a length of 2.5cm of syringe needle；Syringe tip outer diameter is 0.7mm；Distance of the syringe tip away from collecting board be
15cm), spinning is carried out under conditions of electrode voltage is 10kV, obtaining polyacrylonitrile nanofiber cloth, (polyacrylonitrile nano is fine
The diameter of dimension is 200-300nm).
3) polyacrylonitrile nanofiber cloth (4cm*4cm) obtained by step 2) is placed in tube furnace, in inert atmosphere protection
Under, 1000 DEG C are warming up to the rate of 5 DEG C/min by room temperature, high temperature cabonization processing is completed in 1000 DEG C of heat preservation 1h, obtains carbon and receive
Rice fiber/composite titania material.
4) carbon nano-fiber/composite titania material is impregnated in 48h in concentrated nitric acid, then takes out and uses deionized water
It repeatedly washs repeatedly, realizes that carbon nano-fiber surface is modified, increase active site and improve the wetting property with solution, obtain table
Face modified composite fiber.
5) surface modified composite fiber obtained by step 4) is immersed in 20ml isopropanol as active template, and successively
2ml ammonium hydroxide, 4ml water and 4ml ethyl orthosilicate is added dropwise, 6h is kept, so that the silicon dioxide layer with a thickness of 50nm is uniformly wrapped
Surface modified composite fiber surface is overlayed on, coated with silica modified composite fiber is obtained.
6) it using coated with silica modified composite fiber obtained by step 5) as template, is immersed in 20ml ethyl alcohol, and
2ml ammonium hydroxide, 4ml water, 0.2g resorcinol and 0.3ml formalin is successively added dropwise, keeps carrying out for 24 hours to react fully,
So that the novolac resin layer with a thickness of 20nm is evenly coated at coated with silica modified composite fiber surface, phenolic resin is obtained
Coating modification composite fibre.
7) phenolic resin coating modification composite fibre obtained by step 6) is placed in tube furnace, under inert atmosphere protection,
900 DEG C are warming up to the rate of 5 DEG C/min by room temperature, high temperature cabonization processing is completed in 900 DEG C of heat preservation 1h, high temperature cabonization is handled
Product is obtained afterwards to immerse in the hydrofluoric acid that mass concentration is 5%, keeps 6h, etches away silicon dioxide layer to get in carbon-coated
The empty carbon-based composite nano-fiber material of core-shell structure, and still there is good three-dimensional self-supporting characteristic.
The embodiment 2 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 0.1ml.
The embodiment 3 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 0.2ml.
The embodiment 4 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 1ml.
The embodiment 5 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 3), pyrocarbon
The temperature for changing processing is 900 DEG C.
The embodiment 6 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 3), pyrocarbon
The temperature for changing processing is 1100 DEG C.
The embodiment 7 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 0.1ml, and in step 3), the temperature of high temperature cabonization processing is 900 DEG C.
The embodiment 8 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 0.2ml, and in step 3), the temperature of high temperature cabonization processing is 900 DEG C.
The embodiment 9 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 1ml, and in step 3), the temperature of high temperature cabonization processing is 900 DEG C.
The embodiment 10 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 0.1ml, and in step 3), the temperature of high temperature cabonization processing is 1100 DEG C.
The embodiment 11 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 0.2ml, and in step 3), the temperature of high temperature cabonization processing is 1100 DEG C.
The embodiment 12 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 1), four chlorinations
The additional amount of titanium is 1ml, and in step 3), the temperature of high temperature cabonization processing is 1100 DEG C.
The embodiment 13 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 5), positive silicic acid
The additional amount of ethyl ester is 1ml.
The embodiment 14 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 5), positive silicic acid
The additional amount of ethyl ester is 2ml.
The embodiment 15 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 5), positive silicic acid
The additional amount of ethyl ester is 3ml.
The embodiment 16 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 5), positive silicic acid
The additional amount of ethyl ester is 5ml.
The embodiment 17 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 6), isophthalic two
The dosage of phenol is 0.1g, and the dosage of formalin is 0.1ml.
The embodiment 18 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 6), isophthalic two
The dosage of phenol is 0.1g, and the dosage of formalin is 0.15ml.
The embodiment 19 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, in step 6), isophthalic two
The dosage of phenol is 0.5g, and the dosage of formalin is 0.75ml.
The embodiment 20 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, be repeated in step 5) and
Step 6), number of repetition are primary, building double layer hollow core-shell structure.
The embodiment 21 of the preparation method of the hollow core-shell structure electrode material of self-supporting of the invention, with self-supporting hollow core
The processing step of the preparation method embodiment 1 of shell structure electrode material is essentially identical, and difference is only that, be repeated in step 5) and
Step 6), number of repetition are secondary, building multilayer hollow core-shell structure.
The Application Example 1 of electrode material of the invention in lithium-sulfur cell, including sulphur anode, cathode of lithium, diaphragm, electrolysis
Liquid, sulphur anode include the 1 the electrode obtained material of preparation method embodiment of sulphur and the hollow core-shell structure electrode material of self-supporting, are used
Conventional melt consolidates sulphur mode (being uniformly mixed electrode material and sulphur in closed container, keep the temperature 12h at 150 DEG C), the face of sulphur
Load capacity and weight percent are respectively 6mg/cm2With 90%；Cathode of lithium is common metal lithium piece；Diaphragm is Celgard
2400；It is 2% vinylene carbonate, 1M LiPF that electrolyte, which is containing mass concentration,6Ethylene carbonate/diethyl carbonate (body
Product is than being 3:7) mixed solution, being built into specification is the button-shaped lithium-sulfur cell of CR 2025 (by lithium-sulfur cell before being tested
Stand 6h).
The Application Example 2-21 of electrode material of the invention in lithium-sulfur cell uses the hollow core-shell structure electricity of self-supporting
The preparation method embodiment 2-21 the electrode obtained material of pole material, Application Example 1 of the reference electrode material in lithium-sulfur cell
Construct corresponding lithium-sulfur cell.
The Application Example 1 of electrode material of the invention in supercapacitor, uses specification for CR2025 button mode
Construct symmetric form supercapacitor.Wherein the preparation method of the hollow core-shell structure electrode material of the direct self-supporting of positive and negative anodes is implemented
1 the electrode obtained material of example, electrolyte are 1M KOH aqueous solution, and diaphragm is conventional glass fibers diaphragm.
The Application Example 2-21 of electrode material of the invention in supercapacitor, uses the hollow core-shell structure of self-supporting
The preparation method embodiment 2-21 the electrode obtained material of electrode material, application implementation of the reference electrode material in supercapacitor
Example 1 constructs corresponding symmetric form supercapacitor.
Test example 1
The optical photograph of the 1 the electrode obtained material of preparation method embodiment of the hollow core-shell structure electrode material of self-supporting is as schemed
Shown in 2, in figure, electrode material can be cut into the shapes such as disc as needed, show good Scalability；Tweezers can be used
The disc electrode material of black is picked up, shows that it, with good self-supporting, can be used as flexible substrate use.
The SEM of 1 the electrode obtained material of preparation method embodiment schemes the electrode fig. 3, it is shown that embodiment preparation
Material has good three-dimensional self-supporting characteristic and hollow core-shell structure.
The SEM figure of 20 the electrode obtained material of preparation method embodiment is as shown in Figure 4, it can be seen that it is with double layer hollow
Core-shell structure, and the appearance regularity and consistency of material are preferable, show good three-dimensional self-supporting characteristic.It is indicated above that
With electrode material shown in Fig. 3 (hollow core-shell structure carbon nano-fiber) for template, related procedure according to the invention can be at
Function synthesis has the carbon nano-fiber materials of double layer hollow core-shell structure.
Test example 2
The electrochemistry for the lithium-sulfur cell that Application Example 1 of this test example detecting electrode material in lithium-sulfur cell is related to
Can, as a result as shown in Figure 5 and Figure 6, the chemical property and the lithium of the lithium-sulfur cell that other lithium-sulfur cell Application Examples are related to
Sulphur battery is suitable.
In fig. 5 and fig., in 27 DEG C of insulating boxs, testing result illustrates this hollow nucleocapsid for the detection of assembly device
Structure carbon nano-fiber has good captured sulfur result as the electrode material of lithium-sulfur cell, can be effectively improved the electric conductivity of sulphur
And its utilization rate is improved, it especially can be good at inhibiting the dissolution of sulphur to shuttle to a certain extent, therefore device entirety body
Reveal good high rate performance and cyclical stability, is 1000mAh/g in 0.1C condition discharge capacity.
Test example 3
The electrification for the supercapacitor that Application Example 1 of this test example detecting electrode material in supercapacitor is related to
Learn performance, as a result as shown in Figure 7 and Figure 8, the electrochemistry for the supercapacitor that other supercapacitor applications embodiments are related to
It can be suitable with the supercapacitor.
In Fig. 7 and Fig. 8, the testing conditions of device are room temperature condition, close to the cyclic voltammetry curve and triangular symmetrical of rectangle
Charging and discharging curve all illustrate that hollow core-shell structure carbon nano-fiber has ideal electricity as the electrode material of supercapacitor
Hold energy storage characteristic, embodies multiplying power energy storage characteristic outstanding.
By the above test result it is found that the hollow core-shell structure electrode material of self-supporting provided by the invention is being applied to lithium sulphur
There is good captured sulfur result, corresponding lithium-sulfur cell device has capacitance outstanding, high rate performance and circulation when battery
Stability.When being applied to supercapacitor, good energy storage effect is shown.
Claims (10)
1. a kind of preparation method of the hollow core-shell structure electrode material of self-supporting, which comprises the following steps:
1) titanium tetrachloride, polyacrylonitrile are dissolved in solvent, obtain precursor solution, precursor solution is subjected to electrostatic spinning,
Obtain polyacrylonitrile nanofiber cloth；
2) polyacrylonitrile nanofiber cloth is subjected under protective atmosphere carbonization treatment, it is multiple obtains carbon nano-fiber/titanium dioxide
Condensation material；
3) carbon nano-fiber/composite titania material is subjected to Surface Oxidation Modification processing, obtains surface modified composite fiber；
4) it using surface modified composite fiber as active template, is immersed in alcohols solvent, ammonium hydroxide, water, positive silicic acid is then added
Ethyl ester is reacted, and coated with silica modified composite fiber is obtained；
5) coated with silica modified composite fiber is immersed in alcohols solvent, ammonium hydroxide, water, resorcinol and first is then added
Aldehyde solution is reacted, and phenolic resin coating modification composite fibre is obtained；
6) phenolic resin coating modification composite fibre is subjected under protective atmosphere carbonization treatment, then will be obtained after carbonization treatment
Product immerse hydrofluoric acid in, etch away coated with silica layer to get.
2. the preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1, which is characterized in that step 1)
In, the additional amount that every gram of polyacrylonitrile corresponds to titanium tetrachloride is 0.1-1ml.
3. the preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1, which is characterized in that step 2)
In, the temperature of the carbonization treatment is 900-1100 DEG C, and the time of carbonization treatment is 1h.
4. the preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1, which is characterized in that step 3)
In, the Surface Oxidation Modification processing is to immerse carbon nano-fiber/composite titania material in concentrated nitric acid to carry out at immersion
Reason.
5. the preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1, which is characterized in that step 4)
In, the dosage that every gram of polyacrylonitrile corresponds to ethyl orthosilicate is 1-5ml.
6. the preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1, which is characterized in that step 5)
In, the dosage that every gram of polyacrylonitrile corresponds to resorcinol is 0.1-0.5g, and the dosage of corresponding formalin is 0.15-0.75ml,
The mass concentration of the formalin is 35-40%.
7. the preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1, which is characterized in that step 6)
In, the temperature of the carbonization treatment is 700-900 DEG C, and the time of carbonization treatment is 1h.
8. such as the preparation method of the hollow core-shell structure electrode material of self-supporting of any of claims 1-7, feature
It is, is repeated in and carries out step 4) and step 5), then carry out step 6) again.
9. electrode material made from a kind of preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1
Application in lithium-sulfur cell.
10. electrode material made from a kind of preparation method of the hollow core-shell structure electrode material of self-supporting as described in claim 1
Expect the application in supercapacitor.
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| CN111986931A (en) * | 2020-07-24 | 2020-11-24 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
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