CN108336313A - Magnetic control elasticity chain Fe3O4The research of/C/red P storage sodium performances - Google Patents
Magnetic control elasticity chain Fe3O4The research of/C/red P storage sodium performances Download PDFInfo
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- CN108336313A CN108336313A CN201711162236.5A CN201711162236A CN108336313A CN 108336313 A CN108336313 A CN 108336313A CN 201711162236 A CN201711162236 A CN 201711162236A CN 108336313 A CN108336313 A CN 108336313A
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- 239000011734 sodium Substances 0.000 title description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title description 16
- 229910052708 sodium Inorganic materials 0.000 title description 16
- 238000003860 storage Methods 0.000 title description 8
- 238000011160 research Methods 0.000 title description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 101
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 30
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 30
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 30
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 30
- 229920001690 polydopamine Polymers 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 8
- 230000001133 acceleration Effects 0.000 claims abstract description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000033001 locomotion Effects 0.000 claims description 5
- 230000008901 benefit Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 230000005518 electrochemistry Effects 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- -1 poly- DOPA Amine Chemical class 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims 1
- 229960004502 levodopa Drugs 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 12
- 238000005457 optimization Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 24
- 239000000523 sample Substances 0.000 description 20
- 238000005516 engineering process Methods 0.000 description 17
- 229960003638 dopamine Drugs 0.000 description 14
- 238000009826 distribution Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000001413 cellular effect Effects 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005556 structure-activity relationship Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910004751 Na15Sn4 Inorganic materials 0.000 description 1
- 229910020666 Na3Sb Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229940050561 matrix product Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses magnetic control optimization prepares Fe3O4/ C/P nucleocapsids, and optimize the friendly process of its chemical property, include the following steps：The uniform Fe of particle is prepared first3O4Ferric trichloride is dissolved in ethylene glycol by particle in advance, during NaOH is also dissolved in, using CTAB as catalyst, makes Fe3O4It is nucleated simultaneously, obtains the Fe of uniform particle diameter3O4Particle.And then in Fe3O4Surface coated Si O2, prepare Fe3O4/SiO2.Poly-dopamine is coated on matrix again, Fe is made3O4/SiO2/polydopamine.In follow-up heat treatment process, with the space of magnetic field control compression sample room, promote deposition of the red phosphorus on matrix.It is successfully prepared uniform Fe3O4/ C/red P particles.And utilize magnetic tuning Fe3O4/ C/red P negative materials, carry out different arrangements on a current collector, and the acceleration using Lorentz force to electronics and ion optimizes the chemical property of material.Haved the function that using magnetic tuning while having optimized materials synthesis and chemical property.
Description
Technical field：
The invention belongs to nano material preparation and regulatory regions, and in particular to and magnetic tuning prepares red phosphorus base negative material,
And the method for optimization chemical property.
Background technology
With the exhaustion of increasingly increased energy requirement and fossil fuel, regenerative resource and sustainable storing technology are found
The main target pursued as China scientific worker.When designing electrochemical storage system, it is desirable that electrode material source is wide, synthesis
Process is environmentally friendly, excellent material performance.For sodium-ion battery relative to lithium ion battery, sodium source is wide, at low cost and environment
Close friend, and sodium and lithium have similar chemical property, have received widespread attention.
Although sodium-ion battery and lithium ion battery have high similarity in terms of positive electrode and electrolyte, it is suitble to sodium
The negative material quantity of ion battery will be far fewer than lithium ion battery.Because sodium ion radius will be far longer than lithium ion radius,
It is one of the bottleneck for developing sodium-ion battery to find suitable negative material.Content is higher in nature, avirulent red phosphorus with
Sodium reacts to form Na3P, Na3P has up to 2595mAh g-1Theoretical capacity, to be significantly larger than other negative materials, germanium
(Na15Ge4, 369mAhg-1), tin (Na15Sn4, 847mAhg-1), lead (Na15Pb4,485mAhg-1), antimony (Na3Sb,660mAhg-1), receive the extensive concern of scholar.
But the actual capacity of red phosphorus will be much smaller than theoretical capacity, main cause be itself existing defect and itself
Utilization rate is low：(1) electric conductivity is very poor, so the chemical property that red phosphorus negative material is showed is poor；(2) red phosphorus with three
During the insertion and abjection of sodium ion, Study of Volume Expansion is very serious, so the multiplying power of red phosphorus base sodium negative material and following
Ring performance is very poor, is unfavorable for large-scale industrial production；(3) in addition in the synthesis process, there are red phosphorus and the mutual of white phosphorus to turn
Change, synthesis technology requires to improve the homogeneity of red phosphorus size, and improves the utilization rate to red phosphorus active component.
In order to improve the electric conductivity of red phosphorus, it is most useful that doping, pattern control and surface modification technology, red phosphorus is embedded in
It is high to electric conductivity, in cavernous three-dimensional structure, its electric conductivity is on the one hand improved, improves contact of the red phosphorus with carbon base body, prevents
Powdered of the red phosphorus particle in cyclic process, active material fall off and unstable solid and the interface electrolyte (SEI)
Formation.Vesicular texture can effectively buffer the volume expansion during sodium deintercalation, improve its cycle and high rate performance, in conjunction with
Surface modification technology further improves material
The storage sodium ability of material.(2) certain environmental stimuli is added, electrostatic interaction makes structure rearrange, and material is inhibited to fill
Volume expansion in discharge process improves chemical property of the material under high current density.(3) because of red phosphorus and white phosphorus
It mutually converts dependent on the driving force in system, is usually affected by capillary force and gasification-condensing pressure, low energy is added
The device of the gas-pressure adjustable of consumption is the high-efficiency environment friendly approach for improving red phosphorus homogeneity and improving active component.
Currently, doping techniques are it is most useful that carbon adulterates, relatively low carbon content can greatly improve the electrochemistry of material
Performance.Red phosphorus and the compound of carbon material have received widespread attention, although these work improve the capacity of material, are recycled improving
Some effects are achieved in performance, but the good contact for enhancing red phosphorus and carbon collective is still a challenge.There is scholar by red phosphorus
It is embedded into cavernous carbon, the composite material of assembling enhances the cycle performance of red phosphorus, but the addition of excessive carbon, results in appearance
The decline of amount.There is work that the poroid graphene of red phosphorus and N doping is compound again, had not only improved its electric conductivity, but also buffered volume
Expansion improves its capacity, but the tightness degree for enhancing red phosphorus and carbon base body contact is still urgently to be resolved hurrily.Improve red phosphorus and carbon base body
Contact, depending on improves deposition efficiency of the red phosphorus particle on carbon base body, increases kinetics driving force.So high
The dynamics Controlling of effect and the compound of carbon material have become key.
The complex method of red phosphorus and carbon is developed to from mechanical mixtures such as the initial ball millings of high energy consumption by gasifying and condensing
Technology is completed, and under capillary force and gasification-condensing pressure driving, red phosphorus relatively evenly deposits on a surface of the carbon, but
Air pressure and capillary force variation are smaller, and red phosphorus still cannot the uniform surface for being efficiently deposited on carbon.Some nearest improved gas
Change and condensation technology is also developed.It being inspired by previous work, development magnetic control technology prepares the photonic crystal of size uniformity,
The optical property of composite material is set to have obtained maximum optimization simultaneously.This low energy consumption, the technology being efficiently precisely controlled swash
It encourages us and goes to probe into whether magnetic control can complete improvement to gasification and condensation technology, be precisely controlled by externally-applied magnetic field, to electricity
The package technique in pond further improves, and completes efficiently to prepare material and optimizes the work of performance.
Synthesis technology thinking based on above-mentioned green high-efficient, we introduce the compound of red phosphorus and carbon the Fe of superparamagnetic3O4
Magnetic core.By red phosphorus and porous carbon and magnetic source Fe3O4It is compound.It in gasification-condensation technology, is pushed by magnetic field, continuous compression sample
The volume of room, with the continuous increase of vapor pressure, the uniform red phosphorus particle of particle is uniformly deposited on the surface of carbon base body, closes
At the Fe of size uniformity3O4/ C/red P-structure.By adjusting Fe3O4The distribution of/C/red P active components on a current collector,
Accelerate the movement of electronics and ion, while this magnetic texure can carry out weight during impulse electricity by electrostatic force, magnetic core
New arrangement, electrostatic force is opposite with the volume expansion power during deintercalation anti-, fundamentally prevents the powder of negative material
Change.This technological design meets environmentally protective efficient requirement.
While being entrained in raising red phosphorus sill electric conductivity of cellular carbon, and buffered the system expansion of system.Three
The structure design applying surface modification technique of dimension makes the electron transfer capacity of material and the diffusivity of ion greatly improve.Together
When externally-applied magnetic field increase synthesis red phosphorus driving force, on the one hand control synthesis high quality and high yield red phosphorus particle；Another party
Face optimizes battery package technique, by adjusting Fe3O4The distribution of/C/red P active components on a current collector, to accelerate electricity
The movement of son and ion, while this magnetic texure can promote structure to carry out weight during impulse electricity by electrostatic force
Row, electrostatic repulsion can contend with the volume expansion power during deintercalation, and the service life of battery further increases.
Invention content
It is low the purpose of the present invention is researching and developing to solve the target of volume expansion for the unstability of red phosphorus preparation process
Cost, the chain cellular Fe of green high-efficient3O4/ C/red P sode cell negative materials.Externally-applied magnetic field improves materials synthesis efficiency
With optimization battery package technique.
Realize that above-mentioned purpose technical solution of the present invention is：
Synthesize Fe3O4Particle, in Fe3O4Substrate deposit SiO2.In Fe3O4/SiO2Upper load poly-dopamine.Then with one
The NaOH of concentration is determined by SiO2Corroded, is prepared into cavernous Fe3O4/polydopamine。
In subsequent heat treatment process, in cavernous Fe3O4Red phosphorus is deposited on/polydopamine.
Finally magnetic field compression sample is utilized to synthesize building volume, increases sample synthesis room pressure and make evengranular red phosphorus
Particle uniform deposition is in Fe3O4On/C Surface, Fe is made3O4/C/red P。
One of the optimization technique of the present invention is to low cost, the chain cellular Fe of green high-efficient3O4/ C/red P cathode
Material carries out the investigation of storage sodium ability.Externally-applied magnetic field improves materials synthesis efficiency and optimization battery package technique.It was preparing
Cheng Zhong prepares stable red phosphorus based composites, improves the conversion ratio of red phosphorus and white phosphorus so that the red phosphorus particle of size uniformity is equal
It is even to be distributed on carbon base body.In terms of battery assembling, magnetic control active material carries out different arrangements on a current collector, studies different rows
Row Lorentz force is with the structure of electronic conduction ability and ion-diffusibility effect property and material electrostatic force to volume expansion energy
Power significantly inhibits effect.Environmental stimuli source is introduced, while achieving the purpose that optimize material preparation and battery package technique.Specifically
Research contents includes following aspect：
(1) effective carbon is combined to adulterate, pattern control, surface modification technology prepares Fe3O4/SiO2/Polydopamine
Compound
Three-dimensional porous structure is designed, is convenient for the infiltration of electrolyte, self-discharge of battery voltage is small, and cycle life is strong.In conjunction with
Effective carbon doping, pattern control technology and surface modification technology greatly improve the electric conductivity of material.Based on this, to Fe3O4It is first
The doping for first carrying out porous carbon, introduces SiO2Template prepares Fe3O4/SiO2, the load of poly-dopamine carbon source is finally carried out, most
The compound of the carbon of composite material and cavernous structure not only improves its electric conductivity afterwards, but also has buffered volume expansion.It was synthesizing simultaneously
Intend using nitrogen surface modification technology in journey, further increases the storage sodium performance of material.
Pattern control is by material dimension from a Bits Expanding to three-dimensional, and to widen the conduction orientation of electronics, electronics is at four sides
It is conducted from all directions, improves the electric conductivity of material.The conduction distance of ion reduces simultaneously, and sodium ion diffusivity is carried
It is high.Three-dimensional structure reduces the diffusion length of sodium ion diffusion, and the ion-diffusibility of sodium ion greatly improved, and ensures material
There is excellent chemical property.Three-dimensional Fe3O4/ P/C cellular nucleocapsids are convenient for the infiltration of electrolyte, self-discharge of battery electricity
Press small, cycle life is strong.
During preparing red phosphorus based composites, the electrochemistry of material is can effectively improve using surface modification technology
Can include electric conductivity, the permeability and the raising embedding sodium efficiency of the battery first run of electrolyte.Sodium ion first with the hetero atom on surface
It is reacted, reaction is more abundant, and the subsequent deintercalation sodium of material is more efficient, so many researchers attempt to introduce N, S etc. is miscellaneous
Atom is to improve the storage sodium ability of material.
(2) distribution of the magnetic-control high efficiency control red phosphorus on matrix
The Fe of superparamagnetic is introduced to the compound of red phosphorus and carbon3O4Magnetic core.In order to preferably complete to red phosphorus in Fe3O4/
SiO2Deposition in/C matrix, design magnetic control compression sample synthesize building volume, improve red phosphorus deposition driving forces, promote red phosphorus in carbon
Good distribution on matrix.By discharging external magnetic field, the volume of sample room constantly reduces, and the indoor steam pressure of sample is continuous
Increase, deposition efficiency of the red phosphorus on matrix can be effectively facilitated.
(3) it investigates chain structure electrostatic force and improves the structure-activity relationship of cycle performance
Compare the Fe of chain3O4/ C/red P-structure, the Fe of the chaining aligned under magnetic fields3O4/C/red
P, chain Fe3O4The electrostatic potential difference of/C/red P-structure is much larger than single Fe3O4/ C/red P structures.Investigate chain simultaneously
Superiority of the structure in terms of sodium ion diffusion length explores contact situation of the chain structure with collector.
(4) arrangement influence to chemical property of the material on matrix is investigated
When inspecting electrode material carries out different arrangements on a current collector, the constant current charge-discharge performance of material itself is forthright again
Energy and cycle performance.By adjusting Fe3O4The distribution of/P/C active components on a current collector discloses suffered magnetic field force not
With the influence to accelerating electronics and ion motion.Controlling active material component in collector with magnet is coated with different angle,
Investigate the influence of the cycle life of active component.
(5) chain Fe is investigated3O4Structure-activity relationship between/C/red P-structure and volume expansion
The beneficial effects of the present invention are：
Method proposed by the present invention is prepared for low cost, the chain cellular Fe of green high-efficient3O4/ C/red P cathode materials
The investigation of material storage sodium ability.Externally-applied magnetic field improves materials synthesis efficiency and optimization battery package technique.In preparation process, system
The standby red phosphorus based composites stablized, improve the conversion ratio of red phosphorus and white phosphorus so that the red phosphorus particle of size uniformity is uniformly distributed
On carbon base body.In terms of battery assembling, magnetic control active material carries out different arrangements on a current collector, studies different arrangement long-range navigations
Hereby power shows volume expansion ability with the structure of electronic conduction ability and ion-diffusibility effect property and material electrostatic force
Write inhibition.Environmental stimuli source is introduced, while achieving the purpose that optimize material preparation and battery package technique.
Description of the drawings
Description of the drawings
When Fig. 1 respectively 10cm with a distance from heating sample room for magnet, 7cm, 5cm, the sample transmission figure of synthesis
Fig. 2 is granular Fe individually3O4The distribution diagram of element of/C/red P
Fig. 3 a are granular Fe3O4/ dopamine, b are cavernous Fe3O4/ dopamine, c are cavernous particle
Fe3O4/ C/P, d are the Fe of chain3O4/SiO2/ dopamine, e are the Fe of amplification3O4/SiO2/ dopamine, f are chain
Fe3O4/C/P
Fig. 4 a are chain Fe3O4The adsorption desorption figure of/C/dopamine, b are chain Fe3O4The pore-size distribution of/C/dopamine
Figure
Fig. 5 a are chain Fe3O4Constant-current discharge figure when/C/dopamine different distributions, b are chain material 0.05
mAg-1When the cyclicity comparison that is
Fig. 6 a are chain Fe3O4The cyclic voltammogram of/C/dopamine, b 0.05mAg-11-100 constant current charge-discharge
Figure, c 0.2mAg-1When circulating ratio performance investigation
Illustrate the present invention below by most preferred embodiment.Those skilled in the art institute it should be understood that, embodiment is only used for
It illustrates rather than for limiting the scope of the invention.
In embodiment, unless otherwise instructed, means used are the means of this field routine.
Embodiment 1：
1)Fe3O4The preparation of cluster
By FeCl3It is dissolved in solution in ethylene glycol and is made into 0.2M, 0.883g PAA are added, are scattered in 20ml ethylene glycol, it will
Solution is heated to 220 DEG C, keeps temperature 0.5h hours, and the NaOH that 0.5M is added is dissolved in ethylene glycol solution 1.5ml, keeps temperature
1.5h generates the Fe of about 100nm3O4Cluster.
2)Fe3O4/SiO2The preparation of nucleocapsid
Next in Fe3O4One layer of SiO of area load2, by 3ml Fe3O4Aqueous solution and 3ml NH3.H2O is mixed and is divided
It dissipates in the ethanol solution of 10ml, 60 μ l orthosilicic acid presomas is added every time, react 1h, repeat and this time operate, until being added
The volume of orthosilicic acid reaches 180 μ l, and last time reaction stops 1.5h, ensures that fully reaction is completed.By resulting product second
Alcohol and water centrifuges 3 times respectively.Sample is scattered in the aqueous solution of 100ml again.
3) cavernous Fe3O4The preparation of/dopamine
Fe is prepared first3O4/SiO2The hydrogen chloride ammonium of 80mg is previously dissolved in the solution of pH=8.5, adds by/dopamine
Enter 5ml Fe3O4/SiO2Solution, at room temperature magnetic agitation 36h, last product ethyl alcohol and water washing are respectively three times.It generates
Product F e3O4/SiO2The poly-dopamine thickness of/dopamine about 240nm, generation are 100nm.Fe3O4/SiO2/
Polydopamine is etched with the NaOH of 0.5M, and cavernous Fe is made3O4 /polydopamine。
4) cavernous Fe3O4The preparation of/polydopamine
First in Fe3O4/SiO2Surface coats poly-dopamine carbon-coating, and the dopamine chlorine hydrogen amine of 80mg is dissolved in pH=in advance
In 8.5 hydrochloric acid buffer solution, the Fe of 5ml is added3O4/SiO236h is stirred at room temperature in solution, then each clear with second alcohol and water
It washes 3 times.The Fe of about 240nm is obtained3O4/SiO2/polydopamine.The thickness of poly-dopamine is about 100nm.Fe3O4/SiO2
It is uniformly coated in poly-dopamine layer.The shelly-shaped Fe of following yolk3O4/ polydopamine structures pass through erosion
Fe3O4/SiO2/ polydopamine is obtained, by product F e3O4/SiO2/ polydopamine is carried out with the NaOH solution of 0.5M
Etching, obtains cavernous Fe3O4/polydopamine。
5) Fe is prepared3O4/C/red P
Red phosphorus and Fe3O4/ polydopamine is placed in the sample room of ceramics, and putting a band above, there are one iron covering.
One block of magnet is put below sample room, is placed below a compressed spring.Sample room is heated to 700 DEG C, keeps 2h, isothermal
Degree drops to 430 DEG C, and the compressed spring of slow release, sample room is compressed continuously, and promotes red phosphorus in Fe3O4It is heavy in/C matrix
Product efficiency.The room distance for adjusting magnet to sample is respectively 10cm, 7cm, 5cm, 3cm, the sample collected.
6) optimize Fe3O4The chemical property of/C/red P
Active material is adjusted with magnet, carries out different arrangements on a current collector, when investigating the arrangement of material difference, electrochemistry
The difference of performance.During material deintercalation sodium, material carries out different arrangements, acceleration of the Lorentz force to electronics and ion
Difference causes the high rate performance of material different.By investigating different arrangements, constant current charge-discharge and high rate performance and cycle performance
Difference, be best arrangement when showing that magnet is parallel with collector.
7) characterization of material
The component of pattern, structure, crystal characteristic and sample uses scanning electron microscope, transmission electron microscope, X-ray diffraction, member respectively
Plain analytic approach is tested.Functional group's infrared test, nitrogen adsorption curve test pore-size distribution and specific surface area, X-ray light
Electron spectrum tests functional group.
8) electro-chemical test
Electro-chemical test is the sodium-ion battery by being assembled in argon atmosphere to be tested.Assembling for battery is
By mixed active material, carbon black, (ratio is 8 to binder PVDF:1:1) it, is scattered in N-Methyl pyrrolidone.Then true
For 24 hours, electrolyte is NaClO for drying in empty drying box4It is 1 to be dissolved in volume ratio:In 1 EC and DMC, constant current charge-discharge
Test is completed in blue electrical measurement test system, and voltage range is 0.01-3V.Battery is first in 50mA g-1It is activated, electricity
Chemical impedance is carried out by electro-chemical test.
Specific implementation mode
Illustrate the present invention below by most preferred embodiment.Those skilled in the art institute it should be understood that, embodiment is only used for
It illustrates rather than for limiting the scope of the invention.
In embodiment, unless otherwise instructed, means used are the means of this field routine.
1. a kind of preparing the high chain Fe of stability by ancillary technique of magnetic field3O4/ C/red P-structure are used as sodium ion electricity
Pond negative material, and investigating under magnetic tuning, the differences of the negative material different arrangement chemical properties on a current collector.Including
Following steps：Synthesize Fe3O4Particle, in Fe3O4Upper deposition SiO2.In Fe3O4/SiO2Upper load poly-dopamine.Then with certain
The NaOH of concentration is by SiO2It erodes, is prepared into cavernous Fe3O4/polydopamine.In subsequent heat treatment process
In, in cavernous Fe3O4Red phosphorus is deposited on/polydopamine, building volume is synthesized using magnetic field compression sample, increases sample
Room pressure is synthesized, evengranular red phosphorus particle uniform deposition is in Fe3O4On/C Surface, Fe is made3O4/C/red P。
2. by the Fe of individual particle3O4/ C/red P expand to the Fe of chain3O4/ C/red P are investigated opposite at chain structure
In the superiority of individual particle.
3. investigating chain Fe3O4/ C/red P negative material differences arrange the influence to chemical property.
4. investigating in charge and discharge process, chain structure slows down volumizing effect into rearrangement, improves battery
Service life.
5. the method as described in claim 1 is prepared for uniform Fe3O4Particle deposits SiO on this basis2With
Polydopamine, its main feature is that making Fe by control3O4It is nucleated simultaneously, generates uniform Fe3O4, while being rationally added
Silica precursor, dopamine source are prepared for uniform Fe3O4/SiO2/dopamine.Compression sample is controlled using magnetic field
Synthesis chamber space increases the deposition pressure of red phosphorus, promotes red phosphorus uniform deposition on matrix, enhances red phosphorus and white phosphorus and converting
Stability in the process, uniform Fe3O4/ C/red P nanostructures are prepared out.
6. method as claimed in claim 2 prepares the Fe of chain by changing the ratio of presoma3O4/C/red P。
Its main feature is that chain structure has advantage relative to single particle in terms of ion is spread and fights volume expansion, to structure
The advantage brought is analyzed.
7. method as claimed in claim 3, it is contemplated that acceleration of the Lorentz force for electronics and ion motion, material
The suffered Lorentz force of material is arranged on a current collector by material to be influenced, and detailed examination material arranges the shadow for chemical property
It rings its main feature is that being analyzed the material of preparation in conjunction with physics and chemical theory.
8. method as claimed in claim 4, material important feature is in charge and discharge process, and magnetic core can be reset,
Its electrostatic force can contend with physical expansion or shrinkage power, further improve the high rate performance and cycle life of material.
Above embodiment be only the preferred embodiment of the present invention is described, not to the scope of the present invention into
Row limits, under the premise of not departing from design spirit of the present invention, technical side of this field ordinary engineering and technical personnel to the present invention
The all variations and modifications that case is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (8)
1. a kind of preparing the high chain Fe of stability by ancillary technique of magnetic field3O4/ C/red P-structure, and it is used as sodium-ion battery
Negative material.It investigates simultaneously under magnetic tuning effect, when which carries out different arrangements on a current collector, to electrochemistry
The influence of energy.Include the following steps：Synthesize Fe3O4Particle, in Fe3O4Substrate deposit SiO2.In Fe3O4/SiO2Load poly- DOPA
Amine.Then with certain density NaOH by SiO2It corrodes, is prepared into cavernous Fe3O4/polydopamine.In subsequent heat
In processing procedure, in cavernous Fe3O4Red phosphorus is deposited on/polydopamine, building volume is synthesized using magnetic field compression sample,
Increase sample and synthesize room pressure, makes evengranular red phosphorus particle uniform deposition in Fe3O4On/C Surface, Fe is made3O4/C/
red P。
2. by the Fe of individual particle3O4/ C/red P particles, expand to the Fe of chain3O4/ C/red P are investigated opposite at chain structure
In the superiority of individual particle.
3. investigating chain Fe3O4/ C/red P negative material differences arrange the influence to chemical property.
4. investigating in charge and discharge process, chain structure resets the confrontation with volume expansion effect, greatly improves the service life of battery.
5. the method as described in claim 1 is prepared for uniform Fe3O4Particle deposits SiO on this basis2With
Polydopamine generates uniform Fe its main feature is that make reaction by control while being nucleated3O4, while being added appropriate two
Siliconoxide precursor, poly-dopamine source are prepared for uniform Fe3O4/SiO2/polydopamine.Compression sample is controlled using magnetic field
Product synthesis chamber space increases the deposition pressure of red phosphorus, promotes red phosphorus uniform deposition on matrix, enhances red phosphorus and white phosphorus and is turning
Stability during change prepares uniform Fe3O4/ C/red P nanostructures.
6. method as claimed in claim 2 prepares the Fe of chain by changing the ratio of presoma3O4/C/red P.It is special
Point is chain structure has significant advantage relative to single particle in terms of ion is spread and fights volume expansion, and
The advantage that structure is brought is analyzed.
7. method as claimed in claim 3 examines acceleration of the rate to Lorentz force for electronics and ion motion, material institute
By Lorentz force arranged and influenced on a current collector by material, detailed examination material arranges the influence for chemical property,
Its main feature is that doing further investigated to the material of preparation in conjunction with physics and chemical theory.
8. method as claimed in claim 4, material important feature is in charge and discharge process, and magnetic core can be reset, quiet
Electrical forces can contend with physical expansion or shrinkage power, further improve the high rate performance and cycle life of material.
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| CN112420999A (en) * | 2020-10-13 | 2021-02-26 | 天津大学 | Phosphorus-based negative electrode material with coating structure and preparation method and application thereof |
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