CN110323429A - Niobium pentaoxide/redox graphene composite negative pole material preparation method - Google Patents
Niobium pentaoxide/redox graphene composite negative pole material preparation method Download PDFInfo
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- CN110323429A CN110323429A CN201910610502.9A CN201910610502A CN110323429A CN 110323429 A CN110323429 A CN 110323429A CN 201910610502 A CN201910610502 A CN 201910610502A CN 110323429 A CN110323429 A CN 110323429A
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- negative pole
- niobium pentaoxide
- composite negative
- pole material
- redox graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006184 cosolvent Substances 0.000 claims abstract description 5
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 17
- 238000013019 agitation Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052744 lithium Inorganic materials 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 19
- 239000002114 nanocomposite Substances 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000008859 change Effects 0.000 description 8
- 239000002070 nanowire Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000010955 niobium Substances 0.000 description 7
- 229910052758 niobium Inorganic materials 0.000 description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
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- 241000446313 Lamella Species 0.000 description 5
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- 230000003647 oxidation Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- -1 compound niobium oxide Chemical class 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000484 niobium oxide Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 241000872198 Serjania polyphylla Species 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M4/362—Composites
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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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- Engineering & Computer Science (AREA)
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- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Niobium pentaoxide/redox graphene composite negative pole material preparation method, comprising the following steps: (1) stannic oxide/graphene nano piece is mixed with water, stirred, ultrasonic disperse obtains the dispersion liquid of stannic oxide/graphene nano；(2) columbium pentachloride is dissolved in water, stirs, obtains columbium pentachloride suspension, organic matter cosolvent and hexamethylenetetramine are sequentially added into columbium pentachloride suspension, stirred, obtain white solution；(3) dispersion liquid of stannic oxide/graphene nano is mixed with white solution, stirs to being uniformly dispersed, obtains mixed solution, gained mixed solution is put into autoclave and carries out hydro-thermal reaction；(4) after the completion of hydro-thermal reaction, resulting precipitating is washed and is dried, solid powder is obtained；(5) solid powder is heat-treated under an argon atmosphere,.Operation of the present invention is convenient, and reaction condition is controllable, and the lithium battery for installing the cathode of lithium battery of useful gained composite negative pole material production has excellent circulation and high rate performance.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion chargeable battery composite negative pole material, and in particular to a kind of five oxygen
Change the preparation method of the compound niobium oxide negative electrode material of two niobiums/redox graphene.
Background technique
Lithium ion chargeable battery is as common energy storage device, for lead-acid battery and nickel-cadmium cell, have compared with
The features such as high voltage, high energy density, long service life, environmentally friendly and memory-less effect, since commercialization with
Very important effect is just played, is widely used to moving electronic components, communication apparatus and backup power source etc..
With the fast development of electric vehicle and hybrid electric vehicle, lithium ion battery is due to its unique advantage, it is considered to be
The ideal candidates of the dynamical system of electric vehicle.The service life of high power density, high energy density and length, becomes existing rank
Section lithium ion battery for electric vehicle researches and develops problem most in the urgent need to address.The performance of energy storage device is heavily dependent on institute
Use the performance of material.Negative electrode material is the important component of lithium ion secondary battery, the cathode material of conventional lithium ion battery
Material is mainly graphite negative electrodes, and with preferable electric conductivity, but its high rate performance is poor, it is difficult to meet lithium ion battery high current
The requirement of charge and discharge.Other most of negative electrode material operating voltages are all lower, will lead to the problems such as such as lithium branch is brilliant in this way
Occur.Therefore the lithium ion battery negative material of high working voltage, better high rate performance, long circulation life by extensive concern and
Research.
Transition metal oxide niobium pentaoxide (Nb2O5) possess unique embedded fake capacitance characteristic, it is a kind of safety
Good, good rate capability novel cathode material for lithium ion battery.In Nb2O5In body phase material, there is no phase transformation in de-/process of intercalation
Occur, charge storage ability is controlled unlike most of battery materials by semo-infinite diffusion process, but is turned by surface
Change process control, causes it with unusual high rate capability, this makes it have capacitive character process, and the response time is fast, is
A kind of li-ion electrode materials that fast charging and discharging may be implemented.But Nb2O5Low (~ 3 × 10-6 S cm of conductivity-1), and its
Yi Fenhua in charge and discharge process and lead to capacity attenuation, so that it is difficult to meet the needs of heavy-duty battery.Therefore effectively enhance it
Electrical conductance and electrode structure stability are to improve Nb2O5The key of negative electrode material chemical property.Grapheme material is special because of its
The transport property of band structure, superelevation gan shifting rate and novelty becomes and explores new physical property, the reason of development of new quantum electronic device
Think system.Grapheme material and niobium pentaoxide progress is compound, not only increase the memory capacity of lithium ion, and graphene
Porous structure equally enhances the transmittability of electrolyte ion, the flexibility of graphene-structured and having constructed for three-dimensional framework
Conducive to buffering lithium ion deintercalation process bring volume expansion, so that not only there is the lithium ion battery made high volume to hold
Amount, while also having the cyclical stability of big charge-discharge magnification performance and length, therefore, graphene can be effectively improved niobium base oxygen
Compound is used for specific capacity, high rate performance and the cycle performance of lithium ion battery negative material.
CN108493427A discloses a kind of method that hydro-thermal method prepares Nb2O5 powder lithium ion battery electrode material, should
Method passes through hydro-thermal method synthetizing micro-nano grade Nb2O5 powder first, then is prepared by mixing into li-ion electrode materials with graphene uniform.
But the Nb2O5 powder body material particle is larger, is micron order, and it is serious to reunite, and not can effectively solve Nb2O5 negative electrode material and is filling
Structural stability difference in discharge process and the problem of lead to capacity attenuation.Exist between the Nb2O5 micron particles of this method synthesis
Gap is unfavorable for the electronic conduction process of the material, can not farthest play graphene to Nb2O5 negative electrode material electric conductivity
Castering action.Partially synthetic process required temperature in this method is higher, and required time is longer, and energy consumption is larger.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, it is steady to provide a kind of structure
Fixed, good conductivity, high rate performance is excellent, and preparation process is simple, low energy consumption, five oxygen low in cost, being suitable for industrialized production
Change two niobiums/redox graphene nano composite anode material preparation method.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of niobium pentaoxide/reduction-oxidation graphite
The preparation method of alkene composite negative pole material, comprising the following steps:
(1) stannic oxide/graphene nano piece is mixed with water, is stirred, ultrasonic disperse obtains the dispersion liquid of stannic oxide/graphene nano；
(2) columbium pentachloride dissolution is dispersed in water, stirs, obtains columbium pentachloride suspension, be added into columbium pentachloride suspension
Organic matter cosolvent, stirring, obtains clear solution, hexamethylenetetramine is added to clear solution, stirring obtains white solution；
(3) dispersion liquid of stannic oxide/graphene nano obtained by step (1) is mixed with white solution obtained by step (2), stirring extremely divides
It dissipates uniformly, obtains mixed solution, gained mixed solution is put into autoclave and carries out hydro-thermal reaction；
(4) after the completion of hydro-thermal reaction, the precipitating that hydro-thermal reaction generates is collected, resulting precipitating is washed and dried, must be consolidated
Body powder；
(5) obtained solid powder in step (4) is heat-treated under an argon atmosphere to get niobium pentaoxide/reduction-oxidation
Graphene composite negative pole.
Further, in step (1), the concentration of the dispersion liquid of the stannic oxide/graphene nano is 0.5~2 mg/mL.
Further, in step (2), the concentration of the columbium pentachloride suspension is 5~15 mg/mL.
Further, in step (2), the organic matter cosolvent is at least one of oxalic acid, acetic acid or ethanedioic acid.
Further, in step (2), the method for the columbium pentachloride dissolution dispersion is magnetic agitation: by columbium pentachloride and water
Mixed solution be placed in water-bath and carry out magnetic agitation, the speed of magnetic agitation is 300~500 r/min, magnetic agitation
Temperature is 10~40 DEG C, and the time of magnetic agitation is the h of 0.5 h~3.
Further, in step (3), volume ratio that the dispersion liquid of the stannic oxide/graphene nano is mixed with the white solution
For 1:1~1:3；
Further, in step (3), the temperature of the hydro-thermal reaction is 140~200 DEG C, and the time is 8~24 h.
Further, in step (4), the method for the drying is freeze-drying, forced air drying or vacuum drying at least one
Kind.
Further, in step (5), the rate of heat addition of the heat treatment is 1~20 DEG C/min, and heating temperature is 400 DEG C
~1000 DEG C, soaking time is 1~3 h.
The invention has the advantages that (1) present invention process is simple, energy consumption is small, low in cost；.(2) five oxygen prepared by the present invention
Change in two niobiums/redox graphene composite negative pole material, pentoxide nanowire by use confinement is in the two dimension of graphene nanometer sheet
In nano-space, the diameter of pentoxide nanowire by use is 5~10 nm, and length is 50~200 nm, and growth in situ is in lamella
With a thickness of the redox graphene surface of 5~10 nm, it can effectively enhance its structural stability and electrical conductance, thus effectively
Improve its chemical property, provides new approaches for the exploitation and research of novel high-performance electrode material；(3) prepared by the present invention
Chemical property is preferable when niobium pentaoxide/redox graphene composite negative pole material is applied to cathode of lithium battery, in 1 C
Under the current density of (mA/g of 1 C=200), discharge capacity may be up to 170 mAh/g；In 10 mA/g of C(1 C=200)
Under current density, specific discharge capacity may be up to 100 mAh/g, illustrate the presence due to graphene, can prevent niobium pentaoxide
Reunion, enhance the electrical conductance of niobium pentaoxide, make material lithium storage content be improved significantly.
Detailed description of the invention
Fig. 1 is 1 niobium pentaoxide of the embodiment of the present invention/redox graphene composite negative pole material XRD diagram；
Fig. 2 is 1 niobium pentaoxide of the embodiment of the present invention/redox graphene composite negative pole material scanning electron microscope (SEM) photograph；
Fig. 3 is 1 niobium pentaoxide of the embodiment of the present invention/redox graphene composite negative pole material transmission electron microscope picture；
Fig. 4 is that 1 niobium pentaoxide of the embodiment of the present invention/redox graphene composite negative pole material and pure phase niobium pentaoxide are negative
The first circle of pole material and the second circle charging and discharging curve comparison diagram；
Fig. 5 is 1 niobium pentaoxide of the embodiment of the present invention/redox graphene composite negative pole material high rate performance test chart.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Embodiment 1
The present embodiment the following steps are included:
(1) 0.0435 g stannic oxide/graphene nano piece is mixed with 40 ml deionized waters, stirs 0.5 h, 0.5 h of ultrasonic disperse
The dispersion liquid of stannic oxide/graphene nano is obtained afterwards；
(2) it disperses 0.872 g columbium pentachloride in 40 mL deionized waters and stirs 0.5 h, obtain columbium pentachloride suspension；By 2
Above-mentioned gained suspension is added in the oxalic acid of g, stirs 0.5 h, obtains clear solution；1.12 g hexamethylenetetramines are added above-mentioned
Clear solution stirs 0.5 h, obtains white solution；
(3) white solution obtained by step (2) is mixed with stannic oxide/graphene nano dispersion liquid obtained by step (1), stirs 0.5 h,
Mixed solution is obtained, mixed solution is put into autoclave, at 180 DEG C, carries out the hydro-thermal reaction of 14 h；
(4) after the completion of hydro-thermal reaction, by gained sediment successively with deionized water centrifugation, washing 3 times, revolving speed is 6000 r/
Min dries 12 h at a temperature of 60 DEG C in air dry oven, obtains solid powder；
(5) under an argon atmosphere by solid powder, with the heating rate of 5 DEG C/min, 3 h is heat-treated at 600 DEG C, obtain five oxygen
Change two niobiums/redox graphene composite negative pole material.
Fig. 1 is that niobium pentaoxide/redox graphene composite negative pole material XRD diagram is prepared in the present embodiment, with
Standard card compares it is found that the material is hexagonal crystal system niobium pentaoxide, and there is no other miscellaneous phases.Fig. 2 obtains for the present embodiment
Niobium pentaoxide/redox graphene nano composite anode material SEM picture, it can be seen that redox graphene dredge
The fluffy reticular structure of pine is fairly obvious, and pentoxide nanowire by use is grown among graphene sheet layer with second particle reunion.
Fig. 3 is the obtained niobium pentaoxide of the present embodiment/redox graphene nano composite anode material transmission electron microscope picture, is led to
The very thin redox graphene single layer of the available lamella of this method is crossed, thickness within 5 ~ 10 nm, receive by niobium pentaoxide
For nanowire growth in single-layer graphene on piece, it is 5 ~ 10 nm that size, which is distributed as diameter, and length is 50 ~ 200 nm, and agglomeration is unknown
It is aobvious.
The assembling of battery: by the present embodiment niobium pentaoxide/redox graphene nano composite anode material and carbon black
It with PVDF with the mass ratio of 8:1:1, and is ground using NMP as dispersant, then be uniformly applied to copper foil surface, obtains five oxygen
Change two niobiums/redox graphene nano composite anode material pole piece；Then, in the closed glove box of applying argon gas, with five oxygen
Changing two niobiums/redox graphene nano composite anode material pole piece is cell working electrode, and metal lithium sheet is to electrode, with micro-
Hole polypropylene screen is diaphragm, 1mol/L LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button electricity of CR2025
Pond carries out charge-discharge test.
As shown in Figure 4, with niobium pentaoxide obtained by the present embodiment/redox graphene nano composite anode material assembling
Battery, in 0 ~ 3 V voltage range, 0.1 mA of C(1 C=200 g-1) first circle and second circle charging and discharging curve, it can be seen that five
Two niobiums/redox graphene nano composite anode material first circle is aoxidized compared with the niobium pentaoxide of pure phase, first circle capacity from
520 mAh/g are promoted to 900 mAh/g, and the second circle is from 250 mAh/g promotion to 540 mAh/g.Illustrate reduction-oxidation graphite
The compound of alkene can greatly promote chemical property of the niobium pentaoxide as negative electrode of lithium ion battery.As shown in figure 5, this hair
Bright embodiment niobium pentaoxide/redox graphene nano composite anode material assembling battery, in 0~3 V voltage model
In enclosing, 0.1 mA/g of C(1 C=200) current density under, discharge capacity can be stablized in 295 mAh/g；It is close in the electric current of 5 C
Under degree, specific discharge capacity may be up to 100 mAh/g, illustrate the presence due to graphene, can prevent niobium pentoxide nano
Grain reunion, enhance the electric conductivity of niobium pentaoxide, make material storage lithium performance be improved significantly.
Embodiment 2
The present embodiment the following steps are included:
(1) 0.0435 g stannic oxide/graphene nano piece is mixed with 40 mL deionized waters, stirs 0.5 h, 0.5 h of ultrasonic disperse,
Obtain stannic oxide/graphene nano dispersion liquid；
(2) it disperses 0.872 g columbium pentachloride in 40 mL deionized waters and stirs 0.5 h, obtain columbium pentachloride suspension；By 2
Above-mentioned gained suspension is added in the oxalic acid of g, stirs 0.5 h, obtains clear solution；1.12 g hexamethylenetetramines are added above-mentioned
Clear solution stirs 0.5 h, obtains white solution；
(3) white solution obtained by step (2) is mixed with stannic oxide/graphene nano dispersion liquid obtained by step (1), stirs 0.5 h,
Mixed solution is obtained, mixed solution is put into autoclave, at 180 DEG C, carries out the hydro-thermal reaction of 8 h；
(4) after the completion of hydro-thermal reaction, hydro-thermal reaction gained sediment is successively centrifuged with deionized water, washing 3 times, revolving speed is
6000 r/min dry 12 h at a temperature of 60 DEG C in air dry oven, obtain solid powder；
(5) under an argon atmosphere by solid powder, with the heating rate of 5 DEG C/min, 3 h is heat-treated at 600 DEG C, obtain five oxygen
Change two niobiums/redox graphene nano composite anode material.
The XRD diagram of material obtained by the present embodiment, it is the oxidation of hexagonal crystal system five two that the material can be obtained by, which comparing with standard card,
Other miscellaneous phases are not present in niobium.The niobium pentaoxide that the present embodiment obtains/redox graphene nano composite anode material
SEM picture, it can be seen that the loose fluffy reticular structure of redox graphene is fairly obvious, and pentoxide nanowire by use is with two
Secondary particle agglomeration is grown among graphene sheet layer.Niobium pentaoxide/redox graphene that this example obtains is nano combined
The transmission electron microscope picture of negative electrode material passes through the very thin redox graphene list of the available lamella of this method, five oxidations two
For niobium nanowire growth in single-layer graphene on piece, agglomeration is unobvious.
The assembling of battery: by the present embodiment niobium pentaoxide/redox graphene nano composite anode material and carbon black
With PVDF with the mass ratio of 8:1:1, and using NMP as solvent mixed grinding, then it is uniformly applied to copper foil surface, obtains nanoscale
The compound niobium oxide negative electrode material smear of redox graphene；Then, in the closed glove box of applying argon gas, with five oxidations two
Niobium/redox graphene nano composite anode material pole piece is cell working electrode, and metal lithium sheet is to be gathered to electrode with micropore
Propylene film is diaphragm, 1mol/L LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025, into
Row charge-discharge test.Charge-discharge performance is similar to Example 1, illustrates niobium pentaoxide/oxygen reduction fossil that the embodiment obtains
Black alkene nano composite anode material can prevent the reunion of niobium pentoxide nano particle in the presence due to graphene, enhancing
The electric conductivity of niobium pentaoxide, improves the storage lithium performance of material.
Embodiment 3
The present embodiment the following steps are included:
(1) 0.0435 g stannic oxide/graphene nano piece is mixed with 40 ml deionized waters, stirs 0.5 h, 0.5 h of ultrasonic disperse,
Obtain stannic oxide/graphene nano dispersion liquid；
(2) it disperses 0.872 g columbium pentachloride in 40 ml deionized waters and stirs 0.5 h, obtain columbium pentachloride suspension；By 2
Above-mentioned gained suspension is added in the oxalic acid of g, stirs 0.5 h, obtains clear solution；1.12 g hexamethylenetetramines are added above-mentioned
Clear solution stirs 0.5 h, obtains white solution；
(3) above-mentioned white solution is mixed with stannic oxide/graphene nano dispersion liquid, stirs 0.5 h, obtains mixed solution.It will mixing
Solution is put into autoclave, at 180 DEG C, carries out the hydro-thermal reaction of 24 h.
(4) after the completion of hydro-thermal reaction, by hydro-thermal reaction gained sediment successively with deionized water centrifugation, washing 3 times, revolving speed
For 6000 r/min, 12 h are dried at a temperature of 60 DEG C in air dry oven, obtain solid powder；
(5) under an argon atmosphere by solid powder, with the heating rate of 5 DEG C/min, 3 h is heat-treated at 600 DEG C, obtain five oxygen
Change two niobiums/redox graphene nano composite anode material.
The XRD diagram of material obtained by the present embodiment, it is the oxidation of hexagonal crystal system five two that the material can be obtained by, which comparing with standard card,
Other miscellaneous phases are not present in niobium.The niobium pentaoxide that the present embodiment obtains/redox graphene nano composite anode material
SEM picture, it can be seen that the loose fluffy reticular structure of redox graphene is fairly obvious, and pentoxide nanowire by use is with two
Secondary particle agglomeration is grown among graphene sheet layer.The niobium pentaoxide that the present embodiment obtains/redox graphene nanometer is multiple
The transmission electron microscope picture for closing negative electrode material, by the very thin redox graphene list of the available lamella of this method, although five
Two niobium nanowire growths are aoxidized in single-layer graphene on piece, but agglomeration is obvious, illustrates that hydro-thermal overlong time is easy to lead
The reunion of niobium pentaoxide primary particle is caused, particle growth is uneven.
The assembling of battery: by the present embodiment niobium pentaoxide/redox graphene nano composite anode material and carbon black
With PVDF with the mass ratio of 8:1:1, and using NMP as solvent mixed grinding, then it is uniformly applied to copper foil surface, obtains nanoscale
The compound niobium oxide negative electrode material smear of redox graphene；Then, in the closed glove box of applying argon gas, with five oxidations two
Niobium/redox graphene nano composite anode material pole piece is cell working electrode, and metal lithium sheet is to be gathered to electrode with micropore
Propylene film is diaphragm, 1mol/L LiPF6/ EC:DMC(volume ratio 1:1) it is electrolyte, it is assembled into the button cell of CR2025, into
Row charge-discharge test.Charge-discharge performance is similar to Example 1, illustrates niobium pentaoxide/oxygen reduction fossil that the embodiment obtains
Black alkene nano composite anode material can prevent the reunion of niobium pentoxide nano particle in the presence due to graphene, enhancing
The electric conductivity of niobium pentaoxide, improves the storage lithium performance of material.
Embodiment the result shows that, the present invention can be by controlling the hydro-thermal time conditions of hydro-thermal method for niobium pentoxide nano
Line homoepitaxial is in the very thin redox graphene nanometer sheet of lamella, niobium pentaoxide content and of uniform size controllable.It will
When this material is used for lithium ion battery negative material, show much higher than the lithium storage content of pure phase niobium pentaoxide and excellent
High rate performance can be used as next-generation high performance lithium ionic cell cathode material.
Claims (9)
1. a kind of niobium pentaoxide/redox graphene composite negative pole material preparation method, which is characterized in that including following
Step:
(1) stannic oxide/graphene nano piece is mixed with water, is stirred, ultrasonic disperse obtains the dispersion liquid of stannic oxide/graphene nano；
(2) columbium pentachloride dissolution is dispersed in water, stirs, obtains columbium pentachloride suspension, be added into columbium pentachloride suspension
Organic matter cosolvent, stirring, obtains clear solution, hexamethylenetetramine is added to clear solution, stirring obtains white solution；
(3) dispersion liquid of stannic oxide/graphene nano obtained by step (1) is mixed with white solution obtained by step (2), stirring extremely divides
It dissipates uniformly, obtains mixed solution, gained mixed solution is put into autoclave and carries out hydro-thermal reaction；
(4) after the completion of hydro-thermal reaction, the precipitating that hydro-thermal reaction generates is collected, resulting precipitating is washed and dried, must be consolidated
Body powder；
(5) obtained solid powder in step (4) is heat-treated under an argon atmosphere to get niobium pentaoxide/reduction-oxidation
Graphene composite negative pole.
2. niobium pentaoxide according to claim 1/redox graphene composite negative pole material preparation method, special
Sign is, in step (1), the concentration of the dispersion liquid of the stannic oxide/graphene nano is 0.5~2 mg/mL.
3. niobium pentaoxide according to claim 1 or 2/redox graphene composite negative pole material preparation method,
It is characterized in that, the concentration of the columbium pentachloride suspension is 5~15 mg/mL in step (2).
4. niobium pentaoxide described according to claim 1~one of 3/redox graphene composite negative pole material preparation side
Method, which is characterized in that in step (2), the organic matter cosolvent is at least one of oxalic acid, acetic acid or ethanedioic acid.
5. niobium pentaoxide described according to claim 1~one of 4/redox graphene composite negative pole material preparation side
Method, which is characterized in that in step (2), the method for columbium pentachloride dissolution dispersion is magnetic agitation: by columbium pentachloride and water
Mixed solution, which is placed in water-bath, carries out magnetic agitation, and the speed of magnetic agitation is 300~500 r/min, the temperature of magnetic agitation
Degree is 10~40 DEG C, and the time of magnetic agitation is the h of 0.5 h~3.
6. niobium pentaoxide described according to claim 1~one of 5/redox graphene composite negative pole material preparation side
Method, which is characterized in that in step (3), volume ratio that the dispersion liquid of the stannic oxide/graphene nano is mixed with the white solution
It is 1: 1~3.
7. niobium pentaoxide described according to claim 1~one of 6/redox graphene composite negative pole material preparation side
Method, which is characterized in that in step (3), the temperature of the hydro-thermal reaction is 140~200 DEG C, and the time is 8~24 h.
8. niobium pentaoxide described according to claim 1~one of 7/redox graphene composite negative pole material preparation side
Method, which is characterized in that in step (4), the method for the drying is freeze-drying, forced air drying or vacuum drying.
9. niobium pentaoxide described according to claim 1~one of 8/redox graphene composite negative pole material preparation side
Method, which is characterized in that in step (5), the rate of heat addition of the heat treatment is 1~20 DEG C/min, heating temperature is 400 DEG C~
1000 DEG C, soaking time is 1~3 h.
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