CN103078108B - A kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof - Google Patents
A kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof Download PDFInfo
- Publication number
- CN103078108B CN103078108B CN201310014878.6A CN201310014878A CN103078108B CN 103078108 B CN103078108 B CN 103078108B CN 201310014878 A CN201310014878 A CN 201310014878A CN 103078108 B CN103078108 B CN 103078108B
- Authority
- CN
- China
- Prior art keywords
- graphene
- rhombohedron
- composite material
- supported
- ferric oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 8
- -1 graphite alkene Chemical class 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- 239000002356 single layer Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229910002804 graphite Inorganic materials 0.000 abstract description 9
- 239000010439 graphite Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 230000002441 reversible effect Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof.It is typically characterized as using single-layer graphene as matrix skeleton, and rhombohedron iron oxide is at graphene sheet layer two sides homoepitaxial, does is the particle size of rhombohedron iron oxide 50 ~ 150? nm, each face is all the parallelogram of rule.Rhombohedron iron oxide can realize good conductivity by graphene sheet layer, thus improves the bulk electrical conductivity of composite material.The preparation of this material is through two exemplary steps, and one is prepare pyrolytic graphite alkene, and two is the graphene-supported rhombohedron ferric oxide composite materials of Hydrothermal Synthesis.Graphene-supported rhombohedron ferric oxide composite material technique prepared by the inventive method is simple, and reversible capacity is high, good cycle, is a kind of lithium ion battery negative material very with researching value.
Description
Technical field
The present invention relates to a kind of Graphene three-dimensional composite material as lithium cell cathode material, particularly a kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof, belong to electrochemistry and materials synthesis field.
Background technology
Announce to have succeeded in developing a kind of LiCoO from Japanese Sony company nineteen ninety
2/ C rocking chair lithium ion battery starts, and has worldwide started research and the industrialization upsurge of lithium-ions battery.The development of lithium ion battery, as the green high-capacity power supply that a class is novel, due to the combination property that it is outstanding, can meet the needs of hyundai electronics Industry Quick Development, therefore, its prospect is boundless.At present, lithium ion battery technology improves constantly and perfect, and application is expanding day also, and output constantly increases, and will replace other secondary cell system gradually, and occupy an leading position in small-sized secondary batteries.
Iron oxide because having high theoretical specific capacity, abundant reserves, cheap price, the advantage such as environmentally friendly and become the study hotspot of lithium ion battery negative material.But iron oxide also exists problems as lithium cell cathode material, mainly comprise: the electronic conductance of (1) iron oxide self is lower, cause the charge/discharge capacity under high current density to reduce; (2) iron oxide is in charge and discharge process, and change in volume easily causes structure collapses to cause its cycle performance very poor very greatly.At present, the research of iron oxide cathode material is mainly concentrated on improve synthetic method and prepare nanostructure or mesoporous iron oxide to improve its chemical property.
Graphene (graphene) is a kind of individual layer bi-dimensional cellular shape (only including hexagonal primitive unit cell) lattice structure by the tightly packed one-tenth of carbon atom, and it is by sp
2the mono-layer graphite sheet of the carbon atom close-packed arrays of hydridization.There is superpower conductivity, superpower hardness, thermal conductive resin and bigger serface, make it well be applied in field of compound material.Although the Graphene of current report increases at low range charge-discharge performance with ferric oxide composite material, its high magnification and long period cycle performance are also bad.In addition, in composite material, the structure of ferric oxide particles is comparatively single, is all often particle or spheroid, does not relate to the design of material synthesis of microcosmic.And mostly complicated process of preparation, cost are high, are difficult to a large amount of preparation.
Summary of the invention
The object of the invention is to overcome iron oxide as lithium cell cathode material Problems existing, a kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof are provided, prepare that a kind of novel pattern is unique, synthesis technique is simple and the better lithium ion battery negative material of electrical property.This composite material is the compound of rhombohedron iron oxide and graphene sheet layer, Graphene as matrix skeleton has good conductivity, and rhombohedron iron oxide by load on graphene film, can realize its satisfactory electrical conductivity, improve the bulk electrical conductivity of composite material.The volumetric expansion of simultaneous oxidation iron can be carried out in the direction perpendicular to Graphene, thus reduces structure collapses.
For achieving the above object, the present invention adopts following technical scheme:
A kind of graphene-supported rhombohedron ferric oxide composite material, using single-layer graphene as matrix skeleton, rhombohedron iron oxide is at graphene sheet layer two sides homoepitaxial, the rhombohedron ferric oxide particles of growth on Graphene is of a size of 50 ~ 150nm, each face is all the parallelogram of rule, and in composite material, the percentage by weight of iron oxide is 60% ~ 80%.
A hydrothermal synthesis method for graphene-supported rhombohedron ferric oxide composite material, concrete steps are:
1) graphene oxide presoma is prepared;
2) by the presoma of step 1) gained 200 ~ 500 DEG C of low temperature presintering 2 ~ 6h under an inert atmosphere;
3) appropriate step 2 is got) powder ultrasonic that obtains is dissolved in deionized water, and the water-soluble molysite then adding certain mass is dissolved in wherein, stirs;
4) under magnetic stirring apparatus constantly stirs, be that the sodium acetate of 0.04mol/L is slowly added drop-wise in the solution in step 3) by concentration, then stir 0.5h;
5) homogeneous solution of step 4) gained is proceeded in polytetrafluoroethylene reactor, hydro-thermal reaction 6 ~ 24h;
6) by the solution of the gained of step 5), centrifugal, alcohol wash three times, washes three times, dries, finally obtains graphene-supported rhombohedron ferric oxide composite material.
Above-mentioned steps 2) in inert gas be one in nitrogen, argon gas.
Above-mentioned steps 3) water-soluble molysite be the one of ferric nitrate, iron chloride, ferric sulfate or ferric acetate.
Above-mentioned steps 3) and step 4) in water-soluble molysite and the mol ratio of sodium acetate be 0.3 ~ 1:1.
Above-mentioned steps 5) in hydrothermal temperature be 160 ~ 200 DEG C.
The preparation reference YuxiXu of graphene oxide etc. are at J.AM.CHEM.SOC., prepared by the method described in 130 (18), 5856 (2008).First use potassium peroxydisulfate, phosphorus pentoxide, the concentrated sulfuric acid by native graphite pre-oxidation, then potassium permanganate and the concentrated sulfuric acid is utilized to carry out secondary oxidation, obtain graphite oxide, heavy metal ion in pickling removing solution, obtain graphite oxide solution through washing again, high speed centrifugation, drying obtain oxidation graphite solid.
Ferric oxide particles with pure phase is compared, and the nano composite material that we prepare possesses following outstanding stuctures and properties feature, and the outstanding feature of preparation method of the present invention is:
(1) preparation technology is simple, only needs a step Hydrothermal Synthesis, and the process prepared of composite material is reacted under comparatively cryogenic temperature, and manufacturing cycle is short; Output is large, and efficiency is high, can scale application.
(2) design feature of the graphene-supported rhombohedron ferric oxide composite material prepared is that each face of rhombohedron iron oxide is all the parallelogram of rule, grows in graphene sheet layer both sides, makes Graphene can give play to its skeleton function and electric action.
(3) the lithium electrical property of the graphene-supported rhombohedron ferric oxide composite material prepared with this simple hydrothermal method is greatly improved, we use the same method preparation pure phase iron oxide specific discharge capacity 100 circulation after be only 173.4mAh/g, and composite material is 1003.2mAh/g at 5mV-3.0V reversible capacity, and discharge and recharge still can maintain 657.2mAh/g 100 times under the current density of 100mAh/g.Cycle performance rise to the former more than 3 times.
Graphene-supported rhombohedron ferric oxide composite material successfully overcomes two shortcomings of pure phase iron oxide, is the very promising lithium ion battery negative material of one.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of embodiment graphene-supported rhombohedron ferric oxide composite material once.
Fig. 2 is the SEM picture of the graphene-supported rhombohedron ferric oxide composite material under embodiment two.
Fig. 3 is the SEM picture of the graphene-supported rhombohedron ferric oxide composite material under embodiment three.
Fig. 4 is the charging and discharging curve of the graphene-supported rhombohedron ferric oxide composite material under embodiment four.
Fig. 5 is the cycle performance curve of the graphene-supported rhombohedron ferric oxide composite material under embodiment four.
Embodiment
Further illustrate method provided by the present invention below by embodiment, the present invention is not limited thereto.
embodiment one: be that source of iron prepares graphene-supported rhombohedron ferric oxide composite material with ferric sulfate.
By potassium peroxydisulfate (K
2s
2o
8) 2.5g, phosphorus pentoxide (P
2o
5) 2.5g, be dissolved in the 12mL concentrated sulfuric acid, be heated to 80 DEG C; Then 3g native graphite is added above-mentioned solution, be incubated 80 DEG C, 4.5 hours; Be cooled to room temperature, after the dilution of 500mL deionized water, hold over night; Filter, remove residual acid with 0.2mmfilter is floating; Dry in 60 DEG C of vacuum drying chambers; The pre-oxidation thing obtained is joined in the concentrated sulfuric acid of 120mL ice bath, under agitation slowly adds 15gKMnO
4, in the process added, maintain the temperature at less than 20 DEG C.Then be that temperature controls to stir 2h at 35 DEG C.Add the dilution of 250mL deionized water, temperature in dilution, also will be made in ice bath lower than 50 DEG C.Stir 2h again, then add 0.7L deionized water, and add the H of 20mL30% at once
2o
2, mixture produces bubble, and color becomes glassy yellow by brown, reaction terminating after about 0.5h.Said mixture is filtered, and washs with the 1:10 watery hydrochloric acid of 1L, filter to remove part metals ion; Filter with 1L water washing, to remove unnecessary acid again; By above-mentioned solubilize in 1L water, then ultrasonic about 0.5h under 100W ultrasonic power, obtains graphite oxide solution (GO), and after centrifugation, namely the dry product obtaining brownish black obtains the graphene oxide of needs in atmosphere.Under predecessor graphene oxide 0.2g is placed in the protection of inert gas, carry out pyrolysis processing at 200 ~ 500 DEG C, graphite oxide is dewatered, the oxygen-containing functional group such as decarboxylize, hydroxyl, obtains graphene nanometer sheet.
Getting 0.60g ferric sulfate adds in 50mL deionized water, adds 50mg Graphene wherein, stirs 15min, ultrasonic 0.5h, then add 0.25gNaAc stirring 30min, to moving into reactor 180 DEG C of hydro-thermals 12 hours, centrifugal, alcohol wash, wash each 3 times, 80 DEG C of oven dry obtain product.
By product and the conductive black SuperP of preparation, polyfluortetraethylene of binding element (PTFE) makes film after mixing according to mass ratio 8:1:1 ratio uniform on twin rollers, and become diameter to be the diaphragm of 12mm with blunderbuss head blunderbuss, drying is weighed; Then the pressure of pole piece 20MPa is pressed in copper mesh, makes material and copper mesh strong bonded, pole piece makes complete.Electrolyte adopts concentration to be 1mol/LLiPF
6solution (being dissolved in the solvent that the mass ratioes such as DMC and EC are made into), lithium sheet is as negative pole.
Prepare the XRD of the graphene-supported rhombohedron ferric oxide composite material of product as shown in Figure 1, we have successfully prepared graphene-supported composite material as seen from the figure, without obvious impurity peaks, and can observe (002) peak of Graphene at 2 θ=26.5o places.Electric performance test shows, and this product reversible capacity under 5mV-3.0V voltage range 100mA/g current density is 1063.2mAh/g, and charge and discharge cycles still can maintain 665.8mAh/g 50 times.
embodiment two: be that source of iron prepares graphene-supported rhombohedron ferric oxide composite material with ferric nitrate.
Getting 0.808g ferric nitrate adds in 100mL deionized water, adds 100mg Graphene wherein, stirs 15min, ultrasonic 0.5h, then add 0.50gNaAc stirring 30min, to moving into reactor 160 DEG C of hydro-thermals 24 hours, centrifugal, alcohol wash, wash each 3 times, 80 DEG C of oven dry obtain product.
The stereoscan photograph of drying product is shown in Fig. 2, as seen from the figure, the diameter of rhombohedron iron oxide is 50 ~ 100nm, each face is all parallel four distortion, rhombohedron iron oxide great majority are uniformly dispersed at graphenic surface, and all having attachment on Graphene two sides, the reversible capacity of this product under the voltage window 100mA/g current density of 5mV-3.0V is 1037.2mAh/g, and charge and discharge cycles still can maintain 677.2mAh/g 50 times.
embodiment three: be that source of iron prepares graphene-supported rhombohedron ferric oxide composite material with ferric acetate.
Getting 0.246g ferric acetate adds in 50mL deionized water, adds 50mg Graphene wherein, stirs 15min, ultrasonic 0.5h, then add 0.5gNaAc stirring 30min, to moving into reactor 180 DEG C of hydro-thermals 24 hours, centrifugal, alcohol wash, wash each 3 times, 80 DEG C of oven dry obtain product.
The stereoscan photograph of product is shown in Fig. 3, can see diameter be the rhombohedron ferric oxide particles uniform load of 80 ~ 150nm on the surface of Graphene, have no stacking phenomenon of obviously reuniting.And have some particles to be hidden by layer of transparent tulle Graphene, illustrate that rhombohedron ferric oxide particles is distributed in the both sides of Graphene.Electro-chemical test shows that the reversible capacity of material under the voltage window 100mA/g current density of 5mV-3.0V prepared is 1023.9mAh/g, and charge and discharge cycles still can maintain 697.2mAh/g 50 times.
embodiment four: be that source of iron prepares graphene-supported rhombohedron ferric oxide composite material with iron chloride.
Getting 0.27g iron chloride adds in 50mL deionized water, adds 50mg Graphene wherein, stirs 15min, ultrasonic 0.5h, then add 0.25gNaAc stirring 30min, to moving into reactor 200 DEG C of hydro-thermals 6 hours, centrifugal, alcohol wash, wash each 3 times, 80 DEG C of oven dry obtain product.
Fig. 4 is with twice charge/discharge capacity-voltage curve before graphene-supported rhombohedron ferric oxide composite material simulated battery.As seen from the figure, the first reversible capacity of synthetic product under the voltage window 100mA/g current density of 5mV-3.0V is 1003.2mAh/g, discharge curve has three discharge platforms first, respectively at 1.50V ~ 1.75V, 0.75V ~ 1.00V and 0.50V ~ 0.6V place, third time, discharge platform was the longest, and embedding lithium capacity mainly concentrates on this platform.The second time discharge capacity of Graphene iron oxide is 956.2mAh/g, and only has a discharge platform (0.75V ~ 1.0V).Fig. 5 is this composite material cycle performance figure under 100mA/g current density, and test shows, after discharge and recharge 50 times, this material discharging capacity still can maintain 657.2mAh/g, embodies good cycle performance.
Claims (5)
1. the preparation method of a graphene-supported rhombohedron ferric oxide composite material, this composite material is using single-layer graphene as matrix skeleton, rhombohedron iron oxide is at graphene sheet layer two sides homoepitaxial, the rhombohedron ferric oxide particles of growth on Graphene is of a size of 50 ~ 150nm, each face is all the parallelogram of rule, and in composite material, the percentage by weight of iron oxide is 60% ~ 80%; It is characterized in that the concrete steps of the method are:
1) graphene oxide presoma is prepared;
2) by the presoma of step 1) gained 200 ~ 500 DEG C of low temperature presintering 2 ~ 6h under an inert atmosphere;
3) appropriate step 2 is got) the graphene powder ultrasonic dissolution that obtains is in deionized water, and the water-soluble molysite then adding certain mass is dissolved in wherein, stirs;
4) under magnetic stirring apparatus constantly stirs, be that the sodium acetate of 0.04mol/L is slowly added drop-wise in the solution in step 3) by concentration, then stir 0.5h;
5) homogeneous solution of step 4) gained is proceeded in polytetrafluoroethylene reactor, hydro-thermal reaction 6 ~ 24h;
6) by the solution of the gained of step 5), centrifugal, alcohol wash three times, washes three times, dries, finally obtains graphene-supported rhombohedron ferric oxide composite material.
2. the preparation method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 1, is characterized in that, step 2) in inert gas be one in nitrogen, argon gas.
3. the preparation method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 1, it is characterized in that, the water-soluble molysite of step 3) is the one of ferric nitrate, iron chloride, ferric sulfate or ferric acetate.
4. the preparation method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 1, is characterized in that, the water-soluble molysite in step 3) and step 4) and the mol ratio of sodium acetate are 0.3 ~ 1:1.
5. the preparation method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 1, its feature exists, and the hydrothermal temperature in step 5) is 160 ~ 200 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310014878.6A CN103078108B (en) | 2013-01-16 | 2013-01-16 | A kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310014878.6A CN103078108B (en) | 2013-01-16 | 2013-01-16 | A kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103078108A CN103078108A (en) | 2013-05-01 |
| CN103078108B true CN103078108B (en) | 2016-01-13 |
Family
ID=48154573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310014878.6A Expired - Fee Related CN103078108B (en) | 2013-01-16 | 2013-01-16 | A kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103078108B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103560228A (en) * | 2013-10-29 | 2014-02-05 | 中国石油大学(华东) | Method for compositing iron oxide and graphene by virtue of hydrothermal process |
| CN104401980B (en) * | 2014-11-05 | 2016-08-24 | 上海大学 | Fe2o3-SnO2the hydrothermal preparing process of/Graphene tri compound nano material |
| CN104966839A (en) * | 2015-07-15 | 2015-10-07 | 山东大学 | Lithium battery negative electrode material modifying method |
| CN105836851A (en) * | 2015-10-29 | 2016-08-10 | 黄理志 | Graphene based water treatment device and method |
| CN109244354B (en) * | 2018-07-14 | 2021-03-02 | 哈尔滨工业大学 | Self-supporting composite electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130334A (en) * | 2011-01-15 | 2011-07-20 | 中国矿业大学 | Graphene-based nano iron oxide composite material and preparation method thereof |
| CN102184781A (en) * | 2011-03-03 | 2011-09-14 | 上海大学 | Nano-nickel oxide/graphene composite material and preparation method thereof |
| CN102646817A (en) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | Graphene/metal oxide composite cathode material for lithium ion battery and preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8236452B2 (en) * | 2009-11-02 | 2012-08-07 | Nanotek Instruments, Inc. | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
-
2013
- 2013-01-16 CN CN201310014878.6A patent/CN103078108B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130334A (en) * | 2011-01-15 | 2011-07-20 | 中国矿业大学 | Graphene-based nano iron oxide composite material and preparation method thereof |
| CN102646817A (en) * | 2011-02-16 | 2012-08-22 | 中国科学院金属研究所 | Graphene/metal oxide composite cathode material for lithium ion battery and preparation |
| CN102184781A (en) * | 2011-03-03 | 2011-09-14 | 上海大学 | Nano-nickel oxide/graphene composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103078108A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102130334B (en) | Graphene-based nano iron oxide composite material and preparation method thereof | |
| CN105720236B (en) | A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof | |
| CN103077835B (en) | A kind of graphene-supported flower-shaped manganese dioxide composite material and ultrasonic synthetic method thereof | |
| CN104993125B (en) | A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C | |
| CN105789584A (en) | Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material | |
| CN104600315A (en) | Flake MoS2/graphene composite aerogel and preparation method thereof | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| CN104733695A (en) | Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application | |
| CN104617283B (en) | The preparation method of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode and the preparation method of positive pole | |
| CN103151523B (en) | Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material | |
| CN103078108B (en) | A kind of graphene-supported rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof | |
| CN107180954B (en) | Ultra-thin graphene lithium ion single battery and graphene lithium ion battery pack | |
| CN104183832A (en) | Preparation method and application of FeF3 flexible electrode based on carbon nano tube-graphene composite three-dimensional network | |
| CN110534738A (en) | A kind of dianion cobalt-based selenium sulfide and preparation method thereof | |
| Ren et al. | NiCo2O4 nanosheets and nanocones as additive-free anodes for high-performance Li-ion batteries | |
| CN103606672A (en) | Rod-shaped nano iron oxide electrode material, and preparation method and application thereof | |
| Cheng et al. | Application of organic-inorganic hybrids in lithium batteries | |
| CN105702958A (en) | SnO2 quantum dot solution and preparation method and application of composite material thereof | |
| CN104891570A (en) | Liquid phase synthetic Zr<4+> doped bismuth fluoride lithium-ion battery positive electrode material and preparation method thereof | |
| Jin et al. | VO2@ Carbon foam as a freestanding anode material for potassium-ion batteries: first principles and experimental study | |
| CN103531809B (en) | The preparation method and application of a kind of core-shell structure particles and graphene composite material | |
| CN103560280B (en) | The chemical synthesizing method of lithium ion battery | |
| CN113753876B (en) | Potassium ion battery anode material and preparation method thereof | |
| CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
| CN114735660A (en) | Copper selenide-molybdenum selenide heterojunction nano material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160113 |