CN103078108A - Graphene-loaded rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof - Google Patents
Graphene-loaded rhombohedron ferric oxide composite material and hydrothermal synthesis method thereof Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims abstract description 8
- 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 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 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
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 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
- 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
- 238000011160 research Methods 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite 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
- 238000005406 washing Methods 0.000 description 6
- 239000003643 water by type Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process 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
- 239000012141 concentrate Substances 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
- 238000001035 drying 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
- 239000011165 3D composite Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 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
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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
Abstract
The invention relates to a graphene-loaded rhombohedron ferric oxide composite material and a hydrothermal synthesis method thereof. The composite material is characterized in that a single layer of graphene is used as a matrix skeleton, and rhombohedron ferric oxide uniformly grows on two surfaces of the graphene piece layer; and the particle sizes of the rhombohedron ferric oxide are 50-150 nm, and each surface is a regular parallelogram. The rhombohedron ferric oxide can realize a good electrical conductivity through the graphene piece layer, and therefore the apparent electrical conductivity of the composite material is increased. The material is prepared through two typical steps: 1, preparing pyrolytic graphene; and 2, hydrothermally synthesizing the graphene-loaded rhombohedron ferric oxide composite material. Thegraphene-loaded rhombohedron ferric oxide composite material prepared by the method has a simple process, high reversible capacity and good cycle performance and is a lithium-ion battery anode material with a research 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 the synthetic field of electrochemistry and material.
Background technology
Nineteen ninety announces to have succeeded in developing a kind of LiCoO from Japanese Sony company
2/ C rocking chair lithium ion battery begins, and has worldwide started research and the industrialization upsurge of lithium-ions battery.The development of lithium ion battery as the novel green high-capacity power supply of a class, owing to its outstanding combination property, can be satisfied the needs of hyundai electronics Industry Quick Development, and therefore, its prospect is boundless.At present, the lithium-ion electric pool technology improves constantly and is perfect, and application is expanding day also, and output constantly increases, and with replacing gradually other secondary cell system, occupies an leading position in small-sized secondary batteries.
Iron oxide is 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.Yet also there are problems in iron oxide as lithium cell cathode material, mainly comprises: the electronic conductance of (1) iron oxide self is lower, causes the charge/discharge capacity under high current density to reduce; (2) iron oxide is in charge and discharge process, and change in volume causes structure to cave in to cause its cycle performance very poor very greatly easily.At present, mainly concentrate on for the research of iron oxide negative material and improve that synthetic method prepares nanostructure or mesoporous iron oxide improves its chemical property.
Graphene (graphene) is a kind of individual layer bi-dimensional cellular shape (including only the 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 that the carbon atom close-packed arrays of hydridization forms.Have superpower conductivity, superpower hardness, thermal conductive resin and bigger serface, it is well used in field of compound material.Although the Graphene of report increases at the low range charge-discharge performance with ferric oxide composite material at present, its high magnification and long period cycle performance are also bad.In addition, the structure of ferric oxide particles is comparatively single in the composite material, often all is particle or spheroid, and the design of material that does not relate to microcosmic is synthetic.And mostly complicated process of preparation, cost height are difficult to a large amount of preparations.
Summary of the invention
The object of the invention is to overcome the problem that iron oxide exists as lithium cell cathode material, 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 the matrix skeleton has good conductivity, and the rhombohedron iron oxide can be realized its satisfactory electrical conductivity by loading on the graphene film, has improved the apparent conductivity of composite material.The volumetric expansion of simultaneous oxidation iron can be carried out in the direction perpendicular to Graphene, caves in thereby reduce structure.
For achieving the above object, the present invention adopts following technical scheme:
A kind of graphene-supported rhombohedron ferric oxide composite material, with single-layer graphene as the matrix skeleton, the rhombohedron iron oxide is evenly grown on the graphene sheet layer two sides, the rhombohedron ferric oxide particles that is grown on the Graphene is of a size of 50 ~ 150 nm, each face all is the parallelogram of rule, and the percentage by weight of iron oxide is 60% ~ 80% in the composite material.
A kind of hydrothermal synthesis method of graphene-supported rhombohedron ferric oxide composite material, concrete steps are:
1) preparation graphene oxide presoma;
2) with presoma 200 ~ 500 ℃ of low temperature presintering 2 ~ 6 h under inert atmosphere of step 1) gained;
3) get an amount of step 2) resulting powder ultrasonic is dissolved in the deionized water, and the water-soluble molysite that then adds certain mass is dissolved in wherein, stirs;
4) under magnetic stirring apparatus constantly stirs, be that the sodium acetate of 0.04 mol/L slowly is added drop-wise in the solution in the step 3) with concentration, then stir 0.5 h;
5) homogeneous solution with the step 4) gained changes in the polytetrafluoroethylene reactor, hydro-thermal reaction 6 ~ 24 h;
6) with the solution of the gained of step 5), centrifugal, alcohol wash three times is washed three times, and oven dry finally obtains graphene-supported rhombohedron ferric oxide composite material.
Above-mentioned steps 2) inert gas in is a kind of in nitrogen, the argon gas.
Above-mentioned steps 3) water-soluble molysite is a kind of of ferric nitrate, iron chloride, ferric sulfate or ferric acetate.
Above-mentioned steps 3) and the mol ratio of the water-soluble molysite in the step 4) and sodium acetate be 0.3 ~ 1:1.
Above-mentioned steps 5) hydrothermal temperature in is 160 ~ 200 ℃.
The preparation of graphene oxide with reference to Yuxi Xu etc. at J. AM. CHEM. SOC., the method preparation described in 130 (18), 5856 (2008).At first use potassium peroxydisulfate, phosphorus pentoxide, the concentrated sulfuric acid with native graphite pre-oxidation, then utilize potassium permanganate and the concentrated sulfuric acid to carry out secondary oxidation, obtain graphite oxide, the heavy metal ion in the solution is removed in pickling, obtain graphite oxide solution through washing again, high speed centrifugation, drying obtain oxidation graphite solid.
Ferric oxide particles with pure phase is compared, and we possess following outstanding structure and performance characteristics at the nano composite material of preparation, and preparation method's of the present invention outstanding feature is:
(1) preparation technology is simple, only needs a step Hydrothermal Synthesis, and the process of composite material preparation is reacted under the lower temperature temperature, and manufacturing cycle is short; Output is large, and efficient is high, but scale is used.
(2) design feature of the graphene-supported rhombohedron ferric oxide composite material of preparation is that each face of rhombohedron iron oxide all is the parallelogram of rule, is grown in the graphene sheet layer both sides, makes Graphene can give play to its skeleton function and electric action.
(3) the lithium electrical property with the graphene-supported rhombohedron ferric oxide composite material of this simple hydrothermal method preparation is greatly improved, our the use the same method specific discharge capacity of pure phase iron oxide of preparation only is 173.4 mAh/g after 100 circulations, and composite material is 1003.2 mAh/g at 5mV-3.0 V reversible capacity, and discharges and recharges 100 times still can maintain 657.2 mAh/g under the current density of 100 mAh/g.Cycle performance rise to the former more than 3 times.
Graphene-supported rhombohedron ferric oxide composite material has successfully overcome two shortcomings of pure phase iron oxide, is a kind of very promising lithium ion battery negative material.
Description of drawings
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 the embodiment two.
Fig. 3 is the SEM picture of the graphene-supported rhombohedron ferric oxide composite material under the embodiment three.
Fig. 4 is the charging and discharging curve of the graphene-supported rhombohedron ferric oxide composite material under the embodiment four.
Fig. 5 is the cycle performance curve of the graphene-supported rhombohedron ferric oxide composite material under the embodiment four.
Embodiment
Further specify method provided by the present invention below by embodiment, the invention is not restricted to this.
Embodiment one: take ferric sulfate as source of iron prepares graphene-supported rhombohedron ferric oxide composite material.
With potassium peroxydisulfate (K
2S
2O
8) 2.5 g, phosphorus pentoxide (P
2O
5) 2.5 g, be dissolved in the 12 mL concentrated sulfuric acids, be heated to 80 ℃; Then 3 g native graphites are added mentioned solution, be incubated 80 ℃, 4.5 hours; Be cooled to room temperature, after the dilution of 500 mL deionized waters, hold over night; Filter, with the floating residual acid that goes of 0.2 mm filter; Dry in 60 ℃ of vacuum drying chambers; The pre-oxidation thing that obtains is joined in the concentrated sulfuric acid of 120 mL ice baths, under agitation slowly add 15 g KMnO
4, maintain the temperature at below 20 ℃ in the process that adds.Then be that temperature is controlled at 35 ℃ of stirring 2 h.Add the dilution of 250 mL deionized waters, also will in ice bath, make temperature be lower than 50 ℃ in the dilution.Stir again 2 h, add again 0.7 L deionized water, and add at once the H of 20 mL30%
2O
2, mixture produces bubble, and color has become glassy yellow by brown, and about 0.5 h afterreaction stops.Said mixture is filtered, and wash with the 1:10 watery hydrochloric acid of 1 L, filter to remove the part metals ion; Filter with the 1L water washing again, to remove unnecessary acid; Mentioned solution is dissolved in the 1 L water, then under the 100 W ultrasonic powers about ultrasonic 0.5 h, gets graphite oxide solution (GO), after the centrifugation, the product that obtains brownish black at air drying namely gets the graphene oxide that needs.Predecessor graphene oxide 0.2 g is placed under the protection of inert gas, carry out pyrolysis processing at 200 ~ 500 ℃, so that the graphite oxide dehydration, the oxygen-containing functional groups such as decarboxylize, hydroxyl obtain graphene nanometer sheet.
Get 0.60 g ferric sulfate and add in the 50 mL deionized waters, to wherein adding 50 mg Graphenes, stir 15 min, ultrasonic 0.5 h adds 0.25g NaAc again and stirs 30 min, to moving into 180 ℃ of hydro-thermals of reactor 12 hours, centrifugal, alcohol wash, washing each 3 times, 80 ℃ of oven dry obtain product.
With product and the conductive black Super P of preparation, polyfluortetraethylene of binding element (PTFE) is made film at twin rollers after evenly mixing according to mass ratio 8:1:1 ratio, and becoming diameter with blunderbuss head blunderbuss is the diaphragm of 12mm, and drying is weighed; Then pole piece is pressed in copper mesh with the pressure of 20 MPa, makes material and copper mesh strong bonded, pole piece is made complete.It is 1mol/L LiPF that electrolyte adopts concentration
6Solution (being dissolved in the solvent that the mass ratioes such as DMC and EC are made into), the 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, and nothing is impurity peaks obviously, and can observe at 2 θ=26.5o place (002) peak of Graphene.Electric performance test shows that this product reversible capacity under 5mV-3.0 V voltage range 100 mA/g current densities is 1063.2 mAh/g, and charge and discharge cycles still can maintain 665.8 mAh/g 50 times.
Embodiment two: take ferric nitrate as source of iron prepares graphene-supported rhombohedron ferric oxide composite material.
Get the 0.808g ferric nitrate and add in the 100 mL deionized waters, to wherein adding 100 mg Graphenes, stir 15 min, ultrasonic 0.5 h adds 0.50g NaAc again and stirs 30min, to moving into 160 ℃ of hydro-thermals of reactor 24 hours, centrifugal, alcohol wash, washing each 3 times, 80 ℃ of oven dry obtain product.
The stereoscan photograph of oven dry product is seen Fig. 2, as seen from the figure, the diameter of rhombohedron iron oxide is 50 ~ 100 nm, each face all is parallel four distortion, rhombohedron iron oxide great majority are uniformly dispersed on the Graphene surface, and all have on the Graphene two sides and to adhere to, the reversible capacity of this product under the voltage window 100 mA/g current densities of 5mV-3.0 V is 1037.2 mAh/g, and charge and discharge cycles still can maintain 677.2 mAh/g 50 times.
Embodiment three: take ferric acetate as source of iron prepares graphene-supported rhombohedron ferric oxide composite material.
Get 0.246 g ferric acetate and add in the 50 mL deionized waters, to wherein adding 50 mg Graphenes, stir 15 min, ultrasonic 0.5 h adds 0.5g NaAc again and stirs 30min, to moving into 180 ℃ of hydro-thermals of reactor 24 hours, centrifugal, alcohol wash, washing each 3 times, 80 ℃ of oven dry obtain product.
The stereoscan photograph of product is seen Fig. 3, can see diameter be the rhombohedron ferric oxide particles uniform load of 80 ~ 150 nm on the surface of Graphene, have no the stacking phenomenon of obvious reunion.And have some particles to be hidden by layer of transparent tulle Graphene, illustrate that the 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 100 mA/g current densities of 5mV-3.0 V of preparation is 1023.9 mAh/g, and charge and discharge cycles still can maintain 697.2 mAh/g 50 times.
Embodiment four: take iron chloride as source of iron prepares graphene-supported rhombohedron ferric oxide composite material.
Get 0.27g iron chloride and add in the 50 mL deionized waters, to wherein adding 50 mg Graphenes, stir 15 min, ultrasonic 0.5 h adds 0.25g NaAc again and stirs 30min, to moving into 200 ℃ of hydro-thermals of reactor 6 hours, centrifugal, alcohol wash, washing each 3 times, 80 ℃ of oven dry obtain product.
Fig. 4 is the front twice charge/discharge capacity-voltage curve with 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 100 mA/g current densities of 5mV-3.0 V is 1003.2 mAh/g, discharge curve has three discharge platforms first, respectively at 1.50 V～1.75 V, 0.75 V ~ 1.00 V and 0.50V ~ 0.6 V place, discharge platform is the longest for the third time, and embedding lithium capacity mainly concentrates on this platform.The discharge capacity second time of Graphene iron oxide is 956.2 mAh/g, and only has a discharge platform (0.75 V～1.0 V).Fig. 5 is this composite material cycle performance figure under 100 mA/g current densities, and test shows, discharge and recharge 50 times after this material discharging capacity still can maintain 657.2 mAh/g, embody preferably cycle performance.
Claims (6)
1. graphene-supported rhombohedron ferric oxide composite material, it is characterized in that, with single-layer graphene as the matrix skeleton, the rhombohedron iron oxide is evenly grown on the graphene sheet layer two sides, the rhombohedron ferric oxide particles that is grown on the Graphene is of a size of 50 ~ 150 nm, each face all is the parallelogram of rule, and the percentage by weight of iron oxide is 60% ~ 80% in the composite material.
2. the hydrothermal synthesis method of a graphene-supported rhombohedron ferric oxide composite material is characterized in that, concrete steps are:
1) preparation graphene oxide presoma;
2) with presoma 200 ~ 500 ℃ of low temperature presintering 2 ~ 6 h under inert atmosphere of step 1) gained;
3) get an amount of step 2) resulting graphene powder ultrasonic dissolution is in deionized water, and the water-soluble molysite that then adds certain mass is dissolved in wherein, stirs;
4) under magnetic stirring apparatus constantly stirs, be that the sodium acetate of 0.04 mol/L slowly is added drop-wise in the solution in the step 3) with concentration, then stir 0.5 h;
5) homogeneous solution with the step 4) gained changes in the polytetrafluoroethylene reactor, hydro-thermal reaction 6 ~ 24 h;
6) with the solution of the gained of step 5), centrifugal, alcohol wash three times is washed three times, and oven dry finally obtains graphene-supported rhombohedron ferric oxide composite material.
3. the hydrothermal synthesis method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 2 is characterized in that step 2) in inert gas be a kind of in nitrogen, the argon gas.
4. the hydrothermal synthesis method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 2 is characterized in that, the water-soluble molysite of step 3) is a kind of of ferric nitrate, iron chloride, ferric sulfate or ferric acetate.
5. the hydrothermal synthesis method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 2 is characterized in that, the water-soluble molysite in step 3) and the step 4) and the mol ratio of sodium acetate are 0.3 ~ 1:1.
6. the hydrothermal synthesis method of a kind of graphene-supported rhombohedron ferric oxide composite material according to claim 2, its feature exists, and the hydrothermal temperature in step 5) is 160 ~ 200 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104401980A (en) * | 2014-11-05 | 2015-03-11 | 上海大学 | Hydrothermal preparation method of Fe2O3-SnO2/graphene ternary composite 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 |
| CN109244354A (en) * | 2018-07-14 | 2019-01-18 | 哈尔滨工业大学 | A kind of self-supporting combination electrode |
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| US20110104571A1 (en) * | 2009-11-02 | 2011-05-05 | Aruna Zhamu | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| 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 |
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| US20110104571A1 (en) * | 2009-11-02 | 2011-05-05 | Aruna Zhamu | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN104401980A (en) * | 2014-11-05 | 2015-03-11 | 上海大学 | Hydrothermal preparation method of Fe2O3-SnO2/graphene ternary composite nano-material |
| 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 |
| CN109244354A (en) * | 2018-07-14 | 2019-01-18 | 哈尔滨工业大学 | A kind of self-supporting combination electrode |
| CN109244354B (en) * | 2018-07-14 | 2021-03-02 | 哈尔滨工业大学 | Self-supporting composite electrode |
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