CN105591077A - Preparation method of molybdenum carbide/nitrogen-sulfur codoped spongy graphene cathode composite for sodium-ion battery - Google Patents
Preparation method of molybdenum carbide/nitrogen-sulfur codoped spongy graphene cathode composite for sodium-ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a molybdenum carbide/nitrogen-sulfur codoped spongy graphene cathode composite for a sodium-ion battery. According to the molybdenum carbide/nitrogen-sulfur codoped spongy graphene cathode composite prepared through the preparation method, molybdenum carbide particles are uniformly distributed in carbide/nitrogen-sulfur codoped spongy graphene which has a great number of surface folds, has a great number of active sites and is of a three-dimensional structure. The preparation method comprises the steps of dissolving a molybdenum source and a carbon source into a graphene oxide solution, adding a nitrogen source and a sulfur source, adjusting ph value, then conducting a hydrothermal reaction on an obtained mixed solution, conducting freeze-drying on a product, then putting the product in a quartz crucible for high temperature heat treatment, and conducting natural cooling after a reaction is ended, so that the composite is obtained. In the hydrothermal reaction process, graphene doping and reduction, formation of a precursor and composition of the precursor and doped graphene are conducted synchronously. The composite can be obtained by combining the hydrothermal method with the subsequent heat treatment process, and the preparation method is simple in process and low in cost and has good research prospect.
Description
Technical field
The present invention relates to a kind of preparation method of anode material of lithium-ion battery, belong to sodium-ion battery field.
Background technology
Along with the quick change of information age, lithium ion battery is at portable type electronic product (notebook computer, intelligent mobileEquipment, panel computer etc.), obtained fast development in electric automobile, and show good development prospect. But, due to goldBelong to the scarcity of lithium resource, the existence of the limiting factors such as the capacity of the lithium ion battery of battery manufacture cost and maturation, it develops notCan avoid being challenged. Being in the sodium in same main group in the periodic table of elements with lithium has and the similar physicochemical properties of lithium,And compared with lithium, reserves are abundant. What this made that sodium-ion battery becomes a kind of tool potentiality can be used for large-scale commercial applicationBattery system. But, because the ionic radius of sodium ion is larger than the ionic radius of lithium ion, make sodium ion at electrode materialMiddle embedding with deviate from more difficult than lithium ion. Therefore, the electrode material of sodium-ion battery becomes the emphasis of its architectural study.
The following period of time in past, researcher has been carried out broad research to the electrode material of sodium-ion battery, wherein material with carbon element,Alloy material, sulfide, the materials such as oxide have correlative study report, but various material in displaying one's respective advantages alsoShow capacity attenuation fast, the defect of the aspect such as high rate performance is poor.
Summary of the invention
The object of the invention is to provide a kind of technique simple, reproducible, and the simultaneously environmentally friendly preparation of carrying out suitability for industrialized production is usedIn the method for molybdenum carbide/nitrogen sulphur codope sponge Graphene of sodium-ion battery.
Technical scheme of the present invention, comprises the following steps:
(1) thiocarbamide is fully dissolved and is spread in graphene oxide solution under magnetic agitation condition;
(2) molybdenum source and carbon source are dissolved in the solution that is spread in the formation of (1) step, by three (methylol) aminomethane adjusting ph valueBe 9～10;
(3) (2) step being formed to solution inserts and in hydrothermal reaction kettle, carries out 180～220 DEG C of hydro-thermal reactions and obtain the stone that contains presomaChina ink alkene hydrogel;
(4) product (3) step being obtained is carried out after freeze drying, passes into protective atmosphere high warm at 800～900 DEG CAfter processing, obtain molybdenum carbide/nitrogen sulphur codope sponge graphene composite material;
The quality percentage composition of N of adulterating in Graphene is 4.0～10.0%, and the quality percentage composition of doping S is 3.0～8.0%; Molybdenum carbideParticle size be 20～100nm, quality percentage composition is described composite 30～70%.
The method of preparing molybdenum carbide/nitrogen sulphur codope sponge graphene composite material of the present invention also comprises following preferred version:
In preferred scheme, the hydro-thermal reaction time is 10～24h.
In preferred scheme, sublimation drying is 12～24h.
In preferred scheme, the mass ratio of nitrogenous source, sulphur source and graphene oxide is 4:1～10:1.
In preferred scheme, be 2:1～5:1 containing molybdenum source and carbon source mol ratio.
In further preferred scheme, nitrogen sulphur codope sponge Graphene nitrogenous source, sulphur source used is the adjacent aminobenzene mercaptan of thiocarbamide, 2-.
In further preferred scheme, molybdenum source is ammonium tetramolybdate ((NH4)2Mo4O13·2H2Or ammonium paramolybdate ((NH O)4)6Mo7O24·4H2O)。
In further preferred scheme, carbon source is aniline or glucose.
Further preferred described nitrogen sulphur altogether oxygen-doped functionalized graphene solution is to be joined in graphene oxide solution and passed through strongly by thiocarbamideBe uniformly mixed and obtain.
Further the hydrothermal temperature in preferred described step (3) is 180～200 DEG C.
Further described in preferred described step (4), the high-temperature heat treatment time is 5～12h.
Further in preferred molybdenum carbide/nitrogen sulphur codope sponge graphene composite material molybdenum carbide be taking ammonium paramolybdate, glucose asRaw material, makes in conjunction with subsequent heat treatment technique by hydro-thermal method, and the molybdenum carbide nanoparticle deposition of generation is grown in three-dimensional sponge shapeIn Graphene.
The most preferred scheme of the present invention is: first that thiocarbamide is fully molten under magnetic agitation condition according to the mass ratio of 4:1～10:1Solution is spread in the standby graphene oxide solution of Hummers legal system, secondly glucose, ammonium paramolybdate are fully dissolved be spread in above-mentionedIn nitrogenous sulphur graphene oxide solution, then under magnetic agitation condition, make it abundant dissolving, by three (methylols) for mixed solutionIt is 9～10 that aminomethane regulates ph, then at 180-200 DEG C of temperature, carries out hydro-thermal reaction, and synthetic presoma embeds graphiteIn alkene hydrogel, last, by after reactant freeze drying 12～24h, 800～900 DEG C are carried out high-temperature heat treatment, and the time is 5～12h,Can obtain molybdenum carbide/nitrogen sulphur codope sponge graphene composite material.
The present invention used graphene oxide solution be preferably to prepare by improved Hummers method. , by purity notJoin lower than 99.5% flaky graphite in the mixed solution of the concentrated sulfuric acid and phosphoric acid, after fully disperseing, maintain mixed solution temperatureBetween 0～5 DEG C, add in batches potassium permanganate, and stir 2～4h, then in water-bath, be warming up to 40～60 DEG C, at magneticUnder power stirring condition, successive reaction 10～16h, obtains mixed solution; Then,, under condition of ice bath, in mixture, slowly addDeionized water is diluted, and carries out oxidation reaction simultaneously, adds hydrogen peroxide to remove potassium permanganate, finally by gained after having reactedA large amount of deionized water repeated washings for mixing material, pack dialysis in dialysis bag into after centrifugal and within 5～7 days, obtain pure oxidation stoneChina ink alkene solution. Calculate the concentration that can obtain graphene oxide in gained graphite oxide weak solution through heated drying.
Described flaky graphite and the mass ratio of potassium permanganate are 1:6.
The described concentrated sulfuric acid and the volume ratio of phosphoric acid are 7:1～5:1.
Described flaky graphite and the solid-to-liquid ratio of the concentrated sulfuric acid are 2～5g:200～350mL.
Molybdenum carbide/nitrogen sulphur codope sponge graphene composite material that the present invention makes is prepared the method for sodium-ion battery cathode pole piece:
First molybdenum carbide/nitrogen sulphur codope sponge graphene composite material (is conducted electricity according to the mass ratio of 8:1:1 and conductive blackAgent) and fully ground and mixed of sodium alginate (binding agent), then drip a small amount of deionized water shape after abundant ground and mixedBecome uniform liquid pastel, be coated on Copper Foil matrix as test electrode, with sodium metal as a comparison electrode make button electricityPond, its electrolyte is 1MNaClO4/EC:DMC(1:1)+5wt％FEC。
Inventor attempts molybdenum carbide first as anode material of lithium-ion battery, but inventor's discovery, molybdenum carbide is in preparationIn process, there is certain reunion, be unfavorable for the performance of material property. Therefore, inventor considers to add graphene oxide to be prepared,But can not to carry out embedding to sodium ion de-due to grapheme material itself, cause the carrying of the few of essence of performance of material of the present inventionRise. Therefore, inventor need to look for the preparation method who more suitably prepares sodium-ion battery molybdenum carbide negative material. InventorAs the doped source of Graphene, Graphene is improved to doping with thiocarbamide, when increasing Graphene carbon-coating spacing, by GrapheneDoping and reduction, the formation of molybdenum carbide presoma and having synchronizeed with being compounded in water-heat process of doped graphene; TherebyOn the avtive spot that the nitrogen doping that makes molybdenum carbide forerunner physical efficiency be grown in Graphene produces, molybdenum carbide presoma embeds after reductionIn Graphene hydrogel, be combined tight and even with doped graphene; After hydro-thermal reaction is complete by the freeze drying of Graphene hydrogel,The Graphene obtaining has three-dimensional sponge shape structure, and in conjunction with follow-up heat treatment process, thereby successfully by molybdenum carbide nano particleUniform deposition is grown up in nitrogen sulphur codope sponge Graphene, can make molybdenum carbide in sponge Graphene by method of the present inventionDisperse more evenly, effectively promote the performance of molybdenum carbide performance, and then greatly improved the specific discharge capacity of carbon matrix material.In addition, inventor also finds that the present invention adopts three (methylol) aminomethane to regulate ph value to be before hydro-thermal reaction by experiment9～10, be conducive to molybdenum carbide and be distributed in equably on spongy Graphene. By preparation method of the present invention, thereby hadThe anode material of lithium-ion battery of good high rate performance and long circulation life.
Therefore, method of the present invention successfully provides a kind of molybdenum carbide/nitrogen sulphur codope sponge stone for sodium-ion battery firstChina ink alkene anode material, this composite is to be dispersed in structure in nitrogen sulphur codope sponge Graphene by molybdenum carbide nano particleThe three dimensional composite structure becoming.
The composite making by method of the present invention can reduce to a great extent molybdenum carbide and produce in deintercalation sodium ion processRaw volumetric expansion, is ensureing, under the prerequisite of specific capacity, to have improved high rate performance and the stable circulation performance of electrode material, therebyMake up well the deficiency of single molybdenum carbide material. Technical solution of the present invention molybdenum carbide/nitrogen sulphur codope sponge Graphene composite woodThe preparation method of material is simple, and the method preparation technology's flow process is short, reproducible, with low cost, environmental friendliness.
Brief description of the drawings
The X ray diffracting spectrum of molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material that [Fig. 1] makes for embodiment 1(XRD)。
The scanning electron microscope (SEM) photograph (SEM) of molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material that [Fig. 2] makes for embodiment 1.
The sodium-ion battery of molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material assembling that [Fig. 3] makes for embodiment 1Constant current charge-discharge performance map.
The sodium-ion battery of molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material assembling that [Fig. 4] makes for embodiment 1High rate performance figure.
The scanning electron microscope (SEM) photograph (SEM) of molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material that [Fig. 5] makes for comparative example 1.
The scanning electron microscope (SEM) photograph (SEM) of molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material that [Fig. 6] makes for comparative example 2.
Detailed description of the invention
Following examples are intended to content of the present invention to be described in further details; And the protection domain of the claims in the present invention is not subject to realityExecute example restriction.
Embodiment 1
First take the flaky graphite of 3g purity 99.5%, the concentrated sulfuric acid and 50 that to join containing 350mL mass fraction be 98%ML mass fraction is, in 85% the mixed solution of phosphoric acid, to add 18g potassium permanganate to be oxidized, by molten this mixing in batchesLiquid remains under 0 DEG C of condition of ice bath and stirs 2h, then in water-bath, is heated to 45 DEG C and reacts 12h under magnetic agitation conditionObtain mixed solution; Then, under condition of ice bath, in mixture, slowly add 400mL deionized water, after question response is steadySlowly add 20mL hydrogen peroxide to remove unreacted potassium permanganate completely, mixed solution color becomes glassy yellow afterwards; Finally willA large amount of deionized water repeated washings for the mixed solution of gained, pack dialysis in dialysis bag into after centrifugal and within 5～7 days, obtain pure oxygenFunctionalized graphene solution. The concentration that the calculating of process heated drying can obtain graphene oxide in obtained graphite oxide weak solution is 5mg/mL。
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Claim according to nitrogenous source, sulphur source and graphene oxide mass ratio 4:1 subsequentlyGet thiocarbamide 0.2g, add in the graphite oxide weak solution stirring, after thiocarbamide and graphene oxide solution fully mix, continueStir 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 4:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.25g, and successively addIn 40mL deionized water, mixed solution is slowly joined to above-mentioned nitrogenous sulphur graphene oxide solution under magnetic agitation conditionIn, fully, after dispersed with stirring 1h, it is 10 that mixed solution is regulated to ph with three (methylol) aminomethane, then proceeds to waterIn thermal response still, at 180 DEG C of temperature, carry out hydro-thermal reaction 10h, after product freeze drying 12h, be placed on quartzIn crucible, pass into argon gas and carry out high-temperature heat treatment in 800 DEG C, the time is 6h, can obtain molybdenum carbide/nitrogen sulphur codope spongeGraphene composite material.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts the present embodiment to prepare, molybdenum carbide nano particle is dispersedGrow in nitrogen sulphur codope sponge Graphene, granular size is 40～80nm.
Adopt the present embodiment sodium-ion battery composite negative pole material and the sodium sheet prepared to be assembled into button cell, its material list electricity of seeking peaceChemical property is as shown in drawings:
In Fig. 1, can find out position and the relative intensity of each diffraction maximum in molybdenum carbide/nitrogen sulphur codope sponge Graphene anode materialAll match with JCPDS (JCPDS) card (35-0787), show that product is hexagonal crystal systemMo2C crystal.
In Fig. 2, can find out that molybdenum carbide nano particle is evenly grown in nitrogen sulphur codope sponge Graphene.
In Fig. 3, show the electrode that adopts molybdenum carbide/nitrogen sulphur codope sponge graphene composite material to make, at room temperature 100When mA/g constant-current discharge, circulation 100 circle specific capacities still can remain on 136mAh/g; Show good cycle performance.
In Fig. 4, show to adopt the corresponding battery of electrode that molybdenum carbide/nitrogen sulphur codope sponge graphene composite material makes in differenceHigh rate performance figure under discharge-rate, can find that this composite has good high rate performance, at large multiplying power 1000mA/gUnder, capacity still can remain on 120mAh/g, and after current density is got back to 50mA/g by large electric current, capacity returns to again 180mAh/g。
Embodiment 2
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Take according to nitrogenous source sulphur source and graphene oxide mass ratio 6:1 subsequentlyThiocarbamide 0.3g, adds in the graphite oxide weak solution stirring, and after thiocarbamide and graphene oxide solution fully mix, continues to stirMix 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 4:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.25g, and successively addIn 40mL deionized water, mixed solution is slowly joined to above-mentioned nitrogenous sulphur graphene oxide solution under magnetic agitation conditionIn, fully, after dispersed with stirring 1h, it is 10 that mixed solution is regulated to ph with three (methylol) aminomethane, then proceeds to waterIn thermal response still, at 180 DEG C of temperature, carry out hydro-thermal reaction 10h, after product freeze drying 12h, be placed on quartzIn crucible, pass into argon gas and carry out high-temperature heat treatment in 800 DEG C, the time is 12h, can obtain molybdenum carbide/nitrogen sulphur codope spongeGraphene composite material.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts the present embodiment to prepare, molybdenum carbide nano particle is dispersedGrow in nitrogen sulphur codope sponge Graphene, granular size is 40～90nm.
The electrode respective battery that the molybdenum carbide/nitrogen sulphur codope sponge graphene composite material that adopts the present embodiment to prepare is made is in chamberUnder temperature, during with 100mA/g constant-current discharge, circulation 100 circle specific capacities still can remain on 140mAh/g; Show goodCycle performance.
Embodiment 3
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Take according to nitrogenous source sulphur source and graphene oxide mass ratio 8:1 subsequentlyThiocarbamide 0.4g, adds in the graphite oxide weak solution stirring, and after thiocarbamide and graphene oxide solution fully mix, continues to stirMix 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 2:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.5g, and successively joinIn 40mL deionized water, under magnetic agitation condition, mixed solution is slowly joined in above-mentioned nitrogenous sulphur graphene oxide solution,Fully, after dispersed with stirring 1h, it is 10 that mixed solution is regulated to ph with three (methylol) aminomethane, then proceeds to hydro-thermal anti-Answer in still, at 200 DEG C of temperature, carry out hydro-thermal reaction 15h, after product freeze drying 12h, be placed on silica crucibleIn, passing into argon gas and carry out high-temperature heat treatment in 800 DEG C, the time is 6h, can obtain molybdenum carbide/nitrogen sulphur codope sponge graphiteAlkene composite.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts the present embodiment to prepare, molybdenum carbide nano particle is dispersedGrow in nitrogen sulphur codope sponge Graphene, granular size is 30～80nm.
The electrode respective battery that the molybdenum carbide/nitrogen sulphur codope sponge graphene composite material that adopts the present embodiment to prepare is made is in chamberUnder temperature, during with 100mA/g constant-current discharge, circulation 100 circle specific capacities still can remain on 126mAh/g; Show goodCycle performance.
Embodiment 4
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Claim according to nitrogenous source sulphur source and graphene oxide mass ratio 10:1 subsequentlyGet thiocarbamide 0.5g, add in the graphite oxide weak solution stirring, after thiocarbamide and graphene oxide solution fully mix, continueStir 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 5:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.2g, and successively joinIn 40mL deionized water, under magnetic agitation condition, mixed solution is slowly joined in above-mentioned nitrogenous sulphur graphene oxide solution,Fully, after dispersed with stirring 1h, it is 9 that mixed solution is regulated to ph with three (methylol) aminomethane, then proceeds to hydro-thermal anti-Answer in still, at 200 DEG C of temperature, carry out hydro-thermal reaction 10h, after anti-product freeze drying 24h, be placed on quartzy earthenwareIn crucible, pass into argon gas and carry out high-temperature heat treatment in 900 DEG C, the time is 6h, can obtain molybdenum carbide/nitrogen sulphur codope sponge stoneChina ink alkene composite.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts the present embodiment to prepare, molybdenum carbide nano particle is dispersedGrow in nitrogen sulphur codope sponge Graphene, granular size is 30～100nm.
The electrode respective battery that the molybdenum carbide/nitrogen sulphur codope sponge graphene composite material that adopts the present embodiment to prepare is made is in chamberUnder temperature, during with 100mA/g constant-current discharge, circulation 100 circle specific capacities still can remain on 130mAh/g; Show goodCycle performance.
Embodiment 5
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Take according to nitrogenous source sulphur source and graphene oxide mass ratio 4:1 subsequentlyThiocarbamide 0.2g, adds in the graphite oxide weak solution stirring, and after thiocarbamide and graphene oxide solution fully mix, continues to stirMix 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 2:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.5g, and successively joinIn 40mL deionized water, under magnetic agitation condition, mixed solution is slowly joined in above-mentioned nitrogenous sulphur graphene oxide solution,Fully, after dispersed with stirring 1h, it is 9 that mixed solution is regulated to ph with three (methylol) aminomethane, then proceeds to hydro-thermal anti-Answer in still, at 180 DEG C of temperature, carry out hydro-thermal reaction 24h, after product freeze drying 24h, be placed on silica crucibleIn, passing into argon gas and carry out high-temperature heat treatment in 900 DEG C, the time is 12h, can obtain molybdenum carbide/nitrogen sulphur codope sponge graphiteAlkene composite.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts the present embodiment to prepare, molybdenum carbide nano particle is dispersedGrow in nitrogen sulphur codope sponge Graphene, granular size is 20～60nm.
The electrode respective battery that the molybdenum carbide/nitrogen sulphur codope sponge graphene composite material that adopts the present embodiment to prepare is made is in chamberUnder temperature, during with 100mA/g constant-current discharge, circulation 100 circle specific capacities still can remain on 130mAh/g; Show goodCycle performance.
Comparative example 1
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Claim according to nitrogenous source, sulphur source and graphene oxide mass ratio 4:1 subsequentlyGet thiocarbamide 0.2g, add in the graphite oxide weak solution stirring, after thiocarbamide and graphene oxide solution fully mix, continueStir 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 4:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.25g, and successively addIn 40mL deionized water, mixed solution is slowly joined to above-mentioned nitrogenous sulphur graphene oxide solution under magnetic agitation conditionIn, fully, after dispersed with stirring 1h, it is 10 that mixed solution is regulated to ph with ammoniacal liquor, then proceed in hydrothermal reaction kettle,At 180 DEG C of temperature, carry out hydro-thermal reaction 10h, after product freeze drying 24h, product is placed in to silica crucible, pass intoArgon gas carries out high-temperature heat treatment in 800 DEG C, and the time is 6h, can obtain molybdenum carbide/nitrogen sulphur codope sponge Graphene composite woodMaterial.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts this comparative example to prepare, its material characterizes as shown in Figure 5:
In Fig. 5, can find out that spongy Graphene pattern is inhomogeneous and comparatively mixed and disorderly.
Comparative example 2
Measuring the above-mentioned graphene oxide solution of 10mL (graphene oxide content is 10 × 5mg/mL=50mg) with graduated cylinder pours intoMagnetic agitation at ambient temperature in the beaker of 150mL. Claim according to nitrogenous source, sulphur source and graphene oxide mass ratio 4:1 subsequentlyGet thiocarbamide 0.2g, add in the graphite oxide weak solution stirring, after thiocarbamide and graphene oxide solution fully mix, continueStir 1h and can obtain nitrogenous sulphur graphene oxide solution.
Be 4:1 according to molybdenum source and carbon source mass ratio, take respectively ammonium paramolybdate 1.0g, glucose 0.25g, and successively addIn 40mL deionized water, mixed solution is slowly joined to above-mentioned nitrogenous sulphur graphene oxide solution under magnetic agitation conditionIn, fully, after dispersed with stirring 1h, mixed solution is proceeded in hydrothermal reaction kettle, at 180 DEG C of temperature, carry out hydro-thermal reaction10h, after product freeze drying 24h, is placed in silica crucible by product, passes into argon gas and carries out high warm place in 800 DEG CReason, the time is 6h, can obtain molybdenum carbide/nitrogen sulphur codope sponge graphene composite material.
Molybdenum carbide/nitrogen sulphur codope sponge the graphene composite material that adopts this comparative example to prepare, its material characterizes as shown in Figure 6:
In Fig. 6, can find out that spongy graphene layer and interlayer spacing are less, not form well spongelike structure.
Claims (9)
1. for a preparation method for molybdenum carbide/nitrogen sulphur codope sponge Graphene anode material of sodium-ion battery, its feature existsIn, comprise the following steps:
(1) thiocarbamide is fully dissolved and is spread in graphene oxide solution under magnetic agitation condition;
(2) molybdenum source and carbon source are dissolved in the solution that is spread in the formation of (1) step, by three (methylol) aminomethane adjusting ph valueBe 9～10;
(3) (2) step being formed to solution inserts and in hydrothermal reaction kettle, carries out 180～220 DEG C of hydro-thermal reactions and obtain the stone that contains presomaChina ink alkene hydrogel;
(4) product (3) step being obtained is carried out after freeze drying, passes into protective atmosphere high warm at 800～900 DEG CAfter processing, obtain molybdenum carbide/nitrogen sulphur codope sponge graphene composite material;
The quality percentage composition of N of adulterating in Graphene is 4.0～10.0%, and the quality percentage composition of doping S is 3.0～8.0%; Molybdenum carbideParticle size be 20～100nm, quality percentage composition is described composite 30～70%.
2. preparation method according to claim 1, is characterized in that: described thiocarbamide and the mass ratio of graphene oxide are4:1～10:1。
3. preparation method according to claim 1, is characterized in that: in described step (2), molybdenum source and carbon source mol ratio are2:1～5:1。
4. preparation method according to claim 1, is characterized in that: the hydrothermal temperature in described step (3) is180～200℃。
5. preparation method according to claim 1, is characterized in that: described molybdenum source is ammonium tetramolybdate, ammonium paramolybdate, acetylOne or more of acetone molybdenum; Described carbon source is one or more in aniline, o-phenylenediamine, glucose.
6. according to the preparation method described in claim 1-5 any one, the hydro-thermal reaction time is 10～24h.
7. according to the preparation method described in claim 1-5 any one, it is characterized in that: freeze drying described in described step (4)Time is 12～24h.
8. according to the preparation method described in claim 1-5 any one, it is characterized in that: the logical protective atmosphere of high-temperature heat treatment is argon gas,Reaction time is 5～12h.
9. preparation method according to claim 1, is characterized in that: first by thiocarbamide according to the mass ratio of 4:1～10:1 at magneticUnder power stirring condition, fully dissolve and be spread in the standby graphene oxide solution of Hummers legal system, secondly by glucose, ammonium paramolybdateFully dissolve and be spread in above-mentioned nitrogenous sulphur graphene oxide solution, then under magnetic agitation condition, make it abundant dissolving, will mixClosing solution three (methylol) aminomethane adjusting ph is 9～10, then at 180-200 DEG C of temperature, carries out hydro-thermal reaction10～24h, synthetic presoma embeds in Graphene hydrogel, last, by after reactant freeze drying 12～24h, 800～900 DEG CCarry out high-temperature heat treatment, the time is 5～12h, can obtain molybdenum carbide/nitrogen sulphur codope sponge graphene composite material.
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