CN110247050A - A method of four vanadic sulfides/graphene composite material is prepared using containing vanadium leachate - Google Patents
A method of four vanadic sulfides/graphene composite material is prepared using containing vanadium leachate Download PDFInfo
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- CN110247050A CN110247050A CN201910540706.XA CN201910540706A CN110247050A CN 110247050 A CN110247050 A CN 110247050A CN 201910540706 A CN201910540706 A CN 201910540706A CN 110247050 A CN110247050 A CN 110247050A
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- vanadium
- roasting
- leachate
- composite material
- graphene composite
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 111
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 150000003568 thioethers Chemical class 0.000 title 1
- 238000002386 leaching Methods 0.000 claims abstract description 37
- 150000004763 sulfides Chemical class 0.000 claims abstract description 35
- 229910001784 vanadium mineral Inorganic materials 0.000 claims abstract description 22
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 238000007792 addition Methods 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229940037003 alum Drugs 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 239000011435 rock Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000004080 punching Methods 0.000 claims 1
- 238000009991 scouring Methods 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000003321 amplification Effects 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 230000002308 calcification Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Four vanadic sulfides/graphene composite material method is prepared using containing vanadium leachate the present invention relates to a kind of, it is will to contain vanadium mineral to obtain by pretreatments such as roasting-leachings containing vanadium leachate, to contain vanadium leachate as mother liquor, sulphur source thioacetamide and graphene oxide is added, generates four vanadic sulfides/graphene composite material by hydro-thermal reaction.Four vanadic sulfides/graphene composite material can be used as sodium-ion battery or the cathode of lithium ion battery uses.Method provided by the invention eliminates the preparation process of the pure materials such as sodium vanadate, ammonium vanadate in existing four vanadic sulfides/graphene composite material preparation process, directly from containing preparing vanadic sulfide/graphene composite material in vanadium leachate, the preparation flow for shortening material, greatly reduces production cost.
Description
Technical field
Four vanadic sulfides/graphene composite material method is prepared using containing vanadium leachate the present invention relates to a kind of, belongs to vanadium
Chemical Engineering Technology and resource circulation utilization technical field.
Background technique
Nowadays the development and utilization of energy and material has become the top priority of each area research.The each group of lithium ion battery
At part, oneself is deeply developed research, but is not met by the demand of large-scale energy consumption application.Due to sodium-ion battery
Sodium storage capacity it is high and similar to lithium property and be concerned.And transiting state metal such as sulfide is because of its theory with higher
Specific capacity, such as molybdenum sulfide, vanadic sulfide etc., it is considered to be a kind of potential anode material of lithium-ion battery.Production vanadic sulfide at present
Negative electrode material is usually to be synthesized using the pure chemistry reagent of vanadium as vanadium source, usually passes through the vanadium that will contain in vanadium mineral through roasting
The pretreatments such as burning, leaching are transferred to liquid phase, then are made through series of process such as removal of impurities, precipitating, crystallizations, face higher cost, work
The defects of skill is longer.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provide it is a kind of using containing vanadium leachate prepare four vanadic sulfides/
The method of graphene composite material, this method realize four vanadic sulfides/graphene composite material short route, low cost, efficiently system
Standby, four vanadic sulfides/graphene composite material of preparation can be used as the use of lithium/sodium-ion battery negative electrode material.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
A method of four vanadic sulfides/graphene composite material is prepared using containing vanadium leachate comprising following steps:
S1, vanadium mineral will be contained and roasting additive is mixed to get after mixed material to roast or will contain vanadium mineral saltless roasting and obtain
To roasting clinker；
S2, the roasting clinker that step S1 is obtained is leached in leaching medium, is separated by solid-liquid separation later, obtain soaking containing vanadium
Liquid and tailings out；
S3, contain vanadium leachate for what sulphur source and graphene oxide addition step S2 obtained, stirring dissolves sulphur source, aoxidizes stone
Black alkene is uniformly dispersed, and obtains mixed liquor；
S4, the obtained mixed liquor of step S3 is transferred to reaction kettle, heating is reacted, cooled down after reaction；
S5, step S4 products therefrom is dried through being separated by solid-liquid separation, and after repeated flushing precipitating, obtains four vanadic sulfides/graphite
Alkene composite material.
In a preferred embodiment, in step sl, the vanadium mineral that contains is vanadium titano-magnetite, vanadium slag, vanadium extraction
One or more of tailings, Rock coal containing alum or vanadium-containing wasting catalyst, wherein in vanadium titano-magnetite content of vanadium with V2O5It is calculated as
0.2%~1.8%；Vanadium in Vanadium Residue content is with V2O5It is calculated as 5%~20%；Content of vanadium is in tailings in vanadium extraction with V2O5It is calculated as 0.5%~
3%；Content of vanadium is in Rock coal containing alum with V2O5It is calculated as 0.1%~1.2%；Content of vanadium is in vanadium-containing wasting catalyst with V2O5It is calculated as 5%~
8%；
The roasting additive be at least one of calcium oxide, calcium carbonate, calcium chloride, calcium sulfate, it is described contain vanadium mineral
With the amount ratio of roasting additive be by containing vanadium in vanadium mineral with V2O5The molar ratio of meter and calcic in calcium salt is 1: 0.5~1.5.
In this proportional region, vanadium leaching rate with higher not only can guarantee, but also the leaching containing impurity elements such as chromium in vanadium mineral can be limited
Out.
In a preferred embodiment, in step sl, the temperature of the roasting is 800~950 DEG C, the time 30
~180min.
Through many experiments discovery when lower than the roasting of above-mentioned limit temperature, only a small amount of vanadium can be converted into vanadium slag
Soluble vanadate, leaching rate are lower under current Leaching Systems；And when being higher than limit temperature roasting, the object of low melting point in material
It meets and locally melts, vanadium is wrapped up and is unfavorable for leaching.Roasting process material with furnace from room temperature to assigned temperature,
Or material is put into after furnace temperature reaches assigned temperature.The conversion ratio of vanadium is insufficient when calcining time is lower than 30min, i.e. generation vanadium
The amount of hydrochlorate is less.And roast a large amount of losses that will cause cost more than 300min.Material furnace cooling after roasting process
Or it directly takes out；It is 250~300 mesh that clinker, which is roasted, through particle size after cracking, this particle size range is conducive to the leaching of vanadium.
In a preferred embodiment, in step s 2, the leaching medium is that sodium bicarbonate solution, ammonium carbonate are molten
At least one of liquid or ammonium bicarbonate soln；Wherein, sodium bicarbonate solution concentration is 50~80g/L；Sal volatile concentration
For 100~600g/L；Ammonium bicarbonate soln concentration is 100~150g/L.
It is due to the medium that carbonate solution, which why is selected, as the leaching medium of saltless roasting or calcification baking clinker
Compared with the conventional medias such as acid, alkali, resulting leachate foreign ion is less after leaching, will not influence subsequent four vanadic sulfides/stone
The purity of black alkene composite material.
In a preferred embodiment, in step s 2, the leaching medium and roasting clinker press liquid-solid ratio mL/g
It is added for 3~20: 1, the temperature of leaching process is 60 DEG C~100 DEG C；The leaching process time is 30min~180min；Institute
The means of separation of solid and liquid are stated as filtering or centrifugation.
In leaching process, lesser liquid-solid ratio causes leaching process motive force insufficient, and V leaching rate is smaller, and biggish
Leaching rate will lead to leaching process increased costs；Furthermore extraction temperature is too low, extraction time is too short can all cause V leaching rate compared with
It is low；And maturing temperature is excessively high, extraction time is too long all to cause increased costs.
In a preferred embodiment, in step s3, the sulphur source is thioacetamide, described to contain vanadium leachate
It is 1: 3~10 that amount ratio with thioacetamide, which is by the molar ratio containing sulphur in vanadium in vanadium leachate and thioacetamide,；It is described
Graphene oxide dosage is added by volume containing vanadium leachate and graphene oxide quality by the ratio of the ratio of mL/g for 100~500
Enter.
In a preferred embodiment, in step s3, the mode of the stirring be magnetic agitation, mechanical stirring or
Ultrasonic disperse；Whipping temp is room temperature；Mixing time is 30min~180min.
In a preferred embodiment, in step s 4, the reaction kettle is polytetrafluoroethylliner liner hydrothermal synthesis
Reaction kettle；The temperature of addition is 140 DEG C~200 DEG C；The time of reaction is 12h~36h；The mode of the cooling is natural room temperature
Cooling or water cooling.
In a preferred embodiment, in step s 5, it is described be separated by solid-liquid separation for filtering or centrifugation, rinse water and
Ethyl alcohol elutes for several times repeatedly.
In a preferred embodiment, in step s 5, the temperature of the drying is 40 DEG C~80 DEG C vacuum drying
6h~36h.
(3) beneficial effect
The beneficial effects of the present invention are:
The present invention provides a kind of use and prepares four vanadic sulfides/graphene composite material method containing vanadium leachate, will contain
Vanadium mineral is fired, leaches etc. that pretreatments obtain is vanadium source containing vanadium leachate, and thioacetamide is sulphur source, and oxidation stone is added
Black alkene, prepares four vanadic sulfides/graphene composite material, and the technical process of this method is eliminated by the preparation containing vanadium mineral containing vanadium
The process of pure material, substantially reduces process, has saved production cost.
Material prepared by the present invention can be used as sodium-ion battery or the cathode of lithium ion battery uses, and will contain vanadium mineral progress
Effective use, has handled waste residue, substantially increases economic benefit.
Detailed description of the invention
Fig. 1 is four vanadic sulfides/graphene composite material XRD spectrum prepared by the embodiment of the present invention 1；
Fig. 2 is that four vanadic sulfides/graphene composite material prepared by the embodiment of the present invention 2 in amplification factor is 20000 times
SEM photograph；
Fig. 3 is that four vanadic sulfides/graphene composite material prepared by the embodiment of the present invention 2 in amplification factor is 50000 times
SEM photograph；
Fig. 4 is the EDS map of four vanadic sulfides/graphene composite material A point in Fig. 3 prepared by the embodiment of the present invention 2；
Fig. 5 is the EDS map of four vanadic sulfides/graphene composite material B point in Fig. 3 prepared by the embodiment of the present invention 2.
Specific embodiment
The principle of the present invention is to first pass through the series of steps such as roasting-leaching to be transferred to leachate containing the vanadium in vanadium mineral
In.The barium oxide containing indissoluble in vanadium mineral is turned by saltless roasting or addition additive roasting specially in roasting process
The vanadate for dissolving in and leaching medium is turned to, then vanadate is dissolved in leachate by leaching；And containing in vanadium leachate
Vanadium be vanadium source, thioacetamide is sulphur source, and graphene oxide is added and is prepared for four vanadic sulfides/graphene composite material.
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.Following percentage is not known illustrate to be mass percent.
Embodiment 1
A method of four vanadic sulfides/graphene composite material being prepared using containing vanadium leachate, is included the following steps:
(1) by content of vanadium (with V2O5Count) saltless roasting is carried out for 17.5% vanadium slag, maturing temperature is 950 DEG C, roasting
120min obtains roasting clinker.
(2) chamotte crushing will be roasted, granularity is 250~300 mesh, it is added in 80g/L sodium bicarbonate solution and leaches, bicarbonate
Sodium solution and roasting clinker are carried out by liquid-solid ratio by mL/g for 10: 1, and the temperature of leaching is 95 DEG C, and after leaching 180min, filtering divides
It obtains from solid-liquid containing vanadium leachate, the leaching rate by the way that vanadium is calculated is 92.83%.
(3) vanadium leachate will be contained, thioacetamide and graphene oxide is added, wherein graphene oxide is using improvement
The preparation of Hummers method, the amount ratio containing vanadium leachate and thioacetamide is by containing vanadium (in terms of V) and thioacetyl in vanadium leachate
The molar ratio of sulphur (in terms of S) is 1: 5 in amine, and graphene oxide dosage is to press by volume containing vanadium leachate and graphene oxide quality
The ratio of mL/g is 200 additions；Ultrasonic disperse 120min at room temperature.
(4) solution of the ultrasonic disperse after uniform is placed in polytetrafluoroethylliner liner hydrothermal synthesis reaction kettle, is lauched at 180 DEG C
Thermal response 20h, after reaction cooled to room temperature.
(5) reaction product is separated by filtering, precipitating water and ethyl alcohol is eluted for several times repeatedly, and in vacuum oven
In in 60 DEG C of vacuum drying 6h, obtain four vanadic sulfides/graphene composite material.By four vanadic sulfides of acquisition/graphene composite wood
Material carries out X-ray diffraction, obtains XRD spectrum, as shown in Figure 1.The material and four vanadic sulfide standard cards synthesized as can be seen from Figure
Piece coincide, and graphene fails to show in XRD diagram because crystallinity is poor.
Embodiment 2
A method of four vanadic sulfides/graphene composite material being prepared using containing vanadium leachate, is included the following steps:
(1) by content of vanadium (with V2O5Count) calcification baking is carried out for 0.5% vanadium titano-magnetite, roasting additive is oxidation
The amount ratio of calcium, vanadium titano-magnetite and calcium oxide is by vanadium in vanadium titano-magnetite (with V2O5Meter) with calcium oxide in calcic mole
Than being 1: 0.5, maturing temperature is 900 DEG C, calcining time 120min, and roasting clinker is obtained after roasting.
(2) it after chamotte crushing being roasted, selects granularity to be placed in 600g/L sal volatile for 250~300 mesh and is soaked
Out, sal volatile and roasting clinker are carried out by liquid-solid ratio mL/g for 10, and extraction temperature is 80 DEG C, extraction time 120min,
It is separated by filtration solid-liquid after leaching, and obtains containing vanadium leachate, the leaching rate by the way that vanadium is calculated is 91.36%.
(3) thioacetamide and graphene oxide, the dosage containing vanadium leachate and thioacetamide is added containing vanadium leachate
It is 1: 10 than the molar ratio for the sulphur (in terms of S) in containing vanadium (in terms of V) in vanadium leachate and thioacetamide, graphene oxide is used
Amount is by the ratio of mL/g is 100 additions by volume containing vanadium leachate and graphene oxide quality；Mechanical stirring at room temperature
120min。
(4) solution after stirring evenly is placed in hydrothermal reaction kettle, hydro-thermal reaction is for 24 hours, naturally cold after reaction at 160 DEG C
But after 1h water cooling to room temperature.
(5) reaction product is separated by filtering, is eluted for several times repeatedly with water and ethyl alcohol, and in a vacuum drying oven in 80
DEG C vacuum drying 12h, obtains four vanadic sulfides/graphene composite material, carries out X-ray diffraction to it, obtain XRD spectrum and four sulphur
Change vanadium standard card to coincide.
Embodiment 3
A method of four vanadic sulfides/graphene composite material being prepared using containing vanadium leachate, is included the following steps:
(1) by content of vanadium (with V2O5Count) calcification baking is carried out for 13.75% high chrome alum slag, roasting additive is carbonic acid
The amount ratio of calcium, high chrome alum slag and calcium salt is by vanadium in vanadium titano-magnetite (with V2O5Meter) with calcium carbonate in calcic molar ratio be 1
: 1, maturing temperature is 850 DEG C, calcining time 60min, obtains roasting clinker.
(2) roasting chamotte crushing is placed in ammonium hydrogen carbonate and is leached, the liquid-solid ratio of ammonium hydrogen carbonate and roasting clinker presses mL/
G is that 12 extraction temperatures are 70 DEG C, extraction time 180min, and solid-liquid is separated by filtration after leaching and is obtained containing vanadium leachate,
Leaching rate by the way that vanadium is calculated is 90.66%, and the leaching rate of chromium is only 0.05%, and realize vanadium efficiently separates extraction.
(3) thioacetamide and graphene oxide, the dosage containing vanadium leachate and thioacetamide is added containing vanadium leachate
It is 1: 8 than the molar ratio for the sulphur (in terms of S) in containing vanadium (in terms of V) in vanadium leachate and thioacetamide, graphene oxide is used
Amount is by the ratio of mL/g is 500 additions by volume containing vanadium leachate and graphene oxide quality；Magnetic agitation at room temperature
120min。
(4) solution after stirring evenly is placed in polytetrafluoroethylliner liner hydrothermal synthesis reaction kettle, the hydro-thermal reaction at 140 DEG C
28h, after reaction water cooling to room temperature.
(5) reaction product is separated by filtering, is eluted for several times repeatedly with water and ethyl alcohol, and in a vacuum drying oven in 50
DEG C vacuum drying for 24 hours, obtain four vanadic sulfides/graphene composite material.
Four obtained vanadic sulfides/graphene composite material is scanned electron microscope analysis, obtains SEM photograph such as Fig. 2, Fig. 3
Shown, wherein the amplification factor of Fig. 2 is 20000 times, and the amplification factor of Fig. 3 is 50000 times；The power spectrum of A point and B point in its Fig. 3
Figure is as shown in Figure 4, Figure 5.From figure 2 it can be seen that graphene is layer structure, four vanadic sulfides of strip are covered on graphene
On, element species and Elements Atom ratio can get by the EDS map of Fig. 4, Fig. 5, wherein Fig. 4 is the EDS map of A point in Fig. 3, is said
Bright its is four vanadic sulfides, and Fig. 5 is the EDS map of B point in Fig. 3, illustrates that it is graphene；Thus illustrate that the material generated is four
Vanadic sulfide/graphene composite material.
The preparation of existing four vanadic sulfides/graphene composite material usually with sodium metavanadate, ammonium metavanadate, etc. pure reagent containing vanadium
For vanadium source, such as CN105810942A.And the raw material for preparing of the pure reagent containing vanadium exactly contains vanadium mineral, passes through roasting-containing vanadium mineral
Leach and etc. vanadium is transferred to leachate, then inclined vanadium out is prepared by the methods of removal of impurities, precipitating, crystallization, extraction, ion exchange
The pure reagents containing vanadium such as sour sodium, ammonium metavanadate, sodium vanadate, positive ammonium vanadate.So if preparing four vanadic sulfides/stone in terms of source
The starting point of black alkene composite material is first to prepare from containing preparing pure reagent containing vanadium in vanadium mineral, then as raw material containing vanadium mineral
Four vanadic sulfides/graphene composite material.The process flow is longer, higher cost.And the present invention proposes one kind from containing vanadium leachate
In directly prepare the method for vanadic sulfide, substantially reduce process, reduce production cost.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint
What those skilled in the art can use the equivalence enforcement that technology contents disclosed above were changed or be modified as equivalent variations
Example.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to the above embodiments
What simple modification, equivalent variations and remodeling, still falls within the protection scope of technical solution of the present invention.
Claims (10)
1. a method of four vanadic sulfides/graphene composite material is prepared using containing vanadium leachate, which is characterized in that it includes such as
Lower step:
S1, vanadium mineral will be contained and roasting additive is mixed to get after mixed material to roast or will contain vanadium mineral saltless roasting and be roasted
Overburnt material；
S2, the roasting clinker that step S1 is obtained is leached in leaching medium, is separated by solid-liquid separation, is obtained containing vanadium leachate later
And tailings；
S3, contain vanadium leachate for what sulphur source and graphene oxide addition step S2 obtained, stirring dissolves sulphur source, graphene oxide
It is uniformly dispersed, obtains mixed liquor；
S4, the obtained mixed liquor of step S3 is transferred to reaction kettle, heating is reacted, cooled down after reaction；
S5, step S4 products therefrom is dried through being separated by solid-liquid separation, and after repeated flushing precipitating, it is multiple obtains four vanadic sulfides/graphene
Condensation material.
2. the method as described in claim 1, which is characterized in that in step sl, the vanadium mineral that contains is vanadium titano-magnetite, vanadium
One or more of slag, tailings in vanadium extraction, Rock coal containing alum or vanadium-containing wasting catalyst；Wherein, in vanadium titano-magnetite content of vanadium with V2O5
It is calculated as 0.2%~1.8%；Vanadium in Vanadium Residue content is with V2O5It is calculated as 5%~20%；Content of vanadium is in tailings in vanadium extraction with V2O5It is calculated as
0.5%~3%；Content of vanadium is in Rock coal containing alum with V2O5It is calculated as 0.1%~1.2%；Content of vanadium is in vanadium-containing wasting catalyst with V2O5Meter
It is 5%~8%；
The roasting additive be at least one of calcium oxide, calcium carbonate, calcium chloride, calcium sulfate, it is described containing vanadium mineral and roasting
Burn additive amount ratio be by containing vanadium in vanadium mineral with V2O5The molar ratio of meter and calcic in calcium salt is 1: 0.5~1.5.
3. the method as described in claim 1, which is characterized in that in step sl, the temperature of the roasting is 800~950 DEG C,
Time is 30~180min.
4. the method as described in claim 1, which is characterized in that in step s 2, the leaching medium be sodium bicarbonate solution,
At least one of sal volatile or ammonium bicarbonate soln；Wherein, sodium bicarbonate solution concentration is 50~80g/L；Ammonium carbonate
Solution concentration is 100~600g/L；Ammonium bicarbonate soln concentration is 100~150g/L.
5. the method as described in claim 1, which is characterized in that in step s 2, the leaching medium and roasting clinker press liquid
Gu being added than mL/g for 3~20: 1, the temperature of leaching process is 60 DEG C~100 DEG C；The leaching process time be 30min~
180min；It is described to be separated by solid-liquid separation as filtering or centrifugation.
6. the method as described in claim 1, which is characterized in that in step s3, the sulphur source is thioacetamide, described to contain
The amount ratio of vanadium leachate and thioacetamide be 1: 3 by the molar ratio containing sulphur in vanadium in vanadium leachate and thioacetamide~
10；The graphene oxide dosage is added by volume containing vanadium leachate and graphene oxide quality by the ratio of mL/g for 100~500
Enter.
7. the method as described in claim 1, which is characterized in that in step s3, the mode of the stirring is magnetic agitation, machine
Tool stirring or ultrasonic disperse；Whipping temp is room temperature；Mixing time is 30min~180min.
8. the method as described in claim 1, which is characterized in that in step s 4, the reaction kettle is polytetrafluoroethylliner liner
Hydrothermal synthesis reaction kettle；The temperature of addition is 140 DEG C~200 DEG C；The time of reaction is 12h~36h；The mode of the cooling is
Natural room temperature cooling or water cooling.
9. the method as described in claim 1, which is characterized in that in step s 5, described to be separated by solid-liquid separation as filtering or centrifugation, punching
Scouring water and ethyl alcohol elute for several times repeatedly.
10. the method as described in claim 1, which is characterized in that in step s 5, the temperature of the drying is 40 DEG C~80 DEG C
It is dried in vacuo 6h~36h.
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