CN107845788A - Charcoal metal sulfide composite, its preparation method and application - Google Patents

Charcoal metal sulfide composite, its preparation method and application Download PDF

Info

Publication number
CN107845788A
CN107845788A CN201710919278.2A CN201710919278A CN107845788A CN 107845788 A CN107845788 A CN 107845788A CN 201710919278 A CN201710919278 A CN 201710919278A CN 107845788 A CN107845788 A CN 107845788A
Authority
CN
China
Prior art keywords
charcoal
metal sulfide
preparation
mos
carbonized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710919278.2A
Other languages
Chinese (zh)
Inventor
周园
马路祥
申月
海春喜
孙艳霞
张丽娟
张新星
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qinghai Institute of Salt Lakes Research of CAS
Original Assignee
Qinghai Institute of Salt Lakes Research of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qinghai Institute of Salt Lakes Research of CAS filed Critical Qinghai Institute of Salt Lakes Research of CAS
Priority to CN201710919278.2A priority Critical patent/CN107845788A/en
Publication of CN107845788A publication Critical patent/CN107845788A/en
Pending legal-status Critical Current

Links

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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention relates to lithium battery material technical field, more particularly to a kind of charcoal metal sulfide composite, its preparation method and application.The preparation method of the charcoal metal sulfide composite includes：Charing：Heating charing charcoal；Prepare：The reaction solution of preparing metal sulfide；Synthesis：The charcoal carbonized is immersed in reaction solution, heats, obtains charcoal metal sulfide composite.The charcoal metal sulfide composite obtained using the preparation method has excellent electric property, and cost is reasonable, the feature of environmental protection is good, can also simplify the manufacture craft of lithium ion battery.

Description

Charcoal-metal sulfide composite, its preparation method and application
Technical field
The present invention relates to lithium battery material technical field, more particularly to a kind of charcoal-metal sulfide composite, its Preparation method and application.
Background technology
With the trend of economic globalization, the energy and environmental problem are two key issues that we are faced at present. In cell art, lithium ion battery (LIB) is due to its high-energy-density, good high rate performance and excellent stable circulation Property, turn into the key for solving energy problem.However, as people are continuously increased for the demand of the energy, inevitably occur Two problems：First, non-biodegradable of the present battery after its service life will bring huge electronic waste, this is to ring Border will certainly cause necessarily to threaten；Second, battery uses unsustainable material manufacture more, it is limited essentially from mineral resources Availability necessarily causes the increase of cost.
It is in current commercialized li-ion electrode materials to use graphite as GND more.Though graphite cost is low and performance It is good, but graphite belongs to the quasi-mineral of man-made recovery, and exhaustion, especially companion are eventually produced as oil, coal With being stepped up for electric automobile instantly and large-scale power grid construction demand, graphite resource also can be exhausted one day.From long-range From the point of view of angle, it is necessary to look for reproducible, environment-friendly electrode material there should be excellent chemical property in fact, There should be the characteristics of aboundresources again.
Some biological materials (particularly contenting carbon material such as wheat stalk, maize straw), which turn into, makes more preferable electrode material That expects is preferred.Biological material, such as negative material as lithium ion battery, using the teaching of the invention it is possible to provide high capacity, excellent rate capability And cyclical stability.However, it also has many shortcomings, its most of irreversible capacity during charge/discharge cycle, lead It is caused to meet the demand of the growth to energy.In addition, in a practical situation, biological material is not dug fully at present Dig its value, only as paper pulp, feed stripped the purpose of by limited utilization, and these biological materials directly exist mostly Field is burnt, and causes the huge wasting of resources and serious environmental pollution.Therefore, it is necessary that going deep into excavation biological material exists in fact The high value of electrode material application aspect simultaneously solves the problems, such as it in terms of battery performance.
MoS2It is attract attention as a kind of potential electrode material.It shows speed good in theory and held Measure (672mAhg-1) and high coulombic efficiency.However, actually MoS2Low conductivity cause the transmission of ion and electronics, Therefore significant capacitance loss and the cycle performance of difference are caused.Current solution method is received using redox graphene or carbon Mitron and MoS2Synthetic composite material, such as Ziwei Li et al. are using the MoS of graphene quantum dot doping2For lithium ion Storage, Fusen Pan et al. are used for the storage of lithium ion battery using the composite of graphene and CNT.Although using The method of redox graphene or CNT can improve MoS2Electrical conductivity, lift its electric property, but also deposit In problems with：It is complex process first, in redox graphene and CNT during synthesis, process is cumbersome Complexity, this will certainly increase cost, also be unfavorable for the industrialization of technique；Secondly, the concentrated sulfuric acid and height can be used in building-up process Potassium manganate, certain environmental pollution can be caused, it may have certain danger.
As can be seen here, there are some drawbacks in existing electrode material and potential electrode material, or material has It is non-renewable, or manufacturing process complexity cost height, or environmental pollution be present, or electrical performance in the battery It is bad, therefore real the drawbacks of being necessary to be improved to overcome it to exist above-mentioned material.
The content of the invention
For overcome the deficiencies in the prior art, present inventor has performed concentrating on studies, paid a large amount of creative works and After going deep into experimental exploring, so as to complete the present invention.
The present invention includes three aspects, one side, and the present invention provides a kind of charcoal-metal sulfide composite Preparation method, comprise the following steps：
Charing：Heating charing charcoal；
Prepare：The reaction solution of preparing metal sulfide；
Synthesis：The charcoal carbonized is immersed in the reaction solution, heats, obtains the charcoal-metal Sulfide composite.
Further, the carbonization is：0.5h-4h is carbonized under the conditions of anaerobic atmosphere, 500 DEG C -1000 DEG C；Exist again After 0.5h-10h being soaked in acid solution, rinsing, drying, the charcoal carbonized.
Wherein, the anaerobic atmosphere refers to argon gas, helium, xenon or nitrogen atmosphere；The acid solution is that hydrochloric acid is water-soluble Liquid, aqueous sulfuric acid, phosphate aqueous solution or aqueous solution of nitric acid.
Preferably, the carbonization is：Charcoal 2h is carbonized under the conditions of argon atmosphere, 800 DEG C；Again in 0.1mol/L After aqueous hydrochloric acid solution immersion 4h-6h, respectively with water and alcohol rinse, the forced air drying under the conditions of 80 DEG C, the institute carbonized State charcoal.
Further, the inside of the charcoal has foaming structure, and the charcoal is selected from maize straw or kaoliang stalk； The metal sulfide is selected from MoS2、TiS2、WS2Or ZnS2。
Preferably, the biological carbon materials are maize straw, and the metal sulfide is MoS2。
Further, MoS is prepared2Reaction solution the step of be：Water, ethanol, oleic acid are mixed to form mixed liquor；By oil Sour sodium, Na2MoO4It is dissolved in thiocarbamide in the mixed liquor, adjusts pH to less than 3.0 with acid solution, form the MoS2It is anti- Answer liquid.
Further, MoS is being prepared2Reaction solution the step of in, water, ethanol, oleic acid volume ratio be 15:15:2；Oil Sour sodium, Na2MoO4Mass ratio with thiocarbamide is 1.6:1:0.9；PH to 1.0 is adjusted with 2.0mol/L aqueous hydrochloric acid solution.
Further, the synthesis step is：The charcoal carbonized is put into hollow out reaction vessel, then by institute State hollow out reaction vessel to put into reactor, the reaction solution of the metal sulfide is added into the reactor, make the gold The charcoal that the reaction solution of category sulfide flows into the hollow out reaction vessel, immersion has carbonized；Air blast, 150 DEG C -200 DEG C Heat 13h-30h；To obtained after heating product water and ethanol wash, 70 DEG C -90 DEG C drying；Again in anaerobic atmosphere, 500 DEG C of -1000 DEG C annealing 1h-5h, are cooled to room temperature, obtain the charcoal-metal sulfide composite.
Further, in the synthesis step, air blast, 180 DEG C of heating 24h；The product obtained after heating is spent Ionized water and ethanol wash, 80 DEG C of drying；Again argon atmosphere, 850 DEG C annealing 2h, be cooled to room temperature, obtain the charcoal- Metal sulfide composite.
Further, the hollow out reaction vessel includes：Match the lid and cup that cover, the lid and/or described Cup is provided with perforate, the size of the hollow out reaction vessel and the life carbonized being put into the hollow out reaction vessel Thing charcoal is adapted.
Further, the material of the hollow out reaction vessel is selected from glass or ceramics.
Second aspect, the present invention provide a kind of charcoal-metal sulfide composite, the charcoal-metal sulphur Compound composite is made using above-mentioned preparation method.
Further, the thickness of the growth of metal sulfide described in the charcoal-metal sulfide composite is 800nm-850nm。
Preferably, the thickness of the growth of metal sulfide described in the charcoal-metal sulfide composite is 831nm。
Further, the carbonization is：0.5h-4h is carbonized under the conditions of anaerobic atmosphere, 500 DEG C -1000 DEG C；Exist again After 0.5h-10h being soaked in acid solution, rinsing, drying, the charcoal carbonized.
Wherein, the anaerobic atmosphere refers to argon gas, helium, xenon or nitrogen atmosphere；The acid solution is that hydrochloric acid is water-soluble Liquid, aqueous sulfuric acid, phosphate aqueous solution or aqueous solution of nitric acid.
Preferably, the carbonization is：Charcoal 2h is carbonized under the conditions of argon atmosphere, 800 DEG C；Again in 0.1mol/L After aqueous hydrochloric acid solution immersion 4h-6h, respectively with water and alcohol rinse, the forced air drying under the conditions of 80 DEG C, the institute carbonized State charcoal.
Further, the inside of the charcoal has foaming structure, and the charcoal is selected from maize straw or kaoliang stalk； The metal sulfide is selected from MoS2、TiS2、WS2Or ZnS2。
Preferably, the biological carbon materials are maize straw, and the metal sulfide is MoS2。
Further, MoS is prepared2Reaction solution the step of be：Water, ethanol, oleic acid are mixed to form mixed liquor；By oil Sour sodium, Na2MoO4It is dissolved in thiocarbamide in the mixed liquor, adjusts pH to less than 3.0 with acid solution, form the MoS2It is anti- Answer liquid.
Further, MoS is being prepared2Reaction solution the step of in, water, ethanol, oleic acid volume ratio be 15:15:2；Oil Sour sodium, Na2MoO4Mass ratio with thiocarbamide is 1.6:1:0.9；PH to 1.0 is adjusted with 2.0mol/L aqueous hydrochloric acid solution.
Further, the synthesis step is：The charcoal carbonized is put into hollow out reaction vessel, then by institute State hollow out reaction vessel to put into reactor, the reaction solution of the metal sulfide is added into the reactor, make the gold The charcoal that the reaction solution of category sulfide flows into the hollow out reaction vessel, immersion has carbonized；Air blast, 150 DEG C -200 DEG C Heat 13h-30h；To obtained after heating product water and ethanol wash, 70 DEG C -90 DEG C drying；Again in anaerobic atmosphere, 500 DEG C of -1000 DEG C annealing 1h-5h, are cooled to room temperature, obtain the charcoal-metal sulfide composite.
Further, in the synthesis step, air blast, 180 DEG C of heating 24h；The product obtained after heating is spent Ionized water and ethanol wash, 80 DEG C of drying；Again argon atmosphere, 850 DEG C annealing 2h, be cooled to room temperature, obtain the charcoal- Metal sulfide composite.
Further, the hollow out reaction vessel includes：Match the lid and cup that cover, the lid and/or described Cup is provided with perforate, the size of the hollow out reaction vessel and the life carbonized being put into the hollow out reaction vessel Thing charcoal is adapted.
Further, the material of the hollow out reaction vessel is selected from glass or ceramics.
3rd aspect, the present invention also provide charcoal-metal sulfide composite wood made from a kind of above-mentioned preparation method The application of material, the charcoal-metal sulfide composite are used for the electrode material of lithium ion battery.
Compared with prior art, beneficial effects of the present invention are as follows：
First, charcoal-metal sulfide composite obtained by the present invention has excellent electric property.The present invention It is middle that there are the biological carbon materials of internal foam structure as charcoal base using maize straw or kaoliang stalk etc., after annealing, Charcoal base is placed on containing metal sulfide (as having the MoS of layer structure2) reaction solution in heat, make metal sulfide in charcoal base Surface carries out growth in situ, is achieved in metal sulfide (such as MoS2) modification so that composite has excellent electricity Learn performance (as having higher energy density and excellent cycle performance).In addition, after growing in the original location, further to composite wood Material carries out the high temperature anneal, it is improved its being applicable in lithium ion battery as the negative material of lithium ion battery Property.
Secondly, present invention gained composite cost is reasonable, the feature of environmental protection is good.The present invention using charing after maize straw or Kaoliang stalk etc. has the biological carbon materials of internal foam structure as charcoal base, has both been avoided that caused by when maize straw etc. is incinerated Environmental pollution, and can improve the by-product value of the materials such as maize straw, accomplish that resource sufficiently utilizes, thus can rationally reduce compound The production cost of material, while there is the higher feature of environmental protection.Moreover, due to reducing graphite, graphene, CNT etc. The application of carbon material, thus can avoid resource exhaustive exploitation and production process in pollution to environment.
Again, composite can simplify lithium ion battery manufacture craft in the present invention.The making of existing lithium ion battery Cheng Zhong, need to be specifically added into carbon black when sizing mixing, and composite of the present invention has had charcoal base in itself, therefore during sizing mixing The step of adding carbon black can be omitted, is achieved in the simplification of fabrication processing.
Finally, the present invention uses special hollow out reaction vessel, can ensure load capacity of the metal sulfide on charcoal, And can ensures the convenient operation of preparation process.On the one hand, in the preparation process of composite of the present invention, due to charcoal density compared with It is small, easily swim in above reaction solution, reaction solution can not be sufficiently impregnated, the growth for also resulting in metal sulfide is uneven.Therefore this Invention designs a kind of special hollow out reaction vessel, its size is adapted with being put into charcoal therein, plays fixed biology The effect of charcoal, make charcoal without larger floatability space；Set and open on the lid and/or cup of hollow out reaction vessel simultaneously Hole, reaction solution is set to can be good at soaking charcoal and charcoal because, without floating, thereby ensuring that reaction solution pair by fixed Charcoal is sufficiently impregnated, and ensures load capacity of the metal sulfide on charcoal.On the other hand, in the lid of hollow out reaction vessel Perforate is set on body and cup, can both facilitate reagent sufficiently to enter the hollow out reaction vessel, and can react terminate when, Hollow out reaction vessel is taken out, the liquid in container is flowed out therewith.With deionized water and ethanol wash several times, it is possible to complete Into simple to operate.
Brief description of the drawings
Fig. 1 is the structural representation of hollow out reaction vessel in the embodiment of the present invention；
Fig. 2 is the schematic diagram for loading the charcoal carbonized in the embodiment of the present invention in hollow out reaction vessel；
Fig. 3 is that the embodiment of the present invention one prepares each material photo in charcoal-metal sulfide composite material and swept Retouch electron microscope；
Fig. 4 is the synthesis schematic diagram of charcoal in the embodiment of the present invention-metal sulfide composite；
Fig. 5 is maize straw-MoS2Composite, MoS2Maize straw with charing is in 100mAg-1Current density Specific discharge capacity after lower 250 circulations；
Fig. 6 is maize straw-MoS2Composite is in 5000mAg-1Current density it is lower 1000 times circulation after quality Specific capacity；
Fig. 7 is maize straw-MoS2High rate performance of the composite under different current density conditions.
Embodiment
Prepare MoS2Reaction solution
15mL deionized waters, 15mL ethanol and 2mL oleic acid are mixed to form mixed liquor；By 1.6g enuatrols, 1.0g Na2MoO4It is dissolved in 0.9g thiocarbamides in above-mentioned mixed liquor, adjusts pH to 1.0 with 2.0mol/L aqueous hydrochloric acid solution, form MoS2's Reaction solution.In following embodiment, using the MoS of above-mentioned steps preparation2Reaction solution.
Hollow out reaction vessel
To ensure charcoal in MoS2Reaction solution in dipping effect, ensure MoS2The load capacity on charcoal, the present invention A kind of hollow out reaction vessel is specially designed, this hollow out reaction vessel is used in the preparation process of following examples.Such as Fig. 1 institutes Show, the hollow out reaction vessel includes the lid 1 and cup 2 that matching covers, and is equipped with some perforates on lid 1 and cup 2.Tool Body, the hollow out reaction vessel is glass material, can also use ceramic material, the lid of the hollow out reaction vessel according to the actual requirements The first perforate 31 is offered on body 1, the side wall upper part of cup 2 offers the second perforate 32, and the sidewall bottom of cup 2 offers Three perforates 33.The size of the hollow out reaction vessel is adapted (such as Fig. 2 institutes with being placed in the charcoal 100 therein carbonized Show), the charcoal position carbonized can be fixed so that MoS2Reaction solution soak the above-mentioned charcoal carbonized after, carbonized Charcoal there will not be larger space and swim in MoS2Reaction solution upper surface, thus can ensure soak effect, Jin Erbao Demonstrate,prove MoS2Growth in situ effect on charcoal, ensure MoS2Load capacity on charcoal.In addition, each the number of openings and opening The setting of hole site, it can either ensure that reaction solution smoothly enters hollow out reaction vessel, after and can ensures that reaction terminates, can conveniently take Go out the hollow out reaction vessel, and the liquid in the container is smoothly flowed out, the operation such as subsequent wash is also simple and convenient.
Specifically in the present invention, after the charcoal carbonized is placed in hollow out reaction vessel, by the hollow out reaction vessel It is put into the polytetrafluoroethylliner liner of reactor, and MoS is added into hollow out reaction vessel2Reaction solution, then by polytetrafluoroethyl-ne Alkene inner bag is put into the steel bushing of reactor, is tightened reactor and is reacted.
Embodiment one
Charing：Maize straw is cut into 3cm segment with pocket knife, is put into alumina crucible, argon atmosphere, 800 DEG C Under the conditions of carbonize 2h；After soaking 4h-6h in 0.1mol/L aqueous hydrochloric acid solutions again, respectively with deionized water and alcohol rinse number It is secondary, the forced air drying under the conditions of 80 DEG C, the maize straw carbonized.As shown in Figure 3 a, be the maize straw that does not carbonize and The comparison diagram of the maize straw carbonized.
Synthesis：The maize straw carbonized is put into hollow out reaction vessel, then hollow out reaction vessel is put to reactor In, MoS is added into reactor2Reaction solution, make MoS2Reaction solution flow into hollow out reaction vessel, the corn that immersion has carbonized Stalk；Air blast, 180 DEG C of heating 24h；To the product deionized water and ethanol wash that are obtained after heating for several times, 80 DEG C of drying；Again In argon atmosphere, 850 DEG C of annealing 2h, room temperature is cooled to, obtains maize straw-MoS2Composite, i.e. charcoal-metal vulcanization Thing composite.As shown in Figure 3 b, it is the MoS of stratiform2Nanometer sheet；As shown in Figure 3 c, the maize straw obtained for the present embodiment- MoS2The scanning electron microscope (SEM) photograph of composite；As shown in Figure 3 d, in the present embodiment, maize straw-MoS2MoS in composite2It is raw Long thickness is 831nm.
It is understood that the maize straw of charing is also referred to as CCS, maize straw-MoS2Composite can be also simply referred to as MoS2/CCS。
Embodiment two
Charing：Maize straw is cut into 3cm segment with pocket knife, is put into alumina crucible, argon atmosphere, 600 DEG C Under the conditions of carbonize 2h；After soaking 4h-6h in 0.1mol/L aqueous hydrochloric acid solutions again, respectively with deionized water and alcohol rinse number It is secondary, the forced air drying under the conditions of 80 DEG C, the maize straw carbonized.
Synthesis：The maize straw carbonized is put into hollow out reaction vessel, then hollow out reaction vessel is put to reactor In, MoS is added into reactor2Reaction solution, make MoS2Reaction solution flow into hollow out reaction vessel, the corn that immersion has carbonized Stalk；Air blast, 160 DEG C of heating 14h；To the product deionized water and ethanol wash that are obtained after heating for several times, 80 DEG C of drying；Again In argon atmosphere, 600 DEG C of annealing 2h, room temperature is cooled to, obtains maize straw-MoS2Composite, i.e. charcoal-metal vulcanization Thing composite.
Embodiment three
Charing：Maize straw is cut into 3cm segment with pocket knife, is put into alumina crucible, argon atmosphere, 700 DEG C Under the conditions of carbonize 2h；After soaking 4h-6h in 0.1mol/L aqueous hydrochloric acid solutions again, respectively with deionized water and alcohol rinse number It is secondary, the forced air drying under the conditions of 80 DEG C, the maize straw carbonized.
Synthesis：The maize straw carbonized is put into hollow out reaction vessel, then hollow out reaction vessel is put to reactor In, MoS is added into reactor2Reaction solution, make MoS2Reaction solution flow into hollow out reaction vessel, the corn that immersion has carbonized Stalk；Air blast, 200 DEG C of heating 18h；To the product deionized water and ethanol wash that are obtained after heating for several times, 80 DEG C of drying；Again In argon atmosphere, 800 DEG C of annealing 2h, room temperature is cooled to, obtains maize straw-MoS2Composite, i.e. charcoal-metal vulcanization Thing composite.
Example IV
Charing：Maize straw is cut into 3cm segment with pocket knife, is put into alumina crucible, argon atmosphere, 800 DEG C Under the conditions of carbonize 2h；After soaking 4h-6h in 0.1mol/L aqueous hydrochloric acid solutions again, respectively with deionized water and alcohol rinse number It is secondary, the forced air drying under the conditions of 80 DEG C, the maize straw carbonized.
Synthesis：The maize straw carbonized is put into hollow out reaction vessel, then hollow out reaction vessel is put to reactor In, MoS is added into reactor2Reaction solution, make MoS2Reaction solution flow into hollow out reaction vessel, the corn that immersion has carbonized Stalk；Air blast, 200 DEG C of heating 24h；To the product deionized water and ethanol wash that are obtained after heating for several times, 80 DEG C of drying；Again In argon atmosphere, 1000 DEG C of annealing 2h, room temperature is cooled to, obtains maize straw-MoS2Composite, i.e. charcoal-metal sulphur Compound composite.
Embodiment five
Charing：Maize straw is cut into 3cm segment with pocket knife, is put into alumina crucible, argon atmosphere, 800 DEG C Under the conditions of carbonize 2h；After soaking 4h-6h in 0.1mol/L aqueous hydrochloric acid solutions again, respectively with deionized water and alcohol rinse number It is secondary, the forced air drying under the conditions of 80 DEG C, the maize straw carbonized.
Synthesis：The maize straw carbonized is put into hollow out reaction vessel, then hollow out reaction vessel is put to reactor In, MoS is added into reactor2Reaction solution, make MoS2Reaction solution flow into hollow out reaction vessel, the corn that immersion has carbonized Stalk；Air blast, 180 DEG C of heating 24h；To the product deionized water and ethanol wash that are obtained after heating for several times, 80 DEG C of drying；Again In argon atmosphere, 800 DEG C of annealing 2h, room temperature is cooled to, obtains maize straw-MoS2Composite, i.e. charcoal-metal vulcanization Thing composite.
In the present invention, as shown in fig. 4 a, charcoal (maize straw of each embodiment as described above) is carbonized first； As shown in Figure 4 b, the metal sulfide (MoS of each embodiment as described above is then made2) be nucleated on charcoal；As illustrated in fig. 4 c, most Make metal sulfide growth in situ on charcoal eventually, form charcoal-metal sulfide composite.
Electrical performance testing
Preparation work electrode：By the maize straw-MoS in embodiment one2Composite and sodium carboxymethylcellulose according to 8:2 mass ratio mixing, by mixed sample coated in preparation work electrode on copper foil.Film is dried at 90 DEG C, pressure System.Then electrode discs are dried overnight in vacuum drying oven at 75 DEG C.
Button cell is assembled using above-mentioned working electrode：In CR2025 button cells, lithium metal is used as to electrode, 1mol/L is dissolved in the LiPF in ethylene carbonate-dimethyl carbonate6As electrolyte, polypropylene (pp) microporous barrier The barrier film of (Cellgard 2300) as battery, whole battery are assemblied in full of being assembled in high-purity argon glove box.At 25 DEG C Under the conditions of pass through Land CT2001A battery test systems (0.01V-3.0V) test loop performance and high rate performance.
With reference to shown in Fig. 5-Fig. 7, the button cell of assembling is tested in blue electric system, and it is respectively in 100mAg-1、 5000mA·g-1Current density under tested, obtained excellent chemical property and cycle performance.Wherein, using this hair Bright embodiment maize straw-MoS2The button cell of composite assembling is in 100mAg-1Current density under pass through 250 times 1060mAhg is remained in that after circulation-1Specific discharge capacity, and CCS, MoS is respectively adopted2Button cell is not assembled then not With excellent cycle performance and chemical property.In addition, using maize straw of the embodiment of the present invention-MoS2Composite assembles Button cell in 5000mAg-1Current density under by 1000 times circulation after remaining in that 512mAhg-1's Specific discharge capacity, present maize straw-MoS2The high energy density of composite and excellent cycle performance.Simultaneously as schemed Shown in 7, maize straw of the embodiment of the present invention-MoS2The button cell of composite assembling is carried out under different current densities Multiplying power is tested, and equally shows excellent chemical property.On the one hand, maize straw of the embodiment of the present invention-MoS2Composite wood Expect the button cell of assembling respectively in 100mAg-1、500mA·g-1、1000mA·g-1、2000mA·g-1、4000mA·g-1 Current density under circulate 5 times respectively after, remain to keep higher specific discharge capacity, show that it has excellent electrochemistry Energy；On the other hand, from higher 4000mAg-1Current density is down to 100mAg-1When being tested under current density, remain to Recover to the level of proper mass specific capacity, show the maize straw-MoS obtained by the present invention2Composite has higher steady It is qualitative, excellent performance.
It should be appreciated that above-described embodiment is merely to illustrate the present invention and is not intended to limit the scope of the invention. Simultaneously, it should also which understanding, after the technology contents of the present invention have been read, those skilled in the art can not depart from this On the premise of inventive principle, appropriate change is made to the condition in the technical scheme of invention and step, to realize final technical side Case, all these equivalents are equally fallen within the protection domain that the application appended claims are limited.

Claims (14)

1. the preparation method of a kind of charcoal-metal sulfide composite, it is characterised in that comprise the following steps：
Charing：Heating charing charcoal；
Prepare：The reaction solution of preparing metal sulfide；
Synthesis：The charcoal carbonized is immersed in the reaction solution, heated, obtains the charcoal-metal vulcanization Thing composite.
2. preparation method according to claim 1, it is characterised in that the carbonization is：Anaerobic atmosphere, 500 DEG C- 0.5h-4h is carbonized under the conditions of 1000 DEG C；After soaking 0.5h-10h in an acidic solution again, rinsing, drying, the institute carbonized State charcoal.
3. preparation method according to claim 2, it is characterised in that the carbonization is：Argon atmosphere, 800 DEG C Under the conditions of carbonize charcoal 2h；After soaking 4h-6h in 0.1mol/L aqueous hydrochloric acid solutions again, respectively with water and alcohol rinse, Forced air drying under the conditions of 80 DEG C, the charcoal carbonized.
4. preparation method according to claim 1, it is characterised in that：The inside of the charcoal has foaming structure, institute State charcoal and be selected from maize straw or kaoliang stalk；The metal sulfide is selected from MoS2、TiS2、WS2Or ZnS2。
5. preparation method according to claim 4, it is characterised in that：The biological carbon materials are maize straw, the gold Category sulfide is MoS2。
6. preparation method according to claim 5, it is characterised in that prepare MoS2Reaction solution the step of be：By water, second Alcohol, oleic acid are mixed to form mixed liquor；By enuatrol, Na2MoO4It is dissolved in the mixed liquor with thiocarbamide, is adjusted with acid solution PH forms the MoS to being less than 3.02Reaction solution.
7. preparation method according to claim 6, it is characterised in that：Preparing MoS2Reaction solution the step of in, water, second Alcohol, the volume ratio of oleic acid are 15:15:2；Enuatrol, Na2MoO4Mass ratio with thiocarbamide is 1.6:1:0.9；With 2.0mol/L's Aqueous hydrochloric acid solution adjusts pH to 1.0.
8. preparation method according to claim 1, it is characterised in that the synthesis step is：The life that will have been carbonized Thing charcoal is put into hollow out reaction vessel, then the hollow out reaction vessel is put into reactor, and institute is added into the reactor The reaction solution of metal sulfide is stated, has carbonized the reaction solution inflow hollow out reaction vessel of the metal sulfide, immersion The charcoal；Air blast, 150 DEG C of -200 DEG C of heating 13h-30h；To obtained after heating product water and ethanol wash, 70 DEG C of -90 DEG C drying；Again in anaerobic atmosphere, 500 DEG C of -1000 DEG C of annealing 1h-5h, room temperature is cooled to, obtains the charcoal-metal Sulfide composite.
9. preparation method according to claim 8, it is characterised in that：In the synthesis step, air blast, 180 DEG C of heating 24h；To obtained after heating product deionized water and ethanol wash, 80 DEG C drying；Again argon atmosphere, 850 DEG C annealing 2h, Room temperature is cooled to, obtains the charcoal-metal sulfide composite.
10. preparation method according to claim 8, it is characterised in that：The hollow out reaction vessel includes：What matching covered Lid and cup, the lid and/or the cup are provided with perforate, and the size of the hollow out reaction vessel is with being put into described engrave The charcoal carbonized in empty reaction vessel is adapted.
11. preparation method according to claim 10, it is characterised in that：The material of the hollow out reaction vessel is selected from glass Or ceramics.
A kind of 12. charcoal-metal sulfide composite, it is characterised in that：The charcoal-metal sulfide composite It is made using the preparation method described in any one of claim 1 to 11.
13. charcoal according to claim 12-metal sulfide composite, it is characterised in that：Charcoal-the gold It is 800nm-850nm to belong to the thickness that metal sulfide grows in sulfide composite.
A kind of 14. application of charcoal-metal sulfide composite, it is characterised in that：Charcoal-the metal sulfide is multiple Condensation material is made using the preparation method described in any one of claim 1 to 11, the charcoal-metal sulfide composite Electrode material for lithium ion battery.
CN201710919278.2A 2017-09-30 2017-09-30 Charcoal metal sulfide composite, its preparation method and application Pending CN107845788A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710919278.2A CN107845788A (en) 2017-09-30 2017-09-30 Charcoal metal sulfide composite, its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710919278.2A CN107845788A (en) 2017-09-30 2017-09-30 Charcoal metal sulfide composite, its preparation method and application

Publications (1)

Publication Number Publication Date
CN107845788A true CN107845788A (en) 2018-03-27

Family

ID=61661940

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710919278.2A Pending CN107845788A (en) 2017-09-30 2017-09-30 Charcoal metal sulfide composite, its preparation method and application

Country Status (1)

Country Link
CN (1) CN107845788A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110639469A (en) * 2018-06-26 2020-01-03 天津师范大学 Sulfide reduction modified biochar and preparation method and application thereof
CN111293295A (en) * 2020-01-13 2020-06-16 宁夏博尔特科技有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN115763757A (en) * 2022-11-30 2023-03-07 北京航空航天大学 Preparation method of biological carbon-molybdenum sulfide-tungsten sulfide compound and compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102440683A (en) * 2010-09-30 2012-05-09 刘宗熹 Beverage preparation device with automatic water filling function
CN104437361A (en) * 2014-10-24 2015-03-25 东华大学 Method for preparing functional biological carbon by in-situ impregnation
CN106058206A (en) * 2016-08-03 2016-10-26 复旦大学 Composite material of flower-like carbon-loaded MoS2 nanoparticles and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102440683A (en) * 2010-09-30 2012-05-09 刘宗熹 Beverage preparation device with automatic water filling function
CN104437361A (en) * 2014-10-24 2015-03-25 东华大学 Method for preparing functional biological carbon by in-situ impregnation
CN106058206A (en) * 2016-08-03 2016-10-26 复旦大学 Composite material of flower-like carbon-loaded MoS2 nanoparticles and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUNDONG WANG，ET AL.: ""Fe1−xS/C nanocomposites from sugarcane waste-derived microporous carbon for high-performance lithium ion batteries"", 《GREEN CHEM.》 *
XIANG LI，ET AL.: ""MoS2/cotton-derived carbon fibers with enhanced cyclic performance for sodium-ion batteries"", 《APPLIED SURFACE SCIENCE》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110639469A (en) * 2018-06-26 2020-01-03 天津师范大学 Sulfide reduction modified biochar and preparation method and application thereof
CN110639469B (en) * 2018-06-26 2022-03-22 天津师范大学 Sulfide reduction modified biochar and preparation method and application thereof
CN111293295A (en) * 2020-01-13 2020-06-16 宁夏博尔特科技有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN111293295B (en) * 2020-01-13 2021-08-03 博尔特新材料(银川)有限公司 Electrode material for waste rubber material-based secondary battery and preparation method thereof
CN115763757A (en) * 2022-11-30 2023-03-07 北京航空航天大学 Preparation method of biological carbon-molybdenum sulfide-tungsten sulfide compound and compound

Similar Documents

Publication Publication Date Title
CN106531456B (en) A kind of super capacitor material and its preparation and application based on CuCo2S4
CN105914374B (en) Composite material of nitrogen-doped carbon cladding selenizing molybdenum/graphene nucleocapsid array interlayer structure and its preparation method and application
CN108269982B (en) Composite material, preparation method thereof and application thereof in lithium ion battery
CN107342421B (en) High-content pyridine nitrogen-doped porous carbon negative electrode material, and preparation method and application thereof
CN109037664A (en) A kind of carbon-coated Mo of N doping2The preparation method of C/C functional composite material and its application in lithium-sulfur cell
CN107316979A (en) A kind of molybdenum disulfide/carbon fiber network flexible electrode and its preparation method and application
CN107799757A (en) A kind of MoS2/ nitrogen-doped carbon pipe composite and its preparation method and application
CN106356517A (en) Plant biomass carbon doped sulfur-nitrogen composite material of cathode of sodium ion battery and lithium ion battery and preparation method of plant biomass carbon doped sulfur-nitrogen composite material
CN109473606A (en) A kind of self-support functions interlayer and preparation method thereof for lithium-sulfur cell
CN105720236A (en) Foamed nickel self-supported flake-shaped Ni3P/C composite material for sodium ion battery negative electrode and preparation method for composite material
CN107275639B (en) The CoP/C classifying nano line and its preparation method and application of nano particle assembling
CN105870412A (en) Preparation method for poplar catkin based biomass carbon/sulfur composite material
CN110156081A (en) A kind of porous flake TiNb of negative electrode of lithium ion battery2O7Nanocrystalline preparation method
CN109326786A (en) A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application
CN107293710A (en) The preparation method of transition metal oxide/graphene composite material, negative electrode of lithium ion battery, lithium ion battery
CN104319402A (en) Preparation method for multi-layer carbon hollow sphere anode material
CN107845788A (en) Charcoal metal sulfide composite, its preparation method and application
CN107248569A (en) Using the methylimidazole cdicynanmide of 1 ethyl 3 antimony made from carbon source/nitrogen-doped carbon compound and its preparation method and application
CN103872331A (en) Aluminum cladding method for lithium ion positive electrode material
CN109768261A (en) A kind of novel cathode material for lithium ion battery N doping porous graphene preparation method and application
CN107069032A (en) A kind of preparation method of lithium ion battery hollow ball shape lithium-rich manganese-based anode material
CN111312999A (en) Preparation method of graphene-coated nickel-iron bimetallic sulfide sodium-ion battery negative electrode material
CN105585001A (en) Preparation technique of three-dimensional porous carbon and application of three-dimensional porous carbon in sodium-ion batteries
CN114314557A (en) Hard carbon material prepared from biomass waste and application of hard carbon material to sodium ion battery
CN104852029A (en) Lithium ion battery cathode material without binder and conductive agent and preparation method therefor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180327

RJ01 Rejection of invention patent application after publication