CN108172801A - A kind of method of porous carbon materials doping vario-property and application - Google Patents
A kind of method of porous carbon materials doping vario-property and application Download PDFInfo
- Publication number
- CN108172801A CN108172801A CN201711460489.0A CN201711460489A CN108172801A CN 108172801 A CN108172801 A CN 108172801A CN 201711460489 A CN201711460489 A CN 201711460489A CN 108172801 A CN108172801 A CN 108172801A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon materials
- transition
- doping vario
- property
- 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
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of method of porous carbon materials doping vario-property, the method use the Transition-metal dichalcogenide of redox graphene load, mix in porous carbon materials and carry out surface doping modification to porous carbon materials.The chemical adsorptivity having using the unsaturated dangling bonds of Transition-metal dichalcogenide and catalytic action can not only enhance the adsorptivity of porous carbon materials, alleviate " the shuttle effect " of more lithium sulfides, while may also speed up electrochemical reaction dynamic process.The porous carbon materials being modified using the Transition-metal dichalcogenide, for making battery electrode, electrode coating, barrier layer or battery diaphragm, to promote the chemical property of lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of method being modified to porous carbon materials and the porous carbons being modified according to this method
Material makes battery electrode or the purposes as electrode coating, barrier layer.
Background technology
With the continuous high speed development of society, the increasingly consumption of traditional fossil energy material is with giving environment during its use
The huge pollution brought makes human society meet with two big crisis of energy and environment simultaneously.The information age carries energy resource supply simultaneously
Go out many high requirements, be badly in need of the portable energy device of exploitation green cleaning to cope with various crises for 3C and power side
Face, be related to the small-sized high technology equipment such as mobile phone, computer, wearable device, wireless telecom equipment and new-energy automobile, nobody
The civilian, military equipment of the large size such as machine, unmanned monitoring ship, various detectors, it may be said that its use is ubiquitous.Battery is as current
One of most ripe energy storage technology takes into account safety, capacity, access times etc., wherein battery technology the most ripe to count lithium from
Sub- battery.But bottleneck period is faced by the development in more than 30 years, capacity is closely up to the theoretical upper limit.And modern society to battery not
Disconnected to propose higher requirement, the direction lower to high-energy high density, cost is developed.The lithium electric epoch afterwards, lithium-sulfur cell by
In with superelevation theoretical specific capacity and than the advantages such as energy, low cost, environmental-friendly, become in existing energy storage technology most
One kind of industrialization prospect, it is very potential to take over traditional lithium electricity and used on a large scale.
But lithium-sulfur cell limits lithium-sulfur cell due to its own structure, electrochemical reaction feature, also some problems
Commercialization process, such as：Larger, the more lithium sulfide of positive electrode volume change " wears in positive electrode poorly conductive, reaction process
Shuttle effect " etc..Wherein, maximum on battery performance influence is exactly " shuttle effect ", in the intermediate product packet of cell reaction process
All kinds of polysulfide anion are included to be soluble in electrolyte, can concentration difference and electric field effect between the electrodes back and forth, i.e. institute
It calls " shuttle effect ".This phenomenon can significantly increase the migration resistance of electrolyte ion, and the end of indissoluble can be deposited in positive and negative anodes
On the one hand product over cure lithium and lithium sulfide can thus cause the loss of active sulfur, on the other hand also cathode lithium can be produced
Raw certain corrosion failure, hinders the further reaction of anode sulphur.Therefore, the performance of lithium-sulfur cell is improved, " shuttle effect "
It is the key point that must pull against, while accelerate electrochemical reaction process to weaken " shuttle effect to a certain extent
Should ", promote the capacity and cyclical stability of lithium-sulfur cell.
To solve the above-mentioned problems, some scientific research personnel have carried out largely tasting in terms of the modification of porous carbon materials
Examination, and modified obtained porous carbon materials are applied in lithium-sulfur cell, for improving shuttle effect and promoting electrochemistry anti-
Answer rate, but more modification methods are complicated, cost is higher, not only bad for industrialized production, and the modified porous material of gained
After material is applied to battery, effect is also not satisfactory.
Invention content
In order to solve the above problem of the prior art, the present invention provides a kind of method of porous carbon materials doping vario-property, institute
State that method operating process is simple, at low cost, raw material are easy to get, conducive to industrialized production；The porous carbon that the method is obtained
Material is applied to battery, can obtain desired electrochemical performance.
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of method of porous carbon materials doping vario-property, the method use the transition metal of redox graphene load
Chalcogenide mixes and porous carbon materials is modified in porous carbon materials.
Transition-metal dichalcogenide general formula in the present invention is MX2(M=iron, cobalt, nickel, chromium, molybdenum, tungsten；X=sulphur, selenium,
Tellurium), but wherein transition metal can be unitary can also be it is polynary, chalcogen can also be polynary, such as
FeSySe1-yOr FeyNi1-ySe2Etc., but can also be similar Co more than being not limited to8S9, NiCo2S6, CuS, Cu2Mo
(SySe1-y)4Etc. the Transition-metal dichalcogenide (0 ＜ y≤1) of different stoichiometric ratios.
In an embodiment of the invention, the method is by graphene oxide dispersion, transition metal salt, sulfur family simple substance
Or the compound of two or more sulfur family simple substance mixtures or the chalcogen containing negative valency, three's mixing, under reducing agent existence condition,
Using hydro-thermal method, the Transition-metal dichalcogenide of redox graphene load is obtained by the reaction, then by the reduction-oxidation
Graphene-supported Transition-metal dichalcogenide incorporation porous carbon materials, mixed grinding obtain redox graphene load
The porous carbon materials of Transition-metal dichalcogenide doping vario-property；Wherein described transition metal salt for water-soluble transition metal salt or
Dissolve in the transition metal salt of the reducing agent.
In an embodiment of the invention, described method includes following steps：
1) pretreatment：
Graphene oxide, transition metal salt are configured to aqueous solution respectively, by sulfur family simple substance or two or more sulfur family simple substance
The compound of mixture or the chalcogen containing negative valency, which is dissolved in during reducing agent is matched, is made solution or suspension；
2) Transition-metal dichalcogenide of redox graphene load is prepared：
Each solution of step 1) is mixed, using hydro-thermal method, the transition metal of reaction generation redox graphene load
Chalcogenide, separation, drying obtain the Transition-metal dichalcogenide powder of dry redox graphene load.
In a feasible embodiment of the invention, the concentration of aqueous solution for the graphene oxide that the step 1) is prepared is
0.2~5.0mgml-1, the concentration of aqueous solution of the transition metal salt is 1~3molml-1, the transition metal salt is iron
Salt, chromic salts, molybdenum salt, tungsten salt, cobalt salt, nickel salt or vanadic salts.
Preferably, when the transition metal salt is molysite, the molysite is frerrous chloride, ferrous sulfate, ferrous nitrate, nitre
Sour iron or iron chloride.
In a feasible embodiment of the invention, sulfur family simple substance described in the step 1) is sulphur powder, selenium powder, tellurium powder；
The sulfur family simple substance mixture is sulphur selenium mixture, sulphur tellurium mixture, selen-tellurjum mixture or sulfur selenium tellurium mixture；It is described to contain negative valency
The compound of chalcogen is the organic matter or inorganic matter of the chalcogen containing negative valency；The reducing agent for ethylenediamine, hydrazine hydrate or
Hydroiodic acid；The sulfur family simple substance or the compound of two or more sulfur family simple substance mixtures or the chalcogen containing negative valency, solution are dense
It spends for 2~6molml-1。
The wherein compound of the chalcogen containing negative valency, including organic matter and inorganic matter, and organic matter such as thiocarbamide and its derivative
Object etc., inorganic matter such as vulcanized sodium, potassium sulfide etc. of the chalcogen containing negative valency.
In a feasible embodiment of the invention, the hydro-thermal method of the step 2) is reacted at 130 DEG C -220 DEG C, reaction
Between be 6~24 hours.Control reaction duration obtains the transition of the redox graphene load of different crystalline states and load capacity
Metal chalcogenide compound.
In a feasible embodiment of the invention, the middle drying of the step 2) is freeze-drying.
In a feasible embodiment of the invention, step 3) mixed grinding is further included：
The Transition-metal dichalcogenide powder incorporation of the redox graphene load for the drying that step 2) is obtained
In porous carbon materials, using high-energy ball milling or standard machinery grind redox graphene load transition metal sulfur family chemical combination
The porous carbon materials of object doping vario-property.
By controlling the time of grinding, the modified porous carbon material for it is expected particle size is obtained.
Wherein, the porous carbon materials in the step 3) can be used for any of the porous carbon materials of lithium-sulfur cell.
The invention also includes the Transition-metal dichalcogenide doping that above method is obtained to redox graphene load
Modified porous carbon materials, applied to porous carbon electrodes, anode coating, barrier layer or the diaphragm for making battery.
The beneficial effects of the invention are as follows：The present invention prepares to change using method that is simple, can industrializing large-scale production
The property-modifying additive of property porous carbon materials promotes the chemical property of lithium-sulfur cell.
The present invention is as carrier, carrying transition metal chalcogenide, by reduction-oxidation using redox graphene
Graphene-Transition-metal dichalcogenide complex mixes common lithium-sulfur cell and is obtained with porous carbon materials as dopant material
To modified porous carbon materials, the chemisorbed having using the unsaturated dangling bonds of Transition-metal dichalcogenide in ingredient
Property and catalytic action【The characteristic of Transition-metal dichalcogenide is recorded by pertinent literature, referring to illustrating citation inventory
Document 1-3】, can not only enhance adsorptivity of the porous carbon materials to polysulfide, while may also speed up electrochemical reaction
Dynamic process, thus " shuttle effect " can be weakened well and promote cycle performance of battery and capacity.Due to modified porous carbon
Material surface band has more highly polar key, has suction-operated to all kinds of polysulfide anion in electrochemical reaction process, can be with
Alleviate shuttle effect.The Transition-metal dichalcogenide doping that the redox graphene made using the method for the present invention is loaded changes
Property porous carbon materials can be used for making battery electrode, electrode coating, barrier layer or battery diaphragm promote the electrification of lithium-sulfur cell
Learn performance.On the one hand redox graphene as dispersible carrier, prevents sulfide from reuniting, while redox graphene is in itself
With active chemical property, can reinforcing material electric conductivity, further improve the electrochemical properties of modified porous carbon material.
Experiments verify that, had again using the lithium-sulfur cell of carbon material assembling modified porous made of the method for the present invention higher
Capacity and excellent cyclical stability, while the excellent in stability of material it is comprehensive relative to unmodified porous carbon materials battery
Performance is closed to significantly improve.
The present invention provides a new thinking and direction for the modification of battery porous carbon materials, while is lithium-sulfur cell
It is commercialized large-scale application and technical foundation is provided.
The doping modification method of the porous carbon materials of the present invention, operating process is simple, and raw material is porous carbon, elemental sulfur, selenium
With frerrous chloride etc., cost of material is less expensive, reaction condition mild (maximum temperature is only at 220 DEG C or so) therefore equipment requirement
It is low, production process is safe and reliable, method is simple, suitable for large-scale production application.
Description of the drawings
Fig. 1 is the method flow diagram of present pre-ferred embodiments；
Fig. 2 is that the Transition-metal dichalcogenide of redox graphene load that present pre-ferred embodiments 1 obtain is straight
Connect dried SEM figures；
Fig. 3 is the transition metal sulfur family loaded using redox graphene that present pre-ferred embodiments 1 finally obtain
The SEM figures of the porous carbon materials of compound doped modification.
Fig. 4 is that the electrode coated for the porous carbon materials slurrying of the modification of the present embodiment 1 is made experimental example and is not done any
The battery of the ordinary electrode assembling of processing is made to ratio, the cycle performance comparison chart in the case where 0.2C puts rate of charge.It can be seen that electricity
The cycle performance in pond is promoted apparent.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific embodiment, to this hair
It is bright to be described in detail.
The method of the porous carbon materials doping vario-property of the present invention is mainly characterized by using redox graphene load
Transition-metal dichalcogenide mixes and porous carbon materials is modified in porous carbon materials.
The method is specifically with by graphene oxide dispersion, transition metal salt, sulfur family simple substance or two or more sulfur family lists
The compound of matter mixture or the chalcogen containing negative valency, three's mixing, under reducing agent existence condition, using hydro-thermal method, reaction
Obtain the Transition-metal dichalcogenide (redox graphene-Transition-metal dichalcogenide of redox graphene load
Complex), the Transition-metal dichalcogenide for then loading the redox graphene mixes porous carbon materials, and mixing is ground
Mill obtains the porous carbon materials of the Transition-metal dichalcogenide doping vario-property of redox graphene load；Wherein described transition
Metal salt is water-soluble transition metal salt or the transition metal salt for dissolving in the reducing agent.Hydro-thermal method, also known as pyrohydrolytic method,
Refer to the predecessor of certain forms being placed in autoclave aqueous solution, hydro-thermal reaction is carried out under high temperature, condition of high voltage, then pass through
The milling method of the post processings such as separation, washing, dry.
Graphene oxide is generally aoxidized through strong acid by graphite and is obtained.There are mainly three types of the methods for preparing graphite oxide：
Brodie methods, Staudenmaier methods and Hummers methods.Wherein the timeliness of the preparation process of Hummers methods relatively preferably and
And it is also relatively safer in preparation process, it is current most common one kind.Hummers methods are prepared into graphite oxide during the present invention uses
Alkene.I.e. using the potassium permanganate under concentrated sulfuric acid environment with powdered graphite is oxidized react after, obtain having at edge for brown and spread out
It gives birth to carboxylic acid group and predominantly phenolic hydroxyl group and the graphite flake of epoxy group, this graphene layers can be through ultrasound or height in the plane
Shearing is vigorously stirred stripping as graphene oxide, and is formed stablize in water, the single-layer graphene oxide suspension of sundown.
Since conjugate network is by serious functionalization, graphene oxide thin slice has the speciality of insulation.Portion can be carried out through reduction treatment
Divide reduction, obtain the graphene platelet of chemical modification.Although the graphite ene product or redox graphene that finally obtain all have
There is the defects of more, lead to its electric conductivity not as good as original graphene, but the processing procedure of this oxidation-stripping-reduction can be effective
Ground allows insoluble powdered graphite to become to process and (be easy to participate in reacting in water and be modified) in water, provides making reduction
The approach of graphene oxide.
In the method for the present invention, graphene oxide is because containing the hydroxyl or carboxyl aoxidized, with hydrophily, thus being easy to match
Aqueous solution is made, then under the conditions of existing for transition metal salt, sulfur family simple substance, reducing agent, graphene oxide is reduced, simultaneously
Transition metal salt and reducing agent and sulfur family simple substance generation Transition-metal dichalcogenide, Transition-metal dichalcogenide be carried on by
On the graphene oxide of reduction, redox graphene-Transition-metal dichalcogenide complex is formed.
The method more specifically includes the following steps：
1) pretreatment：
Graphene oxide, transition metal salt are configured to aqueous solution respectively, by sulfur family simple substance or two or more sulfur family simple substance
Mixture or chalcogen, which are dissolved in the compound of negative valency during reducing agent is matched, is made solution or suspension；
2) Transition-metal dichalcogenide of redox graphene load is prepared：
Each solution of step 1) is mixed, using hydro-thermal method, the transition metal of reaction generation redox graphene load
Chalcogenide, separation, drying obtain the Transition-metal dichalcogenide powder of dry redox graphene load.
3) mixed grinding：
The Transition-metal dichalcogenide powder incorporation of the redox graphene load for the drying that step 2) is obtained
In porous carbon materials, obtain what redox graphene loaded using high-energy ball milling (or being fully ground using other mechanical grinders)
The porous carbon materials of Transition-metal dichalcogenide doping vario-property.
It is illustrated below with reference to specific embodiment, attached drawing and experiment baseline results：
With reference to shown in Fig. 1, including three pretreatment, Reaction Separation and mixed grinding steps, each step is as follows：
(1) pretreatment：It is 0.2~5.0mgml that graphene oxide is dissolved in compound concentration in deionized water-1GO
(graphene oxide) dispersion liquid；It is 1~3molml that frerrous chloride is dissolved in compound concentration in deionized water-1Aqueous solution；It will
It is 2~6molml that sulphur powder, which is dissolved in compound concentration in reducing agent ethylenediamine,-1Solution.Three of the above solution is pressed 30：10：3
Volume ratio mixes, and stirs evenly.
Wherein, frerrous chloride can use the replacements such as iron chloride, ferrous sulfate, ferrous nitrate, ferric nitrate, it is also possible to which other are water-soluble
Property transition metal salt replace, more even dissolve in the transition metal salt of the specific reducing agent.Wherein sulphur powder can be replaced
Selenium powder or sulphur selenium mixture or vulcanized sodium etc..Wherein reducing agent ethylenediamine (NH2-(C2H4)-NH2) it can be replaced hydrazine hydrate
(N2H4·H2) or hydroiodic acid (HI) solution etc. O.
(2) Transition-metal dichalcogenide of synthesis redox graphene load:
Three kinds of solution that (1) step prepares are mixed, are stirred evenly, using hydro-thermal method at 130~220 DEG C, reaction 12 is small
When.In other embodiments, the control reaction time, between 6~24 hours, different amounts of transition metal sulfur family was loaded to prepare
The redox graphene of compound.The substance filtering and washing that hydro-thermal reaction is generated, freeze-drying obtain reduction-oxidation graphite
The complex of the ferrous disulfide of alkene load.SEM schemes with reference to shown in Fig. 2, is two sulphur of redox graphene load obtained
Change the shape appearance figure after ferrous iron is directly dried (if the freeze-drying more preferable hole of pattern is more complete), material surface can be seen
See, there are many tiny micropores (see in black line circle), tiny microcellular structure (the broken particle for reduced size) can be with
After making the material and porous carbon mixed grinding it is easier to that Transition-metal dichalcogenide is made to evenly spread to porous carbon materials surface.
(3) mixing and high-energy ball milling:
By redox graphene derived above-ferrous disulfide complex and porous carbon materials (1~20):10 matter
Than mixing, high-energy ball milling 2h is uniformly mixed to get to the more of the ferrous disulfide doping vario-property loaded by redox graphene amount
Hole carbon material.The pattern of modified porous carbon material is observed under electron-microscope scanning instrument, as shown in figure 3, as a result, it has been found that the present embodiment is mixed
For the pore structure of miscellaneous modified porous carbon materials compared to porous carbon source materials, the variation of the two pore structure is little, only changes
The grain size of material becomes smaller, and Transition-metal dichalcogenide is distributed to the surface of porous carbon materials after property.
Wherein, porous carbon materials are available for any of lithium-sulfur cell porous carbon materials.High-energy ball milling is to utilize ball milling
Rotation or vibration, make hard sphere that raw material are carried out with strong shock, grinding and stirring, powder crushed as nano-scale particle
Method.Shown in Figure 4, the electrode of the porous carbon materials slurrying coating of the modification for the present embodiment 1 is made experimental example and is not done
The battery of the ordinary electrode assembling of any processing is made to ratio, the cycle performance comparison chart in the case where 0.2C puts rate of charge.
Experimental example：By the ferrous disulfide loaded according to the redox graphene that above-mentioned steps (1)-(3) obtain
(FeS2) doping vario-property porous carbon materials carry sulphur after obtain sulphur/porous carbon composite powder, take aforementioned powder 2.8g, with
SP, PVDF press 7：1：2 ratio mixings make slurry (solvent NMP), and (preparation of middle layer is only pressed with the load sulfur powder with PVDF
Ratio mixes, and solvent is still for NMP, coated in removing after dry on aluminium foil), slurry is coated in common batteries anode on aluminium foil
On, assembled battery, cathode is lithium piece, and it be volume ratio is 1 that electrolyte, which is electrolyte solvent,:1 1,3- dioxolanes (DOL)/second
The ether-based organic solvent of glycol dimethyl ether (DME), bis trifluoromethyl sulfimide lithium (LiTFSI) of the lithium salts for 1.0M, additive
LiNO for 1wt.%3(1.0M LiTFSI in DOL:DME=1:1Vol%with 1wt.%LiNO3), assembled battery follows
Ring performance test, the cycle performance in the case where 0.2C puts rate of charge.
Comparative example：With the anode of common uncoated porous carbon materials, according to electrolyte and cathode same as described above
Batteries assembling condition is waited, cycle performance test is done in assembled battery, the cycle performance in the case where 0.2C puts rate of charge.
In the case where other conditions are all identical, cyclical stability comparison is as shown in Figure 4.Discharge battery holds experimental example for the first time
It measures as 1457mAh/g, by 300 cycles, stills remain in 643mAh/g, coulombic efficiency is close to 100%.On the contrary, comparative example
Discharge battery capacity is 1291mAh/g for the first time, by 300 cycles, has arrived 485mAh/g, capacity retention ratio 37.57%,
Less than the 44.13% of experimental example.And it can be seen that the cell reaction of experimental example is more stable from coulombic efficiency.Provable reality as a result,
A battery is tested with higher capacity and better cyclical stability.
In conclusion the Transition-metal dichalcogenide doping vario-property of the invention by redox graphene load is porous
The method of carbon material, the modified porous carbon material being prepared compared to unmodified preceding porous carbon materials, can enhance porous carbon
The absorption of more lithium sulfides of the material to being generated in lithium-sulfur cell charge and discharge process so as to inhibit " shuttle effect ", promotes lithium sulphur electricity
The cyclical stability in pond；Meanwhile there is the porous carbon materials that Transition-metal dichalcogenide is modified catalytic action can accelerate electricity
Pond electrochemical reaction dynamic process promotes lithium-sulfur cell performance.The porous carbon materials of the modification are due to maintaining porous carbon original
The excellent pore structure of material, can be well by the more lithium sulfide absorption of intermediate product on porous carbon materials surface, and weakening " is shuttled
Effect ", and then promote cycle performance of battery and capacity.
The method of the present invention is simple for process, and working condition is mild, and equipment requirement is low, and process safety is reliable, low toxic and environment-friendly, system
The lithium-sulfur cell of standby modified porous carbon material assembling has higher capacity and excellent cyclical stability, while material is steady
It is qualitative excellent, it is improved relative to unmodified porous carbon materials battery comprehensive performance, is the commercial applications of lithium-sulfur cell
Provide technical support.
The application citation inventory：
[1]Zhang S S,Tran D T.Pyrite FeS2as an efficient adsorbent of lithium
polysulfide for improved lithium–sulfur batteries[J].Journal of Materials
Chemistry A,2016,4(12):4371-4374.
[2]Huang S,He Q,Chen W,et al.Ultrathin FeSe2Nanosheets:Controlled
Synthesis and Application as a Heterogeneous Catalyst in Dye-Sensitized Solar
Cells[J].Chemistry-A European Journal,2015,21(10):4085-4091.
[3]Chen Y,Xu S,Li Y,et al.FeS2Nanoparticles Embedded in Reduced
Graphene Oxide toward Robust,High-Performance Electrocatalysts[J].Advanced
Energy Materials,2017,7(19):1700482
Claims (10)
- A kind of 1. method of porous carbon materials doping vario-property, which is characterized in that the method is loaded using redox graphene Transition-metal dichalcogenide, mix porous carbon materials in doping vario-property is surface modified to porous carbon materials.
- 2. a kind of method of porous carbon materials doping vario-property according to claim 1, which is characterized in that the method be by Graphene oxide dispersion, transition metal salt, sulfur family simple substance or two or more sulfur family simple substance mixtures or chalcogen are in negative valency Compound, under reducing agent existence condition, using hydro-thermal method, redox graphene load is obtained by the reaction in three's mixing Transition-metal dichalcogenide, the Transition-metal dichalcogenide for then loading the redox graphene mix porous carbon Material, mixed grinding, obtain redox graphene load Transition-metal dichalcogenide doping vario-property porous carbon materials；Its Described in transition metal salt for water-soluble transition metal salt or dissolve in the transition metal salt of the reducing agent.
- 3. a kind of method of porous carbon materials doping vario-property according to claim 2, which is characterized in that the method includes Following steps：1) pretreatment：Graphene oxide, transition metal salt are configured to aqueous solution respectively, sulfur family simple substance or two or more sulfur family simple substance are mixed Object or chalcogen, which are dissolved in the compound of negative valency in reducing agent, is configured to solution or suspension；2) Transition-metal dichalcogenide of redox graphene load is prepared：Each solution of step 1) is mixed, using hydro-thermal method, the transition metal sulfur family of reaction generation redox graphene load Compound, separation, drying obtain the Transition-metal dichalcogenide powder of dry redox graphene load.
- 4. the method for a kind of porous carbon materials doping vario-property according to claim 3, which is characterized in that the step 1) is matched The concentration of aqueous solution of the graphene oxide of system is 0.2~5.0mgml-1, the concentration of aqueous solution of the transition metal salt for 1~ 3mol·ml-1, the transition metal salt is molysite, chromic salts, molybdenum salt, tungsten salt, cobalt salt, nickel salt or vanadic salts.
- 5. the method for a kind of porous carbon materials doping vario-property according to claim 4, which is characterized in that the molysite is chlorine Change ferrous iron, ferrous sulfate, ferrous nitrate, ferric nitrate or iron chloride.
- 6. the method for a kind of porous carbon materials doping vario-property according to claim 3, which is characterized in that in the step 1) The sulfur family simple substance is sulphur powder, selenium powder, tellurium powder；The sulfur family simple substance mixture is sulphur selenium mixture, sulphur tellurium mixture, selen-tellurjum mix Close object or sulfur selenium tellurium mixture；The chalcogen is in the organic matter or inorganic that the compound of negative valency is the chalcogen containing negative valency Object；The reducing agent is ethylenediamine, hydrazine hydrate or hydroiodic acid；The sulfur family simple substance or two or more sulfur family simple substance mixtures contain The compound of negative valency chalcogen, solution concentration are 2~6molml-1。
- 7. the method for a kind of porous carbon materials doping vario-property according to claim 3, which is characterized in that the step 2) At 130~220 DEG C, the reaction time is 6~24 hours for hydro-thermal method reaction.
- 8. the method for a kind of porous carbon materials doping vario-property according to claim 7, which is characterized in that the step 2) Middle drying is freeze-drying.
- 9. the method for a kind of porous carbon materials doping vario-property according to claim 3, which is characterized in that further include step 3) Mixed grinding：The Transition-metal dichalcogenide powder incorporation of the redox graphene load for the drying that step 2) is obtained In porous carbon materials, using high-energy ball milling grind redox graphene load Transition-metal dichalcogenide doping vario-property Porous carbon materials.
- 10. according to porous carbon materials prepared by a kind of method of any one of claim 1-9 porous carbon materials doping vario-properties, Applied to porous carbon electrodes, anode coating, barrier layer or the diaphragm for making battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711460489.0A CN108172801A (en) | 2017-12-28 | 2017-12-28 | A kind of method of porous carbon materials doping vario-property and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711460489.0A CN108172801A (en) | 2017-12-28 | 2017-12-28 | A kind of method of porous carbon materials doping vario-property and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108172801A true CN108172801A (en) | 2018-06-15 |
Family
ID=62519388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711460489.0A Pending CN108172801A (en) | 2017-12-28 | 2017-12-28 | A kind of method of porous carbon materials doping vario-property and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108172801A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037634A (en) * | 2018-08-01 | 2018-12-18 | 桑德集团有限公司 | Sulfur-based positive electrode material and preparation method thereof |
| CN109148861A (en) * | 2018-08-30 | 2019-01-04 | 广东工业大学 | Sulphur/iron oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell |
| CN109301182A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application |
| CN109742359A (en) * | 2019-01-07 | 2019-05-10 | 清华大学深圳研究生院 | Lithium sulfur battery anode material, preparation method, positive plate and lithium-sulfur cell |
| CN109755442A (en) * | 2019-02-28 | 2019-05-14 | 大连理工大学 | A kind of preparation method of network-like carbon load iron base compound material and its application on lithium-sulfur cell |
| CN109920955A (en) * | 2019-04-05 | 2019-06-21 | 浙江理工大学 | A kind of cementite compound Nano carbon fiber film and preparation method thereof applied to lithium-sulfur cell interlayer |
| CN110380019A (en) * | 2019-06-18 | 2019-10-25 | 华南农业大学 | A kind of metal chalcogenide compound for kalium ion battery/three-dimensional network level hole carbon composite and its preparation method and application |
| CN110660977A (en) * | 2019-08-23 | 2020-01-07 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
| CN111217355A (en) * | 2020-01-16 | 2020-06-02 | 中南大学 | Preparation and application of iron sulfide @ sulfur hybrid porous carbon anode precursor material and sulfur-carrying anode active material thereof |
| CN111883758A (en) * | 2020-07-29 | 2020-11-03 | 江西师范大学 | Three-dimensionally crosslinked composite Fe3O4/FeS/rGO and preparation method and application thereof |
| CN112018359A (en) * | 2020-08-18 | 2020-12-01 | 五邑大学 | NiTe2/MXene composite material and preparation method and application thereof |
| CN112201785A (en) * | 2019-07-08 | 2021-01-08 | 中国科学院上海硅酸盐研究所 | Lithium-philic and sulfur-philic co-doped two-dimensional layered graphitized porous carbon material and preparation method and application thereof |
| CN112234170A (en) * | 2020-08-13 | 2021-01-15 | 五邑大学 | MoTe2Mxene composite material and preparation method thereof |
| CN112952292A (en) * | 2020-12-23 | 2021-06-11 | 重庆大学 | Composite diaphragm capable of being used for metal lithium battery and metal sodium battery, and preparation method and application thereof |
| CN114759236A (en) * | 2022-04-28 | 2022-07-15 | 厦门大学 | Assembling and testing method of polysulfide flow battery based on membrane electrode |
| CN116002660A (en) * | 2022-12-28 | 2023-04-25 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206841A (en) * | 2015-08-28 | 2015-12-30 | 清华大学 | Pyritoides additive used in anode of lithium-sulfur battery |
| CN106299307A (en) * | 2016-09-30 | 2017-01-04 | 上海空间电源研究所 | A kind of lithium-sulfur cell high-performance positive electrode and preparation method thereof |
| CN106532144A (en) * | 2016-12-23 | 2017-03-22 | 中物院成都科学技术发展中心 | Ternary composite electrode material for thermal batteries and preparation method thereof |
-
2017
- 2017-12-28 CN CN201711460489.0A patent/CN108172801A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206841A (en) * | 2015-08-28 | 2015-12-30 | 清华大学 | Pyritoides additive used in anode of lithium-sulfur battery |
| CN106299307A (en) * | 2016-09-30 | 2017-01-04 | 上海空间电源研究所 | A kind of lithium-sulfur cell high-performance positive electrode and preparation method thereof |
| CN106532144A (en) * | 2016-12-23 | 2017-03-22 | 中物院成都科学技术发展中心 | Ternary composite electrode material for thermal batteries and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| J. D. LIU ET AL.: "Sulfur/mesoporous carbon composites combined with γ-MnS as cathode materials for lithium/sulfur batteries", 《IONICS》 * |
| SHENGJIE PENG ET AL.: "Cobalt Sulfide Nanosheet/Graphene/Carbon Nanotube Nanocomposites as Flexible Electrodes for Hydrogen Evolution", 《ANGEW. CHEM. INT. ED.》 * |
| WEIWEI YANG ET AL.: "Ferrous sulfide-assisted hollow carbon spheres as sulfur host for advanced lithium-sulfur batteries", 《CHEMICAL ENGINEERING JOURNAL》 * |
| ZHE YUAN ET AL.: "Powering Lithium−Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts", 《NANO LETT.》 * |
| 郑小双: "锂硫电池正极复合材料介孔碳/过渡金属硫化物（MnS）的制备及性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037634A (en) * | 2018-08-01 | 2018-12-18 | 桑德集团有限公司 | Sulfur-based positive electrode material and preparation method thereof |
| CN109148861A (en) * | 2018-08-30 | 2019-01-04 | 广东工业大学 | Sulphur/iron oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell |
| CN109301182A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application |
| CN109742359B (en) * | 2019-01-07 | 2021-07-02 | 清华大学深圳研究生院 | Lithium-sulfur battery positive electrode material, preparation method thereof, positive plate and lithium-sulfur battery |
| CN109742359A (en) * | 2019-01-07 | 2019-05-10 | 清华大学深圳研究生院 | Lithium sulfur battery anode material, preparation method, positive plate and lithium-sulfur cell |
| CN109755442A (en) * | 2019-02-28 | 2019-05-14 | 大连理工大学 | A kind of preparation method of network-like carbon load iron base compound material and its application on lithium-sulfur cell |
| CN109920955A (en) * | 2019-04-05 | 2019-06-21 | 浙江理工大学 | A kind of cementite compound Nano carbon fiber film and preparation method thereof applied to lithium-sulfur cell interlayer |
| CN109920955B (en) * | 2019-04-05 | 2021-12-14 | 浙江理工大学 | Iron carbide composite nano carbon fiber film applied to lithium-sulfur battery interlayer and preparation method thereof |
| CN110380019A (en) * | 2019-06-18 | 2019-10-25 | 华南农业大学 | A kind of metal chalcogenide compound for kalium ion battery/three-dimensional network level hole carbon composite and its preparation method and application |
| CN112201785A (en) * | 2019-07-08 | 2021-01-08 | 中国科学院上海硅酸盐研究所 | Lithium-philic and sulfur-philic co-doped two-dimensional layered graphitized porous carbon material and preparation method and application thereof |
| CN112201785B (en) * | 2019-07-08 | 2021-12-07 | 中国科学院上海硅酸盐研究所 | Lithium-philic and sulfur-philic co-doped two-dimensional layered graphitized porous carbon material and preparation method and application thereof |
| CN110660977A (en) * | 2019-08-23 | 2020-01-07 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
| CN111217355A (en) * | 2020-01-16 | 2020-06-02 | 中南大学 | Preparation and application of iron sulfide @ sulfur hybrid porous carbon anode precursor material and sulfur-carrying anode active material thereof |
| CN111217355B (en) * | 2020-01-16 | 2021-06-01 | 中南大学 | Preparation and application of iron sulfide @ sulfur hybrid porous carbon anode precursor material and sulfur-carrying anode active material thereof |
| CN111883758A (en) * | 2020-07-29 | 2020-11-03 | 江西师范大学 | Three-dimensionally crosslinked composite Fe3O4/FeS/rGO and preparation method and application thereof |
| CN112234170B (en) * | 2020-08-13 | 2021-09-28 | 五邑大学 | MoTe2Mxene composite material and preparation method thereof |
| CN112234170A (en) * | 2020-08-13 | 2021-01-15 | 五邑大学 | MoTe2Mxene composite material and preparation method thereof |
| CN112018359A (en) * | 2020-08-18 | 2020-12-01 | 五邑大学 | NiTe2/MXene composite material and preparation method and application thereof |
| CN112952292A (en) * | 2020-12-23 | 2021-06-11 | 重庆大学 | Composite diaphragm capable of being used for metal lithium battery and metal sodium battery, and preparation method and application thereof |
| CN114759236A (en) * | 2022-04-28 | 2022-07-15 | 厦门大学 | Assembling and testing method of polysulfide flow battery based on membrane electrode |
| CN116002660A (en) * | 2022-12-28 | 2023-04-25 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
| CN116002660B (en) * | 2022-12-28 | 2023-07-18 | 太原科技大学 | Preparation method of carbon-silicon composite material, carbon-silicon composite material and lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108172801A (en) | A kind of method of porous carbon materials doping vario-property and application | |
| Wang et al. | A metal-organic framework host for highly reversible dendrite-free zinc metal anodes | |
| Hou et al. | Ti 3 C 2 MXene as an “energy band bridge” to regulate the heterointerface mass transfer and electron reversible exchange process for Li–S batteries | |
| CN110247047B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| Ma et al. | Phase-transformed Mo4P3 nanoparticles as efficient catalysts towards lithium polysulfide conversion for lithium–sulfur battery | |
| CN105514378B (en) | A kind of imitative eucaryotic cell structure anode composite material of lithium sulfur battery and preparation method thereof | |
| CN107359303A (en) | Lithium-sulfur cell modification barrier film and preparation method thereof and the lithium-sulfur cell with the barrier film | |
| CN109755442A (en) | A kind of preparation method of network-like carbon load iron base compound material and its application on lithium-sulfur cell | |
| CN110233225B (en) | Modified diaphragm for lithium-sulfur battery and preparation method thereof | |
| CN111584804B (en) | Preparation method of lithium-sulfur battery diaphragm barrier layer based on two-dimensional nano clay | |
| Chen et al. | Bamboo-like Co3O4 nanofiber as host materials for enhanced lithium-sulfur battery performance | |
| Liao et al. | Highly dispersed Co-Mo sulfide nanoparticles on reduced graphene oxide for lithium and sodium ion storage | |
| CN108539171A (en) | A kind of preparation method of the zinc sulphide with graphene oxide compound and its application in lithium sulfur battery anode material | |
| Wu et al. | Encapsulation of sulfur cathodes by sericin-derived carbon/Co3O4 hollow microspheres for the long-term cyclability of lithium-sulfur batteries | |
| Zhang et al. | Facile synthesis of Mn2. 1V0. 9O4/rGO: a novel high-rate anode material for lithium-ion batteries | |
| Luo et al. | Interface engineering of metal phosphide on hollow carbons by Dual-template method for High-performance Lithium-sulfur batteries | |
| Yu et al. | Promoting polysulfide redox kinetics by Co9S8 nanoparticle-embedded in N-doped carbon nanotube hollow polyhedron for lithium sulfur batteries | |
| CN112635726A (en) | Bentonite-based composite material and preparation method and application thereof | |
| Fang et al. | MoS2/G interlayer as a polysulfide immobilization apparatus for high-performance lithium–sulfur batteries | |
| Chen et al. | Application of ZIF-8 coated with titanium dioxide in cathode material of lithium-sulfur battery | |
| Qiu et al. | Three-dimensional carbon foam decorated with SnO2 as multifunctional host for lithium sulfur batteries | |
| Zhao et al. | Rational design of Co3S4-CoN@ N-doped carbon hollow spheres with polar S-Co-N bond as bifunctional host materials for lithium-sulfur batteries | |
| Liu et al. | Layered double hydroxides used as the sulfur hosts for lithium-sulfur batteries and the influence of metal composition on their performance | |
| Zhang et al. | Rational design of walnut-like ZnO/Co 3 O 4 porous nanospheres with substantially enhanced lithium storage performance | |
| Chen et al. | Encapsulation of sulfur inside micro-nano carbon/molybdenum carbide by in-situ chemical transformation for high-performance Li-S batteries |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180615 |