CN105406027A - Complex formed from aromatic nitrile compound polymerization product and sulfur, preparation method and uses thereof - Google Patents
Complex formed from aromatic nitrile compound polymerization product and sulfur, preparation method and uses thereof Download PDFInfo
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- CN105406027A CN105406027A CN201410458176.1A CN201410458176A CN105406027A CN 105406027 A CN105406027 A CN 105406027A CN 201410458176 A CN201410458176 A CN 201410458176A CN 105406027 A CN105406027 A CN 105406027A
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Abstract
The invention relates to a complex formed from an aromatic nitrile compound polymerization product and sulfur, a corresponding preparation method, and applications of the complex as a lithium-sulfur battery positive electrode material. According to the present invention, the polymerization product obtained through aromatic nitrile compound monomer polymerization has characteristics of good electric conductivity, high specific surface area, rich pore content, and nitrogen doping, such that the composite material formed from the polymerization product and the sulfur has the high sulfur content, and the sulfur distribution is uniform; with the application of the composite material as the lithium-sulfur battery positive electrode material, the excellent electrochemical property is provided; and the source of the aromatic nitrile compound is rich, and the large-scale preparation of the polymer is easily achieved, such that the application of the complex formed from the aromatic nitrile compound polymerization product and the sulfur in the lithium-sulfur battery provides the great commercial application prospects.
Description
Technical field
The invention belongs to electrochemical field, particularly the compound that formed of aromatic nitrile compounds polymerizate and sulphur and corresponding preparation method and purposes.
Background technology
Along with the progress of science and technology, the energy density of people to battery is had higher requirement, and lithium-sulfur cell theoretical energy density reaches 2600wh/kg (theoretical specific capacity of elemental sulfur is 1680mAh/g).In addition, compared with other battery, sulphur has rich reserves, environmental friendliness, the advantage such as cheap, therefore causes scientific research circle and industrial quarters to pay close attention to widely.
But lithium-sulfur cell still exists some serious problems to be needed to solve, and to show in lithium-sulfur cell performance mainly: cycle performance is poor, capacity attenuation is fast.Reason mainly contains three aspects: many lithium sulfides that, lithium-sulfur cell charge and discharge process produces are soluble in electrolyte, electrode active material is reduced, and the many lithium sulfides dissolved are through barrier film and negative reaction, generate the insoluble and lithium sulfide of poorly conductive, cause the internal resistance of cathode of lithium burn into increase, and then cause capacity attenuation, cycle performance to be deteriorated; Two, the ionic conductivity of sulphur and electron conduction all very low, cause the utilance of sulphur in electrode very low; Three, sulphur is in charge and discharge process, bulk effect large (volume deformation is up to 22%), and sulfur electrode inside may be made to produce micro-crack.Existence and nonconducting lithium sulfide of this micro-crack destroy the globality of electrode in the generation of cracks, finally exacerbate the decay of capacity.
For the problems referred to above, people take different solutions, comprise: the contour conductive network of material with carbon element of porous carbon, Graphene, carbon pipe, finishing and sulphur compound, increase its conductivity and interaction (NatureMaterials, 2009.8 (6): p.500-506 with sulphur; Naturecommunications, 2014.5:p.3410-3410; AdvancedMaterials, 2014,10.1002/adma.201401243.ACSAppliedMaterials & Interfaces, 2014.6 (11): p.8789-95.); Sulphur Surface coating suppresses polysulfide to dissolve (NatureCommunications, 2013.4:p.1331; ProceedingsoftheNationalAcademyofSciences, 2013.110 (18): p.7148-53.); Closed by chemical bond and sulfide linkage, prevent it from dissolving (NatureChemistry, 2013.5 (6): p.518-524.); With the battery diaphragm of modified with functional group, stop the polysulfide dissolved to negative pole diffusion (Energy & EnvironmentalScience, 2014.7 (1): p.347.); Also have the method for protection cathode of lithium general at present: add a small amount of lithium nitrate in the electrolytic solution, make cathode of lithium surface form passivation layer.
In the above-mentioned methods, material with carbon element (comprising the material with carbon element of modification) and sulphur react or " carbon/sulphur " composite material of being compounded to form is the lithium sulfur battery anode material be widely studied and applied at present further.Main cause is because material with carbon element good conductivity, as the passage of ion and electronics, can therefore solve the nonconducting problem of elemental sulfur itself; In addition, material with carbon element abundance, structural controllability (comprises the pore structure of material by force, and surface texture), and with sulphur has certain interaction (comprising physisorption and chemical bonding effect), the loss of sulphur in charge and discharge process therefore can be reduced to a certain extent; In addition, material with carbon element has certain pore structure and toughness, can reduce the bulk effect in sulphur charge and discharge process.Show on chemical property, carbon/sulphur composite material can improve specific capacity and the cyclical stability of lithium-sulfur cell greatly.
But, so far, in the prior art, the not compound that formed of aromatic nitrile compounds polymerizate and sulphur and corresponding preparation method and can be used as the report of lithium sulfur battery anode material.
Summary of the invention
An object of the present invention is to provide a kind of compound; Two of object of the present invention is the preparation method providing described compound; Three of object of the present invention is that described compound is provided as the application of the positive electrode of lithium-sulfur cell.The aromatic nitrile compounds polymerizate comprised in compound of the present invention and sulphur (hereinafter referred to as " polymer/sulphur "), abundant raw material source, cost is lower, preparation method is simple, therefore large-scale preparation can be realized, and it shows excellent performance as lithium sulfur battery anode material, therefore has huge commercial application prospect.
For reaching one of above-mentioned purpose, the present invention adopts following technical scheme:
A kind of compound, it is the compound formed by aromatic nitrile compounds polymerizate and sulphur.
For compound of the present invention, it has the carbon skeleton of porous network structure.Described porous network structure can increase the specific area of aromatic nitrile compounds polymerizate, thus can be conducive to and more substantial sulphur simple substance compound (and improving element sulphur ratio shared in " polymer/sulphur "), thus can the energy density of corresponding raising lithium-sulfur cell.
For compound of the present invention, the specific area of described aromatic nitrile compounds polymerizate is 400 ~ 3000m
2/ g is such as 450m
2/ g, 600m
2/ g, 800m
2/ g, 1000m
2/ g, 1200m
2/ g, 1400m
2/ g, 1600m
2/ g, 1800m
2/ g, 2000m
2/ g, 2200m
2/ g, 2400m
2/ g, 2600m
2/ g, 2800m
2/ g or 3000m
2/ g etc., pore-size distribution is 0.4 ~ 20nm, such as, be 0.4 ~ 3nm, 0.4 ~ 5nm, 0.4 ~ 7nm, 0.4 ~ 9nm, 0.4 ~ 11nm, 0.4-13nm, 0.4-15nm, 0.4-17nm, 0.4-19nm, 0.4-20nm etc.In the present invention, described aromatic nitrile compounds is polymerized the specific area of the polymerizate obtained and pore-size distribution and adopts the isothermal adsorption-desorption method of nitrogen under 77K to measure, and calculates its specific area, calculate its pore-size distribution by DFT method by BET method.
For compound of the present invention, comprising mass ratio in the carbon skeleton of described aromatic nitrile compounds polymerizate is 2.1 ~ 18.4%, such as 2.1%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18% or 18.4% etc., be preferably the atom N of 3.4 ~ 12.6%.The mass ratio of described atom N refers to: the mass percentage content that atom N is shared in polymerizate.
In the present invention, selectable wider range of kind of described aromatic nitrile compounds, the heteroaromatic compounds that the aromatic compound that can replace for cyano group and/or cyano group replace.Because containing cyano group, so described aromatic nitrile compounds is easily polymerized (cyano group trimerization reaction) and rearrangement reaction (the further cross-coupling reaction under high temperature), again because it contains aromatic rings or fragrant heterocycle, so polymerization, reset after product structure be the large π architecture of continuous print, be conducive to the transmission of electronics.
Preferably, the aromatic compound that described cyano group replaces is cyano group benzene and/or cyanobiphenyl, and the number of preferred cyano substituent is 2-3.
Preferably, the heteroaromatic compounds that described cyano group replaces is the hexa-atomic heteroaromatic compounds that cyano group replaces, and the hetero-atom in hexa-atomic heteroaromatic compounds is nitrogen-atoms, is preferably the pyridine that cyano group replaces.
Preferably, in described cyano group replacement, the number of cyano substituent is 2-3.
For compound of the present invention, described aromatic nitrile compounds includes but not limited to, para-Phthalonitrile (p-DCB), isophthalodinitrile (m-DCB), phthalonitrile (o-DCB), benzonitrile, 1,3,5-tricyano benzene (TCB), 2,6-dicyanopyridine (2,6-DCP), 2,4-dicyanopyridine (2,4-DCP) or 4, the mixture of any one or at least two kinds in 4 '-DCNBP (DCBP).The mixture of described mixture such as para-Phthalonitrile and isophthalodinitrile, the mixture of phthalonitrile and benzonitrile, 1, 3, 5-tricyano benzene, 2, 6-dicyanopyridine and 2, the mixture of 4-dicyanopyridine, 4, 4 '-DCNBP, the mixture of para-Phthalonitrile and isophthalodinitrile, phthalonitrile, benzonitrile, 1, 3, 5-tricyano benzene and 2, the mixture of 6-dicyanopyridine, 2, 4-dicyanopyridine and 4, the mixture of 4 '-DCNBP, para-Phthalonitrile, isophthalodinitrile, phthalonitrile, benzonitrile and 1, 3, the mixture of 5-tricyano benzene, 2, 6-dicyanopyridine, 2, 4-dicyanopyridine and 4, the mixture etc. of 4 '-DCNBP.
For compound of the present invention, the preparation method of described aromatic nitrile compounds polymerizate can adopt any known prior art, or adopts following preparation method, comprises the steps:
Under the polymerization conditions, the metal salt contacts of aromatic nitrile compounds and melting is carried out polymerization reaction, obtains polymerizate.
In the present invention, the effect of the slaine of described melting is in the polymerization as solvent and catalyst, and do not decompose as long as it can keep stable in the molten state, therefore the selectable range of the kind of described slaine is wider.Preferably, described slaine is metal halide, more preferably metal chloride, further the mixture of preferred any one or at least two kinds in zinc chloride, copper chloride, frerrous chloride or manganese chloride, most preferably zinc chloride.
The selectable range of the consumption of described slaine is wider, preferably, the mol ratio of described slaine and described aromatic nitrile compounds is 0.5 ~ 10:1, such as 1:1,1.5:1,2:1,2.5:1,3:1,3.5:1,4:1,4.5:1,5:1,5.5:1,6:1,6.5:1,7:1,7.5:1,8:1,8.5:1,9:1 or 9.5:1 etc., more preferably 1 ~ 5:1.
In the present invention, the temperature that described polymeric reaction condition generally comprises contact and the time contacted, the temperature of described contact only need ensure that described slaine is in molten condition, therefore the temperature of described contact can be the boiling point of fusing point to slaine of described slaine, and it does not comprise the boiling point of slaine.The selectable range of the time of described contact is wider, such as described time of contact is 0.5 ~ 80 hour, such as 1 hour, 4 hours, 8 hours, 12 hours, 16 hours, 19 hours, 20 hours, 24 hours, 28 hours, 32 hours, 36 hours, 40 hours, 44 hours, 48 hours, 52 hours, 56 hours, 60 hours, 64 hours, 68 hours, 72 hours or 76 hours etc.In order to ensure the conductivity of material, need certain reaction time, the general pyroreaction time can be very short, and low temperature needs the time longer.But the industrial time is longer, and cost is higher, therefore, the reaction time can not be oversize, and therefore, described time of contact is preferably 1 ~ 20 hour, more preferably 1 ~ 5 hour.
Be that molten condition is temperature required general higher owing to keeping slaine, under opening system, reaction may produce some factors of instability because of the difference of place environment.Under preferable case, described contact is carried out under vacuum or inert atmosphere, thus better avoids the destabilizing factor brought because temperature is high.
Described inert atmosphere can be the gas do not reacted with slaine and the polymerizate of described aromatic nitrile compounds, melting, and preferred described inert atmosphere is selected from the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas, Krypton or xenon.
Preferably, described contact is carried out in closed environment, and described enclosed system not only can avoid the high destabilizing factor brought of temperature, can also avoid the loss because temperature is high, volatility of raw material being caused in open system, and can certain pressure be kept, be conducive to the carrying out reacted.
In the present invention, the preparation method of described polymerizate can also comprise and carries out a series of post-processing step to described polymerizate, comprises cooling, washing and dry.
The conventional method that described cooling can adopt those skilled in the art to expect, described cooling can for being cooled to room temperature (as 20-30 DEG C).The object of described washing is the Small molecular being soluble in Conventional solvents removing rearrangement reaction and/or the decomposition reaction generation occurred in described slaine and polymerization process, and described washing can use this area conventional reagent such as water, hydrochloric acid or oxolane.Described drying purpose is the reagent of removing washing, and therefore can adopt the conventional method that those skilled in the art can expect, as natural drying or oven dry etc., baking temperature can be 20 ~ 300 DEG C.
For compound of the present invention, the mass ratio of sulphur described in compound and polymerizate is 3/7 ~ 9/1, is preferably 4/6 ~ 7/3.
For reaching above-mentioned purpose two, the present invention adopts following technical scheme:
A preparation method for compound of the present invention, comprise the steps: aromatic nitrile compounds polymerizate and sulphur mixing, reaction, obtains the compound of polymerizate and sulphur.
The step of above-mentioned polymerizate and sulphur mixing is Routine Test Lab and industrial general mixed method, for preparation method of the present invention, described mixing can be pulverized and mixed or any one in ball milling for concussion mixing, mortar grinder mixing, pulverizer, preferably concussion mixing and/or ball milling.
Preferably, the mass ratio of described sulphur and polymerizate is 3/7 ~ 9/1, is preferably 4/6 ~ 7/3.
Preferably, described reaction is carried out in inert atmosphere or vacuum environment.
Preferably, described inert gas is selected from the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas, Krypton or xenon.
Preferably, the temperature of described reaction is 150 DEG C ~ 500 DEG C, preferably 150 DEG C ~ 350 DEG C; Comprise and react the regular hour at the same temperature, such as react at 160 DEG C 2 hours, react 1 hour etc. at 450 DEG C, or react the different time at different temperature, such as: 150 DEG C of reaction 3h, then 350 DEG C of reaction 2h; 150 DEG C of reaction 10h, then 300 DEG C of reaction 1h etc.
Preferably, the time of described reaction is 1h ~ 40h, preferred 3h ~ 12h; Comprise and react the regular hour at the same temperature, such as react at 160 DEG C 2 hours, react 1 hour etc. at 450 DEG C, or react the different time at different temperature, such as: 150 DEG C of reaction 3h, then 350 DEG C of reaction 2h; 150 DEG C of reaction 10h, then 300 DEG C of reaction 1h etc.
Or the preparation method of another kind of compound of the present invention, comprises the steps: that aromatic nitrile compounds monomer, sulphur and polymerisation catalysts mix, reaction, obtains the compound of polymerizate and sulphur.
The step of above-mentioned polymerizate and sulphur mixing is Routine Test Lab and industrial general mixed method, for preparation method of the present invention, described mixing can be pulverized and mixed or any one in ball milling for concussion mixing, mortar grinder mixing, pulverizer, preferably concussion mixing and/or ball milling.
Preferably, the mass ratio of described sulphur and aromatic nitrile compounds monomer is 3/7 ~ 9/1, is preferably 4/6 ~ 7/3.Preferably, described reaction is carried out in inert atmosphere or vacuum environment.
Preferably, the mol ratio of described polymerisation catalysts and described aromatic nitrile compounds monomer is 1-10:1, is preferably 2-8:1.
Preferably, described polymerisation catalysts is metal halide, is preferably metal chloride, the mixing of a kind of more preferably in zinc chloride, copper chloride, frerrous chloride and manganese chloride or at least two kinds.Preferably, described inert gas is selected from the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas, Krypton or xenon.
Preferably, the temperature of described reaction is 280 DEG C ~ 600 DEG C, preferably 280 DEG C ~ 400 DEG C.
Preferably, the time of described reaction is 1h ~ 40h, preferred 3h ~ 12h.
Three of object of the present invention is the purposes providing compound of the present invention, and it can be used as positive electrode.
Preferably, described compound is used as the positive electrode of lithium-sulfur cell, sodium-sulphur battery or magnesium sulphur battery.
Preferably, the mass ratio of described compound in positive electrode is 70% ~ 95%, preferably 80% ~ 90%.
Preferably, the coating thickness of described positive electrode is about 10 μm ~ 80 μm, is preferably 20 μm ~ 40 μm; Surface density is about 1mg/cm
2~ 8mg/cm
2, be preferably 2mg/cm
2~ 4mg/cm
2.
Compound provided by the invention be used as the detailed process in electrode material can be as follows:
Polymer/sulphur, conductive additive, binding agent and volatile solvent are together mixed, is then applied to the positive pole as lithium-sulfur cell on collector.
Wherein, compound shared mass ratio in the mixture of compound and conductive additive and binding agent composition is 70% ~ 95%, preferably 80% ~ 90%.
Wherein, conductive additive can be that conductive acetylene is black, one or more in class graphite additive, carbon nano-tube, Graphene; Binding agent can be one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC)/butadiene-styrene rubber (SBR), esters of acrylic acid (LA series) binding agent; Volatile solvent can be one or more in NMP, water, ethanol.Described hybrid mode can be laboratory, a battery industry conventional mixing method, preferred planetary stirring machine, ball mill batch mixing.
Wherein, the thickness of coating can be about 10 μm ~ 80 μm, is preferably 20 μm ~ 40 μm; Surface density is about 1mg/cm
2~ 8mg/cm
2, be preferably 2mg/cm
2~ 4mg/cm
2.Described collector can commonly use collector for battery industry, comprises Copper Foil, aluminium foil, copper mesh, aluminium net etc., preferred aluminium foil.
Wherein, electrolyte in battery is conventional lithium-sulfur cell, sodium-sulphur battery or the electrolyte of magnesium sulphur battery or the conventional electrolyte of lithium ion battery, as being ethers electrolyte, the LiTFSI (two (trifluoromethane sulfonic acid) imine lithium) of such as 1mol/L is dissolved in DOL (dioxolanes)/DME (1 that volume ratio is 1/1,2-dimethoxy-ethane), wherein add a small amount of (mass percent is 1% ~ 5%) LiNO
3; Or the electrolyte of carbonic acid lipid, the LiPF of such as 1M
6be dissolved in EC (ethylene carbonate)/DMC (dimethyl carbonate) etc. that volume ratio is 1/1.
Negative material can be commonly used for the lithium battery after lithium metal or lithiumation as the used in battery negative pole of positive electrode, such as: the active carbon etc. of the graphite of lithiumation, the silica-base material of lithiumation, lithiumation with above-mentioned compound; Preferably, select lithium metal as the negative material of battery.
Compared with the prior art, the present invention has following beneficial effect:
Aromatic nitrile compounds polymerizate provided by the invention has the carbon backbone structure of high-specific surface area, high conductivity (conductivity is 0.01 ~ 2S/m), nitrogen content enrich, therefore the composite material that itself and sulphur are formed has high sulfur content (weight ratio can reach 90%), and element sulphur is evenly distributed.
Using composite material of the present invention as lithium sulfur battery anode material, show excellent specific capacity (capacity can reach 1200mAh/g) and cyclical stability (100 circulation volume conservation rates are 80%).
In addition, aromatic nitrile compounds abundance, simple and the high-efficiency environment friendly of preparation process, and being easy to large-scale preparation, the compound (" polymer/sulphur ") that therefore this type of aromatic nitrile compounds polymerizate and sulphur are formed is applied to battery and especially has huge commercial application prospect in lithium-sulfur cell, sodium-sulphur battery or magnesium sulphur battery.
Accompanying drawing explanation
Fig. 1 is that polymerizate isothermal nitrogen adsorption desorption curve and corresponding DFT model under 77K of aromatic nitrile compounds para-Phthalonitrile in embodiment 4 calculates gained graph of pore diameter distribution;
Fig. 2 is " polymer/sulphur " (75%S content) transmission electron microscope (TEM) light field figure (left side) in embodiment 4, corresponding TEM details in a play not acted out on stage, but told through dialogues figure (upper right), element sulphur distribution map (bottom right);
Fig. 3 is the thermogravimetric test result of " polymer/sulphur " in embodiment 4;
Fig. 4 is the X-ray diffraction test of " polymer/sulphur " in embodiment 4;
Fig. 5 be in embodiment 4 " polymer/sulphur " (75%S content) as the lithium-sulfur cell performance of the positive pole of lithium-sulfur cell;
Fig. 6 be in embodiment 4 " polymer/sulphur " (75%S content) as the lithium-sulfur cell high rate performance test result of the positive pole of lithium-sulfur cell.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
Embodiment 1
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous zinc chloride 0.53g (3.9mmol) mixes, and be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, react 0.5 hour at 700 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 10.3%, and specific area is 1710m
2/ g, pore size distribution range is: 0.5 ~ 4nm.
Mixed according to the ratio of 1:9 by above-mentioned polymer 500mg and S, then 155 DEG C of heating 1h in argon gas atmosphere, obtain " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 7:2:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 10 microns, and (surface density is about 1mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiTFSI of 1mol/L is that in the DOL/DME of 1/1, (wherein adding mass percent is 1%LiNO in volume ratio
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 2
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous zinc chloride 10.64g (78mmol) mixes, and be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, react 80 hours at 700 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.In the oxygen reduction catalyst obtained, nitrogen element content is 2.1%.Specific area is 2980m
2/ g, pore-size distribution is: 0.4 ~ 10nm.
Above-mentioned polymer and S are mixed according to the ratio of 1:4, then 155 DEG C of heating 3h in argon gas atmosphere, obtain " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 7:2:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 20 microns, and (surface density is about 2mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiTFSI of 1mol/L is that in the DOL/DME of 1/1, (wherein adding mass percent is 1%LiNO in volume ratio
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 3
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous zinc chloride 1.06g (7.8mmol) mixes, and be transferred in 10ml glass tube, the air in glass tube is fallen by argon replaces, Muffle furnace is put into after being sealed, react 5 hours at 300 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 18.4%, and specific area is 143m
2/ g, pore size distribution range is: 0.4 ~ 2.8nm.
Mixed according to the ratio of 3:7 by above-mentioned polymer 500mg and S, then 155 DEG C of heating 3h in argon gas atmosphere, obtain " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 7:2:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 20 microns, and (surface density is about 2mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiTFSI of 1mol/L is that in the DOL/DME of 1/1, (wherein adding mass percent is 1%LiNO in volume ratio
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 4
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous zinc chloride 5.32g (39mmol) mixes, and be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, first at 400 DEG C of reaction 20h, then 700 DEG C of reaction 60h are warming up to, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 10.3%.Fig. 1 is that polymerizate isothermal nitrogen adsorption desorption curve and corresponding DFT model under 77K of aromatic nitrile compounds para-Phthalonitrile in the present embodiment calculates gained graph of pore diameter distribution, and the BET specific surface area being calculated the N doped catalyst of preparation by the data of Fig. 1 is 2860m
2/ g, calculates the pore-size distribution of N doped catalyst between 0.5 ~ 6nm by DFT method.
(therefore above-mentioned polymer 500mg and S is mixed according to the ratio of 7:3,6:4,5:5,4:6,3:7,1:3,2:8,3:17 respectively, in raw material, the ratio of S is respectively 30%, 40%, 50%, 60%, 70%, 75%, 80%, 85%), then 155 DEG C of heating 12h in argon gas atmosphere, obtain " polymer/sulphur ".
Fig. 2 is " polymer/sulphur " (75%S content) transmission electron microscope (TEM) light field figure (left side) in the present embodiment, corresponding TEM details in a play not acted out on stage, but told through dialogues figure (upper right), element sulphur distribution map (bottom right), as can be seen from the figure " polymer/sulphur " has loose porous network structure, and element sulphur is evenly distributed on the surface of material.
Fig. 3 is the thermogravimetric test result of " polymer/sulphur " in the present embodiment, calculates the weight ratio of sulphur in raw material and is respectively 70%, 75% and 80%, shows that the ratio of S in " polymer/sulphur " is identical with the ratio of S in raw material.
Fig. 4 is the X-ray diffraction test of " polymer/sulphur " in the present embodiment, as can be seen from the figure the situation of the weight ratio less than 75% of sulphur in compound, the diffraction maximum of obvious sulphur simple substance is not had in " polymer/sulphur " compound, when can illustrate that content as S is below 75%, S and polymer can form extraordinary compound.
Be that " polymer/sulphur ", the conductive additive (conductive acetylene is black) of 75%, CMC, SBR are according to the ratio of 85:10:2:3 by above-mentioned S content, add dispersant (water), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 40 microns, and (surface density is about 4mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiTFSI of 1mol/L is that in the DOL/DME of 1/1, (wherein adding mass percent is 3%LiNO in volume ratio
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Fig. 5 be in the present embodiment " polymer/sulphur " (75%S content) as the lithium-sulfur cell the performance test results of the positive pole of lithium-sulfur cell: 0.1C (current density 168mA/g).As can be seen from Figure 5: under the charging and discharging currents of 0.2C (336mA/g), specific capacity is still greater than 1000mAh/g, and circulation still has the capability retention of more than 80% for 100 times, illustrates that the lithium-sulfur cell that this type of " polymer/sulphur " is positive electrode has high volumetric properties and good stability later.
Fig. 6 be in the embodiment of the present invention 4 " polymer/sulphur " (75%S content) as the lithium-sulfur cell high rate performance test result of the positive pole of lithium-sulfur cell.As can be seen from Figure 6: lithium-sulfur cell, under the condition of the charging and discharging currents of 3C (about 5A/g), still can keep about 50% of initial capacity, illustrate that the lithium-sulfur cell that this type of " polymer/sulphur " is positive electrode has good high rate performance.
Embodiment 5
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous cupric chloride 2.10g (15.62mmol) mixes, and be transferred in 10ml glass tube, the air in glass tube is fallen by argon replaces, Muffle furnace is put into after being sealed, react 5 hours at 600 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 8.1%, and specific area is 1450m
2/ g, pore size distribution range is: 0.4 ~ 8nm.
Above-mentioned polymer and S are mixed according to the ratio of 3:7, then 155 DEG C of heating 3h in argon gas atmosphere, obtain " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 8:1:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 30 microns, and (surface density is about 3mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiTFSI of 1mol/L is that in the DOL/DME of 1/1, (wherein adding mass percent is 1%LiNO in volume ratio
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 6
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By m-dicyanobenzene (No. CAS: 626-17-5) 1g (7.8mmol), anhydrous zinc chloride 1.06g (7.8mmol) mixes, and be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, react 1 hour at 700 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 9.1%, and specific area is 1780m
2/ g, pore size distribution range is: 0.4 ~ 10nm.
Mixed according to the ratio of 3:7 by above-mentioned polymer 500mg and S, then 155 DEG C of heating 10h in argon gas atmosphere, obtain " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), LA132 three according to the ratio of 8:1:1, add dispersant (water), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 40 microns, and (surface density is about 4mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: in TEGDME, (wherein add mass percent is 5%LiNO to the LiTFSI of 1mol/L
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 7
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
By phthalic nitrile (No. CAS: 91-15-6) 1g (7.8mmol), anhydrous zinc chloride 1.06g (7.8mmol) mixes, and be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, react 1 hour at 700 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 10.1%, and specific area is 1690m
2/ g, pore size distribution range is: 0.4 ~ 3.9nm.
Mixed according to the ratio of 4:6 by above-mentioned polymer 500mg and S, then 155 DEG C of heating 40h in argon gas atmosphere, obtain " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (multi-walled carbon nano-tubes), LA132 three according to the ratio of 8:1:1, add dispersant (water), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 80 microns, and (surface density is about 8mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm is cut into slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: in TEGDME, (wherein add mass percent is 5%LiNO to the LiTFSI of 1mol/L
3).Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 8
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
Will to 4, 4 '-DCNBP 1g (4.9mmol), the consumption of anhydrous zinc chloride is that 3.34g (24.5mmol) mixes, be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, at 400 DEG C of reaction 10h, then react 3 hours at being warming up to 700 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 3.8%, and specific area is 3580m
2/ g, pore size distribution range is: 0.4 ~ 20nm.
Mixed according to the ratio of 45:55 by above-mentioned polymer 500mg and S, then vacuum-pumping density is encapsulated in the ampulla of 10ml, then at 350 DEG C of reaction 10h, obtains " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), LA132 three according to the ratio of 85:10:5, add dispersant (water), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 40 microns, and (surface density is about 4mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, be cut into the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm with slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiPF of 1mol/L
6in the EC/DME of 1/1.Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 9
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
Will to 1, 3, 5-tricyano benzene (TCB) 1g (6.53mmol), the consumption of anhydrous zinc chloride is that 4.45g (32.65mmol) mixes, be transferred in 10ml quartz ampoule, the air in quartz ampoule is fallen by argon replaces, Muffle furnace is put into after being sealed, react 5 hours at 700 DEG C, after naturally cooling to room temperature (25 DEG C), open glass tube, polymerizate is taken out, and use the hydrochloric acid of 1mol/L successively, pure water washs, then vacuum drying chamber is put into, drying 10 hours at 120 DEG C, obtain the polymerizate of N doping, it can be used as oxygen reduction catalyst.Wherein, in catalyst, the content of nitrogen element is 3.8%, and specific area is 2492m
2/ g, pore size distribution range is: 0.4 ~ 6nm.
Mixed according to the ratio of 55:45 by above-mentioned polymer 500mg and S, then vacuum-pumping density is encapsulated in the ampulla of 10ml, then at 500 DEG C of reaction 10h, obtains " polymer/sulphur ".
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 8:1:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 30 microns, and (surface density is about 3mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, be cut into the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm with slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiPF of 1mol/L
6in the EC/DME of 1/1.Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 10
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
Para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous zinc chloride 10.632g (78mmol), sulphur 9g are transferred in quartz boat after mixing, then 280 DEG C of heating 12h in argon gas atmosphere, obtain " polymer/sulphur ", the mass ratio wherein shared by sulphur is 54%.
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 8:1:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 30 microns, and (surface density is about 3mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, be cut into the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm with slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiPF of 1mol/L
6in the EC/DME of 1/1.Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Embodiment 11
The preparation method of the present embodiment for illustration of material provided by the invention " polymer/sulphur " and the preparation as lithium sulfur battery anode material and application process.
Para-Phthalonitrile (No. CAS: 623-26-7) 1g (7.81mmol), anhydrous cupric chloride 1.05g (7.8mmol), sulphur 7g are transferred in quartz boat after mixing, then 600 DEG C of heating 2h in argon gas atmosphere, obtain " polymer/sulphur ", the mass ratio wherein shared by sulphur is 42%.
By above-mentioned " polymer/sulphur ", conductive additive (conductive acetylene is black), PVDF three according to the ratio of 8:1:1, add dispersant (NMP), even in stirrer for mixing, then be coated on aluminium foil with coating machine, coating thickness is 20 microns, and (surface density is about 2mg/cm
2), then put it into 60 DEG C of dry 10h in blast dry oven.After taking-up, be cut into the positive pole of disk as button lithium-sulfur cell of diameter 1.4cm with slicing machine, then use lithium sheet as negative pole, barrier film is Celgard2300, and electrolyte is: the LiPF of 1mol/L
6in the EC/DME of 1/1.Then fastening lithium ionic cell (model: 2025) carry out lithium-sulfur cell test is assembled into.
Performance test:
The test of lithium-sulfur cell provided by the invention is on LANHE (the blue electricity in Wuhan) test macro, carries out testing under room temperature; Adopt button cell (2032) during test, negative pole is lithium metal.Table 1 is the performance test results (comprising relevant testing conditions) of the lithium-sulfur cell in above-described embodiment.
Table 1
Shown in embodiment 1-11 and table 1, the polymerizate good conductivity that aromatic nitrile compounds monomer polymerization obtains, specific area are high, hole rich content and containing nitrogen-doping; The composite material (" polymer/sulphur ") formed with sulphur can have high sulfur content, and element sulphur is evenly distributed; Using this composite material as lithium sulfur battery anode material, show excellent chemical property.In addition, aromatic nitrile compounds abundance, and " polymer/sulphur " preparation method is simple and can prepare on a large scale, therefore this type of " polymer/sulphur " is applied in lithium-sulfur cell and has huge commercial application prospect.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a compound, is characterized in that, it is the compound formed by aromatic nitrile compounds polymerizate and sulphur.
2. compound according to claim 1, is characterized in that, it has the carbon skeleton of porous network structure.
3. compound according to claim 1, is characterized in that, the specific area of described aromatic nitrile compounds polymerizate is 400 ~ 3000m
2/ g, pore-size distribution is 0.4 ~ 20nm;
Preferably, comprising mass ratio in the carbon skeleton of described aromatic nitrile compounds polymerizate is 2.1 ~ 18.4%, is preferably the atom N of 3.4 ~ 12.6%.
4. the compound according to any one of claim 1-3, is characterized in that, described aromatic nitrile compounds is the aromatic compound of cyano group replacement and/or the heteroaromatic compounds of cyano group replacement;
Preferably, the aromatic compound that described cyano group replaces is cyano group benzene and/or cyanobiphenyl, and the number of preferred cyano substituent is 2-3.
Preferably, the heteroaromatic compounds that described cyano group replaces is the hexa-atomic heteroaromatic compounds that cyano group replaces, and the hetero-atom in hexa-atomic heteroaromatic compounds is nitrogen-atoms, is preferably the pyridine that cyano group replaces;
Preferably, in described cyano group replacement, the number of cyano substituent is 2-3;
Preferably, described aromatic nitrile compounds is para-Phthalonitrile, isophthalodinitrile, phthalonitrile, benzonitrile, 1,3,5-tricyano benzene, 2,6-dicyanopyridine, 2,4-dicyanopyridines or 4, the mixture of any one or at least two kinds in 4 '-DCNBP.
5. the compound according to any one of claim 1-3, is characterized in that, the mass ratio of sulphur described in compound and polymerizate is 3/7 ~ 9/1, is preferably 4/6 ~ 7/3.
6. the preparation method of compound described in an any one of claim 1-5 comprises the steps: aromatic nitrile compounds polymerizate and sulphur mixing, and reaction, obtains the compound of polymerizate and sulphur.
7. described in an any one of claim 1-5, the preparation method of compound comprises the steps: that aromatic nitrile compounds monomer, sulphur and polymerisation catalysts react, and obtains the compound of polymerizate and sulphur.
8. preparation method according to claim 6, is characterized in that, the mass ratio of described sulphur and aromatic nitrile compounds polymerizate is 3/7 ~ 9/1, is preferably 4/6 ~ 7/3;
Preferably, be mixed into concussion mixing described in, mortar grinder mixing, pulverizer be pulverized and mixed or any one in ball milling, preferably concussion mixing and/or ball milling;
Preferably, described reaction is carried out in inert atmosphere or vacuum environment;
Preferably, described inert gas is selected from the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas, Krypton or xenon;
Preferably, the temperature of described reaction is 150 DEG C ~ 500 DEG C, preferably 150 DEG C ~ 350 DEG C;
Preferably, the time of described reaction is 1h ~ 40h, preferred 3h ~ 12h.
9. preparation method according to claim 7, is characterized in that, the mass ratio of described sulphur and aromatic nitrile compounds monomer is 3/7 ~ 9/1, is preferably 4/6 ~ 7/3;
Preferably, the mol ratio of described polymerisation catalysts and described aromatic nitrile compounds monomer is 1-10:1, is preferably 2-8:1;
Preferably, described polymerisation catalysts is metal halide, is preferably metal chloride, the mixing of a kind of more preferably in zinc chloride, copper chloride, frerrous chloride and manganese chloride or at least two kinds;
Preferably, be mixed into concussion mixing described in, mortar grinder mixing, pulverizer be pulverized and mixed or any one in ball milling, preferably concussion mixing and/or ball milling;
Preferably, described reaction is carried out in inert atmosphere or vacuum environment;
Preferably, described inert gas is selected from the combination of any one or at least two kinds in nitrogen, helium, neon, argon gas, Krypton or xenon;
Preferably, the temperature of described reaction is 280 DEG C ~ 600 DEG C, preferably 280 DEG C ~ 400 DEG C;
Preferably, the time of described reaction is 1h ~ 40h, preferred 3h ~ 12h.
10. the purposes of the compound described in any one of claim 1-5, is characterized in that, it is used as positive electrode; Be preferably used as the positive electrode of lithium-sulfur cell, sodium-sulphur battery or magnesium sulphur battery;
Preferably, the mass ratio of described compound in positive electrode is 70% ~ 95%, preferably 80% ~ 90%;
Preferably, the coating thickness of described positive electrode is 10 μm ~ 80 μm, is preferably 20 μm ~ 40 μm; Surface density is 1mg/cm
2~ 8mg/cm
2, be preferably 2mg/cm
2~ 4mg/cm
2.
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Application publication date: 20160316 |