CN102142554A - Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material - Google Patents

Nano carbon sulfur composite material with network structure and preparation method of nano carbon composite material Download PDF

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CN102142554A
CN102142554A CN2011100390051A CN201110039005A CN102142554A CN 102142554 A CN102142554 A CN 102142554A CN 2011100390051 A CN2011100390051 A CN 2011100390051A CN 201110039005 A CN201110039005 A CN 201110039005A CN 102142554 A CN102142554 A CN 102142554A
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carbon
composite
reaction
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sulphur
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王安邦
苑克国
王维坤
余仲宝
邱景义
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63971 Troops of PLA
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Abstract

The invention relates to a nano carbon material with a network structure consisting of polymer chains, in particular to a nano carbon sulfur composite material with a network structure suitable to be used in a secondary lithium sulfur battery anode and a preparation method thereof. The carbon sulfur composite material is formed by adopting the following steps of: introducing functional groups onto carbon particles by adopting the electric conductivity and the porosity of a carbon material and the reaction capacity of similar condensed aromatics of the carbon material and by means of an irreversible chemical reaction; introducing the polymer chains, wherein the polymer chains are stretched, bent and cross-linked on the surfaces of the carbon particles to form a cross-linked network structure; and compounding a sulfur element or a polysulfide (m is more than 2) containing -Sm- structure into the network structure to form the nano carbon sulfur composite material with the network structure. The carbon sulfur composite material has a rich cross-linked network structure, nano-scale network pores constrain the sulfur element or the polysulfide (m is more than 2) containing the -Sm- structure in the network, and the active substances are limited in a certain region to react, so that the composite material has predominant electrochemical performance.

Description

A kind of nano-sized carbon sulphur composite material and preparation method thereof with network configuration
Technical field
The present invention relates to a kind of nano-carbon material with network configuration, network configuration is made of polymeric chain, relate to particularly that a kind of suitable secondary lithium-sulphur cell positive electrode uses, have nano-sized carbon sulphur composite material of network configuration and preparation method thereof, belong to field of electrochemical batteries.
Background technology
The positive pole of serondary lithium battery mainly is made up of three parts, is respectively active material, binding agent and conductive agent.The LiFePO4 of lithium transition-metal oxide that present commercial active material mainly is stratiform or spinel structure (as cobalt acid lithium, LiMn2O4) and olivine structural.Cobalt acid lithium (LiCoO 2) theoretical capacity relatively large, be 275mAh/g, but its price height, certain toxicity is arranged, and exothermal decomposition reactions easily takes place when overcharging in this material, makes the actual capacity of this material be lower than 200mAh/g on the one hand, also battery security threatened on the other hand.LiMn2O4 (LiMn 2O 4) theoretical capacity be 148mAh/g, actual capacity is lower than 130mAh/g mostly.LiFePO4 (LiFePO 4) theoretical capacity also have only 172mAh/g.Above-mentioned these positive electrode active materials or capacity are on the low side, or price height and poor stability, have limited their application in power and energy-storage battery.Therefore, the sulfur-bearing positive pole of exploitation high power capacity, long circulation life and environmentally safe is significant.
In the battery system of numerous researchs, the metal lithium-sulfur cell is considered to tool application potential.Elemental sulfur theoretical specific capacity as positive active material is 1675mAh/g, and the specific energy of lithium-sulfur cell is that 2600Wh/kg (generates Li after lithium metal and the sulphur complete reaction 2S), be higher than existing lithium rechargeable battery material LiCoO far away 2, LiMnO 2And LiFePO 4Deng.Simultaneously the elemental sulfur positive electrode has the source and enriches low price, environmentally friendly, advantage such as battery security is good.For a long time, the inorganic sulphide of elemental sulfur and sulfur-bearing, organic disulfide, poly-organic disulfide, organic polysulfide, poly-thioated thing and carbon sulphur polymer etc. receive much attention as the positive electrode of high power capacity, and people have carried out a lot of researchs (Feng to it, X., He, X., Pu, W., Jiang, C., Wan, C.2007, Ionics 13 (5), pp.375-377:Trofimov, B.A., Myachina, GE, Rodionova, I.V., Markina, A.G, Dorofeev, I.A., VakuPskaya, T.I, Sinegovskaya, L.M., Skotheim, TA.2008, Journal ofApplied Polymer Science 107 (2) pp.784-787), however also there are a lot of problems in the development of lithium-sulfur cell.At first, the conductivity of elemental sulfur and sulfide itself is very poor.Elemental sulfur at room temperature is typical electronic and ion insulator (5 * 10 -3025 ℃ of S/cm), generally need to add a large amount of conductive agents to increase its conductivity when practical application, this has reduced the specific capacity of electrode integral body to a great extent.Secondly, as the positive pole of active material, the elemental sulfur reduction generates Li concerning elemental sulfur 2The process of S is a multistep reaction, and many lithium sulfides of product are soluble in organic liquid electrolyte in the middle of it, and a large amount of dissolvings of many lithium sulfides can cause the active material of a part to run off, and also can cause the increase of electrolyte viscosity and the reduction of ionic conductivity simultaneously.Though elementary sulfur that exists on the positive pole when charging fully and the Li that exists when discharging fully 2S is insoluble in the polarity organic electrolyte, but many lithium sulfides that positive pole contains when part charging and discharge condition are soluble in the polarity organic electrolyte, equally, the micromolecule sulfide that poly-organic sulfur compound produces when discharging also is soluble in organic electrolyte, the many lithium sulfides that have been partly dissolved diffuse to negative pole, also can be with lithium generation self discharge reaction and in the negative pole deposition, this a series of problem has all caused the electrode active material utilance low poor with cycle performance of battery.(Kolosnitsyn,V.S.,Karaseva,E.V?Russian,Journal?of?Electrochemistry?2008,44(5),pp.506-509)。Therefore, how to improve the conductivity of material, and solve and to discharge and recharge intermediate product dissolving and the electrode slice structure problem of caving in, the raising cycle performance of battery is the research emphasis of sulfenyl positive electrode.
Common a kind of thinking of studying is the composite material that preparation is made up of sulfenyl material and the material that possesses adsorptivity and conductivity.Because elemental sulfur has relative high theoretical specific capacity, therefore first-selected elemental sulfur is as the active material of composite material.
A kind of material is the compounded carbon sulphur of the material with carbon element composite material with elemental sulfur and high-ratio surface high filler loading capacity.By with high pore volume (0.1~3cm 3/ g), high conductivity (0.01~200S/cm), high-ratio surface (50~1900m 2/ g) macropore carbon material is a matrix, it with content 10%~95% elemental sulfur soaks into the carbon-based material that is penetrated into big mesoporous composite material under fusion or vaporized state micropore, and be filled in the nanometer and micrometer grade hole of matrix, the combination reaction of sulphur and carbon also can take place simultaneously, makes the carbon sulphur composite material that sulphur exists with one or more chemical states in the raw material of wood-charcoal material.The sulfur content that the high pore volume that this composite materials is done can hold is big, can guarantee the high power capacity of material: the little conduction distance that can reduce ion, electronics of the granularity of sulphur, can increase the utilance of sulphur: can suppress the to discharge dissolving of intermediate product and of the characterization of adsorption of raw material of wood-charcoal material high-ratio surface to the migration of negative pole, can reduce self discharge, and avoid the bulk deposition of nonconducting discharging product lithium sulfide outside carbon granule, reduce internal resistance.The head of battery is put specific capacity and is reached 1101.1mAh/g (calculating with sulphur), after 20 circulations, leave the specific capacity of 756mAh/g (referring to Wang Weikun, Zhao Chunrong, Yu Zhongbao, Wang Anbang, Yuan Keguo, Yang Yusheng, a kind of novel carbon-sulfur compound that is used for lithium one sulphur battery, Chinese patent publication number CN 101587951A).Another kind is used for the ordered nano-structure sulphur/mesoporous carbon composite material of lithium battery anode, is carrier with orderly carbon back mesoporous material, has nanometer sulphur to form at its duct internal burden.The composite material sulfur content height, good dispersion, capacity height, good stability of invention (referring to Li Yong, Xu Jiaqiang, Dong Xiaowen, Zhao Hongbin, Zhu Yongheng is used for the ordered nano-structure sulphur/mesoporous carbon composite material of lithium ion cell positive, application publication number CN101728538A).Also have a kind of material, (mesoporous 5.0~8.0nm, pore volume are 1.0~2.5cm to utilize the symmetric ordered mesoporous carbon of p6m 3/ g, specific area is 1000~2400m 2/ g, the pore space structure that has 0~4nm size on the mesoporous charcoal skeleton of while), this ordered mesoporous carbon and sublimed sulfur mix by the metering ratio, put into closed container, heating makes the compound 5~24h of sulphur fusion under 120~159 ℃, prepared ordered mesoporous carbon one sulphur nano composite positive pole material, this material has higher utilization efficiency, good cyclicity, conservation rate and big current ratio performance.With sulfur-bearing 50% material is example, when electrolyte is 1mol/L LiN (CF 3SO 2) 2DOL+DME (V: V, 1: 1) solution the time, under about 250mA/g (calculating) current density, discharge and recharge by active material sulphur, elemental sulfur discharge capacity first reaches 1364mAh/g, can also keep about 570mAh/g after the circulation of 200 weeks.When charge-discharge velocity is about 13A/g, 70 all discharge capacities still can be maintained at about 280mAh/g (referring to Sun Shigang, Chen Shuru, Zhao Dongyuan, the Jiang Yan rosy clouds, Zhai's Yun uncut jade, yellow order, a kind of ordered mesoporous carbon one sulphur nano composite positive pole material and preparation method thereof, Chinese patent publication number CN 101567437A).
More Zao a kind of material is (referring to Wang Jiulin with elemental sulfur and the compounded elemental sulfur/conducting polymer composite material of conducting polymer, separate sparkling and crystal-clear, Yang Jun, Xu Naixin, Liu Lu etc., electrochemical power source is anodal with elemental sulfur/conducting polymer composite material and preparation method, Chinese patent publication number: CN02111403.X).Elemental sulfur can be penetrated under molten condition in the micropore of polyacrylonitrile formed carbon back network space and material, while is possibility subparticipation binding reaction also, form sulfenyl composite material (Jiulin Wang, Jun Yang, Chunrong Wan, Jingying Xie, and Naixin Xu.Adv.Funct.Mater.2003,13, No.6487:492).With this material in lithium battery for the third time specific discharge capacity can reach 800mAh/g, through 50 times the circulation after, specific capacity remains on more than the 600mAh/g.And the Li/S battery that obtains at room temperature self-discharge rate is lower, discharge back battery was placed after one month fully, the capacitance loss 4.9%/moon.But discharge capacity was lower first when this material still existed charge and discharge cycles, and capacity attenuation is very fast, and the middle threshold voltage of discharge is lower, and certain problems such as self discharge capacitance loss are arranged, and 50 times circulation back capacity descends nearly 25%.Another kind of material is to use the carbon of high-ratio surface and elemental sulfur to be incubated the carbon sulphur composite material of handling under 300 ℃ of temperature, under the current density of 40mA/g, first all discharge capacities are 1155mAh/g, the 50 all capacity that are circulated to are stabilized in 740mAh/g and (referring to Gao Xueping, rely to surpass Pan Guiling, Li Guoran, Ye Shihai, a kind of is the lithium battery and preparation method thereof of positive pole with sulphur/carbon composite, Chinese patent publication number CN 101478061A).
Also having a kind of material is that conductive agent carriers such as elemental sulfur and conductive nano agent carbon black, CNT (carbon nano-tube) are got carbon sulphur composite material by fusion of physical method heat or vaporizing system.The mixture of material with carbon element such as carbon nano-tube, carbon nano-fiber, carbon aerogels, carbon black and elemental sulfur is in the vacuum environment, heating and temperature control is between 300~400 ℃, constant temperature 2~5h, elemental sulfur has deposited in the hole of multi-walled carbon nano-tubes or the gap preparation cathode plate for lithium secondary battery with elemental sulfur/carbon composite by distillation.With this material is that the open circuit voltage of the anodal battery of forming is 3.08V, and at room temperature the current density with 100mA/g discharges and recharges, and the first discharge specific capacity of material is 1487.0mAh/g, and the utilance of sulphur reaches 88.9%.2 tangible discharge platforms have appearred on discharge curve, respectively about 2.3V and 2.0V.50 times circulation back specific discharge capacity also remains on 913.7mAh/g, demonstrated excellent cycle performance (referring to Wu Feng, Wu Shengxian, Chen outstanding personality, old reality, Li Li, Chen Junzheng, Wang Guoqing, the preparation method of elemental sulfur composite material used by lithium secondary battery, Chinese patent publication number CN 101562244A).Composite material with multi-walled carbon nano-tubes and elemental sulfur preparation also has report, multi-walled carbon nano-tubes and elemental sulfur are according to mass ratio 1/5 high speed ball mill mixing, the active material elemental sulfur is refine to the granularity of particle between 3~8um, 350 ℃ of constant temperature kept 4 hours, had prepared elemental sulfur/many walls nanometer tube composite materials.In ethylene carbonate (EC)+dimethyl carbonate (DMC)+methyl ethyl carbonate (EMC) electrolyte of 1mol/L LiPF6 (volume ratio is 1/1/1), this composite material is in the active material elemental sulfur, first discharge specific capacity reaches 700mAh/g, the specific discharge capacity of 60 circulations is 500mAh/g, from the 2nd time to 60 times average each capacitance loss rates is 3.1% (referring to W.Zheng, Y.W.Liu, X.G.Hu, C.F.Zhang, Novel nanosized adsorbing sulfurcomposite cathode materials for the advanced secondary lithium batteries, Electrochimica Acta, 2005).
The preparation of above-mentioned material nearly all is conductivity, porousness and an adsorptivity of utilizing material with carbon element, the use diverse ways makes elementary sulfur enter in the carbon hole or is adsorbed on carbon surface, the cyclicity of attempting to improve the utilance of elementary sulfur and improving battery, all obtained certain progress undoubtedly, but all existed not enough at aspects such as the utilance of structural stability, sulphur or cyclical stabilities.
Summary of the invention
Purpose of the present invention mainly is in the lithium-sulfur cell, anodal many sulfur materials institutional framework instability, the utilance of sulphur is not high and the shortcoming of cyclical stability difference, and cross-linked network structure nano-sized carbon sulphur composite material that is made of polymeric chain of a kind of good conductivity, specific capacity height, good cycling stability and preparation method thereof is provided.
Technical scheme of the present invention: composite material is by nano-sized carbon with network configuration and elementary sulfur or contain-S mThe compound composition of the polysulfide of-structure, m>2; Wherein network configuration is made of polymeric chain, and polymeric chain is polyaniline, polypyrrole, polythiophene, polyacetylene, polyethylene glycol (PEG), poly(ethylene oxide) (PEO), acrylate copolymer, methacrylate polymer, quaternary ammonium cation type methacrylate based polymers or the polymer that is connected with nitro, sulfonic group or mercapto functional group; The molecular weight of polymeric chain (WM) is 1000~10000000.
Elementary sulfur of the present invention is a sublimed sulfur, crystallization sulphur, and colloid sulphur, no crystalline state sulphur, crystallite sulphur, the elemental sulfur of other form, or contain-S mThe polysulfide of-structure is organic polysulfide or inorganic polysulfide, m>2.
In the described carbon sulphur composite material, conductivity, porousness and the adsorptivity of material with carbon element have not only been utilized, also further utilized the respond of the class condensed-nuclei aromatics of material with carbon element, rely on irreversible chemical reaction, functional group is incorporated on the carbon granules, and then introduces polymeric chain, polymeric chain stretches at carbon grain surface, bending, crosslinked, thereby the formation cross-linked network structure is again with elementary sulfur or contain-S mThe polysulfide of-structure (m>2) is compound to the nano-sized carbon sulphur composite material that formation has network configuration in the network configuration.
Be shown below:
The carbon granules polymeric chain is connected carbon grain surface (J~J represents polymeric chain) composite material
Described carbon sulphur composite material has abundant cross-linked network structure, and the network hole of nanoscale is with elementary sulfur or contain-S mThe polysulfide of-structure (m>2) " constraint " is limited in certain regional internal reaction with active matter among network, simultaneously, network configuration also can effectively suppress the dissolving diffusion loss of the many lithium sulfides of discharging product; Abundant cross-linked network structure can improve the combined strength bination of sulphur and carbon just as " reinforcing bar " in the composite material, also can improve the compound quantity of sulphur; When cross-linked network structure abundant in the composite material was made of conducting polymer chain or ion conductor polymeric chain, it can improve electronics or the ion transportation and the response area of material, makes composite material have outstanding electric conductivity; Can also introduce some specific functional groups in the material, improve the chemical property of some aspect of composite material.
More than these effects will solve anodal many sulfur materials institutional framework problem of unstable in the lithium-sulfur cell, improve the utilance of composite material active matter and the high rate performance of active matter, thereby improve specific power, specific energy and the cyclicity of battery.
Component with nano-sized carbon sulphur composite material of network configuration of the present invention:
Have the nano-sized carbon (wherein network configuration is made of polymeric chain) and the elementary sulfur of network configuration or contain-S mThe polysulfide of-structure (m>2)
Content by mass percentage:
Elementary sulfur or contain-S mThe content of the polysulfide of-structure (m>2) in having the nano-sized carbon sulphur composite material of network configuration is 20%~99.9%.
Preparation method with nano-sized carbon sulphur composite material of network configuration of the present invention comprises following three steps:
1) functionalization of carbon granules: carbon granules is by the nano-sized carbon of chemical reaction generation functionalization, and the functional group on the carbon granules can be X, R, CN ,-SCN ,-NCO ,-OH ,-COOH ,-COOR ,-COR ,-COX ,-CONHR ,-CONR 2,-NO 2,-SO 3H ,-OR ,-SH ,-SS-,-S n-, SR ,-SSR ,-NH 2,-NHR ,-NR 2, or-N +R 3Wherein: X=F, Cl, Br or I, R are alkyl, alkylene or aromatic radical, n=1~9; The functionalization of carbon granules also comprises the situation of material with carbon element functionalization in preparation process;
2) chemical bonding of the carbon of functionalization and polymeric chain, obtain having the nano-sized carbon of network configuration: the nano-sized carbon of functionalization utilizes its functional group to form by chemical reaction bonding high molecular polymerization chain, the stretching, extension of polymeric chain, bending, the crosslinked network configuration that constitutes carbon grain surface form the nano-sized carbon with network configuration;
3) have the nano-sized carbon and the elementary sulfur of network configuration or contain-S mThe polysulfide of-structure compound, m>2, the nano-sized carbon sulphur composite material that obtains having network configuration; Complex method can adopt solution composite approach, reaction in-situ composite algorithm, ULTRASONIC COMPLEX method, gel precipitation composite algorithm, fusion composite algorithm, the hot composite algorithm of vacuum or mechanical composite algorithm, and these methods can be used separately, also can two or more unite use:
Solution composite approach: it is compound to be meant that the dissolubility property that utilizes solution carries out in solution, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h;
The reaction in-situ composite algorithm: be meant and utilize the chemical reaction original position to generate sulphur, carry out compoundly again, the method is carried out in solution, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h;
The ULTRASONIC COMPLEX method: the ULTRASONIC COMPLEX method is meant that to utilize ultrasonic wave to carry out compound, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h, power 300~800W;
The gel precipitation composite algorithm: the gel precipitation composite algorithm be adopt colloid sulphur in solution, carry out compoundly, reaction temperature is 0~150 ℃, the reaction time is 2~4h;
The fusion composite algorithm: the fusion composite algorithm is meant that to utilize molten sulfur to carry out compound, and reaction temperature is 100~300 ℃, and the reaction time is 2~4h;
The hot composite algorithm of vacuum: the hot composite algorithm of vacuum is meant that to utilize vacuum degree to carry out compound in closed container, reaction temperature is 100~350 ℃, and the reaction time is 2~4h, vacuum degree 0.1~10mmHg;
The machinery composite algorithm: mechanical composite algorithm is meant that to utilize ball milling, stirring, concussion to carry out compound, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h.
This method step 1) functionalization and the step 2 of carbon granules) carbon of functionalization and the chemical bonding of polymeric chain, obtain having the nano-sized carbon of network configuration, can in same reaction unit, carry out, also can be simultaneously or by successively reacting.
Carbon granules is the carbon granules of carbon black, active carbon, graphite, nanometer carbon granules, other dispersion or their mixture; The size of particle is 0.1~10000 nanometer, and the specific area of carbon granule can be 1~5000m 2/ g, the conductivity of carbon granule can be 0.01~1000S/cm, the pore volume of carbon granule can be 0.01~5cm 3/ g.
Functional group on the nano-sized carbon of functionalization can be converted into by chemical reaction-OH-X or-X is converted into-S-S-, X is a halogen.The polymeric chain that constitutes network configuration has active function groups, and active function groups can be a terminal functionality, also can be the functional group on the monomer in the polymeric chain.When the carbon granules of functionalization and the functional group on the polymeric chain carried out the bonding chemical reaction, polymeric chain can be one or more.When the carbon granules of functionalization and the functional group on the polymeric chain carried out the bonding chemical reaction, the bonding chemical reaction that takes place between them can be class reaction or the above reaction of a class in esterification, etherification reaction, condensation reaction, substitution reaction, the addition reaction.The carbon granules of functionalization also can with generated in-situ PCR; The polymerization reaction of polymer monomer and bonding reaction carry out in same reaction unit, and two reactions can take place simultaneously, also can successively take place.When the carbon granules of functionalization and the functional group on the polymeric chain carried out the bonding chemical reaction, bonding reaction can all take place in functional group, also bonding reaction can take place partly.Functional group introduces by polymeric chain, introduces before or after functionalization carbon and polymeric chain bonding, can all introduce or the part introducing, or introduce respectively or introducing simultaneously on the material with carbon element and on the polymeric chain.
Elementary sulfur or contain-S mThe content of the polysulfide of-structure in having the nano-sized carbon sulphur composite material of network configuration is 20%~99.9%, m>2.
The lithium-sulfur cell of being made up of composite material comprises positive pole, negative pole, electrolyte three parts, wherein positive electrode active material is the nano-sized carbon sulphur composite material with network configuration, negative pole is lithium metal, lithium alloy, mix the carbon of lithium, mix in the graphite of lithium one or more, and electrolyte is one or more in liquid electrolyte, colloidal polymer electrolyte, the solid polymer electrolyte.
Explanation step by step below:
The functionalization of step 1) carbon granules
Carbon is the crucial a kind of element of occurring in nature, and it is in the one-tenth key mode of uniqueness, has formed colourful carbon family.The material with carbon element that is applied in the battery is the meta anthracite cellular construction mostly, carbon atom forms the netted plane of regular hexagon with covalent bonds in the carbon granules, can be considered class condensed-nuclei aromatics structure, utilize the respond of class condensed-nuclei aromatics, rely on irreversible chemical reaction, some functional groups are incorporated on the carbon granules, form the carbon granules of functionalization, as reaction equation (1).
G1~Gn=X, R, CN ,-SCN ,-NCO ,-OH ,-COOH ,-COOR ,-COR ,-COX ,-CONHR ,-CONR 2,-NO 2,-SO 3H ,-OR ,-SH ,-SS-,-S n-(n=1~9), SR ,-SSR ,-NH 2,-NHR ,-NR 2,-N +R 3, azacyclo-, oxa-ring, thia ring etc., wherein X=F, Cl, Br, I, R=alkyl, alkylene and aromatic radical (as phenyl, substituted-phenyl, phenyl derivatives, heterocyclic aromatic base, substituted heterocycle aromatic radical etc.).
G 1~G nCan be identical functional group, also can be different functional groups.
The functional group that introduces can introduce by single step reaction, as reaction equation (2); Also can transform, promptly introduce, as reaction equation (3) by two steps or multistep reaction by the functional group that introduces earlier.
There are two effects greatly in the functional group that introduces:
At first, functional group is as connecting the bridge of carbon granules with polymeric chain, and the functional group reactions in it and the polymeric chain is by the combination of chemical bonding formation carbon granules and polymeric chain, polymeric chain stretches in surfaces of carbon particles, bending, crosslinked, forms the nano carbon particle with network configuration; Another effect is that the functional group that introduces does not further react, and it is retained on the carbon granules, itself has the effect that improves composite property.For example: the nitro of introducing can improve the chemical property of composite material, as reaction equation (4).
Sometimes, the material with carbon element that uses is in its preparation process, some functional groups have been generated at carbon grain surface, as activated carbon, graphite oxide etc., they can be directly used in carries out next step and polymeric chain chemical bonding, also can increase or/and after transforming functional group, carry out next step and polymeric chain chemical bonding again.
The above-mentioned carbon granules that has had the carbon granules of functional group on its surface and will be applied to functionalization; can be the particle of material with carbon element, for example carbon granules of carbon black, active carbon, graphite, nanometer carbon granules, other dispersion or their mixture arbitrarily in the colourful carbon family.The size of particle is 0.1~10000nm; The specific area of carbon granule is 1~5000m 2/ g; The conductivity of carbon granule is 0.01~1000S/cm; The pore volume of carbon granule is 0~5cm 3/ g.
Step 2) chemical bonding of the carbon granules of functionalization and polymeric chain obtains having the nano-sized carbon of network configuration
The carbon granules of the functionalization that obtains by step 1), under the certain reaction condition, carry out the bonding chemical reaction with the functional group on the polymeric chain, obtain the carbon granules that the surface connects polymeric chain, polymeric chain stretches, bending, crosslinked, form network configuration at carbon grain surface, the nano carbon particle that obtains having network configuration is as reaction equation (5).
J~J can be any polymer chain.(J~J) is the polymeric chain that has the polymeric chain of conductivity and have the ion conductor effect to the better polymerization chain, polyaniline for example, polypyrrole, polythiophene, polyacetylene and polyethylene glycol (PEG), poly(ethylene oxide) (PEO) etc., (J~J) also can be hydrophilic polymeric chain to the better polymerization chain, acrylate copolymer for example, quaternary ammonium cation type methacrylate based polymers etc., (J~J) can also be the polymer that is connected with specific functional groups to the better polymerization chain, for example be connected with nitro, sulfonic group, the polymer of functional groups such as sulfydryl, they can improve the chemical property of composite material and can solve anodal many sulfur materials institutional framework problem of unstable well, thereby improve the combination property of composite material.
When the carbon granules of functionalization and the functional group on the polymeric chain carry out the bonding chemical reaction, polymeric chain (J~J) can also can use two or more simultaneously with a kind of; The bonding chemical reaction that takes place between them can be class reaction (as esterification), also can be two classes or multiclass reaction (as esterification, replacement and other reaction).
When the carbon granule of functionalization and the functional group on the polymeric chain carried out bonding reaction, the functional group on the polymeric chain can be a terminal functionality, as reaction equation (6); Also can be the functional group on the monomer in the polymeric chain, as reaction equation (7).
Reaction equation (6) functional group is a terminal functionality
Reaction equation (7) functional group is the functional group on the monomer in the polymeric chain
The carbon granules of functionalization also can with generated in-situ PCR, be that the monomer of the carbon granules of functionalization and polymeric chain coexists in the reaction unit, the polymerization reaction of monomer, the bonding reaction of functional group carries out in same reaction unit on the carbon granules of functionalization and the polymeric chain, two reactions can take place simultaneously, also can successively take place, as reaction equation (8).
J~J can be any polymer chain.(J~J) is the polymeric chain that has the polymeric chain of conductivity and have the ion conductor effect to the better polymerization chain, polyaniline for example, polypyrrole, polythiophene, polyacetylene and polyethylene glycol (PEG), oxirane (PEO) etc., (J~J) also can be hydrophilic polymeric chain to the better polymerization chain, acrylate copolymer for example, quaternary ammonium cation type methacrylate based polymers etc., (J~J) can also be the polymer that is connected with specific functional groups to the better polymerization chain, for example be connected with nitro, sulfonic group, the polymer of functional groups such as sulfydryl, they can improve the chemical property of composite material and can solve anodal many sulfur materials institutional framework problem of unstable well, thereby improve the combination property of composite material.
(J~when J) being conductive chain, for example polyaniline, polypyrrole, polythiophene, polyacetylene etc. can improve the electron conduction of composite material, thereby improve the chemical property of composite material when polymeric chain.
(poly(ethylene oxide) (PEO) etc. can improve the ionic conductivity of composite material, thereby improve the chemical property of composite material for J~when J) being the ion conductor chain, polyethylene glycol (PEG) for example when polymeric chain.
As polymeric chain (J~when J) being the hydrophily chain, for example acrylate copolymer, quaternary ammonium cation type methacrylate based polymers etc., if in the battery pole piece preparation, use aqueous binder, then many sulfur materials institutional framework problem of unstable can be well solved in the pole piece, thereby improve the stability of anode, and then improve the cyclicity of battery.
The performance of the polymeric chain of introducing can be improved the example of performance of composites and enumerate no longer one by one.
Can also be connected with the functional group that improves composite property on the polymeric chain of introducing, nitro for example is as reaction equation (9).
The functional group that improves composite property on the polymeric chain can be that polymeric chain itself contains, as reaction equation (9); Also can be behind the generation bonding reaction of functional group on the carbon granules of functionalization and the polymeric chain, introduce by chemical reaction again, promptly after obtaining having the nanometer carbon granules of network configuration, introduce the functional group that improves composite property again, as reaction equation (10).
The reaction of introducing polymeric chain (during J~J), also can carry out the reaction and the step 2 of step 1) with step 1) in same reaction unit) by chemical bonding on carbon granules can simultaneously or successively be carried out, as reaction equation (11).
(J~J) can be any polymer chain to the polymeric chain of introducing by chemical bonding on the carbon granules of functionalization.(J~J) is the polymeric chain that has the polymeric chain of conductivity and have the ion conductor effect to the better polymerization chain, polyaniline for example, polypyrrole, polythiophene, polyacetylene and polyethylene glycol (PEG), poly(ethylene oxide) (PEO) etc., (J~J) also can be hydrophilic polymeric chain to the better polymerization chain, acrylate copolymer for example, quaternary ammonium cation type methacrylate based polymers etc., (J~J) can also be the polymer that is connected with specific functional groups to the better polymerization chain, for example be connected with nitro, sulfonic group, the polymer of functional groups such as sulfydryl, they can improve the chemical property of composite material and can solve anodal many sulfur materials institutional framework problem of unstable well, thereby improve the combination property of composite material.The molecular weight of polymeric chain (MW) is 1000~10000000.
Step 3) has the nano-sized carbon and the elementary sulfur of network configuration or contains-S mThe polysulfide of-structure (m>2) compound, the nano-sized carbon sulphur composite material that obtains having network configuration
By step 2) nano-sized carbon of the network configuration that obtains, adopt some specific method and elementary sulfur under certain condition or contain-S mThe polysulfide of-structure (m>2) is compound.Can adopt methods such as solution composite approach, reaction in-situ composite algorithm, ULTRASONIC COMPLEX method, gel precipitation composite algorithm, fusion composite algorithm, the hot composite algorithm of vacuum, mechanical composite algorithm with elementary sulfur or contain-S mThe polysulfide of-structure (m>2) is compound in the network configuration of nano-sized carbon, as shown in the formula showing, forms the nano-sized carbon sulphur composite material with network configuration.Said method can use separately, also can unite use.
Bonding has the nano-sized carbon of the network configuration of polymeric chain to have the nano-sized carbon sulphur composite material of network configuration on the carbon granules
Lifting four kinds of complex methods below further specifies:
Solution composite approach
In three mouthfuls of round-bottomed flasks of the 1000ml that the 12g-150g elementary sulfur is housed, add 300-650ml solvent (CS 2, DMF, DMSO, THF equal solvent use separately or two kinds, multiple mixing use) make the sulphur dissolving, the nano-sized carbon that adds the 1g-25g network configuration again, under agitation slowly remove and desolvate (can utilize vacuum), obtain the nano-sized carbon sulphur composite material of network configuration of the weight content 30%-99% of elementary sulfur or/and heat energy.
The hot composite algorithm of vacuum
Prepared 1g-25g network structure nanometer carbon and 12g-150g elementary sulfur are pressed required metering ratio, simple and mechanical stirring or high speed ball milling mix, said mixture is put into porcelain crucible, again porcelain crucible is put into stainless steel pressure pan (anti-26MPa), vacuumize back (it is following that vacuum degree drops to 1mmHg) and close break valve, heat treated in the temperature programmed control muffle furnace then, slowly be warmed up to 150 ℃ from 3 ℃/min of room temperature, keep 3h at 150 ℃, then with 2 ℃/min speed continue to be warmed up to 350 ℃ and keep 2h~4h after, cool to 200 ℃ with 2 ℃/min speed, naturally cool to room temperature then, obtain carbon sulphur composite positive pole, sulfur content is 30%-99%.
The reaction in-situ composite algorithm
At the nano-sized carbon that the 1g-25g network configuration is housed, sodium sulfite, solvent (water, alcohols, acetone etc. use separately or two kinds, multiple mixing use) reactor in, stir and drip sulfuric acid and sodium sulfide solution down, generated in-situ sulphur original position is compound in the network of nano-sized carbon, forms composite material, filters, clean, drying obtains the nano-sized carbon sulphur composite material that sulfur content is the network configuration of 30%-99%.
The gel precipitation composite algorithm
In the reactor of the colloid sulphur that 12g-150g is housed, add the nano-sized carbon of the network configuration of aequum, ball milling or stirring 1h-200h, centrifugal then, to clean 3 times, drying obtains the nano-sized carbon sulphur composite material that sulfur content is the network configuration of 30%-99%.
Above for example just to the explanation of method, their cited conditions do not form method itself and limit.For example the method for original position generation sulphur is just given an example in the reaction in-situ composite algorithm, and the method that other original position generates sulphur is included in the reaction in-situ composite algorithm.
Compared to the prior art, the present invention has not only utilized conductivity, porousness and the adsorptivity of material with carbon element, also utilized the respond of the class condensed-nuclei aromatics of material with carbon element, rely on irreversible chemical reaction, functional group is incorporated on the carbon granules, and then introduces polymeric chain, polymeric chain stretches at carbon grain surface, bending, crosslinked, thereby the formation cross-linked network structure, again by several different methods with elementary sulfur or contain-S mThe polysulfide of-structure (m>2) is compound in the network configuration, has creatively prepared the nano-sized carbon sulphur composite material with network configuration.
Compare with current material, the material of the present invention's preparation has following outstanding advantage:
(1) Fa Ming the nano-sized carbon sulphur composite material with network configuration has abundant cross-linked network structure, and the network hole of nanoscale is with elementary sulfur or contain-S mThe polysulfide of-structure (m>2) " constraint " is among network, active matter is limited in certain regional internal reaction, network configuration can also effectively suppress the dissolving diffusion loss of the many lithium sulfides of discharging product, thereby improves the utilance and the electrochemistry cycle performance of material activity thing;
(2) cross-linked network structure that enriches in the composite material is just as " reinforcing bar " in the composite material, can improve the combined strength bination of sulphur and carbon, also can improve the compound quantity of sulphur, thereby solve many sulfur materials institutional framework problem of unstable and improve the capacity of material, and then improve the circulative specific energy of battery;
(3) when cross-linked network structure abundant in the composite material is made of conducting polymer chain or ion conductor polymeric chain, it can improve electronics or the ion transportation and the response area of material, material has outstanding electric conductivity, thereby improves the specific power and the specific energy of battery.
(4) when introducing some specific functional groups in the composite material, can obviously improve, improve the chemical property of some aspect of composite material.
The nano-sized carbon sulphur composite material with network configuration that the present invention is prepared has higher specific discharge capacity, excellent cycle performance and heavy-current discharge high rate performance, can be used as the positive electrode of secondary lithium-sulfur cell.
Description of drawings
The discharge capacity figure of the nano-sized carbon sulphur composite material of Fig. 1 network configuration
Ordinate: discharge voltage, abscissa: discharge capacity.
The cyclic curve figure of the nano-sized carbon sulphur composite material of Fig. 2 network configuration
Ordinate: specific discharge capacity, abscissa: circulation discharge time.
Embodiment
Following embodiment is that embodiment just illustrates to one of ordinary skill in the art full disclosure material of the present invention and preparation method thereof, is not the restriction to the invention scope of inventor's requirement.
Embodiment 1
Place the there-necked flask whipping process to drip dense HNO the 15g carbon black 3Solution 500mL, ultrasonic 30min, water-bath is heated to 80 ℃, and condensing reflux 4h stops reaction, filters, and cleans, and obtains the carbon of the functionalization of groups such as hydroxyl, carboxyl, ester group.
Embodiment 2
Preparation 0.25mol/L K 2C r 2O 7, 1mol/L hydrochloric acid mixed solution 500mL moves in the 1000mL there-necked flask, adds the 15g carbon black, and ultrasonic dispersion 30min stirs 4h at 80 ℃ of following high speed machines, and cooling is washed till the filtrate neutrality repeatedly with a large amount of deionized waters.Placing vacuum drying chamber 24h to dry the carbon that obtains the functionalization of groups such as hydroxyl, carboxyl, ester group after grind the back product under 80 ℃.
Embodiment 3
Add the 15g carbon black in reaction bulb, stir the mixed solution of the Dropwise 5 ml concentrated sulfuric acid and 100ml acetic anhydride down, be incubated 70 ℃, 1h is added dropwise to complete, be chilled to room temperature after, stir down and carefully pour in the 500ml water, filter, cleaning obtains containing the carbon of sulfonic functionalization.
Embodiment 4
In reaction bulb, add the 15g carbon black, 200ml water, 5g paranitroanilinum, the 20ml aqueous solution of dropping 3g natrium nitrosum under the vigorous stirring, reaction temperature is controlled at 50~60 ℃, be added dropwise to complete the back and continue to stir 2h, at this moment bubble disappears substantially, stops reaction, filter, clean, drying obtains the carbon of the functionalization of nitrobenzene-containing base.
Embodiment 5
In reaction bulb, add the 15g carbon black, 200ml water, 8gl, 4 two amido benzene, drip the 20ml aqueous solution of 3g natrium nitrosum under the vigorous stirring, reaction temperature is controlled at 80 ℃, is added dropwise to complete the back and continues to stir 1 hour, and at this moment bubble disappears substantially, stop reaction, filter, clean, obtain containing the carbon of the functionalization of aminophenyl.
Embodiment 6
In reaction bulb, add the 15g carbon black, 200ml methyl alcohol, 3g 2-amino-pyrroles, the 20ml aqueous solution of dropping 3g natrium nitrosum under the vigorous stirring, reaction temperature is controlled at 60 ℃, being added dropwise to complete the back continues to stir 5 hours, at this moment bubble disappears substantially, stops reaction, filters, clean, obtain containing the carbon of the functionalization of pyrrole radicals.
Embodiment 7
In reaction bulb, add the 15g carbon black, 200ml methyl alcohol, 2.5g the 2-aminothiophene, the 20ml aqueous solution of dropping 3g natrium nitrosum under the vigorous stirring, reaction temperature is controlled at 60 ℃, being added dropwise to complete the back continues to stir 2 hours, at this moment bubble disappears substantially, stops reaction, filters, clean, obtain the carbon of the functionalization of thienyl-containing.
Embodiment 8
The product 10g that in reaction bulb, adds embodiment 2, the 200ml thionyl chloride stirs down and refluxes, 70 ℃ of reaction temperatures, stirring reaction 4 hours, at this moment bubble disappears substantially, stops reaction, removes thionyl chloride under reduced pressure, cleans, and obtains the carbon of chloride functionalization.
Embodiment 9
The product 10g that in reaction bulb, adds embodiment 1,3M aqueous hydrochloric acid solution 150ml ,-5~0 ℃, stir the 20ml aqueous solution that drips the 2.5g natrium nitrosum down, continue reaction 2 hours, stop.Filter, clean, drying obtains containing the carbon of the functionalization of nitrous acid ester group.
Embodiment 10
The product 10g that in reaction bulb, adds embodiment 1,20% nitric acid 200ml stirs down and adds thermal response, be incubated 85~90 ℃, react 5 hours, stop to react, filtration, cleaning, drying obtains containing the carbon of the functionalization of nitro ester group.
Embodiment 11
The product 10g that in reaction bulb, adds embodiment 3, absolute ethyl alcohol 150ml, p-methyl benzenesulfonic acid 100mg stirs down and adds thermal response, be incubated 50~55 ℃, react 10 hours, stop to react, filtration, cleaning, drying obtains containing the carbon of the functionalization of sulfonic acid ethoxycarbonyl.
Embodiment 12
The product 10g that in reaction bulb, adds embodiment 2, DMF150ml, phosphorus pentachloride 10g stirs down and adds thermal response, be incubated 60~65 ℃, react 10 hours, stop to react, filtration, cleaning, drying obtains containing the carbon of the functionalization of acid chloride group.
Embodiment 13
The product 10g that in reaction bulb, adds embodiment 2, absolute ethyl alcohol 150ml, p-methyl benzenesulfonic acid 100mg stirs down and adds thermal response, be incubated 50~55 ℃, react 18 hours, stop to react, filtration, cleaning, drying obtains containing the carbon of the functionalization of carboxylic acid, ethyl ester base.
Embodiment 14
The product 10g that in reaction bulb, adds embodiment 8, ethylenediamine 5ml, anhydrous propanone 150ml, DMAP100mg stirs down and adds thermal response, be incubated 30~35 ℃, react 3 hours, stop to react, filtration, cleaning, drying obtains the carbon of the functionalization of amide containing ethylamino-.
Embodiment 15
The product 10g that in reaction bulb, adds embodiment 1, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, and is incubated 60~65 ℃, reacts 13 hours, stops reaction, filters, and cleans, and drying obtains the nano-sized carbon that surface bond has the PEG cross-linked network.
Embodiment 16
The product 10g that in reaction bulb, adds embodiment 1, PEG (molecular weight 10000) 5g, water 150ml adds thermal response under stirring, and is incubated 60~65 ℃, reacts 20 hours, stops reaction, filters, and cleans, and drying obtains the nano-sized carbon that surface bond has the PEG cross-linked network.
Embodiment 17
The product 10g that in reaction bulb, adds embodiment 1, PEG (molecular weight 18000) 10g, water 150ml adds thermal response under stirring, and is incubated 80~85 ℃, reacts 72 hours, stops reaction, filters, and cleans, and drying obtains the nano-sized carbon that surface bond has the PEG cross-linked network.
Embodiment 18
The product 10g that in reaction bulb, adds embodiment 6, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 60~65 ℃, reacted 18 hours, stop reaction, filter, clean, drying obtains containing the nano-sized carbon that itrate group and bonding have the PEG cross-linked network.
Embodiment 19
The product 10g that in reaction bulb, adds embodiment 5, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 60~65 ℃, reacted 18 hours, stop reaction, filter, clean, drying obtains containing the nano-sized carbon that nitrous acid ester group and bonding have the PEG cross-linked network.
Embodiment 20
The product 10g that in reaction bulb, adds embodiment 3, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 40~45 ℃, reacted 5 hours, stop reaction, filter, clean, drying obtains the nano-sized carbon of surface by sulfonic group bonding PEG cross-linked network.
Embodiment 21
The product 10g that in reaction bulb, adds embodiment 7, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 60~65 ℃, reacted 20 hours, stop reaction, filter, clean, drying obtains containing the nano-sized carbon that sulfonic acid ethoxycarbonyl and bonding have the PEG cross-linked network.
Embodiment 22
The product 10g that in reaction bulb, adds embodiment 1, PEO (molecular weight 60000) 5g, water 150ml adds thermal response under stirring, and is incubated 60~65 ℃, reacts 10 days, stops reaction, filters, and cleans, and drying obtains the nano-sized carbon that surface bond has the PEO cross-linked network.
Embodiment 23
The product 10g that in reaction bulb, adds embodiment 1, polyacrylic acid (molecular weight 15000) 4g, anhydrous propanone 150ml adds thermal response under stirring, be incubated 50~60 ℃, reacted 8 hours, stop reaction, filter, clean, drying obtains the nano-sized carbon that surface bond has polyacrylic cross-linked network.
Embodiment 24
The product 10g that in reaction bulb, adds embodiment 4, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 60~65 ℃, reacted 24 hours, stop reaction, filter, clean, drying obtains containing the nano-sized carbon that nitrobenzophenone and bonding have the PEG cross-linked network.
Embodiment 25
The product 10g that in reaction bulb, adds embodiment 10, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 60~65 ℃, reacted 18 hours, stop reaction, filter, clean, drying obtains containing the nano-sized carbon that acid amides ethylamino-and bonding have the PEG cross-linked network.
Embodiment 26
The product 10g that in reaction bulb, adds embodiment 1, p-nitrophenyl ethene and acrylic acid copolymer (molecular weight 50000) 3g, DMF150ml adds thermal response under stirring, and is incubated 80~85 ℃, reacted 3 hours, stop reaction, filter, clean, drying, obtaining surface bond has the cross-linked network nano-sized carbon that contains the nitro polymeric chain.
Embodiment 27
The product 10g that in reaction bulb, adds embodiment 8, PEG (molecular weight 5000) 3g, water 150ml adds thermal response under stirring, be incubated 60~65 ℃, reacted 24 hours, stop reaction, filter, clean, obtaining the carbon surface bonding has chlorine atom and bonding that the nano-sized carbon of PEG cross-linked network is arranged.
Embodiment 28
The product 10g that in reaction bulb, adds embodiment 27, and sodium polysulfide reactant liquor 150ml (by 2g vulcanized sodium, 6g sulphur, 50ml water, 100mlDMF, preparation in 12 hours refluxes), add thermal response under stirring, be incubated 85 ℃, reacted 24 hours, stop reaction, filter, clean, obtain carbon grain surface and be connected to-S m-(m>1) structure and bonding have the nano-sized carbon of PEG cross-linked network.
Embodiment 29
The product 10g that in reaction bulb, adds embodiment 5, aniline 3g, water 150ml, acetate 5ml stirs the aqueous solution (the 4g ferric trichloride that drips ferric trichloride down, the preparation of 20ml water), room temperature reaction 4 hours stops reaction, filters, clean, obtain the nano-sized carbon that the carbon grain surface bonding has the polyaniline cross-linked network.
Embodiment 30
The product 10g that in reaction bulb, adds embodiment 6, pyrroles 4g, water 150ml, acetate 5ml stirs the aqueous solution (the 4g ferric trichloride that drips ferric trichloride down, the preparation of 20ml water), room temperature reaction 4 hours stops reaction, filters, clean, obtain the nano-sized carbon that the carbon grain surface bonding has the polypyrrole cross-linked network.
Embodiment 31
The product 10g that in reaction bulb, adds embodiment 6, pyrroles 4g, water 150ml, acetate 5ml stirs down and drips 10% hydrogen peroxide 10ml, and room temperature reaction 2 hours stops reaction, filters, and cleans, and obtains the nano-sized carbon that the carbon grain surface bonding has the polypyrrole cross-linked network.
Embodiment 32
The product 10g that in reaction bulb, adds embodiment 7, thiophene 3g, water 150ml, acetate 5ml stirs the aqueous solution (the 4g ferric trichloride that drips ferric trichloride down, the preparation of 20ml water), 20 ℃ were reacted 4 hours, stopped reaction, filtered, clean, obtain the nano-sized carbon that the carbon grain surface bonding has the polythiophene cross-linked network.
Embodiment 33
The product 10g that in reaction bulb, adds embodiment 7, thiophene 3g, water 150ml, acetate 5ml stirs the aqueous solution (the 3g Ammonium Persulfate 98.5 that drips Ammonium Persulfate 98.5 down, the preparation of 40ml water), 20 ℃ were reacted 1 hour, stopped reaction, filtered, clean, obtain the nano-sized carbon that the carbon grain surface bonding has the polythiophene cross-linked network.
Embodiment 34
The product 10g that in reaction bulb, adds embodiment 1, quaternary ammonium salt cation dimethylaminoethyl methacrylate polymer (molecular weight 15000) 4g, anhydrous propanone 150ml, add thermal response under stirring, be incubated 50~60 ℃, reacted 8 hours, stop reaction, filter, clean, obtain the nano-sized carbon that surface bond has the cross-linked network of quaternary ammonium salt cation polyacrylate.
Embodiment 35
In the reactor that the 5g elementary sulfur is housed, add solvent 50mlCS 2, make the sulphur dissolving, add the nano-sized carbon 1g of the network configuration of embodiment 15 preparations again, under agitation slowly remove and desolvate, obtain the network structure nanometer carbon sulphur composite material of element sulfur content 83%.
Embodiment 36
In the reactor that the 5g elementary sulfur is housed, add solvent 500mlTHF, stir and make the sulphur dissolving, add the nano-sized carbon 1g of the network configuration of embodiment 15 preparations again, under agitation slowly remove and desolvate, obtain the network structure nanometer carbon sulphur composite material that contains the PEG chain of element sulfur content 83%.
Embodiment 37
In the reactor that the 5g elementary sulfur is housed, add solvent 50mlCS 2, make the sulphur dissolving, add the nano-sized carbon 1g of the network configuration of embodiment 18 preparations again, under agitation slowly remove and desolvate, the carbon grain surface bonding that obtains element sulfur content 83% has the network structure nanometer carbon sulphur composite material of itrate group.
Embodiment 38
In the reactor that the 5g elementary sulfur is housed, add solvent 50mlCS 2, make the sulphur dissolving, add the nano-sized carbon 1g of the network configuration of embodiment 30 preparations again, under agitation slowly remove and desolvate, the carbon grain surface bonding that obtains element sulfur content 83% has polypyrrole network structure nanometer carbon sulphur composite material.
Embodiment 39
In the reactor that the 5g elementary sulfur is housed, add solvent 50mlCS 2, make the sulphur dissolving, add the nano-sized carbon 1g of the network configuration of embodiment 33 preparations again, under agitation slowly remove and desolvate, the carbon grain surface bonding that obtains element sulfur content 83% has polythiophene network structure nanometer carbon sulphur composite material.
Embodiment 40
In the reactor that the 5g elementary sulfur is housed, add solvent 50mlCS 2, make the sulphur dissolving, add the nano-sized carbon 1g of the network configuration of embodiment 29 preparations again, under agitation slowly remove and desolvate, the carbon grain surface bonding that obtains element sulfur content 83% has polyaniline network structure nanometer carbon sulphur composite material.
Embodiment 41
In the reactor of network structure nanometer carbon 1g, sodium sulfite 6.5g that embodiment 20 preparations are housed, add 100ml water, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 8g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, obtain the network structure nanometer carbon sulphur composite material of the surface of sulfur content 83% by sulfonic group bonding PEG.
Embodiment 42
In the reactor of network structure nanometer carbon 1g, sodium sulfite 10g that embodiment 20 preparations are housed, add 200ml ethanol, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 10g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, obtain the network structure nanometer carbon sulphur composite material of the surface of sulfur content 85% by sulfonic group bonding PEG.
Embodiment 43
In the reactor of network structure nanometer carbon 1g, sodium sulfite 6.5g that embodiment 26 preparations are housed, add 100ml water, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 8g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material that contains the nitro polymeric chain.
Embodiment 44
In the reactor of network structure nanometer carbon 1g, sodium sulfite 6.5g that embodiment 33 preparations are housed, add 100ml water, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 8g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, obtain the network structure nanometer carbon sulphur composite material of the surface bond polythiophene chain of sulfur content 83%.
Embodiment 45
In the reactor of network structure nanometer carbon 1g, sodium sulfite 6.5g that embodiment 30 preparations are housed, add 100ml water, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 8g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material of polypyrrole chain.
Embodiment 46
In the reactor of network structure nanometer carbon 1g, sodium sulfite 6.5g that embodiment 28 preparations are housed, add 100ml water, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 8g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, the surface bond that obtains sulfur content 83% has-S m-(m>1) structure and bonding have PEG cross-linked network structure nano-sized carbon sulphur composite material.
Embodiment 47
In the reactor of network structure nanometer carbon 1g, sodium sulfite 6.5g that embodiment 34 preparations are housed, add 100ml water, stir the aqueous solution 30ml that drips dilute sulfuric acid 20ml and 8g vulcanized sodium down, generated in-situ sulphur original position is compound in the polymer network of nano-sized carbon, form composite material, filter, clean, the surface bond that obtains sulfur content 83% has the cross-linked network structure nano-sized carbon sulphur composite material of quaternary ammonium salt cation polyacrylate.
Embodiment 48
Network structure nanometer carbon 10g with preparation among the embodiment 34, elemental sulfur 50g, grind with mortar respectively, cross 200 mesh sieve, put into the 1000mL beaker at 1: 5 by mass ratio, mechanical agitation fully mixes, and mixture is packed in the inner bag crucible of stainless steel high-pressure reaction pot, after with the vacuum oil pump jar being evacuated, close break valve.Stainless steel high-pressure reaction pot after the sealing is placed box temperature programming Ma Fulu, slowly be warmed up to 150 ℃ from 3 ℃/min of room temperature, keep 3h at 150 ℃, then with 2 ℃/min speed continue to be warmed up to 350 ℃ and keep 2h-4h after, cool to 200 ℃ with 2 ℃/min speed, naturally cool to room temperature then and obtain the cross-linked network structure nano-sized carbon sulphur composite material that surface bond has the quaternary ammonium salt cation polyacrylate, the sulfur content in this composite material is 82%.
Embodiment 49
Operation changes network structure nanometer carbon into embodiment 28 preparations with embodiment 48, and the surface bond that obtains sulfur content 83% has-S m-(m>1) structure and bonding have PEG cross-linked network structure nano-sized carbon sulphur composite material.
Embodiment 50
Operation changes network structure nanometer carbon into embodiment 30 preparations with embodiment 48, and the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material of polypyrrole chain.
Embodiment 51
Operation changes network structure nanometer carbon into embodiment 33 preparations with embodiment 48, and the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material of polythiophene chain.
Embodiment 52
Operation changes network structure nanometer carbon into embodiment 26 preparations with embodiment 48, and the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material that contains the nitro polymeric chain.
Embodiment 53
Operation changes network structure nanometer carbon into embodiment 20 preparations with embodiment 48, obtains the network structure nanometer carbon sulphur composite material of the surface of sulfur content 83% by sulfonic group bonding PEG.
Embodiment 54
Operation changes network structure nanometer carbon into embodiment 29 preparations with embodiment 48, and the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material of polyaniline chain.
Embodiment 55
Operation changes network structure nanometer carbon into embodiment 15 preparations with embodiment 48, and the surface bond that obtains sulfur content 83% has the network structure nanometer carbon sulphur composite material of PEG chain.
Embodiment 56
Network structure nanometer carbon 10g with preparation among the embodiment 34, elemental sulfur 50g, grind with mortar respectively, cross 200 mesh sieve, put into the 1000mL beaker at 1: 4 by mass ratio, mechanical agitation fully mixes, and mixture is packed in the inner bag crucible of stainless steel high-pressure reaction pot, after with the vacuum oil pump jar being evacuated, close break valve.Stainless steel high-pressure reaction pot after the sealing is placed box temperature programming Ma Fulu, slowly be warmed up to 150 ℃ from 3 ℃/min of room temperature, keep 3h at 150 ℃, then with 2 ℃/min speed continue to be warmed up to 350 ℃ and keep 2h~4h after, cool to 200 ℃ with 2 ℃/min speed, naturally cool to room temperature then and obtain the cross-linked network structure nano-sized carbon sulphur composite material that surface bond has the quaternary ammonium salt cation polyacrylate, the sulfur content in this composite material is 78%.
Embodiment 57
In the reactor that 10g colloid sulphur is housed, add methyl alcohol 200ml, stir ultrasonic dispersion, the network structure nanometer carbon 2g that adds preparation among the embodiment 34, stir ultrasonic 5 hours, centrifugal then, clean, obtaining surface bond has the cross-linked network structure nano-sized carbon sulphur composite material of quaternary ammonium salt cation polyacrylate, and the sulfur content in this composite material is 83%.
Embodiment 58
Sodium polysulfide reactant liquor 150ml is being housed (by 2g vulcanized sodium, 12g sulphur, 50ml water, 100mlDMF, preparation in 12 hours refluxes) reactor in, add the network structure nanometer carbon 2g of preparation among the embodiment 34, stirred ultrasonic 5 hours, centrifugal then, clean, obtaining surface bond has the cross-linked network structure nano-sized carbon of quaternary ammonium salt cation polyacrylate/contain-S mThe polysulfide of-structure (m>2) composite material, the sulfur content in this composite material is 81%.
Embodiment 59
Sodium polysulfide reactant liquor 150ml is being housed (by 2g vulcanized sodium, 12g sulphur, 50ml water, 100mlDMF, preparation in 12 hours refluxes) reactor in, add the network structure nanometer carbon 2g of preparation among the embodiment 29, stirred ultrasonic 5 hours, centrifugal then, clean, obtaining surface bond has the cross-linked network structure nano-sized carbon of polyaniline chain/contain-S mThe polysulfide of-structure (m>2) composite material, the sulfur content in this composite material is 81%.
Embodiment 60
Sodium polysulfide reactant liquor 150ml is being housed (by 2g vulcanized sodium, 12g sulphur, 50ml water, 100mlDMF, preparation in 12 hours refluxes) reactor in, add the network structure nanometer carbon 2g of preparation among the embodiment 33, stirred ultrasonic 5 hours, centrifugal then, clean, obtaining surface bond has the cross-linked network structure nano-sized carbon of polythiophene chain/contain-S mThe polysulfide of-structure (m>2) composite material, the sulfur content in this composite material is 81%.
Embodiment 61
Cross-linked network structure nano-sized carbon sulphur composite material, acetylene black, the Kynoar (PVDF) of the quaternary ammonium salt cation polyacrylate of embodiment 57 preparation are mixed by mass ratio at 80: 10: 10, with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in agate jar with the speed ball milling 8h of 500rpm, the slurry that obtains is uniformly coated on the collector aluminium foil, then in 60 ℃ vacuum tank dry 24 hours standby.With Celgrad2400 is barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)-1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery is at first with 0.4mA/cm 2Current density carry out constant current charge-discharge, cut-ff voltage is 1.5-2.8V, the first discharge specific capacity of composite positive pole elemental sulfur is 1186mAh/g, has occurred 2 tangible discharge platforms on the discharge curve, and 50 times circulation back specific discharge capacity remains on 948mAh/g.Its circulation specific discharge capacity is than the circulation specific discharge capacity with the cross-linked network structure nano-sized carbon sulphur composite material of the polyacrylate of quaternary ammonium salt cation functional group is not high by 15%.
Embodiment 62
Cross-linked network structure nano-sized carbon sulphur composite material, acetylene black, the LA132 binder of the quaternary ammonium salt cation polyacrylate of embodiment 57 preparation are mixed by mass ratio at 80: 10: 10, with normal propyl alcohol-water is solvent, in agate jar with the speed ball milling 8h of 500rpm, the slurry that obtains is uniformly coated on the collector aluminium foil, then in 60 ℃ vacuum tank dry 24 hours standby.With Celgrad2400 is barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)-1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.With Celgrad2400 is barrier film, 0.4mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)+0.4mol/L lithium nitrate/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery is at first with 0.4mA/cm 2Current density carry out constant-current discharge, with 1mA/cm 2Current density carry out constant current charge, discharging and recharging cut-ff voltage is 1.5-2.8V, the first discharge specific capacity of composite positive pole elemental sulfur is 1208mAh/g, has occurred 2 tangible discharge platforms on the discharge curve, and 55 times circulation back specific discharge capacity remains on 918mAh/g.Its circulation specific discharge capacity is than the circulation specific discharge capacity with the cross-linked network structure nano-sized carbon sulphur composite material of the polyacrylate of quaternary ammonium salt cation functional group is not high by 18%.
Embodiment 63
The surface of embodiment 42 preparation network structure nanometer carbon sulphur composite material, acetylene black, the LA132 binder by sulfonic group bonding PEG mixed by mass ratio at 80: 10: 10, with normal propyl alcohol-water is solvent, in agate jar with the speed ball milling 24h of 500rpm, the slurry that obtains is uniformly coated on the collector aluminium foil, then in 60 ℃ vacuum tank dry 24 hours standby.With Celgrad2400 is barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)+0.4mol/L lithium nitrate/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery is at first with 0.4mA/cm 2Current density carry out constant current charge-discharge, cut-ff voltage is 1.5-2.8V, the first discharge specific capacity of composite positive pole elemental sulfur is 1181mAh/g, 2 tangible discharge platforms have appearred on the discharge curve, 55 times circulation back specific discharge capacity remains on 1045mAh/g, place after 30 days, specific discharge capacity remains on 988mAh/g.The obstructed persulfonic acid base key of its self-discharge rate specific surface closes the self-discharge rate low 30% of the network structure nanometer carbon sulphur composite material of PEG.
Embodiment 64
The surface bond of embodiment 40 preparations there are polyaniline network structure nanometer carbon sulphur composite material, acetylene black, polyethylene glycol oxide (PEO, 5000000) mix at 80: 10: 10 by mass ratio, with isopropyl alcohol-water is solvent, in agate jar with the speed ball milling 24h of 500rpm, the slurry that obtains is uniformly coated on the collector aluminium foil, then in 60 ℃ vacuum tank dry 24 hours standby.With Celgrad2400 is barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery is at first with 0.8mA/cm 2Current density carry out constant current charge-discharge, cut-ff voltage is 1.5-2.8V, the first discharge specific capacity of composite positive pole elemental sulfur is 1068mAh/g, has occurred 2 tangible discharge platforms on the discharge curve, and 30 times circulation back specific discharge capacity remains on 960mAh/g.Its power characteristic is apparently higher than the network structure nanometer carbon sulphur composite material that does not contain the conducting polymer chain.
Embodiment 65
The network structure nanometer carbon sulphur composite material, acetylene black, the polyethylene glycol oxide (PEO that the surface bond of embodiment 37 preparations are had itrate group, 5000000) mix at 80: 10: 10 by mass ratio, with isopropyl alcohol-water is solvent, in agate jar with the speed ball milling 24h of 500rpm, the slurry that obtains is uniformly coated on the collector aluminium foil, then in 60 ℃ vacuum tank dry 24 hours standby.With Celgrad2400 is barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery is at first with 0.4mA/cm 2Current density carry out constant current charge-discharge, cut-ff voltage is 1.5-2.8V, the first discharge specific capacity of composite positive pole elemental sulfur is 1168mAh/g, 2 tangible discharge platforms have appearred on the discharge curve, 50 times circulation back specific discharge capacity remains on 960mAh/g, and the efficiency for charge-discharge of battery is greater than 95%.Its efficiency for charge-discharge specific surface does not have the efficiency for charge-discharge of network structure nanometer carbon sulphur composite material of bonding itrate group high by 15%.
Embodiment 66
The surface bond of embodiment 59 preparation there is the cross-linked network structure nano-sized carbon of polyaniline chain/contain-S mThe polysulfide of-structure (m>2) composite material, acetylene black, polyethylene glycol oxide (PEO, 5000000) mix at 80: 10: 10 by mass ratio, with isopropyl alcohol-water is solvent, in agate jar with the speed ball milling 24h of 500rpm, the slurry that obtains is uniformly coated on the collector aluminium foil, then in 60 ℃ vacuum tank dry 24 hours standby.With Celgrad2400 is barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery is at first with 0.4mA/cm 2Current density carry out constant current charge-discharge, cut-ff voltage is 1.5-2.8V, the first discharge specific capacity of composite positive pole elemental sulfur is 1218mAh/g, has occurred 2 tangible discharge platforms on the discharge curve, and 50 times circulation back specific discharge capacity remains on 990mAh/g.

Claims (14)

1. nano-sized carbon sulphur composite material with network configuration that is applied to lithium-sulfur cell is characterized in that this material is by nano-sized carbon with network configuration and elementary sulfur or contain-S mThe compound composition of the polysulfide of-structure, m>2; Wherein network configuration is made of polymeric chain, polymeric chain can be any polymer chain, is polyaniline preferably, polypyrrole, polythiophene, polyacetylene, polyethylene glycol (PEG), poly(ethylene oxide) (PEO), acrylate copolymer, methacrylate polymer, quaternary ammonium cation type methacrylate based polymers, or be connected with the polymer of nitro, sulfonic group or mercapto functional group; The molecular weight of polymeric chain (WM) is 1000~10000000.
2. composite material according to claim 1 is characterized in that elementary sulfur is a sublimed sulfur, crystallization sulphur, and colloid sulphur, no crystalline state sulphur, crystallite sulphur, the elemental sulfur of other form, or contain-S mThe polysulfide of-structure; Polysulfide is organic polysulfide or inorganic polysulfide, m>2.
3. preparation method with nano-sized carbon sulphur composite material of network configuration is characterized in that this method comprises following three steps:
1) functionalization of carbon granules: carbon granules is by the nano-sized carbon of chemical reaction generation functionalization, and the functional group on the carbon granules can be X, R, CN ,-SCN ,-NCO ,-OH ,-COOH ,-COOR ,-COR ,-COX ,-CONHR ,-CONR 2,-NO 2,-SO 3H ,-OR ,-SH ,-SS-,-S n-, SR ,-SSR ,-NH 2,-NHR ,-NR 2, or-N +R 3Wherein: X=F, Cl, Br or I, R are alkyl, alkylene or aromatic radical, n=1~9; The functionalization of carbon granules also comprises the situation of material with carbon element functionalization in preparation process;
2) chemical bonding of the carbon of functionalization and polymeric chain, obtain having the nano-sized carbon of network configuration: the nano-sized carbon of functionalization utilizes its functional group to form by chemical reaction bonding high molecular polymerization chain, the stretching, extension of polymeric chain, bending, the crosslinked network configuration that constitutes carbon grain surface form the nano-sized carbon with network configuration;
3) have the nano-sized carbon and the elementary sulfur of network configuration or contain-S mThe polysulfide of-structure compound, m>2, the nano-sized carbon sulphur composite material that obtains having network configuration; Complex method can adopt solution composite approach, reaction in-situ composite algorithm, ULTRASONIC COMPLEX method, gel precipitation composite algorithm, fusion composite algorithm, the hot composite algorithm of vacuum or mechanical composite algorithm, and these methods can be used separately, also can two or more unite use:
Solution composite approach: it is compound to be meant that the dissolubility property that utilizes solution carries out in solution, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h;
The reaction in-situ composite algorithm: be meant and utilize the chemical reaction original position to generate sulphur, carry out compoundly again, the method is carried out in solution, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h;
The ULTRASONIC COMPLEX method: the ULTRASONIC COMPLEX method is meant that to utilize ultrasonic wave to carry out compound, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h, power 300~800W;
The gel precipitation composite algorithm: the gel precipitation composite algorithm be adopt colloid sulphur in solution, carry out compoundly, reaction temperature is 0~150 ℃, the reaction time is 2~4h;
The fusion composite algorithm: the fusion composite algorithm is meant that to utilize molten sulfur to carry out compound, and reaction temperature is 100~300 ℃, and the reaction time is 2~4h;
The hot composite algorithm of vacuum: the hot composite algorithm of vacuum is meant that to utilize vacuum degree to carry out compound in closed container, reaction temperature is 100~350 ℃, and the reaction time is 2~4h, vacuum degree 0.1~10mmHg;
The machinery composite algorithm: mechanical composite algorithm is meant that to utilize ball milling, stirring, concussion to carry out compound, and reaction temperature is 0~150 ℃, and the reaction time is 2~4h.
4. composite material and preparation method thereof according to claim 3, it is characterized in that this method step 1) functionalization and the step 2 of carbon granules) carbon of functionalization and the chemical bonding of polymeric chain, obtain having the nano-sized carbon of network configuration, can in same reaction unit, carry out, also can react simultaneously or by priority.
5. composite material and preparation method thereof according to claim 3 is characterized in that carbon granules is the carbon granules of carbon black, active carbon, graphite, nanometer carbon granules, other dispersion or their mixture; The size of particle is 0.1~10000nm, and the specific area of carbon granule can be 1~5000m 2/ g, the conductivity of carbon granule can be 0.01~1000S/cm, the pore volume of carbon granule can be 0.01~5cm 3/ g.
6. composite material and preparation method thereof according to claim 3, it is characterized in that the functional group on the nano-sized carbon of functionalization can be converted into by chemical reaction-OH-X or-X is converted into-S-S-, X is a halogen.
7. composite material and preparation method thereof according to claim 3 is characterized in that the polymeric chain that constitutes network configuration has active function groups, and active function groups can be a terminal functionality, also can be the functional group on the monomer in the polymeric chain.
8. composite material and preparation method thereof according to claim 3, when it is characterized in that the carbon granules of functionalization and the functional group on the polymeric chain carry out the bonding chemical reaction, polymeric chain can be one or more.
9. composite material and preparation method thereof according to claim 3, when it is characterized in that the carbon granules of functionalization and the functional group on the polymeric chain carry out the bonding chemical reaction, the bonding chemical reaction that takes place between them can be class reaction or the above reaction of a class in esterification, etherification reaction, condensation reaction, substitution reaction, the addition reaction.
10. composite material and preparation method thereof according to claim 3, the carbon granules that it is characterized in that functionalization also can with generated in-situ PCR; The polymerization reaction of polymer monomer and bonding reaction carry out in same reaction unit, and two reactions can take place simultaneously, also can successively take place.
11. composite material and preparation method thereof according to claim 3, when it is characterized in that the carbon granules of functionalization and the functional group on the polymeric chain carry out the bonding chemical reaction, bonding reaction can all take place in functional group, also bonding reaction can take place partly.
12. composite material and preparation method thereof according to claim 3, it is characterized in that functional group introduces by polymeric chain, before or after functionalization carbon and polymeric chain bonding, introduce, can all introduce or the part introducing, or introducing respectively or introducing simultaneously on the material with carbon element and on the polymeric chain.
13. composite material according to claim 1 and 2, it is characterized in that elementary sulfur or contain-content of polysulfide in having the nano-sized carbon sulphur composite material of network configuration of Sm-structure is 20%~99.9%, m>2.
14. according to the composite material described in the claim 1, it is characterized in that comprising positive pole, negative pole, electrolyte three parts by the lithium-sulfur cell that composite material is formed, wherein positive electrode active material is the nano-sized carbon sulphur composite material with network configuration, negative pole is lithium metal, lithium alloy, mix the carbon of lithium, mix in the graphite of lithium one or more, and electrolyte is one or more in liquid electrolyte, colloidal polymer electrolyte, the solid polymer electrolyte.
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