CN101891930B - Carbon nano tube-containing sulfur-based composite cathode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a carbon nano tube-containing sulfur-based composite cathode material and a preparation method thereof. The sulfur-based composite cathode material is a ternary composite material AxByCz, wherein A is a dehydrocyclization product of an acrylonitrile-itaconic acid copolymer; B is elemental sulfur; C is a carbon nano tube; x is more than or equal to 30 weight percent and less than or equal to 60 weight percent; y is more than or equal to 30 weight percent and less than or equal to 60 weight percent; and z is more than or equal to 1 weight percent and less than or equal to 20 weight percent, wherein the surface of the C is cladding by A. The preparation method comprises the following steps of: in-situ polymerizing an acrylonitrile-itaconic acid monomer on the surface of the multi-wall carbon nano tube, and performing thermal treatment on both of the acrylonitrile-itaconic acid copolymer and the elemental sulfur, so that the sulfur is uniformly dispersed in a substrate formed by the dehydrocyclization of the acrylonitrile-itaconic acid copolymer. The carbon nano tube-containing sulfur-based composite cathode material and a lithium cathode form a secondary lithium-sulfur battery which is charged and discharged at the room temperature. The carbon nano tube-containing sulfur-based composite cathode material has the reversible specific capacity of 697 mAh/g and high cyclical stability.
Description
Technical field
The present invention relates to sulfur-based composite anode material of a kind of positive electrode for battery material and preparation method thereof, particularly a kind of carbon nanotubes and preparation method thereof.
Background technology
Battery is the indispensable device of contemporary society.From the portable type electronic product of mobile phone and so on, to electromobile and aerospacecraft, the utilization of arriving renewable energy source again, battery is just being brought into play irreplaceable effect as the storage and the transfer equipment of energy.Lithium ion battery is compared with other types secondary cell commonly used, because of it has very high specific energy with energy density per unit volume has very big advantage, has attracted concern widely.The secondary cell of low cost, high-energy-density, high security, long circulation life, environmental protection is a lithium cell hot of research and development of future generation.
The iron lithium phosphate of lithium transition-metal oxide that present commercial positive electrode material mainly is stratiform or spinel structure (like cobalt acid lithium, lithium manganate) and olivine structural etc.Cobalt acid lithium (LiCoO
2) theoretical capacity relatively large, 275mAh/g, but its price is high, and certain toxicity is arranged, and this material is prone to take place exothermal decomposition reactions when overcharging makes the about 140mAh/g of actual capacity of this material also battery security to be threatened on the other hand on the one hand.Lithium manganate (LiMn
2O
4) theoretical capacity be 148mAh/g, actual capacity is lower than 130mAh/g.Iron lithium phosphate (LiFePO
4) theoretical capacity have only 172mAh/g.Above-mentioned these positive electrode active materials capacity are lower, and price height and poor stability, can not satisfy the requirement of high-energy density secondary battery of future generation.Elemental sulfur can generate lithium sulfide (Li with the lithium reaction
2S), its theoretical capacity be more than 6 times of lithium of cobalt acid, and elemental sulfur is cheap, safety non-toxic, is the novel anode active material that has development potentiality up to 1672mAh/g.
Since long period; The inorganic sulphide of elemental sulfur and sulfur-bearing, organic disulfide, gather organic disulfide, organic polysulfide, gather the thioated thing and carbon-sulphur polymkeric substance etc. is extensively paid close attention to as the positive electrode material of heavy body, but still there are a lot of problems in these materials.At first, the electroconductibility of elemental sulfur and sulfide itself is very poor, must add a large amount of static eliminators to increase its electroconductibility.Secondly, concerning elemental sulfur as the positive pole of active material, though the Li of the elementary sulfur that exists on the positive pole when charging fully existence when discharging fully
2S is insoluble in the polarity organic electrolyte, but many lithium sulfides that positive pole contains when partial charging and discharge condition are soluble in the polarity organic electrolyte, and is same; The small molecules sulfide that produces when gathering the organic sulfide discharge also is soluble in organic electrolyte, and in the negative pole deposition, influences the cycle performance (Kolosnitsyn of battery; V.S., Karaseva, E.V.Russian Journal of Electrochemistry 2008; 44 (5), pp.506-509).Therefore, how improving the electroconductibility of material, and solve the problems of dissolution that discharges and recharges intermediate product, improve cycle performance of battery, is the research emphasis of sulfenyl positive electrode material.
Because elemental sulfur has higher embedding lithium capacity relatively, therefore first-selected elemental sulfur is as the active body of matrix material.Chinese patent CN02111403.X provides a kind of electrochemical power source anodal with elemental sulfur/conducting polymer composite material and method.Research show elemental sulfur and polyacrylonitrile (PAN) high temperature (about 300 ℃) can the generation polyacrylonitrile cyano-cyclization reaction, elemental sulfur has dehydrogenation, makes the PAN dehydrogenation generate the conductive polymers of similar polyacetylene earlier; Then make its cyanic acid cyclisation form a kind of conductive polymers with macromole aperture (Jiulin Wang, Jun Yang, Chunrong Wan of complicacy; Jingying Xie; And Naixin Xu.Adv.Funct.Mater 2003,13, No.6487:492).Elemental sulfur can be penetrated under molten state in the micropore of polyacrylonitrile formed carbon back grid space and material, and the while is possibility subparticipation binding reaction also, forms the sulfenyl matrix material.With this material in lithium ion battery for the second time specific discharge capacity can reach 800mAh/g, after 50 circulations, specific storage remains on more than the 600mAh/g.
Because elemental sulfur is the electronic isolation material, traditional sulfenyl positive electrode material exists electron conduction low, and the lithium secondary battery power characteristic difference of making etc. are shortcoming significantly.
Summary of the invention
The object of the present invention is to provide sulfur-based composite anode material of a kind of carbon nanotubes and preparation method thereof.
The composition of the sulfur-based composite anode material of a kind of carbon nanotubes of the present invention is following:
Trielement composite material A for black powder
xB
yC
zWherein A is the dehydrocyclization product of polyacrylonitrile, the dehydrocyclization product of acrylonitrile itaconic acid multipolymer, the dehydrocyclization product of acrylonitrile itaconic acid ammonium multipolymer, the dehydrocyclization product of acrylonitrile itaconic acid lithium multipolymer or the dehydrocyclization product of acrylonitrile itaconic acid sodium multipolymer, and wherein methylene-succinic acid, methylene-succinic acid ammonium, methylene-succinic acid lithium or the mass content of sodium itaconate in multipolymer are 0.1-20wt%; B is an elemental sulfur; C is a carbon nanotube; Wherein 30≤x≤60wt%, 30≤y≤60wt%, 1≤z≤20wt%; Wherein A is coated on the surface of C.
The preparation method of the sulfur-based composite anode material of a kind of carbon nanotubes of the present invention is following, below all representes with mass parts:
It is in 1: 1 the mixed solvent that the carbon nanotube of 0.3-0.7 part is dispersed in 100 parts of DMSO 99.8MIN.s and quality ratio; The vinyl cyanide that adds 15-25 part again; The methylene-succinic acid of 0-8 part, methylene-succinic acid ammonium, methylene-succinic acid lithium or sodium itaconate; 0.1-0.5 the initiator of part; Under argon gas or nitrogen protection, continue to stir and temperature is risen to 40-100 ℃, be incubated 0.5-12 hour, washing and filtering obtains being coated on polyacrylonitrile, acrylonitrile itaconic acid multipolymer, acrylonitrile itaconic acid ammonium multipolymer, acrylonitrile itaconic acid lithium multipolymer or the acrylonitrile itaconic acid sodium multipolymer of carbon nano tube surface; With elemental sulfur and the polyacrylonitrile that is coated on carbon nano tube surface, acrylonitrile itaconic acid multipolymer, acrylonitrile itaconic acid ammonium multipolymer, acrylonitrile itaconic acid lithium multipolymer or acrylonitrile itaconic acid sodium multipolymer by mass ratio 2-20: 1 mixes; Under argon gas or nitrogen protection, be heated to 200-400 ℃ and be incubated 1-20 hour, obtain a kind of sulfur-based composite anode material of carbon nanotubes.
Carbon nanotube external diameter used in the present invention is that 5-95 nanometer, length are 5-50 micron multi-walled carbon nano-tubes or SWCN.
The molecular-weight average of polyacrylonitrile used in the present invention, acrylonitrile itaconic acid multipolymer, acrylonitrile itaconic acid ammonium multipolymer, acrylonitrile itaconic acid lithium multipolymer or acrylonitrile itaconic acid sodium multipolymer is 10000-1000000.
Initiator used in the present invention is Diisopropyl azodicarboxylate, Sodium Persulfate, ammonium persulphate, VAL-DROP or ammonium chlorate.
Sulfur-based composite anode material of a kind of carbon nanotubes of the present invention and preparation method thereof has following advantage:
The sulfur-based composite anode material of a kind of carbon nanotubes of the present invention, at first polymer overmold is in carbon nano tube surface, and thermal treatment is inlaid into elemental sulfur in the polymkeric substance again.Help when cell positive material, giving full play to the high conductivity of multi-walled carbon nano-tubes and, improve the power characteristic of battery the stabilization of material structure.And the thickness size with respect to its particle of polymkeric substance that is coated on the multi-wall carbon nano-tube tube-surface is less; Help permeating with the sulphur compound tense; Realize compoundly more up hill and dale, increase the content of elemental sulfur in matrix material, thereby improve the energy density of matrix material.
The preparation method of the sulfur-based composite anode material of a kind of carbon nanotubes of the present invention; The method that at first adopts in-situ polymerization with polymer overmold in carbon nano tube surface; Adopt then and elemental sulfur thermal treatment, it is simple to have compound method, the material pattern the is adjustable controlled remarkable advantage that waits.
Adopt the positive pole and the lithium anode of the present invention's preparation to form the secondary lithium-sulfur cell, at room temperature discharge and recharge, the reversible capacity of the sulfur-based composite anode material of carbon nanotubes can reach 697mAh/g, and has good cyclical stability.
Description of drawings
Fig. 1 is a kind of TEM photo that is coated on the polyacrylonitrile of multi-wall carbon nano-tube tube-surface that obtains by embodiment 1.
Fig. 2 is the TEM photo of the sulfur-based composite anode material of a kind of carbon nanotubes of obtaining by embodiment 2.
Fig. 3 is the second time charging and discharging curve of sulfur-based composite anode material in lithium secondary battery of a kind of carbon nanotubes of obtaining by embodiment 2.
Fig. 4 is the cycle performance curve of sulfur-based composite anode material in lithium secondary battery of a kind of carbon nanotubes of obtaining by embodiment 2.
Embodiment
Following embodiment further specifies the present invention, but does not limit the scope of the invention.
Embodiment 1
It is in 1: 1 the mixed solvent that the 0.7g multi-walled carbon nano-tubes is dispersed in 100g DMSO 99.8MIN. and quality ratio; Add vinyl cyanide again with 20g; 0.3g initiator ammonium persulfate; Under under nitrogen protection, continuing to stir temperature is appreciated 50 ℃, be incubated 3 hours, washing and filtering obtains being coated on the polyacrylonitrile of carbon nano tube surface.Fig. 1 is the TEM photo that is coated on the polyacrylonitrile of multi-wall carbon nano-tube tube-surface, can find out that vinyl cyanide is coated on the surface of multi-walled carbon nano-tubes more equably through the original position polymers, and thickness is between 10-100nm.Elemental sulfur is mixed by mass ratio with the polyacrylonitrile that is coated on carbon nano tube surface at 16: 1; Under nitrogen protection, be heated to 400 ℃ and be incubated 1 hour; Obtain a kind of sulfur-based composite anode material of carbon nanotubes, wherein the content of carbon nanotube is 10wt%, and elemental sulfur content is 45wt%.
Embodiment 2
It is in 1: 1 the mixed solvent that the 0.5g multi-walled carbon nano-tubes is dispersed in 100g DMSO 99.8MIN. and quality ratio; Add the 20g vinyl cyanide again, 1g methylene-succinic acid, 0.5g initiator Diisopropyl azodicarboxylate; Under under nitrogen protection, continuing to stir temperature is appreciated 65 ℃; Be incubated 2 hours, washing and filtering obtains being coated on the acrylonitrile itaconic acid multipolymer of carbon nano tube surface, and wherein the content of methylene-succinic acid is 4wt%.Elemental sulfur is mixed by mass ratio with the acrylonitrile itaconic acid multipolymer that is coated on carbon nano tube surface at 8: 1; Under nitrogen protection, be heated to 300 ℃ and be incubated 4 hours; Obtain a kind of sulfur-based composite anode material of carbon nanotubes; Wherein the content of carbon nanotube is 6wt%, and elemental sulfur content is 42wt%.
Fig. 2 is the TEM photo of the sulfur-based composite anode material of carbon nanotubes, and visible elemental sulfur and polymkeric substance are coated on carbon nano tube surface preferably.The sulfur-based composite anode material of the carbon nanotubes that obtains and sticker PTFE, static eliminator SuperP are mixed according to 8: 1: 1 mass ratios and be made into positive plate; With the metallic lithium is negative pole, and Cellgard 2400 is a barrier film, and the NSC 11801 of 1mol/L lithium hexafluoro phosphate and methylcarbonate (volume ratio 1: 1) mixing solutions is an electrolytic solution; In being full of the glove box of argon gas, be assembled into the CR2016 button cell; Carry out the charge-discharge performance test under the room temperature, first discharge specific capacity is 862mAh/g, and specific discharge capacity reaches 697mAh/g for the second time; See Fig. 3, its cycle performance is seen Fig. 4.
Embodiment 3
It is in 1: 1 the mixed solvent that the 0.3g multi-walled carbon nano-tubes is dispersed in 100g DMSO 99.8MIN. and quality ratio; Add the 25g vinyl cyanide again, 5g methylene-succinic acid ammonium, 0.4g initiator ammonium chlorate; Under under nitrogen protection, continuing to stir temperature is appreciated 80 ℃; Be incubated 8 hours, washing and filtering obtains being coated on the acrylonitrile itaconic acid ammonium multipolymer of carbon nano tube surface, and wherein the content of methylene-succinic acid ammonium is 10wt%.Elemental sulfur is mixed by mass ratio with the acrylonitrile itaconic acid ammonium multipolymer that is coated on carbon nano tube surface at 4: 1; Under argon shield, be heated to 350 ℃ and be incubated 2 hours; Obtain a kind of sulfur-based composite anode material of carbon nanotubes; Wherein the content of carbon nanotube is 3wt%, and elemental sulfur content is 50wt%.
Embodiment 4
It is in 1: 1 the mixed solvent that the 0.5g SWCN is dispersed in 100g DMSO 99.8MIN. and quality ratio; Add the 15g vinyl cyanide again, 3g sodium itaconate, 0.5g initiator Sodium Persulfate; Under under argon shield, continuing to stir temperature is appreciated 70 ℃; Be incubated 5 hours, washing and filtering obtains being coated on the acrylonitrile itaconic acid sodium multipolymer of carbon nano tube surface, and wherein the content of sodium itaconate is 18wt%.Elemental sulfur is mixed by mass ratio with the acrylonitrile itaconic acid sodium multipolymer that is coated on carbon nano tube surface at 18: 1; Under nitrogen protection, be heated to 250 ℃ and be incubated 18 hours; Obtain a kind of sulfur-based composite anode material of carbon nanotubes; Wherein the content of carbon nanotube is 10wt%, and elemental sulfur content is 60wt%.
Claims (4)
1. the sulfur-based composite anode material of a carbon nanotubes is characterized in that forming as follows:
Trielement composite material AxByCz for black powder; Wherein A is the dehydrocyclization product of polyacrylonitrile, the dehydrocyclization product of acrylonitrile itaconic acid multipolymer, the dehydrocyclization product of acrylonitrile itaconic acid ammonium multipolymer, the dehydrocyclization product of acrylonitrile itaconic acid lithium multipolymer or the dehydrocyclization product of acrylonitrile itaconic acid sodium multipolymer; Wherein methylene-succinic acid, methylene-succinic acid ammonium, methylene-succinic acid lithium or the mass content of sodium itaconate in multipolymer are 0.1-20wt%; B is an elemental sulfur; C is a carbon nanotube, 30≤x≤60wt%, 30≤y≤60wt%, 1≤z≤20wt%; Wherein a kind of sulfur-based composite anode material preparation method of carbon nanotubes is following, below all representes with mass parts:
It is in 1: 1 the mixed solvent that the carbon nanotube of 0.3-0.7 part is dispersed in 100 parts of DMSO 99.8MIN.s and quality ratio; The vinyl cyanide that adds 15-25 part again; The methylene-succinic acid of 0-8 part, methylene-succinic acid ammonium, methylene-succinic acid lithium or sodium itaconate; 0.1-0.5 the initiator of part; Under argon gas or nitrogen protection, continue to stir and temperature is risen to 40-100 ℃, be incubated 0.5-12 hour, washing and filtering obtains being coated on polyacrylonitrile, acrylonitrile itaconic acid multipolymer, acrylonitrile itaconic acid ammonium multipolymer, acrylonitrile itaconic acid lithium multipolymer or the acrylonitrile itaconic acid sodium multipolymer of carbon nano tube surface; With elemental sulfur and the polyacrylonitrile that is coated on carbon nano tube surface, acrylonitrile itaconic acid multipolymer, acrylonitrile itaconic acid ammonium multipolymer, acrylonitrile itaconic acid lithium multipolymer or acrylonitrile itaconic acid sodium multipolymer by mass ratio 2-20: 1 mixes; Under argon gas or nitrogen protection, be heated to 200-400 ℃ and be incubated 1-20 hour, obtain a kind of sulfur-based composite anode material of carbon nanotubes.
2. the sulfur-based composite anode material of a kind of carbon nanotubes according to claim 1 is characterized in that employed carbon nanotube external diameter is that 5-95 nanometer, length are 5-50 micron multi-walled carbon nano-tubes or SWCN.
3. the sulfur-based composite anode material of a kind of carbon nanotubes according to claim 1 is characterized in that the molecular-weight average of polyacrylonitrile, acrylonitrile itaconic acid multipolymer, acrylonitrile itaconic acid ammonium multipolymer, acrylonitrile itaconic acid lithium multipolymer or acrylonitrile itaconic acid sodium multipolymer is 10000-1000000.
4. the sulfur-based composite anode material of a kind of carbon nanotubes according to claim 1 is characterized in that employed initiator is Diisopropyl azodicarboxylate, Sodium Persulfate, ammonium persulphate, VAL-DROP or ammonium chlorate.
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| WO2012040934A1 (en) * | 2010-09-30 | 2012-04-05 | Shanghai Jiao Tong University | Cathode material for li-s battery and method for forming the same |
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| WO2012149672A1 (en) * | 2011-05-03 | 2012-11-08 | Shanghai Jiao Tong University | Cathode material containing graphene for li-s battery and method for forming the same |
| CN102208608B (en) * | 2011-05-18 | 2013-05-29 | 刘剑洪 | Preparation method of carbon-sulfur composite material for lithium ion battery carbon cathode material |
| CN102820454B (en) * | 2011-06-11 | 2016-05-18 | 苏州宝时得电动工具有限公司 | Electrode composite material and preparation method thereof, positive pole, there is this anodal battery |
| WO2012171450A1 (en) | 2011-06-11 | 2012-12-20 | 苏州宝时得电动工具有限公司 | Electrode composite material, method thereof, positive electrode and battery including the same |
| CN103000934B (en) * | 2011-09-16 | 2016-03-30 | 苏州宝时得电动工具有限公司 | Lithium-sulfur cell |
| WO2013057023A1 (en) | 2011-10-17 | 2013-04-25 | Volkswagen Ag | Active material for batteries |
| WO2014027272A2 (en) * | 2012-08-14 | 2014-02-20 | Basf Se | Composite materials for lithium-sulfur batteries |
| CN103682353A (en) * | 2012-09-12 | 2014-03-26 | 苏州宝时得电动工具有限公司 | Electrode composite material as well as preparation method thereof, positive electrode and battery with same |
| US9773581B2 (en) | 2012-11-30 | 2017-09-26 | Robert Bosch Gmbh | Cathode material for a Li—S battery and the method for preparing the same, a cathode made of the cathode material and a Li—S battery comprising the cathode |
| CN104241612A (en) * | 2013-06-14 | 2014-12-24 | 中国科学院大连化学物理研究所 | Sulphidepolymer coated sulfur / carbon composite material and preparation method thereof |
| US10601031B2 (en) | 2014-06-06 | 2020-03-24 | Robert Bosch Gmbh | Polymer electrolyte for a lithium sulfur cell |
| WO2016019544A1 (en) * | 2014-08-07 | 2016-02-11 | Robert Bosch Gmbh | Sulfur-polyacrylonitrile composite, preparation and use thereof |
| CN105591073A (en) * | 2014-10-23 | 2016-05-18 | 深圳华粤宝电池有限公司 | A cathode material used for secondary lithium batteries and a preparing method thereof |
| CN104538606B (en) * | 2014-12-19 | 2017-04-05 | 江苏华东锂电技术研究院有限公司 | Sulfur-based composite anode material and preparation method thereof |
| CN105161689A (en) * | 2015-09-28 | 2015-12-16 | 吉林大学 | Preparing method and application of polypyrrole/multi-wall carbon nanotube/sulfur composite material |
| DE102016211036A1 (en) | 2016-06-21 | 2017-12-21 | Robert Bosch Gmbh | Method for producing a cathode and battery cell |
| CN110707298B (en) * | 2018-07-10 | 2021-11-12 | 比亚迪股份有限公司 | Cathode material, preparation method thereof, lithium ion battery and vehicle |
| CN110835105A (en) * | 2018-08-17 | 2020-02-25 | 汉达精密电子(昆山)有限公司 | Surface treatment method of carbon nano tube |
| CN111285949B (en) * | 2020-02-13 | 2021-07-06 | 山东大学 | Polyacrylonitrile-coated graphene composite material and preparation method and application thereof |
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| FR2880353B1 (en) * | 2005-01-05 | 2008-05-23 | Arkema Sa | USE OF CARBON NANOTUBES FOR THE MANUFACTURE OF A CONDUCTIVE ORGANIC COMPOSITION AND APPLICATIONS THEREOF |
| CN101555007B (en) * | 2009-05-14 | 2011-02-16 | 上海理工大学 | Method for preparing multi-walled carbon nanometer tube by polyacrylonitrile nanometer microsphere |
| CN101577323B (en) * | 2009-06-11 | 2011-08-31 | 上海交通大学 | Sulfenyl anode of lithium-sulfur rechargeable battery and preparation method thereof |
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