CN110311111A - N adulterates CNT in-stiu coating Co nano particle composite material and preparation and application - Google Patents
N adulterates CNT in-stiu coating Co nano particle composite material and preparation and application Download PDFInfo
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Abstract
The invention belongs to field of nanocomposite materials, a kind of N doping CNT in-stiu coating Co nano particle composite material and preparation and application are disclosed.Urea, boric acid, polyethylene glycol and cobalt nitrate is soluble in water, and after being uniformly mixed, heating makes solvent volatilization completely, dry, obtains precursor powder, is then heat-treated, and obtains N doping CNT in-stiu coating Co nano particle composite material.The present invention obtains the CNT of N doping by in-situ thermo-polymerization, and load C o nano particle in carbon nanotube is acted on by in-situ reducing, prepare the N doping CNT in-stiu coating Co nano particle composite material that morphology controllable, size are uniform and structural stability is good, gained composite material is after carrying out S load, excellent electric conductivity and electrocatalytic effect makes it show excellent chemical property, including good cyclical stability and higher reversible specific capacity as Lithium-sulphur battery anode material.
Description
Technical field
The invention belongs to field of nanocomposite materials, and in particular to a kind of N doping CNT in-stiu coating Co nano-particles reinforcement
Material and preparation and application.
Background technique
With the development of society, lithium ion secondary battery is because of its higher operating voltage, longer cycle life and circulation
The advantages that stability, has become the first choice of all kinds of electronic product power sources.However as portable electronic device and new energy vapour
The fast development of vehicle, demand of the people to the electrochmical power source with high-energy density sharply increase.The lithium ion battery of commercialization
Positive and negative pole material type is more, and if positive and negative anodes active material is lithium ion " deintercalation " material, specific energy is difficult
With more than 300Wh/kg, therefore it is badly in need of developing the novel battery material with higher quality specific energy, to meet future
The demand of social and economic development.Currently, exploitation model electrochemical energy-storage system be countries in the world researcher concern emphasis and
The common technology challenge faced.Therefore, a kind of completely new, specific energy with higher novel energy-storing system is sought always
It is the research hotspot of energy storage field.
The concept of lithium-sulfur cell appears in the sixties in 19th century earliest.Even to this day, demand of the society for high-energy battery
It is increasingly stronger.Lithium-sulfur cell is also concerned, lithium-sulfur cell because of its mass energy density for being up to 2600Wh/kg
It is expected to be applied as next-generation high energy density cells system.In addition, positive active material-sulphur simple substance in lithium-sulfur cell
Also have the advantages that rich reserves, low in cost, environmental-friendly etc. are a series of.Lithium-sulfur cell working principle is to pass through lithium metal
Reversible electrochemical reaction between elemental sulfur is stored and is released energy, and theoretical energy density is existing lithium ion battery
3~5 times.
Although lithium-sulfur cell theoretical specific capacity with higher and energy density, as novel battery one
A little aspects still remain many problems, for example the capacity attenuation of battery is too fast, coulombic efficiency is more low, a series of this problem
It is limited further to commercialized propulsion.The main reason for causing this series of problems include: 1. elemental sulfur itself and its
The final product Li of reaction2S and Li2S2The poorly conductive of electronics and ion；2. due to the Li of sulphur simple substance and generation2S and Li2S's
Density difference is very big, so that the volume expansion (80%) that will cause to a certain extent causes to live so as to cause biggish internal stress
Falling off for property substance, influences the overall performance of battery；3. in charge and discharge process, the intermediate product polysulfide of generation can be generated
The problems such as " shuttle effect " is too fast so as to cause capacity attenuation, and cycle life is short reduce electrode active material utilization rate and
The cycle life of battery.Seriously hinder the commercialization process of lithium-sulfur cell.
Defect in the intrinsic characteristic of sulphur simple substance itself is lithium-sulfur cell main problem " perpetrator ", thus is passed through
It is to improve the main path of battery performance to solve the above problem of lithium-sulfur cell to the study on the modification of positive electrode.
In recent years, sulphur-carbon composite material and nano-metal particle-sulphur composite material etc. have obtained the wide of researcher
General concern.But single sulphur-carbon composite and nano metal chemical combination-sulphur composite material can have the limit to polysulfide
The disadvantages of performance processed is poor and poorly conductive.Therefore, if nano-metal particle and carbon can be obtained in conjunction with the advantages of two kinds of materials
Composite hybridization material will be expected to further promote the performance of lithium-sulfur cell.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, mixed the primary purpose of the present invention is that providing a kind of N
The preparation method of miscellaneous CNT in-stiu coating Co nano particle composite material.This method is by adjusting containing for the Co nano particle coated
Amount obtains presoma by high molecular polymerization effect and in-situ reducing, and the CNT for being then heat-treated to obtain N doping is in situ
Coat Co nano particle composite material.
Another object of the present invention is to provide a kind of N being prepared by the above method to adulterate CNT in-stiu coating Co
Nano particle composite material.
A further object of the present invention is to provide above-mentioned N doping CNT in-stiu coating Co nano particle composite materials as lithium-
The application of sulphur cell positive electrode material.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of N doping CNT in-stiu coating Co nano particle composite material, including following preparation step:
(1) urea, boric acid, polyethylene glycol (PEG) and cobalt nitrate is soluble in water, after being uniformly mixed, heating makes molten
Agent volatilization is completely, dry, obtains precursor powder；
(2) precursor powder that step (1) obtains is heat-treated, obtains N doping CNT in-stiu coating Co nano particle
Composite material.
Preferably, the mass ratio of polyethylene glycol described in step (1) and cobalt nitrate is 0.5:(0.2~0.6)；More preferably
0.5:0.4。
Preferably, temperature dry described in step (1) is 60~80 DEG C.
Preferably, it being heat-treated described in step (2) and carries out under an argon atmosphere, heat treatment temperature is 700~900 DEG C, when
Between be 4~6h.
A kind of N doping CNT in-stiu coating Co nano particle composite material, is prepared by the above method.
Further, N doping CNT diameter is 1~1.5 in the N doping CNT in-stiu coating Co nano particle composite material
μm。
Application of the above-mentioned N doping CNT in-stiu coating Co nano particle composite material as Lithium-sulphur battery anode material, institute
State application process are as follows: be uniformly mixed N doping CNT in-stiu coating Co nano particle composite material with elemental sulfur, heating and thermal insulation is anti-
It answers, reaction product further progress is heat-treated, remove extra S, obtain Lithium-sulphur battery anode material.
Preferably, the mass ratio of N doping CNT in-stiu coating Co nano particle composite material and elemental sulfur be 1:(3~
4)。
Preferably, the temperature of the heating and thermal insulation reaction is 155~200 DEG C, and the time is 12~16h.
Preferably, the heat treatment refers under an argon atmosphere, 200 are warming up to the heating rate of 1~3 DEG C/min~
250 DEG C of 0.5~2h of heat preservation.
Compared with prior art, the invention has the following advantages and beneficial effects:
(1) preparation method of the invention acts on the carbon nanotube of in-situ preparation N doping by high temperature polymerization.
(2) Co nano particle is supported on inside carbon nanotube by thermal reduction in situ and is obtained by preparation method of the invention
Co@CNT。
(3) the Co@CNT composite material of present invention gained N doping is after carrying out S load, the excellent double-deck absorption and catalysis
Effect makes it show excellent chemical property as Lithium-sulphur battery anode material, including outstanding cyclical stability and compared with
High reversible specific capacity.
Detailed description of the invention
Fig. 1 is the SEM figure of Co@CNT (4h) powder obtained in embodiment 1；
Fig. 2 is the SEM figure of Co@CNT (5h) powder obtained in embodiment 2；
Fig. 3 is the SEM figure of Co@CNT (6h) powder obtained in embodiment 3；
Fig. 4 is the SEM figure of Co@CNT (5h-1) powder obtained in embodiment 4；
Fig. 5 is the SEM figure of Co@CNT (5h-2) powder obtained in embodiment 5；
Fig. 6 is the SEM figure of Co@CNT (5h-3) powder obtained in embodiment 6；
Fig. 7 is the XRD diagram of the Co@CNT (5h-2) and standard control that prepare in embodiment 5；
Fig. 8 is the TG figure of Co@CNT (5h-2) positive electrode prepared by embodiment 7；
It is prepared by the Co@CNT (5h-1) and embodiment 9 that Fig. 9 is the Co@CNT (5h-2) of the preparation of embodiment 7, prepared by embodiment 8
Co@CNT (5h-3) positive electrode 0.1C cycle performance figure；
Figure 10 is charge and discharge electrograph of Co CNT (5h-2) positive electrode in 0.1C of the preparation of embodiment 7.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) 5 grams of urea is dissolved in 150mL deionized water, and be stirred at room temperature 10 minutes；
(2) 0.5 milligram of PEG is added to solution in (1), keeps magnetic agitation at room temperature；
(3) by 0.4 milligram of Co (NO3)2·6H2O is added to solution in (2), keeps magnetic agitation at room temperature；
(4) stirring 30 minutes in addition (3) solution of 0.3 milligram of boric acid, will be continued；
(5) finally by (4) mixed solution, make within heating and continuous 12 hours in oil bath pan solvent volatilization complete；
(6) by the pink precipitate that obtains in (5), precursor powder is collected, is put into baking oven, 80 DEG C of dry 8h；
(7) powder of the pink in (6) is put into porcelain boat, under an argon atmosphere, 900 is heated in tube furnace
DEG C, and 4 hours are kept the temperature, obtain N doping CNT in-stiu coating Co nano particle composite material Co@CNT (4h).
The SEM figure of obtained Co@CNT (4h) powder is as can be seen from the figure flooded with a large amount of piece referring to Fig. 1 in material
Shape object and a portion tablet have been changed to the tube that diameter is 200nm.
Embodiment 2
(1) 5 grams of urea is dissolved in 150mL deionized water, and be stirred at room temperature 10 minutes；
(2) 0.5 milligram of PEG is added to solution in (1), keeps magnetic agitation at room temperature；
(3) by 0.4 milligram of Co (NO3)2·6H2O is added to solution in (2), keeps magnetic agitation at room temperature；
(4) stirring 30 minutes in addition (3) solution of 0.3 milligram of boric acid, will be continued；
(5) finally by (4) mixed solution, make within heating and continuous 12 hours in oil bath pan solvent volatilization complete；
(6) by the pink precipitate that obtains in (5), precursor powder is collected, is put into baking oven, 80 DEG C of dry 8h；
(7) powder of the pink in (6) is put into porcelain boat, under an argon atmosphere, 900 is heated in tube furnace
DEG C, and 5 hours are kept the temperature, obtain N doping CNT in-stiu coating Co nano particle composite material Co@CNT (5h).
The SEM figure of obtained Co@CNT (5h) powder referring to fig. 2, as can be seen from the figure has no tablet, institute in product
Some presomas become being about 1~1.5 μm of carbon nanotube.
Embodiment 3
(1) 5 grams of urea is dissolved in 150mL deionized water, and be stirred at room temperature 10 minutes；
(2) 0.5 milligram of PEG is added to solution in (1), keeps magnetic agitation at room temperature；
(3) by 0.4 milligram of Co (NO3)2·6H2O is added to solution in (2), keeps magnetic agitation at room temperature；
(4) stirring 30 minutes in addition (3) solution of 0.3 milligram of boric acid, will be continued；
(5) finally by (4) mixed solution, make within heating and continuous 12 hours in oil bath pan solvent volatilization complete；
(6) by the pink precipitate that obtains in (5), precursor powder is collected, is put into baking oven, 80 DEG C of dry 8h；
(7) powder of the pink in (6) is put into porcelain boat, under an argon atmosphere, 900 is heated in tube furnace
DEG C, and 6 hours are kept the temperature, obtain N doping CNT in-stiu coating Co nano particle composite material Co@CNT (6h).
The SEM figure of obtained Co@CNT (6h) powder is referring to Fig. 3, and presoma has turned to carbon nanotube, but its table
Face has been covered with a large amount of nano particle.
Embodiment 4
(1) 5 grams of urea is dissolved in 150mL deionized water, and be stirred at room temperature 10 minutes；
(2) 0.5 milligram of PEG is added to solution in (1), keeps magnetic agitation at room temperature；
(3) by 0.2 milligram of Co (NO3)2·6H2O is added to solution in (2), keeps magnetic agitation at room temperature；
(5) stirring 30 minutes in addition (3) solution of 0.3 milligram of boric acid, will be continued；
(5) finally by (4) mixed solution, make within heating and continuous 12 hours in oil bath pan solvent volatilization complete；
(6) by the pink precipitate that obtains in (5), precursor powder is collected, is put into baking oven, 80 DEG C of dry 8h；
(7) powder of the pink in (6) is put into porcelain boat, under an argon atmosphere, 900 is heated in tube furnace
DEG C, and 5 hours are kept the temperature, obtain N doping CNT in-stiu coating Co nano particle composite material Co@CNT (5h-1).
Referring to fig. 4, presoma all becomes carbon nanometer of uniform morphology to the SEM figure of obtained Co@CNT (5h-1) powder
Pipe.
Embodiment 5
(1) 5 grams of urea is dissolved in 150mL deionized water, and be stirred at room temperature 10 minutes；
(2) 0.5 milligram of PEG is added to solution in (1), keeps magnetic agitation at room temperature；
(3) by 0.4 milligram of Co (NO3)2·6H2O is added to solution in (2), keeps magnetic agitation at room temperature；
(5) stirring 30 minutes in addition (3) solution of 0.3 milligram of boric acid, will be continued；
(5) finally by (4) mixed solution, make within heating and continuous 12 hours in oil bath pan solvent volatilization complete；
(6) by the pink precipitate that obtains in (5), precursor powder is collected, is put into baking oven, 80 DEG C of dry 8h；
(7) powder of the pink in (6) is put into porcelain boat, under an argon atmosphere, 900 is heated in tube furnace
DEG C, and 5 hours are kept the temperature, obtain N doping CNT in-stiu coating Co nano particle composite material Co@CNT (5h-2).
The SEM figure of obtained Co@CNT (5h-2) powder is referring to Fig. 5, the carbon nano tube surface that as can be seen from the figure obtains
Smooth, pattern is uniform, and does not have tablet, it can be seen that the carbon nanotube pattern obtained under the condition and proportion is best.
The XRD diagram of Co CNT (5h-2) powder and standard control obtained in the present embodiment, as shown in fig. 7, can be in figure
To find out, the peak value for the Co@CNT (5h-2) being prepared is consistent with standard card JCPDF#01-089-7093, it can thus be appreciated that I
Successfully obtained load and have the carbon nanotube of Co nano particle.
Embodiment 6
(1) 5 grams of urea is dissolved in 150mL deionized water, and be stirred at room temperature 10 minutes；
(2) 0.5 milligram of PEG is added to solution in (1), keeps magnetic agitation at room temperature；
(3) by 0.6 milligram of Co (NO3)2·6H2O is added to solution in (2), keeps magnetic agitation at room temperature；
(5) stirring 30 minutes in addition (3) solution of 0.3 milligram of boric acid, will be continued；
(5) finally by (4) mixed solution, make within heating and continuous 12 hours in oil bath pan solvent volatilization complete；
(6) by the pink precipitate that obtains in (5), precursor powder is collected, is put into baking oven, 80 DEG C of dry 8h；
(7) powder of the pink in (6) is put into porcelain boat, under an argon atmosphere, 900 is heated in tube furnace
DEG C, and 5 hours are kept the temperature, obtain N doping CNT in-stiu coating Co nano particle composite material Co@CNT (5h-3).
The SEM figure of obtained Co@CNT (5h-3) powder is received referring to Fig. 6 it can be seen that presoma has turned side for carbon
Mitron, but since the amount of the cobalt nitrate of addition is more, numerous particulate materials is precipitated in carbon tube outside.
Embodiment 7
The preparation of Co@CNT (5h-2) positive electrode, specifically comprises the following steps:
(1) by Co@CNT (5h-2) obtained in embodiment 5 and sulphur simple substance according to mass ratio 1:4 ratio after mixing,
It is put into reaction kettle and keeps the temperature 12 hours for 155 DEG C, obtain Co@CNT (5h-2)-S；
(2) Co@CNT (5h-2)-S obtained in (1) is respectively put into tube furnace, under argon atmosphere, with heating rate 1
DEG C 200 DEG C are warming up to per minute, soaking time 0.5 hour, get rid of the S simple substance of adsorption, obtain Co@CNT (5h-2)-S
Positive electrode.
Co@CNT (the 5h-2)-S positive electrode prepared is subjected to thermogravimetric analysis, analyzes result as shown in figure 8, by Fig. 8
It is found that the mass ratio of S in the material is 76%.
Co@CNT (the 5h-2)-S positive electrode prepared is pressed with conductive agent (Super-P) and binder (sodium alginate)
Mass ratio be the ratio of 7:2:1 after mixing, coated on electrode slice is fabricated on aluminium foil, vacuum oven is 12 hours dry.
Above-mentioned electrode slice is used in argon atmosphere glove box, is carried out using lithium metal as to electrode assembling at button cell
Test.Test condition are as follows: charging and discharging currents density is that 0.1C (1C=1675mA/g) charge and discharge blanking voltage is 1.7-2.8V.It surveys
Recurring number-specific capacity performance chart that examination obtains is as shown in Figure 9, and as shown in Figure 9, the reversible capacity for the first time of battery is
1440mA h g-1, capacity attenuation is 1080mA h g after 100 weeks circulations-1, attenuation rate 0.25%.
Embodiment 8
The preparation of Co@CNT (5h-1)-S positive electrode, specifically comprises the following steps:
(1) Co@CNT (5h-1) obtained in embodiment 4 is uniformly mixed with sulphur simple substance according to the ratio of mass ratio 1:4
Afterwards, it is put into reaction kettle and reacts 12 hours for 155 DEG C, obtain Co@CNT (5h-1)-S；
(2) Co@CNT (5h-1)-S obtained in (1) is respectively put into tube furnace, under argon atmosphere, with heating rate 1
DEG C 200 DEG C are warming up to per minute, soaking time 0.5 hour, get rid of the S simple substance of adsorption, obtain Co@CNT (5h-1)-S
Positive electrode.
By obtained Co@CNT (5h-1)-S positive electrode and conductive agent (Super-P) and binder (sodium alginate) by matter
After mixing than the ratio for 7:2:1, coated on electrode slice is fabricated on aluminium foil, vacuum oven is 12 hours dry for amount.
Above-mentioned electrode slice is used in argon atmosphere glove box, is carried out using lithium metal as to electrode assembling at button cell
Test.Test condition are as follows: charging and discharging currents density is that 0.1C (1C=1675mA/g) charge and discharge blanking voltage is 1.7-2.8V.It surveys
The cycle performance figure for trying to obtain is shown in Fig. 9, and as shown in Figure 9, the reversible capacity for the first time of battery is 1360mA h g-1, after 100 times recycle
Discharge capacity is maintained at 780mA h g-1, the invertibity and cyclical stability of battery be not so good as Co@CNT (5h-2)-S.
Embodiment 9
The preparation of Co@CNT (5h-3)-S positive electrode, specifically comprises the following steps:
(1) Co@CNT (5h-3) obtained in embodiment 6 is uniformly mixed with sulphur simple substance according to the ratio of mass ratio 1:4
Afterwards, it is put into reaction kettle and reacts 12 hours for 155 DEG C, obtain Co@CNT (5h-3)-S；
(2) Co@CNT (5h-3)-S obtained in (1) is respectively put into tube furnace, under argon atmosphere, with heating rate 1
DEG C 200 DEG C are warming up to per minute, soaking time 0.5 hour, get rid of the S simple substance of adsorption, obtain Co@CNT (5h-3)-S
Positive electrode.
By obtained Co@CNT (5h-3)-S positive electrode and conductive agent (Super-P) and binder (sodium alginate) by matter
After mixing than the ratio for 7:2:1, coated on electrode slice is fabricated on aluminium foil, vacuum oven is 12 hours dry for amount.
Above-mentioned electrode slice is used in argon atmosphere glove box, is carried out using lithium metal as to electrode assembling at button cell
Test.Test condition are as follows: charging and discharging currents density is that 0.1C (1C=1675mA/g) charge and discharge blanking voltage is 1.7-2.8V.It surveys
The cycle performance figure for trying to obtain is shown in Fig. 9, and as shown in Figure 9, the reversible capacity for the first time of battery is 1200mA h g-1, after 100 times recycle
Discharge capacity is maintained at 490mA h g-1, the invertibity and cyclical stability of battery be not so good as Co@CNT (5h-2)-S and Co@CNT
(5h-1)-S。
In summary it is found that when the relative quantity of cobalt nitrate is 2, being obtained when heating temperature is at 900 DEG C, soaking time 5h
Material C o@CNT (5h-2) have best chemical property.The charging and discharging curve figure of the material such as Figure 10, can be with from figure
Find out, shows two apparent discharge platforms in 2.3v and 2.1v during discharge.It is showed during the charging process in 2.35v
Apparent charging platform out.These platforms are typical lithium-sulfur cell charge and discharge platform.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of N doping CNT in-stiu coating Co nano particle composite material, it is characterised in that including preparing as follows
Step:
(1) urea, boric acid, polyethylene glycol and cobalt nitrate is soluble in water, after being uniformly mixed, heating is evaporated completely solvent
Entirely, dry, obtain precursor powder；
(2) precursor powder that step (1) obtains is heat-treated, obtains N doping CNT in-stiu coating Co nano-particles reinforcement
Material.
2. a kind of preparation method of N doping CNT in-stiu coating Co nano particle composite material according to claim 1,
Be characterized in that: the mass ratio of polyethylene glycol described in step (1) and cobalt nitrate is 0.5:(0.2~0.6).
3. a kind of preparation method of N doping CNT in-stiu coating Co nano particle composite material according to claim 2,
Be characterized in that: the mass ratio of the polyethylene glycol and cobalt nitrate is 0.5:0.4.
4. a kind of preparation method of N doping CNT in-stiu coating Co nano particle composite material according to claim 1,
Be characterized in that: dry temperature described in step (1) is 60~80 DEG C.
5. a kind of preparation method of N doping CNT in-stiu coating Co nano particle composite material according to claim 1,
Be characterized in that: being heat-treated described in step (2) and carry out under an argon atmosphere, heat treatment temperature be 700~900 DEG C, the time be 4~
6h。
6. a kind of N adulterates CNT in-stiu coating Co nano particle composite material, it is characterised in that: any by Claims 1 to 5
Method described in is prepared.
7. a kind of N according to claim 6 adulterates CNT in-stiu coating Co nano particle composite material, it is characterised in that: institute
Stating N doping CNT diameter in N doping CNT in-stiu coating Co nano particle composite material is 1~1.5 μm.
8. N described in claim 6 or 7 adulterates CNT in-stiu coating Co nano particle composite material as lithium-sulfur cell anode material
The application of material, it is characterised in that the application process are as follows: N is adulterated into CNT in-stiu coating Co nano particle composite material and simple substance
Sulphur is uniformly mixed, and reaction product further progress is heat-treated, removes extra S, obtain lithium-sulfur cell by heating and thermal insulation reaction
Positive electrode.
9. N doping CNT in-stiu coating Co nano particle composite material according to claim 8 is as lithium-sulfur cell anode
The application of material, it is characterised in that: the mass ratio of N doping the CNT in-stiu coating Co nano particle composite material and elemental sulfur
For 1:(3~4).
10. N doping CNT in-stiu coating Co nano particle composite material according to claim 8 is as lithium-sulfur cell anode
The application of material, it is characterised in that: the temperature of the heating and thermal insulation reaction is 155~200 DEG C, and the time is 12~16h；The heat
Processing refers under an argon atmosphere, is warming up to 200~250 DEG C of 0.5~2h of heat preservation with the heating rate of 1~3 DEG C/min.
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