CN103708535A - Preparation method of negative material of carbon-doped stannic dioxide nanowire lithium battery - Google Patents
Preparation method of negative material of carbon-doped stannic dioxide nanowire lithium battery Download PDFInfo
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- CN103708535A CN103708535A CN201310733497.3A CN201310733497A CN103708535A CN 103708535 A CN103708535 A CN 103708535A CN 201310733497 A CN201310733497 A CN 201310733497A CN 103708535 A CN103708535 A CN 103708535A
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Abstract
The invention relates to a preparation method of a negative material of a carbon-doped stannic dioxide nanowire lithium battery. The preparation method comprises the following steps of preparing mesoporous phenolic resin in a hexagonal accumulative phase structure by virtue of self-assembling processes of soluble phenolic resin and a pore-foaming agent, further carrying out carbonization to obtain mesoporous carbon, growing stannic dioxide in nanometer pore passages of the mesoporous carbon by taking the mesoporous carbon as a template, and firing to control the content of the carbon, so as to obtain the negative material of the carbon-doped stannic dioxide nanowire lithium battery. Due to the stable structure of the negative material, the lithium storage capacity and the lithium ion diffusion speed can be improved, and the structural damage caused by the volume change and the agglomeration is relieved, so that the capacity and cycling stability of an electrode are remarkably improved.
Description
Technical field
The preparation method who the present invention relates to a kind of carbon doped stannic oxide nanometer line lithium cell cathode material, belongs to lithium ion battery field.
Background technology
Along with rapid development of economy, facing mankind the severe challenge of energy dilemma and environmental pollution, and the green energy resource of clean environment firendly more is all constantly being sought in countries in the world.Wherein, lithium ion battery is high with its energy density, operating voltage is high, have extended cycle life, the advantage such as self-discharge rate is little, memory-less effect, safety non-pollution, in fields such as portable electric appts, electromobile, space technology, national defense industry, show wide application prospect and huge potential economic benefit, be called as the ideal source of 21 century.
In lithium ion battery, the capacity of negative material is one of important factor affecting cell container.At present, commercial lithium ion battery mainly adopts graphite or modified graphite as negative material.Yet the theoretical embedding lithium maximum capacity of graphite is only 372mAh/g, and irreversible loss is large, multiplying power discharging property is poor first.Therefore, try to explore the novel non-carbon negative pole material that specific storage is high, capacity attenuation rate is little, safety performance is good, become international research and development focus.Wherein, tindioxide receives much attention because have the advantages such as height ratio capacity (theoretical charge/discharge capacity is 790mAh/g), low embedding lithium electromotive force, safety performance are good, and tindioxide aboundresources, low price, environmental pollution is little, and being expected to substitute carbon material becomes novel lithium battery cathode material.But, in doff lithium process, there is serious volume effect in tindioxide, first charge-discharge rate of expand to shrink is up to more than 50%, and cycle period lithium ion embedding repeatedly with deviate from process, to be prone to powder phenomenon-tion, thereby irreversible capacity is larger first to cause tindioxide, chemical property declines rapidly, and cyclical stability is poor, has limited its widespread use in lithium ion battery.
Research shows, preparing nanostructured tin dioxide is a kind of effective ways that improve material cyclical stability.Compare with the electrode materials of micro-meter scale, nano material can shorten the transmission range of electronics, ion, increases the area at electrode/electrolyte interface, the stress that particularly available buffer volume change produces, and then the cyclical stability of raising electrode materials.That research is more at present is matrix material (Wang X, Zhou X, Yao K, Zhang J, Liu Z, " the A SnO of tin oxide nano particles and carbon
2/ graphene composite as a high stability electrode for lithium ion batteries ", Carbon, 2011,49,133; Zhang L S, Jiang L Y, Yan H J, Wang W D, Song W G, Guo Y G, Wan L J, " Monodispersed SnO
2nanoparticles on both sides of single layer graphene sheets as anode materials in Li-ion batteries "; J.Mater.Chem., 2010,20; 5462), promoting, electrode electro Chemical aspect of performance effect is more obvious.But the general surface of nano material can be higher, thermodynamic instability, in repeated charge process, migration, diffusion due to ion between nano particle there will be significant reunion, fusion phenomenon, affect cycle performance and the capacity of electrode materials.
Summary of the invention
The preparation method that technical problem to be solved by this invention is to provide a kind of carbon doped stannic oxide nanometer line lithium cell cathode material, utilizes its structural stability, and the structure deteriorate of alleviating volume change and reuniting and cause improves electrode capacity and cyclical stability.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of carbon doped stannic oxide nanometer line lithium cell cathode material, comprises the following steps:
1) phenol of 80～100 parts is carried out to heating and melting, the formaldehyde solution that the sodium hydroxide solution that the mass concentration that drips successively while stirring 10～30 parts is 20% and the mass concentration of 80～160 parts are 37%, then heat up, react after 40～80 minutes, carry out again cooling, then add hydrochloric acid to be adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol;
2) the low-molecular-weight soluble resol obtaining in step 1) is dissolved in the ethanol of 1500～4000 parts, the pore-creating agent that adds 40～200 parts, stir to clarify transparent, standing under room temperature, after ethanol is evaporated completely, being placed in baking oven heats again, make described low-molecular-weight soluble resol crosslinking curing, obtain intermediate product A, and then under nitrogen or argon atmosphere, intermediate product A is carried out in tube furnace to carbonization, obtain having the meso-porous carbon material in continuous duct;
3) by step 2) in the described meso-porous carbon material that obtains be immersed in the tindioxide presoma of melting, under vacuum condition, carry out standing, tindioxide presoma is fully penetrated in the duct of meso-porous carbon material, obtain intermediate product B, in the water-ethanol that is 1:1 by described intermediate product B in volume ratio again, soak, then take out, then in the mixed gas of rare gas element and air, carry out calcination, obtain described carbon doped stannic oxide nanometer line lithium cell cathode material;
Wherein, the volume ratio 1:10～10:1 of described rare gas element and air;
Above-mentioned umber all refers to parts by weight.
The invention has the beneficial effects as follows: the present invention controls the content of carbon by calcination, make carbon material effectively support tin dioxide nano line array structure, improve electrode cyclical stability, optimize lithium cell cathode material electrode performance.
Carbon doped stannic oxide nanometer line lithium cell cathode material prepared by the present invention has continuous nano pore, high-specific surface area (being up to 393m2/g) and porosity (being up to 0.76cm3/g), can improve storage lithium ability and lithium ion rate of diffusion, guarantee that every nano wire can fully contact with electrolytic solution with collector simultaneously.
Carbon doped stannic oxide nanometer line lithium cell cathode material prepared by the present invention interconnects support by branch each other, structure is more stable, the structure deteriorate that can alleviate volume change and reunite and cause, thereby when improving electrode capacity, reduce irreversible capacity decay, improve cyclical stability.In addition, carbon in matrix material can play a supportive role to stannic oxide nanometer array, further cushions the volume change of tindioxide in charge and discharge process, prevents efflorescence and reunion, can increase electroconductibility again, by controlling the content of carbon, can make electrode specific storage and cycle performance be optimized simultaneously.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described pore-creating agent comprises any one in PCE, polyox-yethylene-polyoxypropylene block copolymer, polyoxyethylene-polystyrene block copolymer or polystyrene-poly vinyl pyridine segmented copolymer.
Further, described tindioxide presoma comprises SnCl
22H
2o, SnCl
45H
2any one in O or stannous iso caprylate.
Further, in step 1), described in carry out heating and melting Heating temperature be 40～45 ℃.
Further, in step 1), described in be warming up to 65～75 ℃.
Further, in step 2) in, the temperature in described baking oven is 100～150 ℃, the time of heating is 1～2 day.
Further, in step 2) in, described in carry out carbonization temperature be 700～1200 ℃.
Further, in step 3), described in to carry out the standing time be 1～5 hour.
Further, in step 3), described in time of soaking be 0.5～5 hour.
Further, in step 3), described in carry out calcination processing condition be calcination at the temperature of 400 ℃ 1～5 hour.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the carbon doped stannic oxide nanometer line lithium cell cathode material of embodiment 3 preparations;
Fig. 2 is the carbon doped stannic oxide nanometer line lithium cell cathode material of embodiment 3 preparations and first charge-discharge curve comparison figure (the current density 150mAg of commercial stannic oxide particle
-1);
Fig. 3 is the carbon doped stannic oxide nanometer line lithium cell cathode material of embodiment 3 preparations and the cycle performance curve comparison figure of commercial stannic oxide particle.
Embodiment
Below in conjunction with accompanying drawing, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
A preparation method for carbon doped stannic oxide nanometer line lithium cell cathode material, comprises the following steps:
1) phenol of 80～100 parts is carried out at 40～45 ℃ to heating and melting, the formaldehyde solution that the sodium hydroxide solution that the mass concentration that drips successively while stirring 10～30 parts is 20% and the mass concentration of 80～160 parts are 37%, then be warming up to 65～75 ℃, react after 40～80 minutes, carry out again cooling, then add hydrochloric acid to be adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol;
2) the low-molecular-weight soluble resol obtaining in step 1) is dissolved in the ethanol of 1500～4000 parts, the pore-creating agent that adds 40～200 parts, stir to clarify transparent, standing under room temperature, after ethanol is evaporated completely, the baking oven that is placed in temperature again and is 100～150 ℃ heats 1～2 day, make described low-molecular-weight soluble resol crosslinking curing, obtain intermediate product A, and then under nitrogen or argon atmosphere, intermediate product A is carried out in tube furnace to carbonization, the temperature of carrying out carbonization is 700～1200 ℃, obtain having the meso-porous carbon material in continuous duct,
3) by step 2) in the described meso-porous carbon material that obtains be immersed in the tindioxide presoma of melting, under vacuum condition, carry out standing 1～5 hour, tindioxide presoma is fully penetrated in the duct of meso-porous carbon material, obtain intermediate product B, in the water-ethanol that is 1:1 by described intermediate product B in volume ratio again, soak 0.5～5 hour, then take out, calcination 1～5 hour at the temperature of 400 ℃ in the mixed gas of rare gas element and air again, obtains described carbon doped stannic oxide nanometer line lithium cell cathode material;
Wherein, the volume ratio 1:10～10:1 of described rare gas element and air;
Above-mentioned umber all refers to parts by weight.
Below by several specific embodiments so that the present invention is specifically described.
Embodiment 1
By 90 weight part phenol heat fused at 40 ℃, drip successively while stirring 20 weight part 20% sodium hydroxide solutions and 160 weight part 37% formaldehyde solutions, be then warming up to 70 ℃, react 60 minutes.Cooling, with hydrochloric acid, solution is adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol.
Above-mentioned resol is dissolved in 3000 parts by weight of ethanol, adds 75 weight part pore-creating agent polyox-yethylene-polyoxypropylene block copolymer Pluronic P123(PEO
20-PPO
70-PEO
20), stir to clarify transparent.Standing under room temperature, product is placed in to 100 ℃ of baking ovens after ethanol is evaporated completely and heats 1 day, make resol crosslinking curing.Under nitrogen atmosphere, by product 700 ℃ of carbonizations 5 hours in tube furnace, obtain having the meso-porous carbon material in continuous duct.
At 80 ℃, above-mentioned meso-porous carbon material is immersed in to the SnCl of melting
22H
2in O, under vacuum condition standing 1～5 hour, product is in 1:1(volume ratio) water-ethanol in soak after 1 hour and to take out, calcination 2 hours at 400 ℃ in the mixed gas of nitrogen and air (volume ratio 8:1), obtains the carbon doped stannic oxide nanometer line lithium cell cathode material of carbon content approximately 18%.
Embodiment 2:
By 100 weight part phenol heat fused at 40 ℃, drip successively while stirring 20 weight part 20% sodium hydroxide solutions and 160 weight part 37% formaldehyde solutions, be then warming up to 70 ℃, react 60 minutes.Cooling, with hydrochloric acid, solution is adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol.Above-mentioned resol is dissolved in 2000 parts by weight of ethanol, adds 90 weight part pore-creating agent PCE Brij-56(CH
3(CH
2)
15(OCH
2cH
2)
10oH), stir to clarify transparent.Standing under room temperature, product is placed in to 100 ℃ of baking ovens after ethanol is evaporated completely and heats 1 day, make resol crosslinking curing.Under nitrogen atmosphere, by product 800 ℃ of carbonizations 3 hours in tube furnace, obtain having the meso-porous carbon material in continuous duct.
At 100 ℃, above-mentioned meso-porous carbon material is immersed in the stannous iso caprylate of melting, under vacuum condition standing 1～5 hour, product is in 1:1(volume ratio) water-ethanol in soak after 5 hours and to take out, calcination 2 hours at 400 ℃ in the mixed gas of nitrogen and air (volume ratio 6:1), obtains the carbon doped stannic oxide nanometer line lithium cell cathode material of carbon content approximately 10%.
Embodiment 3:
By 94 weight part phenol heat fused at 40 ℃, drip successively while stirring 20 weight part 20% sodium hydroxide solutions and 160 weight part 37% formaldehyde solutions, be then warming up to 70 ℃, react 60 minutes.Cooling, with hydrochloric acid, solution is adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol.Above-mentioned resol is dissolved in 3600 parts by weight of ethanol, adds 150 weight part pore-creating agent polyox-yethylene-polyoxypropylene block copolymer Pluronic F127 (PEO
106-PPO
70-PEO
106), stir to clarify transparent.Standing under room temperature, product is placed in to 100 ℃ of baking ovens after ethanol is evaporated completely and heats 1 day, make resol crosslinking curing.Under nitrogen atmosphere, by product 750 ℃ of carbonizations 4 hours in tube furnace, obtain having the meso-porous carbon material in continuous duct.
At 100 ℃, above-mentioned meso-porous carbon material is immersed in to the SnCl of melting
45H
2in O, under vacuum condition standing 1～5 hour, product is in 1:1(volume ratio) water-ethanol in soak after 2 hours and to take out, calcination 2 hours at 400 ℃ in the mixed gas of nitrogen and air (volume ratio 5:1), obtains the carbon doped stannic oxide nanometer line lithium cell cathode material of carbon content approximately 8%.
As shown in Figure 1, and the first charge-discharge curve comparison of commercial stannic oxide particle as shown in Figure 2 for the transmission electron microscope photo of the carbon doped stannic oxide nanometer line lithium cell cathode material that embodiment 3 obtains; With the cycle performance curve comparison of commercial stannic oxide particle as shown in Figure 3.
From accompanying drawing 1, carbon doped stannic oxide nanometer line lithium cell cathode material prepared by the present invention has good array structure, and nanowire diameter is about 5 nanometers.
From accompanying drawing 2, at 150mAg
-1current density under, the first loading capacity of carbon doped stannic oxide nanometer line lithium cell cathode material and charging capacity prepared by the present invention are respectively 1597mAhg
-1and 827mAhg
-1, first coulomb efficiency is 51.7%.And the first loading capacity of commercial stannic oxide particle and charging capacity are respectively 1394mAhg
-1and 495mAhg
-1, first coulomb efficiency is 35.5%
From accompanying drawing 3, under identical test condition, circulate after 20 times, carbon doped stannic oxide nanometer line lithium cell cathode material loading capacity prepared by the present invention and charging capacity are still respectively up to 709mAhg
-1and 695mAhg
-1, and commercial stannic oxide particle loading capacity and charging capacity are reduced to respectively 161mAhg
-1and 155mAhg
-1.Carbon doped stannic oxide nanometer line lithium cell cathode material and commercial stannic oxide particle comparison prepared by the present invention are described, charge/discharge capacity and cyclical stability all significantly improve.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a preparation method for carbon doped stannic oxide nanometer line lithium cell cathode material, is characterized in that, comprises the following steps:
1) phenol of 80～100 parts is carried out to heating and melting, the formaldehyde solution that the sodium hydroxide solution that the mass concentration that drips successively while stirring 10～30 parts is 20% and the mass concentration of 80～160 parts are 37%, then heat up, react after 40～80 minutes, carry out again cooling, then add hydrochloric acid to be adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol;
2) the low-molecular-weight soluble resol obtaining in step 1) is dissolved in the ethanol of 1500～4000 parts, the pore-creating agent that adds 40～200 parts, stir to clarify transparent, standing under room temperature, after ethanol is evaporated completely, being placed in baking oven heats again, make described low-molecular-weight soluble resol crosslinking curing, obtain intermediate product A, and then under nitrogen or argon atmosphere, intermediate product A is carried out in tube furnace to carbonization, obtain having the meso-porous carbon material in continuous duct;
3) by step 2) in the described meso-porous carbon material that obtains be immersed in the tindioxide presoma of melting, under vacuum condition, carry out standing, tindioxide presoma is fully penetrated in the duct of meso-porous carbon material, obtain intermediate product B, in the water-ethanol that is 1:1 by described intermediate product B in volume ratio again, soak, then take out, then in the mixed gas of rare gas element and air, carry out calcination, obtain described carbon doped stannic oxide nanometer line lithium cell cathode material;
Wherein, the volume ratio 1:10～10:1 of described rare gas element and air;
Above-mentioned umber all refers to parts by weight.
2. the preparation method of carbon doped stannic oxide nanometer line lithium cell cathode material according to claim 1, it is characterized in that, described pore-creating agent comprises any one in PCE, polyox-yethylene-polyoxypropylene block copolymer, polyoxyethylene-polystyrene block copolymer or polystyrene-poly vinyl pyridine segmented copolymer.
3. the preparation method of carbon doped stannic oxide nanometer line lithium cell cathode material according to claim 1, is characterized in that, described tindioxide presoma comprises SnCl
22H
2o, SnCl
45H
2any one in O or stannous iso caprylate.
4. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 1), described in carry out heating and melting Heating temperature be 40～45 ℃.
5. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 1), described in be warming up to 65～75 ℃.
6. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 2) in, the temperature in described baking oven is 100～150 ℃, the time of heating is 1～2 day.
7. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 2) in, described in carry out carbonization temperature be 700～1200 ℃.
8. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 3), described in to carry out the standing time be 1～5 hour.
9. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 3), described in time of soaking be 0.5～5 hour.
10. according to the preparation method of the carbon doped stannic oxide nanometer line lithium cell cathode material described in claims 1 to 3 any one, it is characterized in that, in step 3), described in carry out calcination processing condition be calcination at the temperature of 400 ℃ 1～5 hour.
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Cited By (4)
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| CN107611412A (en) * | 2017-10-16 | 2018-01-19 | 赵兵 | A kind of tin ash/porous carbon composite lithium ion battery negative material and preparation method |
| CN112018360A (en) * | 2020-08-26 | 2020-12-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
| CN112331836A (en) * | 2020-11-23 | 2021-02-05 | 华中科技大学 | Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof |
| CN114420927A (en) * | 2022-01-24 | 2022-04-29 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof and negative electrode plate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611412A (en) * | 2017-10-16 | 2018-01-19 | 赵兵 | A kind of tin ash/porous carbon composite lithium ion battery negative material and preparation method |
| CN112018360A (en) * | 2020-08-26 | 2020-12-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery cathode material, preparation method thereof and lithium ion battery |
| CN112331836A (en) * | 2020-11-23 | 2021-02-05 | 华中科技大学 | Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof |
| CN114420927A (en) * | 2022-01-24 | 2022-04-29 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof and negative electrode plate |
| CN114420927B (en) * | 2022-01-24 | 2023-08-08 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof and negative electrode sheet |
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