CN103708535B - 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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- CN103708535B CN103708535B CN201310733497.3A CN201310733497A CN103708535B CN 103708535 B CN103708535 B CN 103708535B CN 201310733497 A CN201310733497 A CN 201310733497A CN 103708535 B CN103708535 B CN 103708535B
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- carbon
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- stannic oxide
- nano wire
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 present invention relates to a kind of preparation method of carbon doping stannic oxide nano wire lithium cell cathode material, belong to field of lithium ion battery.
Background technology
Along with rapid development of economy, facing mankind the severe challenge of energy dilemma and environmental pollution, and countries in the world are all at the green energy resource constantly seeking clean environment firendly more.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, illustrate wide application prospect and huge potential economic benefit in fields such as portable electric appts, electromobile, space technology, national defense industry, 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.But the embedding lithium maximum capacity of theory of graphite is only 372mAh/g, and irreversible loss is large first, multiplying power discharging property is poor.Therefore, try to explore the novel non-carbon negative 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 alternative carbon material becomes novel lithium battery cathode material.But, serious volume effect is there is in tindioxide in doff lithium process, first charge-discharge rate of expand to shrink is up to more than 50%, and easily there is powder phenomenon-tion with deviating from process in the cycle period embedding repeatedly of lithium ion, thus irreversible capacity is larger first to cause tindioxide, chemical property declines rapidly, and cyclical stability is poor, limits its widespread use in lithium ion battery.
Research shows, preparing nanostructured tin dioxide is a kind of effective ways improving material circulation stability.Compared with the electrode materials of micro-meter scale, nano material can shorten the transmission range of electronics, ion, the stress that the area, particularly available buffer volume change that increase electrode/electrolyte interface produce, and then the cyclical stability improving electrode materials.Matrix material (Wang X, Zhou X, Yao K, Zhang J, Liu Z, " the A SnO of what current research was more is 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), more obvious in lifting electrode electro Chemical aspect of performance effect.But the general surface energy of nano material is higher, thermodynamic instability, in repeated charge process, because the migration of ion, diffusion there will be significant reunion, fusion phenomenon between nano particle, affect cycle performance and the capacity of electrode materials.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of carbon doping stannic oxide nano wire lithium cell cathode material, utilizes its structural stability, alleviates volume change and the structure deteriorate caused of reuniting, 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 doping stannic oxide nano wire lithium cell cathode material, comprises the following steps:
1) phenol of 80 ~ 100 parts is carried out heating and melting, the mass concentration dripping 10 ~ 30 parts while stirring is successively the sodium hydroxide solution of 20% and the mass concentration of 80 ~ 160 parts is the formaldehyde solution of 37%, then heat up, react after 40 ~ 80 minutes, cool again, then add hydrochloric acid and be adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol;
2) the low-molecular-weight soluble resol obtained in step 1) is dissolved in the ethanol of 1500 ~ 4000 parts, add the pore-creating agent of 40 ~ 200 parts, stir to clarify transparent, left at room temperature, after ethanol is evaporated completely, be placed in baking oven again to heat, 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 carbonization in tube furnace, obtains the meso-porous carbon material with continuous duct;
3) by step 2) in the described meso-porous carbon material that obtains be immersed in the tindioxide presoma of melting, leave standstill under vacuum condition, tindioxide presoma is fully penetrated in the duct of meso-porous carbon material, obtain intermediate product B, be soak in the water-ethanol of 1:1 again in volume ratio by described intermediate product B, then take out, then carry out calcination in the mixed gas of rare gas element and air, namely obtain described carbon doping stannic oxide nano wire lithium cell cathode material;
Wherein, the volume ratio 1:10 ~ 10:1 of described rare gas element and air;
Above-mentioned number all refers to parts by weight.
The invention has the beneficial effects as follows: the present invention controls the content of carbon by calcination, makes carbon material effectively support tin dioxide nano line array structure, improve electrode cycle stability, optimize lithium cell cathode material electrode performance.
Carbon doping stannic oxide nano wire lithium cell cathode material prepared by the present invention has continuous print nano pore, high-specific surface area (being up to 393m2/g) and porosity (being up to 0.76cm3/g), storage lithium ability and lithium ion rate of diffusion can be improved, ensure that every root nano wire fully can contact with electrolytic solution with collector simultaneously.
Carbon doping stannic oxide nano wire lithium cell cathode material prepared by the present invention is interconnected support each other by branch, structure comparison is stablized, volume change can be alleviated and the structure deteriorate caused of reuniting, thus irreversible capacity decay is reduced while raising electrode capacity, improve cyclical stability.In addition, carbon in matrix material can play a supportive role to stannic oxide nanometer array, cushions the volume change of tindioxide in charge and discharge process further, prevents efflorescence and reunion, can electroconductibility be increased again simultaneously, electrode specific storage and cycle performance can be made to be optimized by the content controlling carbon.
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-Polyethylene pyridine block 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 DEG C.
Further, in step 1), described in carry out being warming up to 65 ~ 75 DEG C.
Further, in step 2) in, the temperature in described baking oven is 100 ~ 150 DEG C, and the time of carrying out heating is 1 ~ 2 day.
Further, in step 2) in, described in carry out carbonization temperature be 700 ~ 1200 DEG C.
Further, in step 3), described in time of carrying out leaving standstill be 1 ~ 5 hour.
Further, in step 3), described in time of carrying out soaking be 0.5 ~ 5 hour.
Further, in step 3), described in carry out calcination processing condition be calcination 1 ~ 5 hour at the temperature of 400 DEG C.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of carbon doping stannic oxide nano wire lithium cell cathode material prepared by embodiment 3;
Fig. 2 is the carbon doping stannic oxide nano wire lithium cell cathode material of embodiment 3 preparation and first charge-discharge curve comparison figure (the current density 150mAg of commercial stannic oxide particle
-1);
Fig. 3 is the carbon doping stannic oxide nano wire lithium cell cathode material of embodiment 3 preparation and the cycle performance curve comparison figure of commercial stannic oxide particle.
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
A preparation method for carbon doping stannic oxide nano wire lithium cell cathode material, comprises the following steps:
1) phenol of 80 ~ 100 parts is carried out heating and melting at 40 ~ 45 DEG C, the mass concentration dripping 10 ~ 30 parts while stirring is successively the sodium hydroxide solution of 20% and the mass concentration of 80 ~ 160 parts is the formaldehyde solution of 37%, then carry out being warming up to 65 ~ 75 DEG C, react after 40 ~ 80 minutes, cool again, then add hydrochloric acid and be adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol;
2) the low-molecular-weight soluble resol obtained in step 1) is dissolved in the ethanol of 1500 ~ 4000 parts, add the pore-creating agent of 40 ~ 200 parts, stir to clarify transparent, left at room temperature, after ethanol is evaporated completely, being placed in temperature is again that the baking oven of 100 ~ 150 DEG C carries out heating 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 carbonization in tube furnace, the temperature of carrying out carbonization is 700 ~ 1200 DEG C, obtain the meso-porous carbon material with continuous duct,
3) by step 2) in the described meso-porous carbon material that obtains be immersed in the tindioxide presoma of melting, standing 1 ~ 5 hour is carried out under vacuum condition, tindioxide presoma is fully penetrated in the duct of meso-porous carbon material, obtain intermediate product B, be carry out immersion 0.5 ~ 5 hour in the water-ethanol of 1:1 again in volume ratio by described intermediate product B, then take out, calcination 1 ~ 5 hour at the temperature of 400 DEG C in the mixed gas of rare gas element and air again, namely obtains described carbon doping stannic oxide nano wire lithium cell cathode material;
Wherein, the volume ratio 1:10 ~ 10:1 of described rare gas element and air;
Above-mentioned number all refers to parts by weight.
Below by way of several specific embodiment to be specifically described the present invention.
Embodiment 1
By 90 parts by weight of phenol heat fused at 40 DEG C, drip 20 weight part 20% sodium hydroxide solutions and 160 weight part 37% formaldehyde solutions while stirring successively, be then warming up to 70 DEG C, 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.Left at room temperature, is placed in 100 DEG C of baking oven heating 1 day, makes resol crosslinking curing after ethanol is evaporated completely by product.Under nitrogen atmosphere, by product 700 DEG C of carbonizations 5 hours in tube furnace, the meso-porous carbon material with continuous duct is obtained.
At 80 DEG C, above-mentioned meso-porous carbon material is immersed in the SnCl of melting
22H
2in O, 1 ~ 5 hour is left standstill under vacuum condition, product is in 1:1(volume ratio) water-ethanol in soak after 1 hour and take out, in the mixed gas of nitrogen and air (volume ratio 8:1), calcination 2 hours at 400 DEG C, obtains the carbon doping stannic oxide nano wire lithium cell cathode material of carbon content about 18%.
Embodiment 2:
By 100 parts by weight of phenol heat fused at 40 DEG C, drip 20 weight part 20% sodium hydroxide solutions and 160 weight part 37% formaldehyde solutions while stirring successively, be then warming up to 70 DEG C, 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.Left at room temperature, is placed in 100 DEG C of baking oven heating 1 day, makes resol crosslinking curing after ethanol is evaporated completely by product.Under nitrogen atmosphere, by product 800 DEG C of carbonizations 3 hours in tube furnace, the meso-porous carbon material with continuous duct is obtained.
At 100 DEG C, above-mentioned meso-porous carbon material is immersed in the stannous iso caprylate of melting, 1 ~ 5 hour is left standstill under vacuum condition, product is in 1:1(volume ratio) water-ethanol in soak after 5 hours and take out, in the mixed gas of nitrogen and air (volume ratio 6:1), calcination 2 hours at 400 DEG C, obtains the carbon doping stannic oxide nano wire lithium cell cathode material of carbon content about 10%.
Embodiment 3:
By 94 parts by weight of phenol heat fused at 40 DEG C, drip 20 weight part 20% sodium hydroxide solutions and 160 weight part 37% formaldehyde solutions while stirring successively, be then warming up to 70 DEG C, 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.Left at room temperature, is placed in 100 DEG C of baking oven heating 1 day, makes resol crosslinking curing after ethanol is evaporated completely by product.Under nitrogen atmosphere, by product 750 DEG C of carbonizations 4 hours in tube furnace, the meso-porous carbon material with continuous duct is obtained.
At 100 DEG C, above-mentioned meso-porous carbon material is immersed in the SnCl of melting
45H
2in O, 1 ~ 5 hour is left standstill under vacuum condition, product is in 1:1(volume ratio) water-ethanol in soak after 2 hours and take out, in the mixed gas of nitrogen and air (volume ratio 5:1), calcination 2 hours at 400 DEG C, obtains the carbon doping stannic oxide nano wire lithium cell cathode material of carbon content about 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 doping stannic oxide nano wire 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 doping stannic oxide nano wire 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, carbon doping stannic oxide nano wire lithium cell cathode material initial discharge capacity prepared by the present invention and charging capacity are respectively 1597mAhg
-1and 827mAhg
-1, first coulombic efficiency is 51.7%.And commercial stannic oxide particle initial discharge capacity and charging capacity are respectively 1394mAhg
-1and 495mAhg
-1, first coulombic efficiency is 35.5%
From accompanying drawing 3, circulate after 20 times under identical testing conditions, carbon doping stannic oxide nano wire 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 reduce to 161mAhg respectively
-1and 155mAhg
-1.Illustrate that carbon doping stannic oxide nano wire lithium cell cathode material prepared by the present invention compares with commercial stannic oxide particle, charge/discharge capacity and cyclical stability all significantly improve.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a preparation method for carbon doping stannic oxide nano wire lithium cell cathode material, is characterized in that, comprises the following steps:
1) phenol of 80 ~ 100 parts is carried out heating and melting, the mass concentration dripping 10 ~ 30 parts while stirring is successively the sodium hydroxide solution of 20% and the mass concentration of 80 ~ 160 parts is the formaldehyde solution of 37%, then heat up, react after 40 ~ 80 minutes, cool again, then add hydrochloric acid and be adjusted to neutrality, vacuum-drying obtains low-molecular-weight soluble resol;
2) by step 1) in the low-molecular-weight soluble resol that obtains be dissolved in the ethanol of 1500 ~ 4000 parts, add the pore-creating agent of 40 ~ 200 parts, stir to clarify transparent, left at room temperature, after ethanol is evaporated completely, be placed in baking oven again to heat, 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 carbonization in tube furnace, obtains the meso-porous carbon material with continuous duct; Described pore-creating agent comprise in PCE, polyox-yethylene-polyoxypropylene block copolymer, polyoxyethylene-polystyrene block copolymer or Polystyrene-Polyethylene pyridine block copolymer any one;
3) by step 2) in the described meso-porous carbon material that obtains be immersed in the tindioxide presoma of melting, leave standstill under vacuum condition, tindioxide presoma is fully penetrated in the duct of meso-porous carbon material, obtain intermediate product B, be soak in the water-ethanol of 1:1 again in volume ratio by described intermediate product B, then take out, then carry out calcination in the mixed gas of rare gas element and air, namely obtain described carbon doping stannic oxide nano wire lithium cell cathode material; Described tindioxide presoma comprises SnCl
22H
2o, SnCl
45H
2any one in O or stannous iso caprylate; Described processing condition of carrying out calcination are calcination 1 ~ 5 hour at the temperature of 400 DEG C;
Wherein, the volume ratio 1:10 ~ 10:1 of described rare gas element and air;
Above-mentioned number all refers to parts by weight.
2. the preparation method of carbon doping stannic oxide nano wire lithium cell cathode material according to claim 1, is characterized in that, in step 1) in, described in carry out heating and melting Heating temperature be 40 ~ 45 DEG C.
3. the preparation method of carbon doping stannic oxide nano wire lithium cell cathode material according to claim 1, is characterized in that, in step 1) in, described in carry out being warming up to 65 ~ 75 DEG C.
4. the preparation method of carbon doping stannic oxide nano wire lithium cell cathode material according to claim 1, is characterized in that, in step 2) in, the temperature in described baking oven is 100 ~ 150 DEG C, and the time of carrying out heating is 1 ~ 2 day.
5. the preparation method of carbon doping stannic oxide nano wire lithium cell cathode material according to claim 1, is characterized in that, in step 2) in, described in carry out carbonization temperature be 700 ~ 1200 DEG C.
6. the preparation method of carbon doping stannic oxide nano wire lithium cell cathode material according to claim 1, is characterized in that, in step 3) in, described in time of carrying out leaving standstill be 1 ~ 5 hour.
7. the preparation method of carbon doping stannic oxide nano wire lithium cell cathode material according to claim 1, is characterized in that, in step 3) in, described in time of carrying out soaking be 0.5 ~ 5 hour.
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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 |
| CN112018360B (en) * | 2020-08-26 | 2022-02-18 | 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 |
| 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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| CN101659440A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Preparation method of tin dioxide nano wire |
| CN101857264A (en) * | 2010-05-26 | 2010-10-13 | 上海大学 | Method for preparing nano tin dioxide gas-sensitive material |
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