CN110137466A - Lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation method - Google Patents
Lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation method Download PDFInfo
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- CN110137466A CN110137466A CN201910397769.4A CN201910397769A CN110137466A CN 110137466 A CN110137466 A CN 110137466A CN 201910397769 A CN201910397769 A CN 201910397769A CN 110137466 A CN110137466 A CN 110137466A
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Abstract
The present invention provides a kind of lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation methods, belong to lithium ion battery negative material field.Specific preparation process is as follows: silico-carbo nanotube complex microsphere is prepared after nano silicon oxide is mixed with carbon nanotube；Then porous silico-carbo nanotube complex microsphere is obtained by magnesiothermic reduction；Then one layer of organic carbon source is coated with Dopamine hydrochloride again, carbon-coated silicon-carbon-carbon nanotube composite microsphere negative electrode material is just obtained by pyrolysis.The composite negative pole material is using porous nano silicon as basis material, porous nano silicon face coats carbon-coating, carbon nanotube runs through, interweave be distributed in inside microballoon and surface constitutes unique multistage conductive network, improve the electric conductivity of material, specific capacity with higher, and then the comprehensive cycle life for promoting material.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, and in particular to a kind of lithium ion battery silicon-carbon-carbon is received
The preparation method of mitron composite microsphere negative electrode material.
Background technique
With the fast development of 3C industry, the lithium ion battery as power supply also becomes a southern exposure of great prospect
Industry.Lithium ion battery is high with energy density, have extended cycle life, self discharge is few, charging rate is fast and advantages of environment protection,
It is the best secondary cell of current market prospects with fastest developing speed.Energy consumption increasingly increases simultaneously, and environmental pollution is got worse, because
This environment friendly and pollution-free new-energy automobile receives the extensive concern of national governments and enterprise.Power battery is as electric car
Core, " made in China 2025 " specify the development plan of power battery: the year two thousand twenty, battery energy density reach 300Wh/
kg；2025, battery energy density reached 400Wh/kg.
Realize above-mentioned target, there is an urgent need to develop lithium ion battery with high energy densities out.Currently, lithium ion battery is universal
The graphite cathode theoretical capacity of use is only 372mAh/g, and actual capacity is difficult to be improved again, it is difficult to meet already close to the limit
The electric car demand higher and higher to battery energy density.
The theoretical capacity of silicon is 4200mAh/g, is more than ten times of graphite capacity, be at present most the lithium of industrialization prospect from
Sub- cell negative electrode material.But volume change of the silicon in charge and discharge process is up to 300%, easily causes active material powder
Change, fall off, and the rapid decay of final conductive tankage, further limits its commercial applications.Nanosizing, system are carried out to silicon
Standby silicon nanowires, nano particle, the special constructions such as nano-hollow ball can inhibit volume effect of the silicon in charge and discharge process significantly
It answers, reduces the dusting of particle.But the large specific surface area of nano material, serious reunion and low tap density can be caused, no
Conducive to industrial applications.Therefore, prepare low surface area, do the silicon based anode material of tap density have to the business network of silicon it is important
Realistic meaning.
Summary of the invention
It prepares with high-tap density it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of, low compare table
The silicon-carbon of the lithium ion battery silicon-carbon of area-carbon nanotube composite microsphere negative electrode material preparation method, this method preparation is compound
Porous microsphere negative electrode material specific capacity with higher and excellent cycle performance.
The present invention provides a kind of lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation method, institutes
Silicon-carbon-carbon nanotube composite microsphere negative electrode material is stated to be passed through specifically by three kinds of porous silicon, carbon nanotube and agraphitic carbon materials
Distribution mode is composed, and porous nano silicon face coats carbon-coating, and carbon-coated porous nano silicon is assembled into micron-sized spherical shape
Porous silicon, carbon nanotube runs through, interweave be distributed in inside microballoon and surface；It is described porous for micropore and mesoporous, the silicon-carbon
Microballoon is the micron ball that granularity is 1~50 μm.Specifically preparation step includes:
(1) hydrophilic SiO2Synthesis: according to the volume ratio 1:8 of water and ethyl alcohol configure ethanol solution, then be added ammonium hydroxide and
Tetraethyl orthosilicate, stirring obtain the hydrophilic SiO of 200~400nm after a certain period of time2；
(2)SiO2The preparation of carbon nanotube complex microsphere: according to silica: water: oily 0.2~0.5g:5 of ratio~10mL:
30~40mL, by the hydrophilic SiO in step 12It is added in deionized water, adds hydrophilic SiO21~20% hydrophilic carbon nanometer
Pipe, is dispersed with stirring；Above-mentioned dispersant liquid drop is added in the octadecylene oil phase containing emulsifier, high-speed stirred 2~3min, 98~100
DEG C heat preservation 3h, obtain the SiO of the centre of sphere2Carbon nanotube complex microsphere；
(3) prepared by silico-carbo nanotube complex microsphere: step 2 is obtained SiO2Carbon nanotube complex microsphere is pressed with potassium chloride
It is mixed according to mass ratio 1:21~30, adds SiO2The magnesium powder of quality 50%~100%, ground and mixed, in hydrogen-argon-mixed guarantor
Under shield, 600~800 DEG C are warming up to, 1~5h is kept the temperature, is cleaned after cooling with acid, it is dry, it is compound porous micro- to obtain silico-carbo nanotube
Ball；
(4) prepared by carbon coating silico-carbo nanotube complex microsphere: by the sample dispersion prepared in step (3) in buffer,
Then the Dopamine hydrochloride of sample quality 20%~100% is added, centrifugal drying after a certain period of time is stirred at room temperature, will dry
Product afterwards is placed in tube furnace, is warming up to 400~1000 DEG C, 1~10h of constant temperature under an inert atmosphere with certain heating rate,
It is cooled to room temperature and obtains carbon-coated silicon-carbon-carbon nanotube composite microsphere negative electrode material；
Further, the certain time in the step (1) is 2~10h.
Further, the oil in the step (2) is octadecylene；The hydrophilic carbon nanotube is hydroxyl, carboxyl, amination
One of carbon nanotube is a variety of；The emulsifier be Hypermer2296, Hypermer2524, Hypermer1031,
Hypermer B-210, one of Hypermer2234 or multiple combinations.
Further, the acid in the step (3) is hydrochloric acid, and the collocation of one or both of hydrofluoric acid uses.
Further, the buffer in the step (4) is the solution that the pH of Tris-base configuration is 8；The stirring one
Fix time as 1~for 24 hours, preferably 5~for 24 hours；The protective atmosphere is nitrogen, argon gas, helium.
Step (1), (2), (3) and (4) of the present invention is an organic unity, indivisible overall plan, each step
Rapid organic cooperation, plays synergistic effect.The silicon-carbon composite porous microspheres negative electrode material is by porous silicon, carbon nanotube and unformed
Three kinds of materials of carbon are composed by specific distribution mode, and porous nano silicon face coats carbon-coating, carbon-coated porous nano
Silicon is assembled into micron-sized spherical porous silicon, carbon nanotube runs through, interweave be distributed in inside microballoon and surface, auxiliary building three
The conductive network of connection is tieed up, the electric conductivity of reinforcing material reduces impedance；It is empty between pore structure and nano particle inside nano-silicon
Gap provides the space of release for the volume expansion of silicon；Micron-sized microballoon reduces specific surface area, helps to improve vibration density
Degree；The carbon coating on silicon particle surface can improve the electric conductivity of silicon；The comprehensive circulation for promoting material of the coordinative role of above-mentioned several respects
Service life.
Detailed description of the invention
Fig. 1 is silicon-carbon-carbon nanotube complex microsphere SEM spectrum prepared by the embodiment of the present invention 1；
Fig. 2 is silicon-carbon-carbon nanotube complex microsphere XRD photo prepared by the embodiment of the present invention 1；
Fig. 3 is silicon-carbon-carbon nanotube complex microsphere tap density optical photograph prepared by the embodiment of the present invention 1；
Fig. 4 is silicon-carbon-carbon nanotube complex microsphere charging and discharging curve prepared by the embodiment of the present invention 1.
Specific embodiment
In order to which density of the invention, technical solution and advantage is more clearly understood, below in conjunction with attached drawing and specific implementation
Mode, the present invention will be described in further detail.Obviously, described embodiment is only that a part of the invention is implemented
Example, instead of all the embodiments.Based on the embodiments of the present invention, those skilled in the art is not making creative labor
Every other embodiment obtained under the premise of dynamic, shall fall within the protection scope of the present invention.It should be appreciated that tool described herein
Body embodiment only to explain the present invention, is not intended to limit the present invention.
Embodiment one
(1) mixed solution containing 10mL water and 80mL ethyl alcohol is configured, 3mL ammonium hydroxide is added and stirs evenly, later again quickly
6mL tetraethyl orthosilicate is added, obtains hydrophilic SiO after stirring 2h2And centrifugal drying；
(2) by 500mg hydrophilic SiO2It is dispersed in 10mL water with 5mg hydroxyl carbon nano tube, ultrasonic disperse obtains
Dispersion liquid；It measures 30mL octadecylene and 100mg Hypermer2296 is stirred evenly, obtain oily phase；Dispersant liquid drop is added to oily phase
In, with homogenizer high-speed stirred 2min, in 98 DEG C of heat preservation 3h, centrifugal drying obtains SiO2Carbon nanotube complex microsphere；
(3) SiO will be obtained2Carbon nanotube complex microsphere is mixed with potassium chloride according to mass ratio 1:21, adds SiO2Matter
The magnesium powder of amount 50%, ground and mixed are warming up to 600 DEG C under hydrogen-argon-mixed protection, keep the temperature 1h, are cleaned after cooling with hydrochloric acid
And centrifugal drying, obtain silico-carbo nanotube composite porous microspheres；
(4) 500mg silico-carbo nanotube composite porous microspheres are dispersed in buffer, sample quality 200mg is then added
Dopamine hydrochloride, 1h centrifugal drying is stirred at room temperature, the product after drying is placed in tube furnace, under an inert atmosphere with
Certain heating rate is warming up to 400 DEG C, constant temperature 1h, is cooled to room temperature and obtains carbon-coated silicon-carbon-carbon nanotube complex microsphere
Negative electrode material.
SEM test is carried out to obtained silicon-carbon-carbon nanotube composite microsphere negative electrode material, as a result as shown in Figure 1.From Fig. 1
In it can be seen that, silicon-carbon-carbon nano tube compound material is spherical in shape, and there is an interspersed cladding of uniform carbon nanotube in outside, granularity 1~
10 μm or so.
XRD test is carried out to obtained silicon-carbon composite cathode material, as a result as shown in Figure 2.From fig. 2 it can be seen that going out
The characteristic diffraction peak of existing silicon, the diffraction maximum of carbon nanotube is not since content causes very little.
Tap density test is carried out to obtained silicon-carbon-carbon nanotube composite microsphere negative electrode material, as a result as shown in Figure 3.
Only it is respectively nano-silicon, silica and silicon-carbon-carbon nanotube complex microsphere from a left side, can be regarded as from figure, silicon-carbon-carbon nanotube
The tap density of complex microsphere is maximum.
By silicon-carbon made from embodiment-carbon nanotube composite microsphere negative electrode material and the sea conductive agent Super P and binder
Mosanom carries out ground and mixed according to mass ratio 8:1:1, is prepared into slurry, is then coated uniformly on copper foil with scraper, and
10h is dried in vacuum tank at 80 DEG C, carries out punching later, is to electrode assembling button cell with lithium metal.Fig. 4 is in current density
For the charging and discharging curve under 1C, reversible specific capacity is~660mAh/g.
The present invention has no special requirement and limitation to the rate of the heating, using liter well known to those skilled in the art
Warm rate.
Embodiment two
(1) mixed solution containing 10mL water and 80mL ethyl alcohol is configured, 3mL ammonium hydroxide is added and stirs evenly, later again quickly
6mL tetraethyl orthosilicate is added, obtains hydrophilic SiO after stirring 2h2And centrifugal drying；
(2) by 300mg hydrophilic SiO2It is dispersed in 10mL water with 40mg carboxylic carbon nano-tube, ultrasonic disperse obtains
To dispersion liquid；It measures 40mL octadecylene and 90mg Hypermer2524 is stirred evenly, obtain oily phase；Dispersant liquid drop is added to oil
Xiang Zhong, with homogenizer high-speed stirred 3min, in 99 DEG C of heat preservation 3h, centrifugal drying obtains SiO2Carbon nanotube complex microsphere；
(3) SiO will be obtained2Carbon nanotube complex microsphere is mixed with potassium chloride according to mass ratio 1:25, adds SiO2Matter
The magnesium powder of amount 80%, ground and mixed are warming up to 800 DEG C under hydrogen-argon-mixed protection, keep the temperature 5h, use hydrochloric acid, hydrogen fluorine after cooling
Acid cleaning and centrifugal drying, obtain silico-carbo nanotube composite porous microspheres；
(4) 500mg silico-carbo nanotube composite porous microspheres are dispersed in buffer, sample quality 500mg is then added
Dopamine hydrochloride, centrifugal drying for 24 hours is stirred at room temperature, the product after drying is placed in tube furnace, under an inert atmosphere
1000 DEG C, constant temperature 3h are warming up to certain heating rate, is cooled to room temperature that obtain carbon-coated silicon-carbon-carbon nanotube compound micro-
Ball negative electrode material.The silicon-carbon-carbon nanotube composite microsphere negative electrode material has structure and performance similar to Example 1.
The present invention has no special requirement and limitation to the rate of the heating, using liter well known to those skilled in the art
Warm rate.
Embodiment three
(1) mixed solution containing 10mL water and 80mL ethyl alcohol is configured, 3mL ammonium hydroxide is added and stirs evenly, later again quickly
6mL tetraethyl orthosilicate is added, obtains hydrophilic SiO after stirring 2h2And centrifugal drying；
(2) by 500mg hydrophilic SiO2It is dispersed in 8mL water with 100mg carboxylic carbon nano-tube, ultrasonic disperse obtains
To dispersion liquid；It measures 40mL octadecylene and 80mg Hypermer B-210 is stirred evenly, obtain oily phase；Dispersant liquid drop is added to
In oily phase, with homogenizer high-speed stirred 2min, in 100 DEG C of heat preservation 3h, centrifugal drying obtains SiO2Carbon nanotube complex microsphere；
(3) SiO will be obtained2Carbon nanotube complex microsphere is mixed with potassium chloride according to mass ratio 1:25, adds SiO2Matter
The magnesium powder of amount 90%, ground and mixed are warming up to 700 DEG C under hydrogen-argon-mixed protection, keep the temperature 4h, use hydrochloric acid, hydrogen fluorine after cooling
Acid cleaning and centrifugal drying, obtain silico-carbo nanotube composite porous microspheres；
(4) 500mg silico-carbo nanotube composite porous microspheres are dispersed in buffer, sample quality 400mg is then added
Dopamine hydrochloride, 5h centrifugal drying is stirred at room temperature, the product after drying is placed in tube furnace, under an inert atmosphere with
Certain heating rate is warming up to 800 DEG C, constant temperature 4h, is cooled to room temperature and obtains carbon-coated silicon-carbon-carbon nanotube complex microsphere
Negative electrode material.
Tap density test is carried out to obtained silicon-carbon-carbon nanotube composite microsphere negative electrode material, as a result as shown in Figure 3.
Only it is respectively nano-silicon, silica and silicon-carbon-carbon nanotube complex microsphere from a left side, can be regarded as from figure, silicon-carbon-carbon nanotube
The tap density of complex microsphere is maximum.
The silicon-carbon-carbon nanotube composite microsphere negative electrode material has structure and performance similar to Example 1.
The present invention has no special requirement and limitation to the rate of the heating, using liter well known to those skilled in the art
Warm rate.
Example IV
(1) mixed solution containing 10mL water and 80mL ethyl alcohol is configured, 3mL ammonium hydroxide is added and stirs evenly, later again quickly
6mL tetraethyl orthosilicate is added, obtains hydrophilic SiO after stirring 2h2And centrifugal drying；
(2) by 200mg hydrophilic SiO2It is dispersed in 5mL water with 20mg aminated carbon nano tube, ultrasonic disperse obtains
Dispersion liquid；It measures 40mL octadecylene and 100mg Hypermer2234 is stirred evenly, obtain oily phase；Dispersant liquid drop is added to oily phase
In, with homogenizer high-speed stirred 2min, in 98 DEG C of heat preservation 3h, centrifugal drying obtains SiO2Carbon nanotube complex microsphere；
(3) SiO will be obtained2Carbon nanotube complex microsphere is mixed with potassium chloride according to mass ratio 1:30, adds SiO2Matter
The magnesium powder of amount 100%, ground and mixed are warming up to 600 DEG C under hydrogen-argon-mixed protection, keep the temperature 5h, use hydrochloric acid, hydrogen after cooling
Hydrofluoric acid cleaning and centrifugal drying, obtain silico-carbo nanotube composite porous microspheres；
(4) 500mg silico-carbo nanotube composite porous microspheres are dispersed in buffer, sample quality 300mg is then added
Dopamine hydrochloride, 8h centrifugal drying is stirred at room temperature, the product after drying is placed in tube furnace, under an inert atmosphere with
Certain heating rate is warming up to 900 DEG C, constant temperature 5h, is cooled to room temperature and obtains carbon-coated silicon-carbon-carbon nanotube complex microsphere
Negative electrode material.
The silicon-carbon-carbon nanotube composite microsphere negative electrode material has structure and performance similar to Example 1.
The present invention has no special requirement and limitation to the rate of the heating, using liter well known to those skilled in the art
Warm rate.
Embodiment five
(1) mixed solution containing 10mL water and 80mL ethyl alcohol is configured, 3mL ammonium hydroxide is added and stirs evenly, later again quickly
6mL tetraethyl orthosilicate is added, obtains hydrophilic SiO after stirring 2h2And centrifugal drying；
(2) by 400mg hydrophilic SiO2It is dispersed in 10mL water with 80mg aminated carbon nano tube, ultrasonic disperse obtains
To dispersion liquid；It measures 40mL octadecylene and 95mg Hypermer1031 is stirred evenly, obtain oily phase；Dispersant liquid drop is added to oil
Xiang Zhong, with homogenizer high-speed stirred 2min, in 99 DEG C of heat preservation 3h, centrifugal drying obtains SiO2Carbon nanotube complex microsphere；
(3) SiO will be obtained2Carbon nanotube complex microsphere is mixed with potassium chloride according to mass ratio 1:25, adds SiO2Matter
The magnesium powder of amount 100%, ground and mixed are warming up to 650 DEG C under hydrogen-argon-mixed protection, keep the temperature 4h, use hydrochloric acid, hydrogen after cooling
Hydrofluoric acid cleaning and centrifugal drying, obtain silico-carbo nanotube composite porous microspheres；
(4) 500mg silico-carbo nanotube composite porous microspheres are dispersed in buffer, sample quality 200mg is then added
Dopamine hydrochloride, 20h centrifugal drying is stirred at room temperature, the product after drying is placed in tube furnace, under an inert atmosphere
700 DEG C, constant temperature 4h are warming up to certain heating rate, is cooled to room temperature that obtain carbon-coated silicon-carbon-carbon nanotube compound micro-
Ball negative electrode material.
The silicon-carbon-carbon nanotube composite microsphere negative electrode material has structure and performance similar to Example 1.
The present invention has no special requirement and limitation to the rate of the heating, using liter well known to those skilled in the art
Warm rate.
Claims (6)
1. a kind of lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material preparation method, it is characterised in that the silicon
Carbon-to-carbon nanotube composite microsphere negative electrode material is passed through specific by three kinds of porous nano silicon, carbon nanotube and agraphitic carbon materials
Distribution mode is composed, and porous nano silicon face coats carbon-coating, and carbon-coated porous nano silicon is assembled into micron-sized spherical shape
Porous silicon, carbon nanotube runs through, interweave be distributed in inside microballoon and surface；It is described porous for micropore and mesoporous, the silicon-carbon
Microballoon is the micron ball that granularity is 1~50 μm；Specifically preparation step includes:
(1) hydrophilic SiO2Synthesis: configure ethanol solution according to the volume ratio 1:8 of water and ethyl alcohol, ammonium hydroxide and positive silicic acid be then added
Tetra-ethyl ester, stirring obtain the hydrophilic SiO of 200~400nm after a certain period of time2；
(2)SiO2The preparation of carbon nanotube complex microsphere: according to silica: water: oily 0.2~0.5g:5 of ratio~10mL:30~
40mL, by the hydrophilic SiO in step (1)2It is added in deionized water, adds hydrophilic SiO21~20% hydrophilic carbon nanotube,
It is dispersed with stirring；Above-mentioned dispersant liquid drop is added in the octadecylene oil phase containing emulsifier, 2~3min of high-speed stirred, 98~100 DEG C of guarantors
Warm 2.5-3.5h obtains the SiO of the centre of sphere2Carbon nanotube complex microsphere；
(3) prepared by silico-carbo nanotube complex microsphere: step (2) is obtained SiO2Carbon nanotube complex microsphere and potassium chloride according to
Mass ratio 1:21~30 is mixed, and adds SiO2The magnesium powder of quality 50%~100%, ground and mixed, in hydrogen-argon-mixed protection
Under, 600~800 DEG C are warming up to, 1~5h is kept the temperature, is cleaned after cooling with acid, it is dry, it is compound porous micro- to obtain silico-carbo nanotube
Ball；
(4) prepared by carbon coating silico-carbo nanotube complex microsphere: by the sample dispersion prepared in step (3) in buffer, then
The Dopamine hydrochloride of sample quality 20%~100% is added, centrifugal drying after a certain period of time is stirred at room temperature, after drying
Product is placed in tube furnace, is warming up to 400~1000 DEG C, 1~10h of constant temperature under an inert atmosphere with certain heating rate, cooling
Carbon-coated silicon-carbon-carbon nanotube composite microsphere negative electrode material is obtained to room temperature.
2. lithium ion battery silicon-carbon described according to claim 1-carbon nanotube composite microsphere negative electrode material preparation method,
The certain time being characterized in that in the step (1) is 2~10h.
3. lithium ion battery silicon-carbon described according to claim 1-carbon nanotube composite microsphere negative electrode material preparation method,
The oil being characterized in that in the step (2) is octadecylene；The hydrophilic carbon nanotube is hydroxyl, carboxyl, aminated carbon nano tube
One of or it is a variety of；The emulsifier is Hypermer2296, Hypermer2524, Hypermer1031, Hypermer B-
One of 210, Hypermer2234 or multiple combinations.
4. lithium ion battery silicon-carbon described according to claim 1-carbon nanotube composite microsphere negative electrode material preparation method,
The acid being characterized in that in the step (3) is hydrochloric acid, and the collocation of one or both of hydrofluoric acid uses.
5. lithium ion battery silicon-carbon described according to claim 1-carbon nanotube composite microsphere negative electrode material preparation method,
The buffer being characterized in that in the step (4) is the solution that the pH of Tris-base configuration is 8；The stirring certain time is 1
~for 24 hours；The protective atmosphere is nitrogen, argon gas, helium.
6. a kind of preparation side of lithium ion battery silicon-carbon-carbon nanotube composite microsphere negative electrode material according to claim 5
Method, which is characterized in that the stirring certain time is 5~20h.
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| CN110854379A (en) * | 2019-11-26 | 2020-02-28 | 焦作聚能能源科技有限公司 | Silicon-carbon composite negative electrode material and preparation method thereof, negative electrode plate and lithium ion battery |
| CN111082005A (en) * | 2019-12-06 | 2020-04-28 | 欣旺达电动汽车电池有限公司 | Negative electrode material, composite material and preparation method thereof |
| CN111293292A (en) * | 2020-02-19 | 2020-06-16 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN112290005A (en) * | 2020-11-23 | 2021-01-29 | 山东硅纳新材料科技有限公司 | Method for preparing novel silicon-carbon negative electrode material by utilizing dopamine hydrochloride |
| CN113725409A (en) * | 2021-07-29 | 2021-11-30 | 合肥国轩高科动力能源有限公司 | Silicon-based negative electrode material and preparation method thereof |
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| CN115448287A (en) * | 2022-10-13 | 2022-12-09 | 西华大学 | Lithium ion battery cathode material and preparation method thereof |
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