CN110203920A - A kind of preparation method of chemical vapor deposition modified graphite - Google Patents
A kind of preparation method of chemical vapor deposition modified graphite Download PDFInfo
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- CN110203920A CN110203920A CN201910470395.4A CN201910470395A CN110203920A CN 110203920 A CN110203920 A CN 110203920A CN 201910470395 A CN201910470395 A CN 201910470395A CN 110203920 A CN110203920 A CN 110203920A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
Abstract
The invention discloses a kind of preparation methods of chemical vapor deposition modified graphite, using ethyl alcohol as carbon source, using Ni as catalyst, catalyst loading 1wt%, 2wt%, 3wt%, 4wt% and 4.5wt%, using graphite as substrate, graphite is modified by chemical vapour deposition technique.The present invention is assisted using ultrasonic wave, and freeze-drying and chemical vapour deposition technique realize growth multi-walled carbon nanotube in situ on the surface of graphite, and the size uniformity of gained carbon nanotube, optimal caliber is in 20~30nm.Modified graphite cell capacity battery capacity compared with unmodified increases 149mAg‑1, using low loading Ni catalyst, reduce noble metal waste, reduce cost；The catalyst dispersion that ultrasonic wave added freeze-drying supports is more uniform, specific surface area increases, and changes the microstructure of graphite surface, the modified modified graphite of the chemical vapor deposition being prepared improves the electrical property of battery as electrode material.
Description
Technical field
The invention belongs to graphite modified technical fields, and in particular to a kind of preparation side of chemical vapor deposition modified graphite
Method.
Background technique
Since lithium ion battery is commercialized Sony company, Japan since 1991, lithium ion battery is high with its energy, works
The features such as voltage is high, load characteristic is good, charging rate is fast, the pollution of safe object, rapidly in mobile phone, micro-camera, palm electricity
The fields such as brain, laptop have a wide range of applications.
One of an important factor for anode material capacity is influence battery capacity, graphite specific capacity inexpensive with its, nontoxic, high
(200mAg-1~400mAg-1), low electrode potential and the advantages that high cycle efficieny (> 95%) become current mainstream
Lithium ion battery negative electrode material.
However, since graphite layers distance is less than (d002≤ 0.34nm) graphite lithium intercalation compound LixC6Crystal face interlayer
Away from (0.37nm).Cause in charge and discharge process, graphite layers away from change, easily cause graphite linings peel off, dusting, and occur
Lithium ion and organic solvent molecule are embedded in graphite linings jointly and organic solvent decomposes, and then affect the cycle performance of battery.Cause
This, needs to be modified graphite, using the method for chemical vapor deposition, the growth carbon nanometer in situ on the surface of graphite
Pipe, the specific surface area and activity for increasing substrate graphite are a kind of research tendencies.
Publication No. CN101355150B disclosed on 2 16th, 2011, entitled " lithium ion battery graphitic carbon nano
Pipe the preparation method of combination electrode material " patent achieves wherein being exactly growth carbon nanotube in situ on the surface of graphite
Preferable performance.But the loading of the catalyst n i used in its technical solution is 5~40%, the big higher cost of loading is urged
Agent dispersion is uneven and catalyst reference area is small, causes catalytic performance bad.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of chemical vapor deposition modified graphite, solve in the prior art
The problem that existing catalyst loading is high, catalyst dispersion is uneven and reference area is small.
The technical scheme adopted by the invention is that a kind of preparation method of chemical vapor deposition modified graphite, with nickel acetate
For catalyst source, graphite is carrying body, the catalyst of Ni/C is prepared by ultrasonic wave auxiliary, vacuum freeze drying, wherein Ni/
The catalyst of C is monatomic catalyst, finally utilizes chemical vapour deposition technique modified graphite.
Detailed step is as follows:
Step 1, the deionized water solution by nickel acetate are slowly added into carrying body graphite under fast stirring, at ultrasound
Reason is uniformly mixed it, is placed in liquid nitrogen and carries out vacuum freeze drying, and the Ni/C that mass ratio is 1~4.5wt% is prepared and urges
Agent presoma；
The catalyst precursor of the obtained Ni/C of step 1 is placed in chemical vapor deposition stove by step 2, in argon gas gas
In atmosphere, 340 DEG C~360 DEG C are warming up to the speed of 2 DEG C/min, heat preservation then turns to hydrogen atmosphere, with 2 DEG C/min speed liter
Temperature is restored to 480 DEG C~520 DEG C, obtains Ni/C catalyst；
Stop being passed through hydrogen after step 3, reduction, then passes to argon gas for the hydrogen of remnants middle in chemical vapor deposition stove
Gas is discharged, and ethyl alcohol is injected into vaporizer after being finally warming up to the reaction temperature of setting, the ethyl alcohol after vaporizing by vaporizer
Catalytic cracking reaction is carried out in into chemical vapor deposition stove, and chemical vapor deposition modified graphite is made.
The features of the present invention also characterized in that:
Sonication treatment time is 5~7h in step 1.
Graphite average grain diameter 18.3um is supported in step 1.
It is 96.0wt%~99.0wt% that graphite phosphorus content is supported in step 1.
Soaking time is 1~3h in step 2, and the recovery time is 0.5~2h.
Argon gas flow velocity is 30~50ml/min in step 3.
Catalytic cracking reaction temperature is 500~700 DEG C in step 3.
The catalytic cracking reaction time is 60min in step 3.
Ethanol injection flow velocity is 0.2~0.5ml/h in step 3.
Nanotube is multi-walled carbon nanotube on the chemical vapor deposition modified graphite obtained, and caliber is in 20~30nm.
The beneficial effects of the present invention are: reducing noble metal waste using low loading Ni catalyst, reducing cost；Ultrasound
The catalyst dispersion that auxiliary freeze-drying supports is more uniform, specific surface area increases, and changes the microstructure of graphite surface,
The nanotube modified graphite being prepared improves the electrical property of battery as electrode material.
Detailed description of the invention
Fig. 1 is that differential responses temperature chemical vapor deposits modified graphite SEM figure；
Fig. 2 is the SEM figure of the chemical vapor deposition modified graphite of 600 DEG C of different loadings；
The TEM figure of chemical vapor deposition modified graphite when Fig. 3 (a) is catalyst loading 3wt%；
The TEM figure of chemical vapor deposition modified graphite when Fig. 3 (b) is catalyst loading 3wt%；
Fig. 4 (a) is chemical vapor deposition modified graphite charging and discharging curve；
Fig. 4 (b) chemical vapor deposition modified graphite charge and discharge cycles stability curve；
Fig. 5 (a) is to support graphite charging and discharging curve；
Fig. 5 (b) is to support graphite charge and discharge cycles stability curve.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The invention discloses a kind of preparation method of chemical vapor deposition modified graphite, used specific steps are as follows:
Step 1, the deionized water solution by nickel acetate are slowly added into carrying body graphite under fast stirring, at ultrasound
5~7h of reason is uniformly mixed it, is placed in liquid nitrogen and carries out vacuum freeze drying, and it is 1~4.5wt%'s that mass ratio, which is prepared,
Ni/C catalyst precursor；
Wherein, Vacuum Freezing & Drying Technology is to freeze wet stock or solution under lower temperature (- 10 DEG C~-50 DEG C)
Form solid-state, then so that moisture therein is directly sublimed into gaseous state without liquid at vacuum (1.3~13Pa), finally make material
The dry technology of dehydration.Its major advantage is: (1) material after dry keeps original chemical composition and physical property and material
In the moisture substantially frost below at 0 DEG C the surface of solids distillation and be dried, substance itself is then left when freezing
Ice shelf in, therefore, it is dry after small product size it is constant, loose porous；(2) heat consumption is fewer than other drying means.Cause
The preparation of this Ni/C catalyst precursor uses vacuum freeze-drying method, and the Ni/C catalyst precursor specific surface area prepared increases
Add.
The catalyst precursor of the obtained Ni/C of step 1 is placed in chemical vapor deposition stove by step 2, in argon gas gas
In atmosphere, 340 DEG C~360 DEG C are warming up to the speed of 2 DEG C/min, 1~3h is kept the temperature, then turns to hydrogen atmosphere, with 2 DEG C/min speed
Degree is warming up to 480 DEG C~520 DEG C 0.5~2h of reduction, obtains Ni/C catalyst；
Wherein, preparation-obtained Ni/C catalyst is monatomic catalyst, the monatomic surface being catalyzed because increased dramatically
Free energy, quantum size effect, unsaturated coordination environment and the interaction of Metal-Support etc., it is excellent to assign monatomic catalyst
Catalytic performance more.Not only content of metal is extremely low but also greatly improves the utilization effect of metallic atom for monatomic catalyst
Rate.
Stop being passed through hydrogen after step 3, reduction, is passed through argon gas and arranges the hydrogen of remnants middle in chemical vapor deposition stove
Completely, flow velocity is then heated to after 500~700 DEG C of reaction temperature of setting controllably with 0.2~0.5ml/h into vaporizer
Ethyl alcohol is injected, the ethyl alcohol after vaporizing by vaporizer, which enters, carries out catalytic cracking reaction in chemical vapor deposition stove, chemistry is made
Be vapor-deposited modified graphite.
By each embodiment, the present invention is described in detail below.
Embodiment 1
Preparing chemical vapor deposition modified graphite material, the content of substrate graphite is 96.5wt%, reaction temperature 500,
600 and 700 DEG C.The specific steps of which are as follows:
1,0.1486g nickel acetate is added in deionized water, under fast stirring, is slowly added into 3g carrying body graphite,
Ultrasonic treatment 6h makes to be uniformly mixed, and then places it in vacuum freeze drying in liquid nitrogen and obtains catalyst precursor.
2, the catalyst precursor that loading is 1.0wt% is placed in chemical vapor deposition stove, in argon atmosphere, first
With 2 DEG C/min temperature programming to 350 DEG C, 2h is kept the temperature, hydrogen atmosphere is then turned to, rises to 500 with the heating rate of 2 DEG C/min
DEG C reduction 1h, obtain Ni/C catalyst.
3, stop being passed through hydrogen after restoring, continue to be passed through argon gas that flow velocity is 40ml/min for H remaining in pipe2Row
Completely, after being warming up to the reaction temperature of setting, second is injected into vaporizing chamber with 0.3ml/h speed with flow velocity controllable syringe
Alcohol enters after vaporization and carries out catalytic cracking reaction, reaction time 60min, the material SEM being modified in chemical vapor deposition stove
Such as Fig. 1.SEM such as Fig. 1 a, b and the c of material, correlation performance parameters are shown in Table 1 sample when reaction temperature is 500,600 and 700 DEG C
S1。
Embodiment 2
Chemical vapor deposition modified graphite material is prepared, the content of substrate graphite is 97.5wt%, specific steps are such as
Under:
1,0.2972g nickel acetate is added in deionized water, under fast stirring, is slowly added into 3g carrying body graphite,
Ultrasonic treatment 5h makes to be uniformly mixed, and then places it in liquid nitrogen vacuum freeze drying and obtains catalyst precursor.
2, the catalyst precursor that loading is 2.0wt% is placed in chemical vapor deposition stove, in argon atmosphere, first
340 DEG C are warming up to 2 DEG C/min heating rate, 1h is kept the temperature, then turns to hydrogen atmosphere, be warming up to 2 DEG C/min heating rate
490 DEG C of reductase 12 h, obtain Ni/C catalyst.
3, stop being passed through hydrogen after restoring, continue to be passed through argon gas that flow velocity is 30ml/min for hydrogen remaining in pipe
It is discharged, with the controllable syringe of flow velocity, with 0.2ml/h speed, the constant speed into vaporizer injects ethyl alcohol, vapour after being warming up to 600 DEG C
Ethyl alcohol, which enters, after change carries out catalytic cracking reaction, reaction time 60min, SEM such as Fig. 2 a, correlation in chemical vapor deposition stove
Energy parameter is shown in Table 1 sample S2。
Embodiment 3
Chemical vapor deposition modified graphite material is prepared, the content of substrate graphite is 97.5wt%, specific steps are such as
Under:
1,0.4458g nickel acetate is added in deionized water, under fast stirring, is slowly added into 3g and supports graphite, surpassed
Sonication 6h makes to be uniformly mixed, and then places it in vacuum freeze drying in liquid nitrogen and obtains catalyst precursor.
2, the catalyst precursor that loading is 3.0wt% is placed in chemical vapor deposition stove, in argon atmosphere, first
350 DEG C are warming up to 2 DEG C/min speed, 2.5h is kept the temperature, then turns to hydrogen atmosphere, is warming up to 500 DEG C also with 2 DEG C/min speed
Former 1.5h obtains Ni/C catalyst.
3, stop being passed through hydrogen after restoring, be passed through the argon gas that flow velocity is 35ml/min and drain hydrogen remaining in pipe
Only, with the controllable syringe of flow velocity, with 0.4ml/h speed, the constant speed into vaporizer injects ethyl alcohol after being warming up to 600 DEG C, after vaporization
Catalytic cracking reaction is carried out in into chemical vapor deposition stove, reaction time 60min, SEM such as Fig. 2 b, correlation performance parameters are shown in
1 sample S of table3。
Embodiment 4
Chemical vapor deposition modified graphite material is prepared, the content of substrate graphite is 97.5wt%, specific steps are such as
Under:
1,0.5944g nickel acetate is added in deionized water, under fast stirring, is slowly added into 3g and supports graphite, surpassed
Sonication 7h makes to be uniformly mixed, and then places it in vacuum freeze drying in liquid nitrogen and obtains catalyst precursor.
2, the catalyst precursor that loading is 4.0wt% is placed in chemical vapor deposition stove, in argon atmosphere, first
350 DEG C are warming up to 2 DEG C/min speed, 3h is kept the temperature, then turns to hydrogen atmosphere, 510 DEG C/min is warming up to also with 2 DEG C/min
Former 2h obtains Ni/C catalyst.
3, stop being passed through hydrogen after restoring, continue to be passed through argon gas that flow velocity is 50ml/min for hydrogen remaining in pipe
It is discharged, with the controllable syringe of flow velocity, with 0.5ml/h speed, the constant speed into vaporizer injects ethyl alcohol, second after being warming up to 600 DEG C
Enter after alcohol vaporization and carries out catalytic cracking reaction, reaction time 60min, SEM such as Fig. 2 c, correlation in chemical vapor deposition stove
Energy parameter is shown in Table 1 sample S4。
Embodiment 5
Chemical vapor deposition modified graphite material is prepared, the content of substrate graphite is 98.5wt%, the specific steps of which are as follows:
1,0.6687g nickel acetate is added in deionized water, under fast stirring, is slowly added into 3g and supports graphite, surpassed
7 hours of sonication make to be uniformly mixed, and then place it in vacuum freeze drying in liquid nitrogen and obtain catalyst precursor.
2, the catalyst precursor that loading is 4.5wt% is placed in chemical vapor deposition stove, in argon atmosphere, first
360 DEG C are warming up to 2 DEG C/min, 1.5h is kept the temperature, then turns to hydrogen atmosphere, 520 DEG C/reduction is warming up to 2 DEG C/min speed
0.5h obtains Ni/C catalyst.
3, stop being passed through hydrogen after restoring, continue to be passed through argon gas that flow velocity is 45ml/min for hydrogen remaining in pipe
It is discharged, with the controllable syringe of flow velocity, with 0.3ml/h speed, the constant speed into vaporizer injects ethyl alcohol, second after being warming up to 600 DEG C
Enter after alcohol vaporization and carries out catalytic cracking reaction, reaction time 60min, SEM such as Fig. 2 d, correlation in chemical vapor deposition stove
Energy parameter is shown in Table 1 sample S5。
Chemical vapor deposition modified graphite electric performance test:
First in mass ratio, i.e. mActive sample:mAcetylene black:mKynoar=85:5:10 sampling mixing, is dissolved in N- crassitude
It is slurried object in ketone, the slurry of electrode is then coated on as the Cu afflux of 19mm by diameter with 20MPa with double rod formula rollers
Negative electrode tab is made through 80 DEG C of vacuum drying 10h in body.The assembled battery in glove box, using above-mentioned pole piece as working electrode, diameter is
18mm is graphite-carbon nanotube pair with a thickness of the lithium piece (it is 99.99% that non-ferrous metal total institute in Beijing, which provides purity) of 0.5mm
Than electrode, diaphragm is 2400 layers of micropore polypropylene diaphragm of Celgard, and electrolyte is molten using the EC/DMC/EMC of 1mol/LiPF6
Liquid assembles Li/C button cell as shown in the figure in the glove box full of argon gas.By stainless steel gasket-positive plate-diaphragm-cathode
Piece-stainless steel gasket-spring is assembled into finished battery from the upper electrolyte that is sequentially injected into, sealing, activates 8h.Chemical vapor deposition
Product modified graphite button cell test is the detector measurement by the blue electricity CT2001 type of Wuhan Jin Nuo Electronics Co., Ltd..
According to the situation of the charge-discharge principle of lithium ion battery and button cell, determine the process of the embedding lithium of carbon complex electrode for electric discharge
Process, the process for taking off lithium is charging process.Test condition: charging or discharging current 0.1C, discharge voltage 3.0V, charging: constant current is filled
Electric 0.4mA, by voltage charging 3.00V, discharge 0.005V, tests resulting relevant parameter and is shown in Table 1.
A, b and c are respectively the SEM that ethyl alcohol cracks the multi-walled carbon nanotube of growth in Ni (1wt%)/C catalyst in Fig. 1
Figure, growth temperature is respectively 500 DEG C, 600 DEG C and 700 DEG C, and as seen from the figure, the carbon nanotube caliber that 500 DEG C of whens generate is thicker, point
Cloth is uneven, and the length of pipe is shorter, Fig. 1 a；When reaction temperature is 600 DEG C, the caliber of carbon nanotube is more uniform, such as Fig. 1 b；
When temperature increases to 700 DEG C, carbon product is mainly relatively thick shorter carbon fiber and carbon coating, such as Fig. 1 c, therefore, optimal cracking
Reaction temperature is 600 DEG C.
1 chemical vapour deposition technique modified graphite material property parameter table of table
Loading increases to 3wt%, and Diameter distribution is uniform, and wrapping phenomena is unobvious, and the quality of carbon nanotube is preferable, such as schemes
Shown in 2b, TEM schemes as shown in Fig. 3 a, b；With the increase of loading, the reunion of catalyst is more and more obvious, such as Fig. 2 c and
2d, therefore, optimal loading are 3wt%.
The charge-discharge performance test of different catalysts loading chemical vapour deposition technique modified graphite material is shown in Table 1, by table 1
It is found that the charge/discharge capacity three times for supporting graphite is 281mAg-1And 265mAg-1, charge and discharge electrograph such as Fig. 5 a, cyclical stability are bent
Line such as Fig. 5 b, coulombic efficiency 94.3%；Chemical vapor deposition modified graphite charge and discharge three times when catalyst loading is 3.0wt%
Capacitance is 430mAg-1And 415mAg-1, coulombic efficiency 96.5%, performance is best, charge and discharge electrograph such as Fig. 4 a, cyclical stability
Curve such as Fig. 4 b, charging capacity increases 149mAg compared with supporting graphite-1.This is because the big specific surface of carbon nanotube
Product, the size of carbon nanotube are Nano grade, carbon nanotube be curled by the coaxial carbon of single-layer or multi-layer and it is similar
The structure of graphite, this structure allows Li+ to be embedded into the inside of pipe, while can also be embedded between tube wall, so carbon
The storage lithium performance of nanotube is better than graphite.Due to the special structure of carbon nanotube, so that the depth of lithium ion insertion is small, stroke
Short, the position of embedding lithium is more, and supports graphite-phase ratio, and the specific capacity as negative electrode material battery increases, meanwhile, carbon nanotube is deposited
Bridge beam action is being played for graphite, " island effect " generation is being avoided, increases the electric conductivity of material.
Claims (10)
1. a kind of preparation method of chemical vapor deposition modified graphite, which is characterized in that be specifically implemented according to the following steps:
Step 1, the deionized water solution by nickel acetate are slowly added into carrying body graphite under fast stirring, and ultrasonic treatment makes
It is uniformly mixed, and is placed in liquid nitrogen and carries out vacuum freeze drying, and the catalysis for the Ni/C that mass ratio is 1~4.5wt% is prepared
Agent presoma；
The catalyst precursor of the obtained Ni/C of step 1 is placed in chemical vapor deposition stove by step 2, in argon atmosphere,
340 DEG C~360 DEG C are warming up to the speed of 2 DEG C/min, heat preservation then turns to hydrogen atmosphere, is warming up to 480 DEG C with 2 DEG C/min
~520 DEG C of reduction, obtain Ni/C catalyst；
Stop being passed through hydrogen after step 3, reduction, then passes to argon gas and arrange the hydrogen of remnants middle in chemical vapor deposition stove
Completely, ethyl alcohol is injected into vaporizer after being finally warming up to the reaction temperature of setting, the ethyl alcohol after vaporizing by vaporizer enters
Catalytic cracking reaction is carried out in chemical vapor deposition stove, and chemical vapor deposition modified graphite is made.
2. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 1
Middle sonication treatment time is 5~7h.
3. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 1
In support graphite average grain diameter 18.3um.
4. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 1
In support graphite phosphorus content be 96.0wt%~99.0wt%.
5. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 2
Middle soaking time is 1~3h, and the recovery time is 0.5~2h.
6. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 3
Middle argon gas flow velocity is 30~50ml/min.
7. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 3
Middle catalytic cracking reaction temperature is 500~700 DEG C.
8. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 3
The middle catalytic cracking reaction time is 60min.
9. a kind of preparation method of chemical vapor deposition modified graphite according to claim 1, it is characterised in that: step 3
Middle ethanol injection flow velocity is 0.2~0.5ml/h.
10. the preparation method of described in any item chemical vapor deposition modified graphites according to claim 1~9, it is characterised in that:
Nanotube is multi-walled carbon nanotube on the chemical vapor deposition modified graphite obtained, and caliber is in 20~30nm.
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| CN112938961A (en) * | 2021-02-04 | 2021-06-11 | 自然资源部第三海洋研究所 | Device and method for preparing graphite by online catalytic reduction method |
| CN114956055A (en) * | 2022-06-10 | 2022-08-30 | 湖南元锂新材料科技有限公司 | Preparation process of high-capacity lithium ion battery cathode material |
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Inventor after: Diao Jinxiang Inventor after: Zhang Yuzhu Inventor after: Wang Xianmeng Inventor before: Diao Jinxiang |