CN108584923A - A kind of preparation method of ultra-thin shell graphene hollow ball - Google Patents
A kind of preparation method of ultra-thin shell graphene hollow ball Download PDFInfo
- Publication number
- CN108584923A CN108584923A CN201810412009.1A CN201810412009A CN108584923A CN 108584923 A CN108584923 A CN 108584923A CN 201810412009 A CN201810412009 A CN 201810412009A CN 108584923 A CN108584923 A CN 108584923A
- Authority
- CN
- China
- Prior art keywords
- graphene
- ball
- ultra
- silica
- hollow ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
Abstract
The invention discloses a kind of preparation methods of ultra-thin shell graphene hollow ball, it is first depending on Hummers methods and prepares graphene oxide dispersion, modified Stober legal system prepared silicon dioxide ball template dispersion liquids, the two ultrasonic mixing is uniform, is thermally treated resulting in silica/graphene (SiO2@Gs) nuclear shell ball；By silica/graphene (SiO2@Gs) nuclear shell ball is redissolved in hydrofluoric acid (HF), be filtered, washed, dry after ultra-thin shell graphene hollow ball is made.Ultra-thin shell graphene hollow ball preparation method of the present invention, technological process is short, it operates easy, convenient for high-volume industrial production, ultra-thin shell graphene hollow ball obtained can well solve the problem of graphene nanometer sheet influences its chemical property due to the accumulation that the factors such as Van der Waals force generate, and show to be widely applied foreground in pure electric vehicle and hybrid electric.
Description
Technical field
The present invention relates to graphene nano field of material technology, are specifically related to a kind of system of ultra-thin shell graphene hollow ball
Preparation Method.
Background technology
The common negative material graphite capacity of lithium ion battery is smaller at present, greatly limits its energy density
With the raising of power density.That develops at present crosses the body in charge and discharge process such as metal oxide, silica-base material and tin-based material
Product expansion is very big, leads to the cycle performance dramatic decrease of battery.New carbon graphene have superelevation electron conduction,
The advantages that specific surface area of superelevation and the mechanical strength stablized, but since the factors such as Van der Waals force are easy between graphene sheet layer
Accumulation occurs or reunites, this significantly impacts graphene and plays its chemical property.
Ultra-thin shell graphene hollow ball can inhibit the accumulation of graphene nanometer sheet while graphene itself can be kept excellent
Chemical property more.The common synthetic method of graphene hollow ball is template, and template is a kind of creation hollow structure
Better method, but the compatibility that template realizes both presoma and template need to be acted on using expensive surfactant, this
Sample increases cost, therefore a kind of method of simple synthesizing graphite alkene hollow ball of searching has very real meaning.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of preparation sides of ultra-thin shell graphene hollow ball
Method, the ultra-thin shell graphene hollow ball can inhibit the accumulation of graphene nanometer sheet while graphene itself can be kept superior
Chemical property, and have many advantages, such as that preparation process is simple, at low cost, reaction process is easy to control, it is suitable for large-scale
Industrialized production.
A kind of preparation method of ultra-thin shell graphene hollow ball, it is characterized in that：Preparation process is as follows：
（1）Pretreatment：Graphene oxide is prepared by well known Hummers methods, the graphene oxide is scattered in
In ionized water, graphene oxide dispersion is obtained；
（2）Ammonium hydroxide, ethyl alcohol, deionized water, ethyl orthosilicate (TEOS) are added in reaction kettle and are stirred evenly, 360 r/min
It is stirred 2 hours under rotating speed, obtained sediment is washed 6 times with ethyl alcohol respectively and deionized water is washed 3 times, and 100 DEG C of dryings obtain for 24 hours
The silica ball template is scattered in deionized water by silica ball template, obtains silica ball template dispersion liquid；
（3）By graphene oxide dispersion, silica ball template dispersion liquid according to volume ratio 1:1 is uniformly mixed, ultrasonic disperse
3h is then placed in -45 DEG C of freeze driers, obtains fluffy yellow powder, as silica@graphene oxides
(SiO2@GOs) nuclear shell ball, silica@graphene oxide nuclear shell balls are put into plasma high-temperature pipe reaction stove, are taken out true
It is airborne to be depressed into 10~20Pa, it is thermally treated resulting in black even powder, as silica@graphenes (SiO2@Gs) nuclear shell ball；
（4）By silica/graphene (SiO2@GOs) nuclear shell ball is redissolved in 20% hydrofluoric acid (HF), 360 r/min
It is stirred 4 hours under rotating speed, the sediment for filtering gained is washed 6 times with ethyl alcohol and deionized water is washed 3 times, dry in vacuum tank
The fluffy powder of black is obtained for 24 hours, obtains ultra-thin shell graphene hollow ball.
Preferably, step（1）Described in graphene oxide dispersion it is a concentration of（4~10）mg/mL.
Preferably, step（2）Described in ammonium hydroxide, ethyl alcohol, deionized water, ethyl orthosilicate (TEOS) amount ratio be：（8
~10）mL ：（50~60）mL ：（25~30）mL ：（4~10）The mass percent concentration of mL, the ammonium hydroxide are 25~30%,
The silica ball template dispersion liquid it is a concentration of（5~12）mg/mL.
Preferably, step（3）Described in be heat-treated reaction temperature be 800~1000 DEG C.
Preferably, step（4）Described in hydrofluoric acid (HF) it is a concentration of（20~25）mg/mL.
Beneficial effects of the present invention：
（1）Ultra-thin shell graphene hollow ball can inhibit the accumulation of graphene nanometer sheet while graphene itself can be kept superior
Chemical property, remarkable application prospect is shown in pure electric vehicle and hybrid electric.
（2）The preparation method of the present invention is simple, can be completed by existing technical matters, production cost is low.
Description of the drawings
Fig. 1 is silica/graphene (SiO2@Gs) scanning electron microscope diagram；
Fig. 2 is the scanning electron microscope diagram piece of the ultra-thin shell graphene hollow ball of the present invention.
Specific implementation mode
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of ultra-thin shell graphene hollow ball, it is characterized in that：Preparation process is as follows：
（1）Pretreatment：Graphene oxide is prepared by well known Hummers methods, the graphene oxide is scattered in
In ionized water, graphene oxide dispersion is obtained；
（2）Ammonium hydroxide, ethyl alcohol, deionized water, ethyl orthosilicate (TEOS) are added in reaction kettle and are stirred evenly, 360 r/min
It is stirred 2 hours under rotating speed, obtained sediment is washed 6 times with ethyl alcohol respectively and deionized water is washed 3 times, and 100 DEG C of dryings obtain for 24 hours
The silica ball template is scattered in deionized water by silica ball template, obtains silica ball template dispersion liquid；
（3）By graphene oxide dispersion, silica ball template dispersion liquid according to volume ratio 1:1 is uniformly mixed, ultrasonic disperse
3h is then placed in -45 DEG C of freeze driers, obtains fluffy yellow powder, as silica@graphene oxides
(SiO2@GOs) nuclear shell ball, silica@graphene oxide nuclear shell balls are put into plasma high-temperature pipe reaction stove, are taken out true
It is airborne to be depressed into 10~20Pa, it is thermally treated resulting in black even powder, as silica@graphenes (SiO2@Gs) nuclear shell ball；
（4）By silica/graphene (SiO2@GOs) nuclear shell ball is redissolved in 20% hydrofluoric acid (HF), 360 r/min
It is stirred 4 hours under rotating speed, the sediment for filtering gained is washed 6 times with ethyl alcohol and deionized water is washed 3 times, dry in vacuum tank
The fluffy powder of black is obtained for 24 hours, obtains ultra-thin shell graphene hollow ball.
Described, step（1）Described in graphene oxide dispersion a concentration of 5mg/mL.
Described, step（2）Described in ammonium hydroxide, ethyl alcohol, deionized water, ethyl orthosilicate (TEOS) amount ratio be：9mL
：60mL ：25mL ：The mass percent concentration of 5mL, the ammonium hydroxide are 28%, the concentration of the silica ball template dispersion liquid
For 6mg/mL.
Described, step（3）Described in be heat-treated reaction temperature be 800 DEG C.
Described, step（4）Described in hydrofluoric acid (HF) a concentration of 20mg/mL.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is any without departing from the present invention essence and principle made by change, simplify, be included in protection scope of the present invention it
It is interior.
Claims (5)
1. a kind of preparation method of ultra-thin shell graphene hollow ball, it is characterized in that：Preparation process is as follows：
（1）Pretreatment：Graphene oxide is prepared by well known Hummers methods, the graphene oxide is scattered in deionization
In water, graphene oxide dispersion is obtained；
（2）Ammonium hydroxide, ethyl alcohol, deionized water, ethyl orthosilicate (TEOS) are added in reaction kettle and are stirred evenly, 360 r/min
It is stirred 2 hours under rotating speed, obtained solid sediment is washed 6 times with ethyl alcohol respectively and deionization is washed 3 times, and 100 DEG C of dryings obtain for 24 hours
To silica ball template, the silica ball template is scattered in deionized water, obtains the dispersion of silica ball template
Liquid；
（3）By graphene oxide dispersion, silica ball template dispersion liquid according to volume ratio 1:1 is uniformly mixed, ultrasonic disperse
3h is then placed in -45 DEG C of freeze driers, obtains fluffy yellow powder, as silica@graphene oxides
(SiO2@GOs) nuclear shell ball, silica@graphene oxide nuclear shell balls are put into plasma high-temperature pipe reaction stove, are taken out true
It is airborne to be depressed into 10~20Pa, it is thermally treated resulting in black even powder, as silica@graphenes (SiO2@Gs) nuclear shell ball；
（4）By silica/graphene (SiO2@GOs) nuclear shell ball is dissolved in hydrofluoric acid (HF), stirred under 360 r/min rotating speeds
It mixes 4 hours, the sediment for filtering gained is washed 6 times with ethyl alcohol and deionization is washed 3 times, dry in vacuum tank to obtain black for 24 hours
Fluffy powder obtains ultra-thin shell graphene hollow ball.
2. a kind of preparation method of ultra-thin shell graphene hollow ball as described in claim 1, it is characterized in that：Step（1）Middle institute
State a concentration of of graphene oxide dispersion（4~10）mg/mL.
3. a kind of preparation method of ultra-thin shell graphene hollow ball as described in claim 1, it is characterized in that：Step（2）Middle institute
State ammonium hydroxide, ethyl alcohol, deionized water, ethyl orthosilicate (TEOS) amount ratio be：（8~10）mL ：（50~60）mL ：（25~
30）mL ：（4~10）The mass percent concentration of mL, the ammonium hydroxide are 25~30%, the silica ball template dispersion liquid
It is a concentration of（5~12）mg/mL.
4. a kind of preparation method of ultra-thin shell graphene hollow ball as described in claim 1, it is characterized in that：Step（3）Middle institute
The temperature for stating heat treatment reaction is 800~1000 DEG C.
5. a kind of preparation method of ultra-thin shell graphene hollow ball as described in claim 1, it is characterized in that：Step（4）Middle institute
State a concentration of of hydrofluoric acid (HF)（20~25）mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412009.1A CN108584923A (en) | 2018-05-03 | 2018-05-03 | A kind of preparation method of ultra-thin shell graphene hollow ball |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412009.1A CN108584923A (en) | 2018-05-03 | 2018-05-03 | A kind of preparation method of ultra-thin shell graphene hollow ball |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108584923A true CN108584923A (en) | 2018-09-28 |
Family
ID=63619696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810412009.1A Pending CN108584923A (en) | 2018-05-03 | 2018-05-03 | A kind of preparation method of ultra-thin shell graphene hollow ball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108584923A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072019A (en) * | 2018-10-22 | 2020-04-28 | 中国科学院上海硅酸盐研究所 | Graphene hollow microsphere conductive powder for lithium battery and preparation method thereof |
| CN113304749A (en) * | 2021-04-21 | 2021-08-27 | 中科院广州化学有限公司 | Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof |
-
2018
- 2018-05-03 CN CN201810412009.1A patent/CN108584923A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072019A (en) * | 2018-10-22 | 2020-04-28 | 中国科学院上海硅酸盐研究所 | Graphene hollow microsphere conductive powder for lithium battery and preparation method thereof |
| CN113304749A (en) * | 2021-04-21 | 2021-08-27 | 中科院广州化学有限公司 | Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20180134362A (en) | Method for manufacturing boron-doped porous carbon spheres | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| CN104860304B (en) | A kind of silica with great specific surface area hydridization graphene aerogel and preparation method thereof | |
| CN104167302B (en) | Preparation method for grapheme/melamine resin hollow ball composite material | |
| CN105470486A (en) | Preparation method of granular tin dioxide/two-dimensional nano titanium carbide composite material | |
| CN107301922B (en) | Three-dimensional porous graphene nano material and its preparation method and application | |
| CN103779544B (en) | A kind of preparation method of porous silicon/carbon composite material | |
| CN108539186A (en) | A kind of high-volume silicon-carbon negative electrode material and its preparation method and application | |
| WO2017000525A1 (en) | Transition metal oxide/graphene composite material having yolk-shell structure and manufacturing method and application thereof | |
| CN103253657A (en) | Preparation method of three-dimensional graphene/hollow carbon sphere composite material | |
| CN103441247A (en) | High-performance silicon/graphene oxide negative electrode material based on chemical bond and preparation method thereof | |
| CN105655561B (en) | A kind of synthetic method of manganese phosphate lithium nanosheet | |
| CN104183392A (en) | Mesoporous nickel oxide and carbon composite nano-material and preparation method thereof | |
| CN104091952A (en) | Novel negative electrode material for lithium ion battery and preparation method of negative electrode material | |
| CN110429264B (en) | Method for preparing rice hull-based negative electrode material | |
| CN104124442B (en) | A kind of nanometer Fe2O3The preparation method of/rGO composite and application | |
| CN104045080A (en) | Activated graphene sheet and preparation method thereof | |
| CN108584923A (en) | A kind of preparation method of ultra-thin shell graphene hollow ball | |
| CN110707301A (en) | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof | |
| CN104852024A (en) | Iron trioxide monocrystal nanotube/graphene composite electrode material and preparation method thereof | |
| CN108470891B (en) | Method for preparing silicon-carbon negative electrode material based on micron silicon dioxide | |
| CN110137465A (en) | A kind of carbon@Fe2O3@carbosphere composite material and its application | |
| CN103832997A (en) | Graphene/carbon black composite material, preparation method and application thereof | |
| CN104282894B (en) | A kind of preparation method of porous Si/C complex microsphere | |
| CN105206802B (en) | Rich lithium sulfonated graphene nano silicon oxide negative material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |