CN107579232A - A kind of preparation method of graphene in-situ modified graphite carbon electrode material - Google Patents
A kind of preparation method of graphene in-situ modified graphite carbon electrode material Download PDFInfo
- Publication number
- CN107579232A CN107579232A CN201710808118.0A CN201710808118A CN107579232A CN 107579232 A CN107579232 A CN 107579232A CN 201710808118 A CN201710808118 A CN 201710808118A CN 107579232 A CN107579232 A CN 107579232A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite
- situ modified
- graphite carbon
- electrode material
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 discloses a kind of preparation method of graphene in-situ modified graphite carbon electrode material, in closed reactor, using mass ratio as 10:1 graphite oxide and talcum powder obtains the graphitic carbon material of graphene in-situ modified in 200 300 DEG C of pyrolysis expansions, the graphite oxide obtains preferably by Hummers methods, and by the graphitic carbon material of graphene in-situ modified and acetylene black, binding agent mix, tabletting produces graphene-based graphite carbon composite electrode material.The present invention is by graphene in-situ modified graphite carbon, and graphene distribution is uniform compared with physical doping in product；The use of closed reactor expansion technique reduces experimental cost and simplifies technological process；The advantages of graphene in-situ modified graphite carbon combination electrode material combines graphene and graphitic carbon each, storage lithium ability, cycle life and coulombic efficiency significantly improve, and charge and discharge platform is obvious.
Description
Technical field
The present invention relates to a kind of preparation method of graphene in-situ modified graphite carbon electrode material, and specifically, being related to should
The method that graphene-based graphite carbon electrode material is prepared with in-situ modified technology, belong to lithium ion battery graphite electrode material system
Standby technical field.
Background technology
Lithium rechargeable battery has, discharging voltage balance bigger than energy, electricity as a kind of new high energy secondary power supply
Pressure high and low temperature performance is good, environmentally friendly, security performance is superior, memory-less effect and the advantages that have extended cycle life, it is considered to be
The 21 century new high-tech industry significant to national economy and people's lives.However, the hair with battery smart
Exhibition, the exploitation of more height ratio capacity and more cycle-index lithium ion batteries become more and more urgent.Graphite is as lithium ion battery
Negative material, it is main in use at present the problem of for specific capacity is low and loop attenuation is fast.Therefore, it is necessary to graphite material
Material is modified processing, to lift its specific capacity and cycle life.
The research of graphene turns into the new direction for improving the research of carbon negative pole material lithium reserves, and graphene is due to highly conductive
Property, big specific surface area, it is considered as following extremely potential electrode material the advantages that chemical inertness.Existing technical staff
The grapheme material of the different numbers of plies is prepared by chemical oxidization method, electrochemical property test is carried out to it and finds that such material has
Storage lithium ability well（Initial charge capacity is up to 540 mAh/g）, further increase grapheme material also by chemical method
Randomness and defect, the storage lithium ability of such material is got a promotion（Initial charge capacity is up to 1054 mAh/g）.It can be seen that
Grapheme material plays the role of very big in terms of the storage lithium ability of lithium ion battery is improved.However, at present graphene as lithium from
During the negative material of sub- battery, following deficiency be present：First charge-discharge coulombic efficiency is low, and charging voltage hysteresis is obvious, nothing
The defects of obvious voltage platform and too fast loop attenuation, these are the notable feature of hard carbon material.Therefore, grapheme material can not
Separately as electrode material, need to form combination electrode material with other materials can just be expected to overcome itself defect, and it is excellent to play its
Different storage lithium ability.
The content of the invention
It is an object of the invention to provide the graphene in-situ modified stone that a kind of cost is low, specific capacity is high, cycle performance is excellent
The preparation method of black carbon electrode material.
The implementation process of the present invention is as follows：
Graphene in-situ modified graphite carbon electrode material consisting of：Graphene/Graphite, Graphene represent graphite
Alkene, Graphite represent graphitic carbon.
A kind of preparation method of graphene in-situ modified graphite carbon electrode material, in closed reactor, using mass ratio as
10:1 graphite oxide and talcum powder obtains the graphitic carbon material of graphene in-situ modified in 200-300 DEG C of pyrolysis expansion, oxidation
Graphite at least pyrolysis expansion 30 minutes；Graphite oxide preferably carries out pyrolysis expansion at 250 DEG C.
The graphite oxide is prepared preferably by Hummers methods, and preparation method comprises the following steps：
（1）Graphite is dissolved in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, stirs lower addition potassium permanganate；
（2）In 30 minutes oxidation intercalated graphite carbon materials derived above of -10-95 DEG C of reactions；
（3）The above-mentioned oxidation intercalated graphite carbon material being prepared is washed with H2O2；
（4）Vacuum drying obtains aoxidizing intercalated graphite carbon material powder at 50~70 DEG C；
The mass volume ratio of above-mentioned graphite and KMnO4, H2SO4 and HNO3 is（1-2）：（3-6）：（85-95）：(20-40), wherein
With KMnO4 in gram, H2SO4 and HNO3 are in terms of milliliter for graphite.
In closed reactor, oxidation intercalated graphite carbon material powder is expanded at least 30 minutes in 200-300 DEG C
The graphitic carbon material of graphene in-situ modified is obtained, graphite expansion temperature is preferably 250 DEG C.
By the graphitic carbon material of graphene in-situ modified and acetylene black, binding agent mix, tabletting produces graphene-based graphite
Carbon composite electrode material.
Above-mentioned steps（2）In, 30 minutes oxygen derived above is reacted respectively at -10-10 DEG C, 30-40 DEG C and 85-95 DEG C successively
Change the graphitic carbon material of intercalation.
The present invention is different from prior art：1）It is by in-situ modified reality using graphene modified graphite carbon negative pole material
Now, it is graphene through chemical reaction process portions turn by graphite, reaches the purpose of graphene modified graphite, rather than pass through handle
Graphene is uniformly mixed in the method in graphite as a kind of additive.2）Graphene is by the way that low temperature occurs in a kettle
（200-300℃）Middle pressure reaction obtains, and the non-used high temperature being commonly used（1000℃）Reaction produces, and such research exists
The international, country is showed no document report.
Advantage of the present invention is as follows：1）By graphene in-situ modified graphite carbon, graphene is distributed compared with physical doping in product
Uniformly；2）Pyrolysis expansion temperature is advantageously reduced using reactor pyrolysis expansion technology, experimental cost is reduced and simplifies work
Skill flow；3）The advantages of graphene in-situ modified graphite carbon combination electrode material combines graphene and graphitic carbon each, store lithium
Ability, cycle life and coulombic efficiency significantly improve, and charge and discharge platform is obvious.
Embodiment
Embodiment 1：
Key step prepared by graphene in-situ modified graphite carbon electrode material is as follows：
（1）Low-temp reaction, in 500 ml beakers, 1 g raw graphites, the 90 ml concentrated sulfuric acids and 25 are added under the conditions of ice-water bath
Ml concentrated nitric acids, 3 g potassium permanganate are slowly added to after stirring 15 min, stir, 60 min are reacted in ice-water bath；
（2）Medium temperature is reacted, will（1）Step solution is to slowly warm up to 35 DEG C, reacts 30 min；
（3）Pyroreaction, to（2）350 ml distilled water are slowly added in step solution, while is warming up to 90 DEG C of 30 min of reaction and obtains
To the graphitic carbon material of oxidation intercalation；
（4）Washing filters, and treats（3）Step solution, which is cooled to, to be added 18 ml 30% hydrogen peroxide after room temperature and reacts 10 min.Then use
Distillation water washing simultaneously filters, and is detected when with barium chloride to sulfate radical-free ion, stops filtering；
（5）24 h are dried at 60 DEG C in vacuum drying oven；
（6）Expansion reaction, weigh 0.5 g（5）Step gained carbon material and 0.05g talcum powder, insert the reactor that volume is 25 ml
In, it is put immediately into after sealing in 250 DEG C of baking oven, is slowly dropped to room temperature after reacting 60 min, product is that graphene original position changes
Property graphitic carbon material, specific surface area is 424 m2/g, and through 50 discharge and recharge reactions, cycle life is stable in 430 mAh/g.
Embodiment 2：
With LAND CT2001A type discharge and recharge instrument, carry out in testing example 1 charge-discharge performance of sample prepared, specific steps are such as
Under：
（1）Mixed with acetylene black, binding agent PTFE with powdered negative electrode active material（Weight ratio：5：10：85）, it is agitated equal
After even, the negative material of pulpous state is made.
（2）It is pressed on after with twin rollers, manufactured slurry is rolled uniformly with 20 MPa pressure on copper mesh, drying is
Cathode pole piece.
（3）By positive plate（Lithium metal）The top-down order of-barrier film-negative plate stacks, and injects electrolyte（1
Mol/l LiPF6 EC/DMC/EMC (volume ratios 1:1:1) solution）Afterwards button electricity is completed by the technique such as buckle closure and sealing
The assembling process in pond.
（4）With battery charging/discharging apparatus LAND CT2001A couple（3）In the button cell that assembles carry out constant current charge-discharge
Test, current density is 0.25 mA/cm2.
Determine graphitic carbon former state, the lithium ion battery of graphene modified graphite carbon material and pure graphene as negative pole
Charge-discharge performance, the results showed that the modified graphite electrode material prepared of the present invention has height ratio capacity, stable 430
MAh/g, there is an obvious voltage platform far above the non-modified mAh/g of graphite capacity 320, and in 0.2V, and same test condition
Under pure graphene without charge and discharge platform.Coulombic efficiency and cycle life, which are compared, can find graphene modified graphite carbon material
There is higher coulombic efficiency than graphite and pure graphene（First charge-discharge coulombic efficiency is up to 85%, the lower coulomb effect of other circulations
Rate maintains 99%）And the longer life-span（50 Capacity fadings<5%）.
Embodiment 3：It is similar to Example 1, unlike only react 30 minutes at 90 DEG C, by wash, it is dry and swollen
Swollen to obtain graphene in-situ modified graphite carbon material, the material specific surface area that the process obtains is 200 m2/g, and cycle life is
320 mAh/g。
Embodiment 4：It is similar to Example 1, unlike take 2 g material carbons, 6 g potassium permanganate, the 95 ml concentrated sulfuric acids and
35ml concentrated nitric acids are reacted, and remaining process is same as Example 1, the ratio table of obtained graphene in-situ modified graphite carbon material
Area is 405 m2/g, stable in 425 mAh/g through 50 discharge and recharge reactions, cycle life.
Embodiment 5：It is similar to Example 1, the difference is that carrying out expansion 1 hour in 275 DEG C in closed reactor, obtain
The specific surface area of graphene in-situ modified graphite carbon material be 440 m2/g, it is stable through 50 discharge and recharge reactions, cycle life
In 435 mAh/g.
Embodiment 6：Carry out expansion 2 hours, obtained stone in 225 DEG C in closed reactor using commercially available graphite oxide
The specific surface area of the black in-situ modified graphitic carbon material of alkene is 400 m2/g, stable 410 through 50 discharge and recharge reactions, cycle life
mAh/g。
Claims (9)
- A kind of 1. preparation method of graphene in-situ modified graphite carbon electrode material, it is characterised in that：In closed reactor, with Mass ratio is 10:1 graphite oxide and talcum powder obtains the graphite carbon materials of graphene in-situ modified in 200-300 DEG C of pyrolysis expansion Material.
- 2. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 1, it is characterised in that：Oxygen Graphite at least pyrolysis expansion 30 minutes.
- 3. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 1, it is characterised in that：Oxygen Graphite carries out pyrolysis expansion at 250 DEG C.
- 4. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 1, it is characterised in that：Institute Graphite oxide is stated to obtain by Hummers methods.
- 5. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 4, it is characterised in that oxygen The preparation method of graphite comprises the following steps：（1）Graphite is dissolved in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, stirs lower addition potassium permanganate；（2）In 30 minutes oxidation intercalated graphite carbon materials derived above of -10-95 DEG C of reactions；（3）The above-mentioned oxidation intercalated graphite carbon material being prepared is washed with H2O2；（4）Vacuum drying obtains aoxidizing intercalated graphite carbon material powder at 50~70 DEG C；The mass volume ratio of above-mentioned graphite and KMnO4, H2SO4 and HNO3 is（1-2）：（3-6）：（85-95）：(20-40), wherein With KMnO4 in gram, H2SO4 and HNO3 are in terms of milliliter for graphite.
- 6. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 5, it is characterised in that： In closed reactor, oxidation intercalated graphite carbon material powder is subjected to pyrolysis expansion in 200-300 DEG C and obtained within least 30 minutes The graphitic carbon material of graphene in-situ modified.
- 7. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 6, it is characterised in that：Stone Black pyrolysis expansion temperature is 250 DEG C.
- 8. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 6, it is characterised in that：Will The graphitic carbon material and acetylene black of graphene in-situ modified, binding agent mixing, tabletting produce graphene-based graphite carbon composite electrode Material.
- 9. the preparation method of graphene in-situ modified graphite carbon electrode material according to claim 5, it is characterised in that：Step Suddenly（2）In, react 30 minutes oxidation intercalated graphite carbon materials derived above respectively at -10-10 DEG C, 30-40 DEG C and 85-95 DEG C successively Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710808118.0A CN107579232A (en) | 2017-09-08 | 2017-09-08 | A kind of preparation method of graphene in-situ modified graphite carbon electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710808118.0A CN107579232A (en) | 2017-09-08 | 2017-09-08 | A kind of preparation method of graphene in-situ modified graphite carbon electrode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107579232A true CN107579232A (en) | 2018-01-12 |
Family
ID=61032908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710808118.0A Pending CN107579232A (en) | 2017-09-08 | 2017-09-08 | A kind of preparation method of graphene in-situ modified graphite carbon electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107579232A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157728A (en) * | 2011-03-22 | 2011-08-17 | 西安银泰新能源材料科技有限公司 | Method of preparing graphene in-situ modified graphite carbon electrode material for lithium-ion battery |
| CN104240964A (en) * | 2014-09-18 | 2014-12-24 | 上海交通大学 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
-
2017
- 2017-09-08 CN CN201710808118.0A patent/CN107579232A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157728A (en) * | 2011-03-22 | 2011-08-17 | 西安银泰新能源材料科技有限公司 | Method of preparing graphene in-situ modified graphite carbon electrode material for lithium-ion battery |
| CN104240964A (en) * | 2014-09-18 | 2014-12-24 | 上海交通大学 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
Non-Patent Citations (1)
| Title |
|---|
| 朱洪法: "《生活化学品与健康》", 1 April 2013 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Facile synthesis of Fe-MOF/RGO and its application as a high performance anode in lithium-ion batteries | |
| CN103094535B (en) | Sulfur/carbon porous nano composite material and preparation method and application thereof | |
| CN104051729B (en) | NiFe for cathode of lithium battery2o4the preparation method of/graphene composite material | |
| CN108598390A (en) | A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery | |
| CN110034288A (en) | A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method | |
| CN104269555A (en) | Soft carbon anode material for lithium-ion power and energy storage battery as well as preparation method and application of soft carbon anode material | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN109873134A (en) | Iron-based chalcogenide, electrode material, the sodium-ion battery and preparation method thereof of in-situ carbon encapsulation | |
| Huang et al. | Impact of fe doping on performance of NaTi2 (PO4) 3/C anode for aqueous lithium ion battery | |
| CN107046126B (en) | Preparation method of superfine metal oxide/graphene two-dimensional negative electrode composite material | |
| CN102110813B (en) | Graphite material at negative pole of lithium ion battery and preparation method thereof | |
| Xu et al. | A conductive sulfur-hosting material involving ultrafine vanadium nitride nanoparticles for high-performance lithium-sulfur battery | |
| CN114314673B (en) | Preparation method of flaky FeOCl nano material | |
| CN110165210B (en) | Preparation method of carbon fluoride anode material with high specific capacity | |
| CN108598403B (en) | Method for forming binary transition metal oxide cathode material of lithium ion battery | |
| Wang et al. | Stable high capacity cycling of Li metal via directed and confined Li growth with robust composite sponge | |
| CN108539170B (en) | Method for forming nano-sheet negative electrode material of lithium ion battery | |
| CN110137472B (en) | Preparation method of composite positive electrode material | |
| CN109422261A (en) | A kind of preparation method of graphene in-situ modified graphite carbon electrode material | |
| CN105810916B (en) | A kind of SnO2/ graphene/SnO2The preparation method of lithium ion battery negative material | |
| CN110492099B (en) | Layered polyanion positive electrode material, preparation method, potassium ion battery positive electrode, potassium ion battery and application | |
| CN102157728A (en) | Method of preparing graphene in-situ modified graphite carbon electrode material for lithium-ion battery | |
| WO2023134366A1 (en) | Silicon-carbon negative electrode material, and preparation method therefor and use thereof | |
| CN109534401B (en) | Preparation method of copper vanadate, copper vanadate prepared by method and application of copper vanadate in lithium ion battery | |
| CN115939361A (en) | Copper phosphide-doped hard carbon composite material and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180112 |