CN106450310A - Preparation method of porous graphene lithium ion battery anode material - Google Patents
Preparation method of porous graphene lithium ion battery anode material Download PDFInfo
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- CN106450310A CN106450310A CN201610863347.8A CN201610863347A CN106450310A CN 106450310 A CN106450310 A CN 106450310A CN 201610863347 A CN201610863347 A CN 201610863347A CN 106450310 A CN106450310 A CN 106450310A
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- graphene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 preparation method of a porous graphene lithium ion battery anode material. The preparation method comprises the following steps: carrying out ultrasonography on graphene oxide in an aqueous solution to form a uniform graphene oxide solution; adding the graphene oxide solution into a hydrothermal reaction kettle at a constant temperature for a period of time, and cooling to room temperature to form a graphene oxide hydrogel; mixing the graphene oxide hydrogel with alkali, and stirring for a period of time to obtain a solution; transferring the solution into a ball mill for carrying out ball-milling to obtain a dispersion liquid; washing the dispersion liquid with acid and deionized water until a filter liquor becomes neutral so as to obtain porous graphene dispersed in water; carrying out centrifugal treatment on the porous graphene, and then drying the porous graphene after centrifugal treatment in a drying oven to obtain powder, namely the porous graphene lithium ion battery anode material. The porous graphene prepared in the invention as the anode material has high rate capability and cycling stability, and the preparation method is simple in technology, easy to implement and moderate in cost.
Description
Technical field
The invention belongs to lithium ion battery and new material synthesis technical field, be specifically related to a kind of porous graphene lithium ion
The preparation method of cell negative electrode material.
Background technology
Lithium ion battery is widely used in mobile electronic device and electric motor car, and performance and the energy density of battery are main
Depend on the physical and chemical performance of positive electrode and negative material.In recent years, although take in terms of the performance improvement of electrode material
Obtained remarkable effect, but current researchers still paid close attention to the novel electrode material that can improve battery energy density and power density
Material.
As the allotrope of carbon, Graphene is by sp2The monolayer carbon atomic layer composition of key composition.Graphene is superior because of it
Physical property and chemical property, such as high conductivity, bigger serface and strong mechanical performance it is considered to be a kind of very promising
Lithium ion battery negative material.
Work as Li+LiC can be formed during embedded graphite6, corresponding theoretical specific capacity is 372 mAh/g, works as Li+Absorption is at graphite
During alkene both sides, corresponding theoretical specific capacity is 744 mAh/g.But the specific surface area big due to Graphene and strong Van der Waals force,
Graphene nanometer sheet is susceptible to reunite in drying course.Therefore, although diffusion rate in graphene sheet layer for the lithium ion
Height, but low in the diffusion of interlayer, and the migration that lithium ion is between Graphene negative pole may occur mainly in the edge of layer and layer, this
Just significantly limit its chemical property, especially its high rate capability.
Graphene film introduces hole structure and is probably a kind of effective manner of raising Graphene chemical property, because hole
Structure is provided that interlayer Li+Diffusion path.Prior art there is people confirm the Graphene of hole structure as lithium ion battery
Negative pole shows excellent chemical property.But Van der Waals force strong between due to graphene layer so that it is be easily stacked into paper-like knot
Structure.Therefore, although Li+Diffusion in Graphene stack layer is improved, but its diffusion between nanometer sheet limits graphite
The performance of the chemical property of alkene.A kind of good method--the hole structure graphite alkene of preparation porous, it is possible to provide electrolyte permeability
To graphene-structured path, improve electric charge transmission and high magnification storage performance, this structure is by the hole knot of many flat sheet
Structure forms, and these hole structures can reduce the Van der Waals force of piece interlayer.And by random, interlaced hole structure graphite alkene interlayer
Pi-pi bond so that stack, be in stripping state graphene nanometer sheet formed loose structure.
Content of the invention
It is an object of the invention to according to the deficiencies in the prior art, a kind of porous graphene lithium ion battery negative material of design
The preparation method of material so that it is show high rate capability and cyclical stability.
The technical solution adopted for the present invention to solve the technical problems is：A kind of porous graphene lithium ion battery negative material
The preparation method of material, comprises the following steps：
a）, graphene oxide is ultrasonically formed in aqueous uniform graphene oxide solution A；
b）, graphene oxide solution A is joined constant temperature a period of time in hydrothermal reaction kettle, to be cooled after room temperature, formed stone
Ink alkene hydrogel B；
c）, Graphene hydrogel B is mixed with alkali, stir a period of time, obtain solution C；
d）, solution C transferred to carry out ball milling in ball mill obtain dispersion liquid D；
e）, by dispersion liquid D acid and deionized water washing until filtrate becomes neutral, obtain the porous graphene being dispersed in water
E；
f）, by porous graphene E centrifugal treating, the powder being then dried to obtain in an oven is porous graphene lithium-ion electric
Pond negative material.
The preparation method of described a kind of porous graphene lithium ion battery negative material, its step a）In graphite oxide
The concentration of alkene solution A is 15 mg/mL.
The preparation method of described a kind of porous graphene lithium ion battery negative material, its step b）In hydro-thermal reaction
In kettle, temperature is 120 200 DEG C, and the reaction time is 6 24 h.
The preparation method of described a kind of porous graphene lithium ion battery negative material, its step c）In alkali be KOH
Or NaOH, its concentration is 29 mmol/mL, and the addition of corresponding 20 mg Graphene hydrogel B is 10 70 mL, jointly stirs
The time of mixing is 10 18 h.
The preparation method of described a kind of porous graphene lithium ion battery negative material, its step d）In ball mill turn
Speed is 200 500 rpm, and Ball-milling Time is 10 40 h.
The preparation method of described a kind of porous graphene lithium ion battery negative material, its step e）In acid be HCl
Or H3PO4, concentration is 0.5 3 mmol/mL.
The preparation method of described a kind of porous graphene lithium ion battery negative material, its step f）In centrifugal treating
Rotating speed is 10000 25000rpm, and centrifugation time is 10 60 min, and drying temperature is 60 90 DEG C.
The invention has the beneficial effects as follows：
1, the porous graphene that the present invention prepares, show high rate capability and cyclical stability as negative material.Porous
The excellent chemical property of Graphene is mainly due to this loose structure, and this structure is provided that many Lithium-ion embeding activity
Position, shortens effective diffusion path of lithium ion, improves electrical conductivity, reduces electrolyte/interelectrode charge migration resistance, and maintains
The structural stability that during lithium ion deintercalation, Volume Changes produces.
2, present invention process is simple, be easily achieved and moderate cost.
Brief description
Fig. 1 is the stereoscan photograph of porous graphene in the embodiment of the present invention 1；
Fig. 2 is charging and discharging curve under 0.1 C 10 C current density for the porous graphene in the embodiment of the present invention 1；
Fig. 3 is the circulation figure in the embodiment of the present invention 1 under porous graphene 0.5 C current density.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in further detail.
Referring to figs. 1 through shown in Fig. 3, the present invention by hydro-thermal reaction, the porous graphene that the later stage etches and prepared by ball-milling method,
It shows high rate capability and cyclical stability as negative material.Excellent chemical property is mainly due to this porous
Structure, this structure is provided that many Lithium-ion embeding active sites, shortens effective diffusion path of lithium ion, improves electrical conductivity, fall
Low electrolyte/interelectrode charge migration resistance, and maintain the structural stability that Volume Changes produces during lithium ion deintercalation.
Embodiment 1：
a）, by graphene oxide ultrasonic 1 H-shaped uniformly graphene oxide solution in aqueous, the concentration of configuration is 2
mg/mL；
b）, graphene oxide solution is joined in hydrothermal reaction kettle, 180 DEG C of constant temperature 12h, to be cooled after room temperature, formed stone
Ink alkene hydrogel；
c）, by 20 mg Graphene hydrogels and KOH that 50 mL concentration are 6 mmol/mL mixing, stir 12 h；
d）, transfer to above-mentioned solution in ball mill, obtain graphene dispersing solution with speed ball milling 30 h of 300 rpm；
e）, by HCl that graphene dispersing solution concentration is 1 mmol/mL and deionized water washing until filtrate becomes neutral,
To the porous graphene being dispersed in water；
f）, the porous graphene that will be dispersed in water under 15000 rpm rotating speeds, centrifuge 30 min, after then drying at 80 DEG C
The powder obtaining is porous graphene lithium ion battery negative material.
Embodiment 2：
a）, by graphene oxide ultrasonic 1 H-shaped uniformly graphene oxide solution in aqueous, the concentration of configuration is 3.5
mg/mL；
b）, graphene oxide solution is joined in hydrothermal reaction kettle, 150 DEG C of constant temperature 24h, to be cooled after room temperature, formed stone
Ink alkene hydrogel；
c）, by 20 mg Graphene hydrogels and KOH that 70 mL concentration are 5 mmol/mL mixing, stir 18 h；
d）, transfer to above-mentioned solution in ball mill, obtain graphene dispersing solution with speed ball milling 20 h of 450 rpm；
e）, by H that graphene dispersing solution concentration is 1.5 mmol/mL3PO4With deionized water washing until during filtrate becomes
Property, obtain the porous graphene being dispersed in water；
f）, the porous graphene that will be dispersed in water under 18000 rpm rotating speeds, centrifuge 50 min, after then drying at 90 DEG C
The powder obtaining is porous graphene lithium ion battery negative material.
Embodiment 3：
a）, by graphene oxide ultrasonic 1 H-shaped uniformly graphene oxide solution in aqueous, the concentration of configuration is 1
mg/mL；
b）, graphene oxide solution is joined in hydrothermal reaction kettle, 200 DEG C of constant temperature 6h, to be cooled after room temperature, formed graphite
Alkene hydrogel；
c）, by 20 mg Graphene hydrogels and KOH that 70 mL concentration are 2 mmol/mL mixing, stir 12 h；
d）, transfer to above-mentioned solution in ball mill, obtain graphene dispersing solution with speed ball milling 40 h of 200 rpm；
e）, by HCl that graphene dispersing solution concentration is 0.5 mmol/mL and deionized water washing until filtrate becomes neutral,
Obtain the porous graphene being dispersed in water；
f）, the porous graphene that will be dispersed in water under 10000 rpm rotating speeds, centrifuge 60 min, after then drying at 80 DEG C
The powder obtaining is porous graphene lithium ion battery negative material.
Embodiment 4：
a）, by graphene oxide ultrasonic 1 H-shaped uniformly graphene oxide solution in aqueous, the concentration of configuration is 5
mg/mL；
b）, graphene oxide solution is joined in hydrothermal reaction kettle, 120 DEG C of constant temperature 6h, to be cooled after room temperature, formed graphite
Alkene hydrogel；
c）, by 20 mg Graphene hydrogels and KOH that 100 mL concentration are 9 mmol/mL mixing, stir 10 h；
d）, transfer to above-mentioned solution in ball mill, obtain graphene dispersing solution with speed ball milling 10 h of 500 rpm；
e）, by H that graphene dispersing solution concentration is 3 mmol/mL3PO4With deionized water washing until filtrate becomes neutral,
Obtain the porous graphene being dispersed in water；
f）, the porous graphene that will be dispersed in water under 25000 rpm rotating speeds, centrifuge 10 min, after then drying at 60 DEG C
The powder obtaining is porous graphene lithium ion battery negative material.
The principle of above-described embodiment only illustrative present invention and effect thereof, and the embodiment that part is used, for
For those of ordinary skill in the art, without departing from the concept of the premise of the invention, can also make some deformation and
Improving, these broadly fall into protection scope of the present invention.
Claims (7)
1. the preparation method of a porous graphene lithium ion battery negative material, it is characterised in that：Comprise the following steps：
a）, graphene oxide is ultrasonically formed in aqueous uniform graphene oxide solution A；
b）, graphene oxide solution A is joined constant temperature a period of time in hydrothermal reaction kettle, to be cooled after room temperature, formed stone
Ink alkene hydrogel B；
c）, Graphene hydrogel B is mixed with alkali, stir a period of time, obtain solution C；
d）, solution C transferred to carry out ball milling in ball mill obtain dispersion liquid D；
e）, by dispersion liquid D acid and deionized water washing until filtrate becomes neutral, obtain the porous graphene being dispersed in water
E；
f）, by porous graphene E centrifugal treating, the powder being then dried to obtain in an oven is porous graphene lithium-ion electric
Pond negative material.
2. the preparation method of a kind of porous graphene lithium ion battery negative material according to claim 1, its feature exists
In described step a）In the concentration of graphene oxide solution A be 15 mg/mL.
3. the preparation method of a kind of porous graphene lithium ion battery negative material according to claim 1, its feature exists
In described step b）In hydrothermal reaction kettle in temperature be 120 200 DEG C, the reaction time is 6 24 h.
4. the preparation method of a kind of porous graphene lithium ion battery negative material according to claim 1, its feature exists
In described step c）In alkali be KOH or NaOH, its concentration is 29 mmol/mL, corresponding 20 mg Graphene hydrogel B
Addition be 10 70 mL, the time of being stirred together for is 10 18 h.
5. the preparation method of a kind of porous graphene lithium ion battery negative material according to claim 1, its feature exists
In described step d）In drum's speed of rotation be 200 500 rpm, Ball-milling Time is 10 40 h.
6. the preparation method of a kind of porous graphene lithium ion battery negative material according to claim 1, its feature exists
In described step e）In acid be HCl or H3PO4, concentration is 0.5 3 mmol/mL.
7. it is characterised by according to claim 1, described step f）In centrifugal treating rotating speed be 10000 25000rpm, from
The heart time is 10 60 min, and drying temperature is 60 90 DEG C.
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| CN201610863347.8A CN106450310A (en) | 2016-09-29 | 2016-09-29 | Preparation method of porous graphene lithium ion battery anode material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107934942A (en) * | 2017-11-29 | 2018-04-20 | 湖南大学 | A kind of modified 3 D graphene hydrogel and preparation method thereof |
| CN109103430A (en) * | 2018-08-15 | 2018-12-28 | 宝鸡文理学院 | A kind of anode material for lithium-ion batteries and preparation method thereof of porous graphene coating modification |
| CN109534334A (en) * | 2019-01-31 | 2019-03-29 | 清华大学深圳研究生院 | Graphene-based electrode material, preparation method and applications |
| CN111029633A (en) * | 2019-11-15 | 2020-04-17 | 广东轻工职业技术学院 | Microbial fuel cell and preparation method and application thereof |
| CN117753928B (en) * | 2024-02-22 | 2024-04-26 | 潍坊卓安重工科技有限公司 | Lost foam casting method for manufacturing ball mill end cover by utilizing spheroidal graphite cast iron |
Citations (2)
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| CN102107868A (en) * | 2011-03-01 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing porous graphene material |
| CN103011152A (en) * | 2013-01-17 | 2013-04-03 | 中国石油大学(华东) | Graphene material with porous structure and preparation method of graphene material |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107868A (en) * | 2011-03-01 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing porous graphene material |
| CN103011152A (en) * | 2013-01-17 | 2013-04-03 | 中国石油大学(华东) | Graphene material with porous structure and preparation method of graphene material |
Non-Patent Citations (1)
| Title |
|---|
| ZHANGQING JIANG ET AL: ""Randomly stacked holey grapheme anodes for lithium ion batteries with enhanced electrochemical performance"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107934942A (en) * | 2017-11-29 | 2018-04-20 | 湖南大学 | A kind of modified 3 D graphene hydrogel and preparation method thereof |
| CN109103430A (en) * | 2018-08-15 | 2018-12-28 | 宝鸡文理学院 | A kind of anode material for lithium-ion batteries and preparation method thereof of porous graphene coating modification |
| CN109103430B (en) * | 2018-08-15 | 2021-07-02 | 宝鸡文理学院 | Porous graphene coated and modified lithium ion battery positive electrode material and preparation method thereof |
| CN109534334A (en) * | 2019-01-31 | 2019-03-29 | 清华大学深圳研究生院 | Graphene-based electrode material, preparation method and applications |
| CN109534334B (en) * | 2019-01-31 | 2020-10-23 | 清华大学深圳研究生院 | Graphene-based electrode material, preparation method and application thereof |
| CN111029633A (en) * | 2019-11-15 | 2020-04-17 | 广东轻工职业技术学院 | Microbial fuel cell and preparation method and application thereof |
| CN111029633B (en) * | 2019-11-15 | 2023-03-28 | 广东轻工职业技术学院 | Microbial fuel cell and preparation method and application thereof |
| CN117753928B (en) * | 2024-02-22 | 2024-04-26 | 潍坊卓安重工科技有限公司 | Lost foam casting method for manufacturing ball mill end cover by utilizing spheroidal graphite cast iron |
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