CN106784757B - A kind of preparation method of anode composite material - Google Patents
A kind of preparation method of anode composite material Download PDFInfo
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- CN106784757B CN106784757B CN201710200468.9A CN201710200468A CN106784757B CN 106784757 B CN106784757 B CN 106784757B CN 201710200468 A CN201710200468 A CN 201710200468A CN 106784757 B CN106784757 B CN 106784757B
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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
- H01M4/362—Composites
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 present invention is a kind of preparation method of anode composite material.Method includes the following steps: the processed active carbon of acid is added in graphene oxide suspension, mixed solution is obtained；Then sodium ascorbate solution is added, obtains graphene hydrogel；With sulphur mixed grinding after drying, 3-15h is calcined at 150-200 DEG C under argon atmosphere later, obtains graphene/active carbon/sulphur composite positive pole.The raw material that the preparation method of lithium sulfur battery anode material of the present invention uses is cheap and easy to get, preparation process is simple, process is short, process is easy to control, industrialized production easy to accomplish.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to and a kind of graphene/active carbon of lithium ion battery/
The preparation method of sulphur composite positive pole.
Technical background
Current social, energy crisis and environmental problem are a global hot topics, are passed with to coal, petroleum etc.
The exhaustive exploitation of the system energy, causes the continuous improvement of the shortage of resources got worse and cost of winning；Traditional energy is utilized simultaneously
Bring pollution problem also constantly highlights, seriously broken ring earth ecology balance.Therefore, in the age of this energy revolution, people
There is an urgent need to find and develop the effective new energy of green, to meet the needs of social fast development.Lithium-sulfur cell (theoretical specific volume
Amount is 1675mAh/g, specific energy 2500Wh/kg, 2800Wh/L), it is close with the high-energy of application prospect with development potential
Spend secondary cell.But the positive electrode active material utilization of lithium-sulfur cell is poor, poor circulation, anode volume in charge and discharge process
It changes greatly.In addition, there is insulation characterisitic and highly dissoluble of its discharging product in organic electrolyte in elemental sulfur, limitation
Lithium-sulfur cell commercial applications process.
In view of the above problems, numerous scientific research scholars use sulphur and conductive carbon material to be made into composite positive pole at present, it is carbon-based
Material serves as conducting bridge, constructs conductive network between particles, improves electronic conductivity；Due to carbon material high-specific surface area and
Adsorptivity is able to suppress the dissolution of discharging product and improves the electric conductivity of sulfur electrode, to improve the utilization rate and electricity of active material
The cycle performance in pond.
In carbon material, graphene is a kind of electronics with high-specific surface area, high chemical stability and high mechanical strength
And heat conductor.More importantly including numerous defects in graphene-structured, the active site of sulfur loaded can be used as.Graphene
Biggish specific surface area and interlayer structure can provide biggish memory space again for sulphur, and lesser interlayer gap can be certain
The diffusion of long-chain polysulphides is limited in degree, so that graphene/sulfur compound becomes a kind of ideal sulphur positive electrode.
Studies have shown that high electric conductivity can be provided for elemental sulfur by the method that sulphur is scattered in graphene sheet layer, while sulfur granules are inserted
Layer effectively inhibits the volume expansion when dissolution and charge and discharge of discharging product, to improve work in the graphene of high-specific surface area
The property utilization rate of substance and the cycle performance of battery.
At present in sulphur/graphene composite material preparation relevant report, since graphene aperture is larger, what piece interlayer opened
The polysulfide of what duct made to generate in charge and discharge process be soluble in electrolyte is easily from wherein spreading out, directly by sulphur and stone
Black alkene is compound to be difficult to obtain the excellent material of cycle performance.For example, 103515608 A of CN (application publication number) discloses one kind
Graphene/sulphur composite material preparation method.Graphene and elemental sulfur are obtained into graphene-sulfur composite wood with ball mill grinding
Material precursor.Then graphene-sulfur composite material precursor is placed in tube furnace, certain temperature is forged under inert gas protection
Burning certain time to obtain sulfur mass fraction is 50% graphene/sulphur composite material.Since graphene sheet layer structure is easy to assemble,
And aperture is larger, and sulphur is made to be easy to preferential build in macropore, polysulfide is dissolved into electrolyte in charge and discharge process, diffusion
The rapid decay so as to cause battery capacity is reacted to anode and lithium metal.So that battery only 30 times circulation after, battery capacity
Only 43.2%.
Summary of the invention
It is an object of the present invention to provide a kind of preparation side of anode composite material for deficiency present in current techniques
Method.Conductive material active carbon is added in this method during redox graphene, has using active carbon highly developed
The advantages that pore structure and huge specific surface area, adsorption capacity is strong, chemical stability is good, high mechanical strength, thus active carbon
Sulfur granules can be adsorbed in three-dimensional grid, be connected with each other again each other, form big conductive network, reduced intergranular
Resistance is conducive to the electric conductivity for improving material.The graphene coated of the high speed network with high electron transmission is utilized in the present invention
Method of modifying of the absorbent charcoal material as lithium sulfur battery anode material, preparation process is simple, has advance, institute compared with the prior art
The chemical property of acquirement also has conspicuousness raising.
The technical solution of the present invention is as follows:
A kind of preparation method of anode composite material, comprising the following steps:
(1) it adds graphene oxide into deionized water, then ultrasonic disperse 1-3h, obtains graphene oxide suspension
Liquid；
Wherein, 10-40mg graphene oxide is added in every 10mL deionized water；
(2) the processed active carbon of acid is added in the graphene oxide suspension of step (1), at room temperature ultrasound point
It dissipates, then stands at room temperature, obtain mixed solution；Wherein, the mass ratio of active carbon and graphene oxide is 1:1~3；Every milli
It rises suspension and adds 1-4mg active carbon；
(3) mixed solution obtained in (2) is taken, sodium ascorbate solution is then added, heats 120- at 100 DEG C
240min obtains graphene hydrogel；Wherein, every 1mL mixed solution adds 20-100mg sodium ascorbate solution, sodium ascorbate
The concentration of solution is 0.5mol/L-2mol/L；
(4) graphene hydrogel obtained in (3) is placed in drying box at 60-90 DEG C dry 6-24h, obtains graphite
Alkene/absorbent charcoal composite material；
It (5) is that 1:1~2 are fully ground 2-6h by graphene/absorbent charcoal composite material obtained in (4) and sulphur mass ratio,
3-15h is calcined at 150-200 DEG C under an argon atmosphere later, obtains anode composite material.
The sour processing method of the active carbon, comprising the following steps:
The active carbon of 5g is added in the concentrated nitric acid of 50mL, by mixed suspension be placed in magnetic stirring apparatus stirring,
Centrifuge separation；It is finally washed until pH value is 7, after drying to obtain the final product.
Above-mentioned graphene/active carbon/sulphur composite material and preparation method thereof, wherein involved raw material pass through commercially available obtain
, equipment used and technique are known to those skilled in the art.
Substantive distinguishing features of the invention are as follows: the present invention in anode composite material preparation method, it is innovative will be active
Charcoal is introduced into graphene oxide layer structure, and one step generates stable graphene/active carbon three dimensional network under the action of reducing agent
Network, not only effectively avoids the graphene layer rendezvous problem of monolithic layer structure, but also increases the conductivity of composite material.Most
Afterwards under inert atmosphere conditions, by heat treatment, sulphur uniform and close combination with graphene/active carbon is realized, more preferably
Inhibition sulphur and discharging product be dissolved in electrolyte, prevent " shuttle effect ", improve the utilization rate of sulphur, while preferably improving anode
The electric conductivity of material, and then improve the cyclical stability and capacity retention ratio of lithium-sulfur cell.The present invention is to conventional graphite alkene lithium sulphur
Battery material improves, and effectively prevents the rendezvous problem between graphene, while reducing polysulfide in charge and discharge process
It is dissolved into electrolyte, to improve the utilization rate of elemental sulfur.
Beneficial achievement of the invention are as follows:
(1) sulphur is embedded in graphene/active carbon three-dimensional network by the preparation method of lithium sulfur battery anode material of the present invention,
Technical process is easily operated.Excellent sulphur/graphene/the absorbent charcoal composite material of obtained chemical property, compared with traditional technology, electric discharge
Capacity increases, and stable discharge good cycle, and under 0.1C multiplying power, first discharge specific capacity reaches 904mAh/g.
(2) in charge and discharge process, three-dimensional structure is configured with conducive to lithium ion and electronics in various dimensions conducting path
It shuttles, improves ion and electron conductivity.Active carbon present in three-dimensional structure, further shorten between nano-sulfur particles with
And the conduction distance of nano-sulfur and graphene sheet layer, it can preferably improve sulfur electrode electric conductivity and restricted activity substance sulphur in electrode
Volume expansion in reaction achievees the purpose that improve electrochemical performance of sulfur electrode；
(3) the active carbon atom in composite material serves not only as the support frame of sulphur-containing substance, can effectively overcome and fill
The volume expansion of sulphur-containing substance in discharge process effectively reduces shuttle effect, and charcoal also conduct to the chemical adsorption of sulphur
The conduction connector of sulphur improves the cycle life of lithium-sulfur cell；
(4) raw material that the preparation method of the lithium sulfur battery anode material uses is cheap and easy to get, preparation process is simple, process
Short, process is easy to control, industrialized production easy to accomplish.
Detailed description of the invention
Fig. 1 is sulphur, the graphene/active carbon, graphene/active carbon/sulphur composite material XRD diagram that embodiment 1 obtains；
Fig. 2 is graphene/active carbon/electrification of the sulphur composite material as lithium sulfur battery anode material that embodiment 1 obtains
Learn performance.
Specific embodiment
Embodiment 1
(1) graphene oxide is prepared using Hummers method；(Hummers method is existing disclosed method, no longer thin herein
State), take 20mg graphene oxide to be added in 10mL deionized water, ultrasonic 1h obtains 2mg/mL graphene oxide suspension；
(2) by the processed active carbon of 3mg acid (sour treatment process are as follows: 1, the active carbon of 5g is added to 50mL mass hundred
Divide in the concentrated nitric acid that concentration is 68%, mixed suspension is placed in magnetic stirring apparatus and stirs 1h；2, by gained suspension in 1
Centrifugation obtains the active carbon of acid processing；3, by processed active carbon massive laundering until pH value be 7, be finally placed in drying box
Dry 10h at 60 DEG C) it is added in the graphene oxide suspension (2mg/mL) of 1.5mL, ultrasound 10min at room temperature, then
10min is stood at room temperature；
(3) mixed solution 1mL obtained in (2) is taken, the sodium ascorbate solution of 20mg 1mol/L is then added, later
It is placed in oil bath pan, heats 120min at 100 DEG C, obtain graphene hydrogel；
(4) graphene hydrogel obtained in (3) is placed in drying box at 60 DEG C dry 12h, obtains graphene/work
Property carbon composite；
It (5) is that 1:1 is fully ground 3h by graphene/active carbon obtained in (4) and sulphur mass ratio, ball milling is selected in grinding
Machine is put in tube furnace later and calcines 10h at 155 DEG C under an argon atmosphere, obtains graphene/active carbon/sulphur anode composite
Material；
(6) graphene/active carbon/sulphur positive electrode for obtaining embodiment 1 and conductive agent Super P and binder are poly- inclined
Vinyl fluoride (PVDF) is fully ground mixing with mass ratio 8:1:1 and is made into slurry, and even application applies thickness in aluminum foil current collector
Degree is about 0.3mm, the dry 12h at 60 DEG C.Dry positive plate is cut into disk, positive plate and lithium cathode sheet are assembled
To button cell.
Fig. 1 is sulphur, graphene/active carbon, graphene/active carbon/sulphur composite material X-ray diffractogram.As shown,
It is multiple to show that sulphur is dispersed in unformed shape without apparent sulphur characteristic peak for graphene/active carbon/sulphur composite material XRD diagram
In condensation material, sulphur carbon is uniformly mixed, and it is good to further illustrate preparation process.
Chemical property analysis (BTS-5V5mA, new prestige) is carried out to prepared battery.Fig. 2 is obtained by the present embodiment
Graphene/active carbon/sulphur composite material as lithium-sulphur cell positive electrode charging and discharging curve figure: as seen from the figure, graphene/activity
Head all discharge capacity of the charcoal/sulphur composite material in the case where multiplying power is 0.1C is up to 904mAh/g.
Embodiment 2
(1) graphene oxide is prepared using Hummers method, 40mg graphene oxide is taken to be added in 10mL deionized water, surpassed
Sound 3h obtains 4mg/mL graphene oxide suspension；
(2) the processed active carbon of 3mg acid is added in the graphene oxide suspension (4mg/mL) of 1.5mL, in room
The lower ultrasound 10min of temperature, then stands 10min at room temperature；
(3) mixed solution 1mL obtained in (2) is taken, the sodium ascorbate solution of 60mg 1mol/L is then added, later
It is placed in oil bath pan, heats 120min at 100 DEG C, obtain graphene hydrogel；
(4) graphene hydrogel obtained in (3) is placed in drying box at 90 DEG C dry 6h, obtains graphene/work
Property carbon composite；
It (5) is that 1:1 is fully ground 3h, grinding choosing by graphene/absorbent charcoal composite material obtained in (4) and sulphur mass ratio
It with ball mill, is put in tube furnace later and calcines 5h at 170 DEG C under an argon atmosphere, it is compound to obtain graphene/active carbon/sulphur
Positive electrode；
(6) graphene/active carbon/sulphur positive electrode for obtaining embodiment 2 and conductive agent Super P and binder are poly- inclined
Vinyl fluoride (PVDF) is fully ground mixing with mass ratio 8:1:1 and is made into slurry, and even application applies thickness in aluminum foil current collector
Degree is about 0.3mm, the dry 12h at 60 DEG C.Dry positive plate is cut into disk, positive plate and lithium cathode sheet are assembled
To button cell.
The characterization result and electrochemical performance data of resulting materials are approximate with embodiment 1.
Embodiment 3
(1) graphene oxide is prepared using Hummers method；It takes 20mg graphene oxide to be added in 10mL deionized water, surpasses
Sound 1h obtains 2mg/mL graphene oxide suspension；
(2) the processed active carbon of 3mg acid is added in the graphene oxide suspension (2mg/mL) of 1.5mL, in room
The lower ultrasound 10min of temperature, then stands 10min at room temperature；
(3) mixed solution 1mL obtained in (2) is taken, the sodium ascorbate solution of 20mg 2mol/L is then added, later
It is placed in oil bath pan, heats 120min at 100 DEG C, obtain graphene hydrogel；
(4) graphene hydrogel obtained in (3) is placed in drying box at 60 DEG C dry 12h, obtains graphene/work
Property carbon composite；
It (5) is that 1:1 is fully ground 3h by graphene/active carbon obtained in (4) and sulphur mass ratio, ball milling is selected in grinding
Machine is put in tube furnace later and calcines 10h at 155 DEG C under an argon atmosphere, obtains graphene/active carbon/sulphur anode composite
Material；
(6) graphene/active carbon/sulphur positive electrode for obtaining embodiment 1 and conductive agent Super P and binder are poly- inclined
Vinyl fluoride (PVDF) is fully ground mixing with mass ratio 8:1:1 and is made into slurry, and even application applies thickness in aluminum foil current collector
Degree is about 0.3mm, the dry 12h at 60 DEG C.Dry positive plate is cut into disk, positive plate and lithium cathode sheet are assembled
To button cell.
The characterization result and electrochemical performance data of resulting materials are approximate with embodiment 1.
Embodiment 4
(1) graphene oxide is prepared using Hummers method；It takes 20mg graphene oxide to be added in 10mL deionized water, surpasses
Sound 1h obtains 2mg/mL graphene oxide suspension；
(2) the processed active carbon of 2mg acid is added in the graphene oxide suspension (2mg/mL) of 1.5mL, in room
The lower ultrasound 10min of temperature, then stands 10min at room temperature；
(3) mixed solution 1mL obtained in (2) is taken, the sodium ascorbate solution of 20mg 1mol/L is then added, later
It is placed in oil bath pan, heats 120min at 100 DEG C, obtain graphene hydrogel；
(4) graphene hydrogel obtained in (3) is placed in drying box at 60 DEG C dry 12h, obtains graphene/work
Property carbon composite；
It (5) is that 1:2 is fully ground 3h by graphene/active carbon obtained in (4) and sulphur mass ratio, ball milling is selected in grinding
Machine is put in tube furnace later and calcines 10h at 155 DEG C under an argon atmosphere, obtains graphene/active carbon/sulphur anode composite
Material；
(6) graphene/active carbon/sulphur positive electrode for obtaining embodiment 1 and conductive agent Super P and binder are poly- inclined
Vinyl fluoride (PVDF) is fully ground mixing with mass ratio 8:1:1 and is made into slurry, and even application applies thickness in aluminum foil current collector
Degree is about 0.3mm, the dry 12h at 60 DEG C.Dry positive plate is cut into disk, positive plate and lithium cathode sheet are assembled
To button cell.
The characterization result and electrochemical performance data of resulting materials are approximate with embodiment 1.
Unaccomplished matter of the present invention is well-known technique.
Claims (1)
1. a kind of preparation method of anode composite material, it is characterized in that method includes the following steps:
(1) it adds graphene oxide into deionized water, then ultrasonic disperse 1-3h, obtains graphene oxide suspension；
Wherein, 10-40mg graphene oxide is added in every 10mL deionized water；
(2) the processed active carbon of acid is added in the graphene oxide suspension of step (1), at room temperature ultrasonic disperse,
Then it stands at room temperature, obtains mixed solution；Wherein, the mass ratio of active carbon and graphene oxide is 1:1~3；Every milliliter
Suspension adds 1-4mg active carbon；
(3) mixed solution obtained in (2) is taken, sodium ascorbate solution is then added, heats 120-240min at 100 DEG C, obtains
To graphene hydrogel；Wherein, every 1mL mixed solution adds 20-100mg sodium ascorbate solution, sodium ascorbate solution it is dense
Degree is 0.5mol/L-2mol/L；
(4) graphene hydrogel obtained in (3) is placed in drying box at 60-90 DEG C dry 6-24h, obtain graphene/
Absorbent charcoal composite material；
It (5) is that 1:1~2 are fully ground 2-6h by graphene/absorbent charcoal composite material obtained in (4) and sulphur mass ratio, later
3-15h is calcined at 150-200 DEG C under an argon atmosphere, obtains anode composite material；
The sour processing method of active carbon in the step (2), comprising the following steps:
The active carbon of 5g is added in the concentrated nitric acid of 50mL, mixed suspension is placed in magnetic stirring apparatus and stirs, be centrifuged
Separation；It is finally washed until pH value is 7, after drying to obtain the final product.
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| CN107768637B (en) * | 2017-10-16 | 2020-08-25 | 河源广工大协同创新研究院 | Preparation method of porous graphene/carbon nanotube lithium-sulfur positive electrode material |
| CN108963206B (en) * | 2018-06-14 | 2021-03-19 | 渤海大学 | V for positive electrode of potassium-sulfur battery2O5Preparation method of/S/PVA composite material and electrode plate thereof |
| CN109378475A (en) * | 2018-09-26 | 2019-02-22 | 武汉理工大学 | Three-dimensional grapheme carried metal compound composite material and its preparation method and application |
| CN109461594B (en) * | 2018-12-25 | 2023-02-28 | 重庆中科超容科技有限公司 | High-voltage-resistance doped three-dimensional porous graphene/activated carbon electrode material and preparation method thereof |
| CN110660977B (en) * | 2019-08-23 | 2021-08-03 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
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| CN102674315A (en) * | 2012-04-25 | 2012-09-19 | 浙江大学 | Graphene-carbon nano tube composite all-carbon ultra-light elastic aerogel and preparation method thereof |
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| CN105732036A (en) * | 2016-01-12 | 2016-07-06 | 山东佳星环保科技有限公司 | Method for preparing three-dimensional graphene/carbon nanotube composite material |
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| CN102674315A (en) * | 2012-04-25 | 2012-09-19 | 浙江大学 | Graphene-carbon nano tube composite all-carbon ultra-light elastic aerogel and preparation method thereof |
| CN104766967A (en) * | 2015-03-18 | 2015-07-08 | 南京师范大学 | Preparation method of S/C composite material used in positive pole of Li-S battery |
| CN105732036A (en) * | 2016-01-12 | 2016-07-06 | 山东佳星环保科技有限公司 | Method for preparing three-dimensional graphene/carbon nanotube composite material |
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