CN107240681A - A kind of porous nano carbon, lithium-sulphur cell positive electrode and preparation method thereof - Google Patents
A kind of porous nano carbon, lithium-sulphur cell positive electrode and preparation method thereof Download PDFInfo
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- CN107240681A CN107240681A CN201710390416.2A CN201710390416A CN107240681A CN 107240681 A CN107240681 A CN 107240681A CN 201710390416 A CN201710390416 A CN 201710390416A CN 107240681 A CN107240681 A CN 107240681A
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Abstract
A kind of porous nano carbon, lithium-sulphur cell positive electrode and preparation method thereof, the preparation method of the porous nano carbon includes：Pitch, nano-oxide, potassium hydroxide are mixed；Using the pitch in organic solvent dissolving mixt, stirring makes pitch obtain mixture of powders after being evenly coated at nano-oxide and potassium hydroxide surface, drying；In an inert atmosphere to mixture of powders high-temperature heat treatment, by potassium hydroxide in-situ activation pore-creating while making asphalt carbonization；By product acid treatment, the potassium hydroxide of nano-oxide and residual is washed away, the porous nano carbon of hierarchical structure is obtained after drying.It using the porous nano carbon as the sulfur-donor material of lithium-sulphur cell positive electrode, can effectively suppress the shuttle effect of lithium-sulfur cell, obtained lithium-sulfur cell cycle performance is excellent, be kept with preferable capacity.
Description
Technical field
The present invention relates to lithium-sulfur cell, more particularly to a kind of porous nano carbon, lithium-sulphur cell positive electrode and preparation method thereof.
Background technology
With developing rapidly for world today's science and technology, the energy density of lithium ion battery can not be met at this stage
One of the requirement of some emerging technologies development, main bottleneck as restriction high performance electronics development.Lithium-sulfur cell conduct
It is a kind of using sulphur, lithium metal as the novel battery system of positive and negative electrode active material, it has advantages below：The reserves of sulphur
It is abundant, it is cheap, it is environment-friendly；The theoretical energy density of lithium-sulfur cell system is up to 1675mAh/g.Lithium-sulfur cell enters one
Step development will provide the energy that once charging travels several hundred kilometers for electric car.But equally to face some serious for lithium-sulfur cell
Technical problem：Sulphur is that insulator can not itself independent discharge and recharge；Sulphur has 80% volumetric expansion in charge and discharge process；Sulphur is filling
The polysulfide for dissolving in electrolyte is formed in discharge process after lithiumation, and is shuttled between both positive and negative polarity, in negative pole side deposition
The cycle performance of battery is reduced afterwards, causes capacity to be decayed rapidly and serious self-discharge of battery behavior.At present, suitable for lithium sulphur
In the carrier material of battery sulphur, most common is carbon material, because carbon material has excellent electric conductivity, the sulphur that can effectively play
Removal lithium embedded performance；The high carbon material of porosity can accommodate substantial amounts of sulphur, and buffer its volumetric expansion in charge and discharge process；
The carbon material of hierarchical structure can also effectively limit dissolving and the shuttle effect of polysulfide.Therefore, a kind of structure is developed
Special, excellent performance stratification carbon material, and applied to lithium-sulphur cell positive electrode sulfur-donor material, to the further of lithium-sulfur cell
The progress tool in development and energy storage field is of great significance.
The content of the invention
It is a primary object of the present invention to overcome the deficiencies in the prior art there is provided a kind of porous nano carbon and lithium-sulfur cell just
The preparation method of pole material.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of porous nano carbon, comprises the following steps：
Step one, pitch, nano-oxide, potassium hydroxide are mixed according to predetermined mass ratio；
Step 2, using the pitch in organic solvent dissolving mixt, stirring makes the pitch be evenly coated at institute
Mixture of powders is obtained after stating nano-oxide and potassium hydroxide surface, drying；
Step 3, in an inert atmosphere to the mixture of powders high-temperature heat treatment so that be coated on described nano oxidized
The asphalt carbonization on thing surface, the carbon material of generation is simultaneously by potassium hydroxide in-situ activation pore-creating；
Step 4, the product acid treatment that high-temperature heat treatment is obtained washes away the nano-oxide, priming reaction by-product
The potassium hydroxide of thing and residual, obtains the porous nano carbon of hierarchical structure after drying.
Further：
The nano-oxide is the nanosphere or nanometer sheet of magnesia, iron oxide, nickel oxide, calcium oxide or aluminum oxide
Grain；The pitch is coal tar asphalt, asphalt or mesophase pitch；The organic solvent is N, N, dimethylformamide
(DMF), 1-METHYLPYRROLIDONE (NMP) or tetrahydrofuran (THF).
In step 3, using high temperature process furnances by the mixture of powders in an inert atmosphere with 600-900 DEG C of temperature
In the range of, high-temperature heat treatment 1-5 hours.
Pitch, nano-oxide, the mass ratio of potassium hydroxide are 1:3~15:1~10, preferably 1:9:5~6.
A kind of preparation method of lithium-sulphur cell positive electrode, comprises the following steps：
Step 5, carries out sulfurizing processing to porous nano carbon made from the preparation method as described porous nano carbon, obtains
It is embedded into the sulphur carbon complex in porous nano carbon pores gap to sulphur；
Step 6, the sulphur carbon complex is mixed with conductive additive, binding agent, is added stirring solvent and is obtained slurry,
Slurry is coated on aluminium foil, through drying, film and punching is rolled, obtains the positive electrode of lithium-sulfur cell.
Further：
In step 5, the sulfurizing processing includes：Porous nano carbon and sulphur powder are mixed with certain mass ratio, in indifferent gas
With 155 DEG C of Temperature Treatment 12 hours in atmosphere, then heat to 200 DEG C and handle 30 minutes.
In step 5, the sulfurizing processing is carried out using solution dipping method or in situ reaction growth method.
In step 6, the conductive additive is conductive black, and the binding agent is Kynoar (PVDF), described molten
Agent is 1-METHYLPYRROLIDONE (NMP).
Lithium-sulphur cell positive electrode made from a kind of preparation method using described lithium-sulphur cell positive electrode.
A kind of lithium-sulfur cell, with the lithium-sulphur cell positive electrode.
Beneficial effects of the present invention：
The porous nano carbon preparation technology cost of the present invention is low and simple and easy to apply, and the porous nano carbon is used as lithium-sulfur cell
The carbon support material of positive pole can effectively suppress the shuttle effect of lithium-sulfur cell, and there is obtained lithium-sulfur cell preferable capacity to protect
Hold.
The preparation-obtained porous nano carbon of the present invention is three-dimensional interconnected nano flake, with the ultra-thin of 3-5nm
Carbon layers having thicknesses, with abundant macropore and mesoporous stratification hole, specific surface area is more than 1000m2/ g, pore volume is more than 2cm3/g。
Under the squeezing action of nano-oxide template, the carbon nano flake thickness that asphalt carbonization is obtained is uniform.Utilize this porous nano
Sulphur carbon composite made from carbon, element sulphur is evenly distributed, and has been well embedded in the hole inside carbon base body.Pass through reality
Test is determined, and when the content of sulphur in sulphur carbon composite is more than 60%, prepared lithium-sulfur cell is in 0.3C (1C=1675mA/
G) under current density, cyclic discharge capacity reaches more than 1000mAh/g first, and specific capacity may remain in after 500 circulations
More than 500mAh/g；When being circulated under 1C high current density, capacity may remain in more than 600mAh/g after 300 circulations.
The lithium sulfur battery anode material is compound with stratification porous nano carbon and sulphur, and suppression lithium-sulfur cell can be played simultaneously
The effect of shuttle effect and protection negative metal lithium；Electrode specific capacity is high, can keep good under low current and high current
Cyclical stability.The use of the high conductivity, high porosity carbon nanosheet is the lithium-sulphur cell positive electrode that sulfur-donor is assembled, the property of battery
There can be extraordinary application prospect better than the lithium-sulfur cell using graphene as sulfur-donor.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of the lithium-sulphur cell positive electrode of the embodiment of the present invention；
Fig. 2 is transmission electron microscope (TEM) figure of the preparation-obtained stratification porous nano carbon of example 1 in the present invention；
Fig. 3 is the elementary analysis surface sweeping Electronic Speculum (SEM) of the preparation-obtained sulphur carbon composite of comparative example 1 in the present invention
Figure.
Embodiment
Embodiments of the present invention are elaborated below.It is emphasized that what the description below was merely exemplary,
The scope being not intended to be limiting of the invention and its application.
Refering to Fig. 1, in one embodiment, a kind of preparation method of porous nano carbon comprises the following steps：
Step one, pitch, nano-oxide, potassium hydroxide are mixed according to predetermined mass ratio；
Step 2, using the pitch in organic solvent dissolving mixt, stirring makes the pitch be evenly coated at institute
Mixture of powders is obtained after stating nano-oxide and potassium hydroxide surface, drying；
Step 3, in an inert atmosphere to the mixture of powders high-temperature heat treatment so that be coated on described nano oxidized
The asphalt carbonization on thing surface, the carbon material of generation is simultaneously by potassium hydroxide in-situ activation pore-creating；
Step 4, the product acid treatment that high-temperature heat treatment is obtained, wash away the nano-oxide, byproduct of reaction and
The porous nano carbon of hierarchical structure is obtained after the potassium hydroxide of residual, drying.
A kind of preparation method of lithium-sulphur cell positive electrode, comprises the following steps：
Step 5, carries out sulfurizing processing to porous nano carbon made from the preparation method as described porous nano carbon, obtains
It is embedded into the sulphur carbon complex in porous nano carbon pores gap to sulphur；
Step 6, the sulphur carbon complex is mixed with conductive additive, binding agent, is added stirring solvent and is obtained slurry,
Slurry is coated on aluminium foil, through drying, film and punching is rolled, obtains the positive electrode of lithium-sulfur cell.
In certain embodiments, a kind of sulphur carbon is combined the preparation method of lithium-sulphur cell positive electrode, comprises the following steps：
Step one, by pitch, magnesium oxide template particle, potassium hydroxide according to 1:3~15:1~10 mass ratio grinding
Mixing；Step 2, using the pitch in organic solvent dissolving mixt, makes it be evenly coated at magnesia and potassium hydroxide table
Homogeneous mixture of powders is obtained after face, drying；Step 3, using high temperature process furnances by powder mixture in inert atmosphere
In, within the temperature range of 600-900 DEG C, high-temperature heat treatment 1-5 hours is preferably heat-treated 2 hours at 850 DEG C, will be coated on
The asphalt carbonization of magnesium oxide nanoparticle template surface, the carbon material of generation is simultaneously by potassium hydroxide in-situ activation pore-creating；Step
Four, the product acid treatment that high-temperature heat treatment is obtained washes away the potassium hydroxide of magnesium oxide template, byproduct of reaction and residual,
The big stratification porous nano carbon of specific surface area is obtained after drying.Step 5, by porous nano carbon and sulphur powder with certain mass ratio
Mixing, 155 DEG C are handled 12 hours in an inert atmosphere, are then heated to 200 DEG C and are handled 30 minutes.Step 6, by obtained sulphur
Carbon complex, conductive additive is well mixed with binding agent by certain mass ratio, is added stirring solvent and is obtained anode sizing agent, will starch
Material is coated on aluminium foil, through drying, is rolled film and punching, is obtained the anode pole piece of lithium-sulfur cell.
It is determined by experiment, when the content of sulphur in sulphur carbon composite is more than 60%, prepared lithium-sulfur cell exists
Under 0.3C (1C=1675mA/g) current density, cyclic discharge capacity reaches more than 1000mAh/g first, after 500 circulations
Specific capacity may remain in more than 500mAh/g；When being circulated under 1C high current density, capacity can reach after 300 circulations
More than 600mAh/g.
In the preferred embodiments of the present invention, carbon source pitch can be coking coal oil asphalt, mesophase pitch or asphalt etc..
In preferred embodiment, nano-oxide template can be magnesia, the nanosphere such as iron oxide or aluminum oxide and nanometer sheet particle.It is excellent
Select in embodiment, the organic solvent for dissolving carbon matrix precursor material can be DMF (DMF), N methyl pyrroles
Pyrrolidone (NMP) or tetrahydrofuran (THF) etc..
Illustrate porous nano carbon, sulphur carbon composite anode material and preparation method thereof below by way of more specifically example, and it is right
Sulphur carbon composite anode obtained by preparation carries out electrochemical property test.
Example 1：
The first step：It is prepared by mixture.By coking coal oil asphalt, magnesium oxide nanoparticle, potassium hydroxide is according to mass ratio
1:9:6 are mixed with mortar grinder；
Second step：It is well mixed.The pitch added in DMF dissolving mixts, makes it be evenly coated at magnesia and hydrogen-oxygen
Change potassium surface, the mixture of powders being mixed thoroughly after drying；
3rd step：Carbonization-activation.Using high temperature process furnances by said mixture powder as in argon gas at 850 DEG C of high warms
Reason 2 hours, will be coated on the asphalt carbonization on potassium hydroxide surface, while potassium hydroxide activates pore-creating in carbon material surface；
4th step：Cleaning.The potassium hydroxide of magnesium oxide template and residual is washed away with hydrochloric acid, after washing several times, is dried
Enriched to specific surface area, stratification hole, three-dimensional carbon nanosheet network.
5th step：It is prepared by sulphur carbon composite.By porous nano carbon and sulphur powder with mass ratio 4:6 mixing, in argon gas
Sulfurizing in 12 hours is handled at 155 DEG C, the sulphur for being handled at 200 DEG C and removing excess surface for 30 minutes is then heated to.
The porous nano carbon prepared is three-dimensional interconnected nano flake, the ultra-thin carbon layers having thicknesses with 3-5nm,
Have and possess abundant macropore and mesoporous stratification hole, specific surface area is more than 1000m2/ g, pore volume is more than 2cm3/g.Receiving
Under the squeezing action of rice oxide template, the carbon nano flake thickness that asphalt carbonization is obtained is uniform.
Fig. 2 shows transmission electron microscope (TEM) figure of the stratification porous nano carbon prepared.
6th step：Prepare positive pole plate of lithium-sulfur cell.By porous nano carbon-sulfur compound of preparation, conductive black with
PVDF binding agents are according to mass ratio 80:10:10 are well mixed, and add organic solvent NMP stirrings and obtain anode sizing agent.Positive pole is starched
Material is coated on aluminium foil, through drying, is rolled film and punching, is obtained positive pole plate of lithium-sulfur cell.
Electrochemical property test：By the sulphur carbon composite anode pole piece group in the glove box full of high-purity argon gas prepared
Dress up 2032 type button cells.Constant current charge-discharge circulation is carried out at room temperature to above-mentioned battery using Land battery test systems
Performance test, charging/discharging voltage scope is 1.7-2.8V, current density selection 0.3C and 1C (1C=1675mA/g).
Test result：Operated according to above-mentioned steps, the sulphur carbon composite anode material that this example is prepared is in 0.3C electric currents
Cycle performance test is carried out under density, reversible capacity is 1026mAh/g first, reversible capacity is 838mAh/g after circulating 100 times,
Capability retention is 81.6%；When being circulated under 1C current densities, reversible capacity is 926mAh/g first, circulates 300 Zhou Houke
Inverse capacity is 583mAh/g, and capability retention is 63%.
Comparative example 1：
The first step：It is prepared by sulphur carbon composite.Graphene and sulphur powder will be commercialized with mass ratio 4:6 mixing, in argon gas
In handle 12 hours at 155 DEG C, and be warming up to the sulphur that 200 DEG C of processing remove excess surfaces for 30 minutes.Fig. 3 is the sulphur prepared
Elementary analysis surface sweeping Electronic Speculum (SEM) figure of carbon composite.
Second step：Prepare positive pole plate of lithium-sulfur cell.By the graphene-sulfur compound of preparation, conductive black glues with PVDF
Agent is tied according to mass ratio 80:10:10 are well mixed, and add organic solvent NMP stirrings and obtain anode sizing agent.Anode sizing agent is coated
In on aluminium foil, through drying, film and punching are rolled, positive pole plate of lithium-sulfur cell is obtained.
Electrochemical property test：The sulphur carbon anode pole piece prepared is assembled into the glove box full of high-purity argon gas
2032 type button cells.Cycle performance test, discharge and recharge are carried out at room temperature to above-mentioned battery using Land battery test systems
Electric current is 0.3C and 1C, and charging/discharging voltage scope is 1.7-2.8V.
Test result：Operated according to above-mentioned steps, the carbon sulphur composite positive pole that this example is prepared is in 0.3C electric currents
Lower progress cycle performance test, reversible capacity is 962mAh/g first, and reversible capacity is 413mAh/g, capacity after circulating 100 times
Conservation rate is 42.9%；When carrying out cycle performance test under 1C current densities, reversible capacity is 634mAh/g, circulation first
Reversible capacity is 279mAh/g after 100 times, and the conservation rate of capacity is 44.0%.
Example 2：
Be with the difference in example 1 that this example chooses in this example by coking coal oil asphalt, magnesia, hydroxide
Potassium mass ratio is 1:9:5, mixed with mortar grinder, electrochemistry is carried out by the carbon sulphur composite prepared to this example
Performance test, test result is：When carrying out cycle performance test under 0.3C electric currents, capacity is 1023mAh/g, circulation first
Reversible capacity is 714mAh/g after 100 times.
The solvent that pitch is dissolved in the present invention also may be selected using THF, NMP, DMSO etc., with having phase using DMF solvent
As effect.The coking coal oil asphalt mentioned in the present invention may be replaced by the similar carbon source such as mesophase pitch, with similar effect
Really.Magnesium oxide template particle in the embodiment of the present invention, may be replaced by other sheets, graininess nano-oxide.Pass through
Knowable to the contrast of example 1 and comparative example 1, the stratification porous nano carbon prepared in preparation method of the invention and common graphite alkene
Carbon material is compared, and the sulphur carbon composite anode of assembling lithium-sulfur cell has higher reversible specific capacity, and more excellent cycle performance.
Understood with reference to example 2, by adjusting the ratio of each component in preparation process, the lithium-sulfur cell of different performance can be obtained.
Above content is to combine specific/preferred embodiment made for the present invention be further described, it is impossible to recognized
The specific implementation of the fixed present invention is confined to these explanations.For general technical staff of the technical field of the invention,
Without departing from the inventive concept of the premise, it can also make some replacements or modification to the embodiment that these have been described,
And these are substituted or variant should all be considered as belonging to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of porous nano carbon, it is characterised in that comprise the following steps：
Step one, pitch, nano-oxide, potassium hydroxide are mixed according to predetermined mass ratio；
Step 2, using the pitch in organic solvent dissolving mixt, stirring makes the pitch be evenly coated at described receive
Rice oxide and potassium hydroxide surface, mixture of powders is obtained after drying；
Step 3, in an inert atmosphere to the mixture of powders high-temperature heat treatment so that be coated on the nano-oxide table
The asphalt carbonization in face, the carbon material of generation is simultaneously by potassium hydroxide in-situ activation pore-creating；
Step 4, the product acid treatment that high-temperature heat treatment is obtained, wash away the nano-oxide, priming reaction accessory substance and
The porous nano carbon of hierarchical structure is obtained after the potassium hydroxide of residual, drying.
2. the preparation method of porous nano carbon as claimed in claim 1, it is characterised in that the nano-oxide is oxidation
Magnesium, iron oxide, nickel oxide, the nanosphere or nanometer sheet particle of calcium oxide or aluminum oxide；The pitch is coal tar asphalt, oil
Pitch or mesophase pitch；The organic solvent is N, N, dimethylformamide (DMF), 1-METHYLPYRROLIDONE or tetrahydrochysene furan
Mutter.
3. the preparation method of porous nano carbon as claimed in claim 1, it is characterised in that in step 3, utilize high-temperature tubular
Stove by the mixture of powders in an inert atmosphere within the temperature range of 600-900 DEG C, high-temperature heat treatment 1-5 hours.
4. the preparation method of the porous nano carbon as described in any one of claims 1 to 3, it is characterised in that pitch, nano oxidized
Thing, the mass ratio of potassium hydroxide are 1:3~15:1~10, preferably 1:9:5~6.
5. a kind of preparation method of lithium-sulphur cell positive electrode, it is characterised in that comprise the following steps：
Step 5, sulfurizing processing is carried out to the porous nano carbon as made from the preparation method described in any one of Claims 1-4,
Obtain the sulphur carbon complex that sulphur is embedded into porous nano carbon pores gap；
Step 6, the sulphur carbon complex is mixed with conductive additive, binding agent, is added stirring solvent and is obtained slurry, will starch
Material is coated on aluminium foil, through drying, is rolled film and punching, is obtained the positive electrode of lithium-sulfur cell.
6. at the preparation method of lithium-sulphur cell positive electrode as claimed in claim 5, it is characterised in that in step 5, the sulfurizing
Reason includes：Porous nano carbon and sulphur powder are mixed with certain mass ratio, it is small with 155 DEG C of Temperature Treatment 12 in an inert atmosphere
When, then heat to 200 DEG C and handle 30 minutes.
7. the preparation method of lithium-sulphur cell positive electrode as claimed in claim 5, it is characterised in that in step 5, is soaked using solution
Stain method or in situ reaction growth method carry out the sulfurizing processing.
8. the preparation method of the lithium-sulphur cell positive electrode as described in any one of claim 5 to 7, it is characterised in that in step 6, institute
Conductive additive is stated for conductive black, the binding agent is Kynoar (PVDF), the solvent is 1-METHYLPYRROLIDONE
(NMP)。
9. lithium-sulphur cell positive electrode made from a kind of preparation method using as described in any one of claim 5 to 7.
10. a kind of lithium-sulfur cell, it is characterised in that：The positive pole just extremely as claimed in claim 9 of the lithium ion battery.
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Cited By (9)
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| CN108640114A (en) * | 2018-05-16 | 2018-10-12 | 合肥工业大学 | A kind of catamaran type activated carbon vacuum sulfurizing device and its application method |
| CN109686902A (en) * | 2018-11-29 | 2019-04-26 | 西交利物浦大学 | Lithium-sulfur cell composite diaphragm, preparation method and application |
| CN110690422A (en) * | 2019-09-16 | 2020-01-14 | 上海电力大学 | Carbon nanosphere wrapped by porous oxide doped carbon nanotube and preparation and application thereof |
| CN111653777A (en) * | 2020-05-20 | 2020-09-11 | 佛山科学技术学院 | Graphene/sulfur porous microsphere composite material used as lithium-sulfur battery anode and preparation method thereof |
| CN112002890A (en) * | 2020-09-15 | 2020-11-27 | 安徽工业大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN112850705A (en) * | 2020-07-04 | 2021-05-28 | 山东八三石墨新材料厂 | Method for preparing electrode material of super capacitor by using asphalt as raw material |
| CN113603089A (en) * | 2021-08-12 | 2021-11-05 | 中国石油化工股份有限公司 | Energy storage carbon material and preparation method and application thereof |
| US11192804B2 (en) | 2019-11-19 | 2021-12-07 | King Fahd University Of Petroleum And Minerals | Method of adsorbing contaminants using a porous carbon compound |
| CN115676821A (en) * | 2022-10-14 | 2023-02-03 | 电子科技大学长三角研究院(湖州) | Preparation method of lithium-sulfur battery positive electrode material, positive electrode material and application |
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