CN109859960A - Sulfonated graphite alkenyl carbon coating lithium titanate composite material and its preparation and application - Google Patents
Sulfonated graphite alkenyl carbon coating lithium titanate composite material and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of sulfonated graphite alkenyl carbon coating lithium titanate composite materials and its preparation and application, composite material to be made of lithium titanate, carbon and sulfonated graphene, wherein Li4Ti5O12It is 92~98% in the mass content on composite material, the mass content of sulfonated graphene and carbon in the composite is 2~8%, and the mass ratio of sulfonated graphene and carbon is (2~4): 1, carbon-coated lithium titanate is attached on sulfonated graphene.Compared with prior art, the electron conduction and ionic conductivity of lithium titanate are improved, so that the sulfonated graphite alkenyl carbon coating lithium titanate (S-GNS/C LTO) of synthesis has excellent high rate performance.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of lithium ion super capacitor negative electrode material.
Background technique
Electric chemical super capacitor is a kind of energy storage device to be worked based on electric double layer or pseudo capacitance mechanism, due to
Have many advantages, such as that charge/discharge speed is fast, power density is high, have extended cycle life, operating temperature range is wide and receives significant attention.With
Lithium ion battery is compared, and electrochemical capacitor energy density is relatively low, but it has extended cycle life, and is widely used in electric car
The fields such as starter, the pulse power and mobile backup power source.With hybrid-electric car and its to high power density and energy
The demand of metric density, lithium ion super capacitor obtain more and more extensive concern as a kind of novel energy storage device.But
Since lithium ion super capacitor uses the electrode of lithium ion battery and supercapacitor to have with double grading simultaneously
Advantage bigger than conventional capacitor energy density, bigger than lithium ion battery power density.Therefore, lithium ion super capacitor is expected to
For the powerful electronics field of the energy types such as electric car, space flight, military affairs.
As the negative electrode material of lithium ion super capacitor, lithium titanate have the advantage that (1) in charge and discharge process,
With the insertion and abjection of lithium ion, lithium titanate hardly happens volume change, therefore is referred to as " zero strain material "；(2) due to
Its embedding lithium platform (1.55V (vs.Li/Li+) it is higher than the reduction potential of most of organic baths, therefore can effectively avoid SEI
Formation and Li dendrite caused by safety problem.However, Li4Ti5O12Lower conductivity and lesser lithium ion diffusion coefficient,
Cause its charge-discharge performance under big multiplying power poor, to limit the extensive use of lithium titanate；Single layer or the few stone of the number of plies
Black alkene has excellent electric conductivity, improves its high rate performance in turn with compound its electric conductivity that can significantly improve of lithium titanate.But
Graphene is easily reunited in composite material synthesis process, itself excellent electric conductivity can not be brought into play well.
Summary of the invention
The invention solves the lithium titanate anode material high rate performance differences of existing method preparation and graphene to be used for composite wood
Expect problem easy to reunite in synthesis process, and a kind of sulfonated graphite alkenyl carbon coating Li is provided4Ti5O12 composite negative pole material and
Preparation method.
To achieve the above object, the specific technical solution of the present invention is as follows,
In sulfonated graphite alkenyl carbon coating Li4In Ti5O12 composite negative pole material, Li4Ti5O12In on composite negative pole material
Mass content is 92~98%, and the gross mass content of sulfonated graphene and carbon in the composite is 2~8%.Sulfonated graphene
With the mass ratio of carbon is (2-4 :): 1.
The best in quality content that the present invention obtains each component in sulfonated graphite alkenyl carbon coating lithium titanate composite material is:
Li4Ti5O12It is 95%, sulfonated graphene and carbon are 5%, and the ratio of sulfonated graphene and carbon is 3:1.Used surface-active
CTAB effect is best in agent.
Sulfonated graphene and carbon preparation method sequentially include the following steps:
(1) be 5:(4~5 in titanium elements and elemental lithium the mass ratio of the material) ratio weigh titanium source and lithium source, be dissolved in steaming
In distilled water, wherein lithium source is that one of lithium carbonate, lithium acetate and lithium hydroxide or two kinds or more mix；Titanium source is four fourth of metatitanic acid
The mixing of one or more of ester, butyl titanate or tetra-n-butyl titanate；Solvent is methanol, ethyl alcohol, isopropanol, ethylene glycol one kind
Or two kinds or more；
(2) it disperses sulfonated graphene (sulfonated graphene) in distilled water, ultrasonic 0.1-1h；
(3) surfactant for the solution that step (2) obtains being added to certain mass score (0.2-0.8wt%) is water-soluble
Liquid, while stirring and heating, time 10-25h, temperature is 25-60 DEG C；
(4) solution that step (1) obtains is added in the solution in step (3), is stirred while adding, stir 2-5h
Afterwards, it is gone in 30-100mL autoclave, and reacts certain time 10-25h at 100-200 DEG C；It is obtained after centrifugation
White precipitate at 60~120 DEG C dry 6~12h；Finally under reducing atmosphere, temperature is forged under conditions of being 600~900 DEG C
3~12h is burnt, sulfonated graphite alkenyl carbon coating lithium titanate composite material is obtained；
Surfactant is dodecyl trimethyl ammonium bromide (DTAB), Cetyltrimethylammonium bromide (STAB), ten
Six alkyl trimethyl ammonium bromides (CTAB), tetradecyltrimethylammonium bromide (TTAB), dioctadecyl dimethyl ammonium chloride
One or more of (DDAC).
Mass concentration of the lithium source in solvent in step (1) is 10-80g/L, and sulfonated graphene quality accounts in step (2)
The 1-5g/L of solvent volume.
In step (2), ultrasonic power is 200~700W, and the speed stirred in step (3) is 100~400rpm.
Reducing atmosphere described in step (3) is H2With the gaseous mixture of inert atmosphere gases, wherein hydrogen Zhan total gaseous mixture
Volumetric concentration is 1%~10%, and inert atmosphere gases are one or more of argon gas, helium or nitrogen.
The sulfonated graphite alkenyl carbon coating lithium titanate composite material is used for lithium ion super capacitor as active constituent
The negative electrode material of device.
Beneficial outcomes of the invention: 1) compared with general graphene, sulfonated graphene does not have to additional work in water and other solvents
It can firmly disperse well (such as ultrasonic disperse), this will simplify the step in materials synthesis.But in material synthesis processes
In, the phenomenon that sulfonated graphene will appear reunion, this will lead to its excellent electric conductivity and cannot fully play.Needle of the present invention
The problem easy to reunite to sulfonated graphene in composite material synthesis process carries out intercalation processing to it, and (surfactant is as intercalation
Agent), so that the surfactant-modified sulfonated graphene with layer pole structure is obtained first, since surfactant is in the material
Supporting role between the bed of material is not susceptible to agglomeration when it being made to be used for conducting base, it is ensured that synthetic material is in the equal of its surface
Even dispersion；
2) certain due to being added in the mixture of titanium source and lithium source simultaneously using hydro-thermal method in preparation process of the invention
The highly conductive substance sulfonated graphene of amount, so that Li4Ti5O12Particle is grown in conductive agent surface in situ, improves ionic conductivity
While can effectively prevent Li4Ti5O12Aggregation, to obtain than pure phase Li4Ti5O12Smaller particle.The surface of introducing is living
Property agent to sulfonated graphene carry out intercalation, the reunion of sulfonated graphene is effectively prevented from, so that Li4Ti5O12Particle can be uniform
Ground is grown on sulfonated graphene lamella, while in Li after surfactant high-temperature calcination4Ti5O12Particle surface forms conductive carbon
Layer improves Li4Ti5O12Electron conduction.To sum up, the present invention improves the electron conduction and ionic conduction of lithium titanate simultaneously
Property, so that the sulfonated graphite alkenyl carbon coating lithium titanate (S-GNS/C LTO) of synthesis has excellent high rate performance, close
At material can be used for lithium ion super capacitor field.
Conducting base of the sulfonated graphene as composite material, improves the ionic conductivity of material；In addition, the surface introduced
Activating agent carries out intercalation to sulfonated graphene, the reunion of sulfonated graphene is effectively prevented from, so that Li4Ti5O12Particle can be equal
It is grown on sulfonated graphene lamella evenly, while in Li after surfactant high-temperature calcination4Ti5O12Particle surface forms conduction
Carbon-coating improves Li4Ti5O12Electron conduction.
Detailed description of the invention
Fig. 1 be embodiment 1, comparative example 1, the negative electrode material of comparative example 2 assembling lithium ion super capacitor it is forthright again
It can comparison diagram.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Embodiment 1:
The present embodiment sulfonated graphite alkenyl carbon coating lithium titanate (S-GNS/C LTO) sequentially includes the following steps:
(1) 16.5mL butyl titanate, 3.46g lithium acetate are weighed and is scattered in 200mL distilled water respectively；
(2) it weighs 0.309g sulfonated graphene and places it in the beaker equipped with 200mL distilled water, with the function of 600W
Rate ultrasound 0.5h；
(3) by the solution that step (2) obtains be added to mass fraction be 0.4wt% Surfactant CTAB it is water-soluble
Liquid, while stirring and heating, the time is that for 24 hours, temperature is 45 DEG C；
(4) solution that step (1) obtains is added in the solution in step (3), is stirred while adding, after stirring 5h,
It is gone in autoclave, and reacts 15h under certain temperature (120 DEG C)；The white precipitate obtained after centrifugation is at 80 DEG C
Lower dry 12h；Finally under reducing atmosphere, temperature calcines 10h under conditions of being 700 DEG C, obtains sulfonated graphite alkenyl carbon coating
Lithium titanate composite material is denoted as S-GNS/C@LTO.
Raw materials used the present embodiment is commercial product.
Performance test:
1) in the sulfonated graphite alkenyl carbon coating lithium titanate material of preparation: the ratio of Super P:PVDF=8:1:1 mixes,
It the use of N-Methyl pyrrolidone is solvent, with the speed of 400rpm, magnetic agitation 4h obtains electrode slurry, is applied to aluminium foil
On, make the control of load amount in~3.5mg/cm2, 100 DEG C at a temperature of, be dried in vacuo 12h, be then washed into sheet-punching machine a length of
7.7cm, width are the electrode slice of 5cm.
2) active carbon, SuperP and (CMC+SBR) are uniformly mixed with the mass ratio of 85:10:5, are taken water as a solvent, with
The speed of 400rpm, magnetic agitation 4h obtain electrode slurry and are coated on aluminium foil, make the control of load amount in~8 mg/cm2,
At a temperature of 100 DEG C, it is dried in vacuo 12h, is then washed into a length of 7.5cm with sheet-punching machine, width is the electrode slice of 5cm.
3) above-mentioned positive and negative electrode pole piece and polypropylene diaphragm folding are coiled into the electrode of rectangular lithium ion super capacitor
Group is encapsulated after injecting electrolyte with aluminum plastic film.
Electrolyte used is methyl ethyl carbonate rouge (EMC), ethylene carbonate (EC), propene carbonate (PC) and dimethyl carbon
One of acid esters (DMC) or in which several mixed liquors, electrolyte used in the present embodiment are the lithium ion battery batteries of business
Liquid is solved, wherein lithium salts is lithium hexafluoro phosphate, and solvent is the mixed liquor of EC, DEC and DMC that volume ratio is 1:1:1.
Embodiment 2:
Sulfonated graphite alkenyl carbon coating lithium titanate composite material and battery are prepared using method same as Example 1, no
Same is the content of sulfonated graphene, and mass percentage is 3%.
Embodiment 3: using method same as Example 1 prepare sulfonated graphite alkenyl carbon coating lithium titanate composite material and
Battery, the difference is that the content of surfactant, mass percentage is 0.3%.
Embodiment 4: method sulfonated graphite alkenyl carbon coating lithium titanate composite material and electricity same as Example 1 are used
Pond, the difference is that the content of sulfonated graphene (sulfonated graphene), mass percentage is 7%.
Comparative example 1: using pure phase lithium titanate material as cathode assembled battery, lithium titanate preparation method and battery assembly method with
Embodiment 1 is identical.
Comparative example 2: using non-modified sulfonated graphene/LTO material as cathode assembled battery, lithium titanate preparation method and
Battery assembly is same as Example 1.
Comparative example 3: it is prepared using sulfonated graphite alkenyl carbon coating lithium titanate composite material same as Example 1 and battery
Method, the difference is that the preparation method of composite material: solid phase method, the specific steps are as follows:
(1) stoichiometrically 5:(4~4.5) ratio weigh titanium dioxide and lithium carbonate, will using ethyl alcohol as dispersing agent
The titanium source and lithium source weighed up is uniformly mixed；
(2) it weighs 0.309g sulfonated graphene and places it in the beaker equipped with 200mL distilled water, with the function of 600W
Rate ultrasound 0.5h；
(3) by the solution that step (2) obtains be added to mass fraction be 0.4wt% Surfactant CTAB it is water-soluble
Liquid, while stirring and heating, the time is that for 24 hours, temperature is 45 DEG C；
(4) solution that step (1) obtains is added in the solution in step (3), then places it in ball milling and carries out
Ball milling, wherein ratio of grinding media to material is 4:1, Ball-milling Time 12h；
(5) the good slurry of above-mentioned ball milling is dried at 80 DEG C, under an argon atmosphere for 24 hours in 900 DEG C of calcinings, obtained sample
Product are sulfonated graphite alkenyl carbon coating lithium titanate composite material, are denoted as S-GNS/C LTO-1.
Evaluation results and analysis:
(three kinds of high rate performance test are carried out respectively to lithium titanate material obtained in embodiment 1, comparative example 1 and comparative example 2
Material is respectively designated as S-GNS/C@LTO, LTO and S-GNS@LTO), test result is shown: adopting CTAB-S-GNS@LTO material
High rate performance obviously due to other two kinds of materials, under 30C discharge-rate, specific capacity still has~110mAh/g.The reason is that using
After Surfactant CTAB carries out intercalation modifying to sulfonated graphene sulfonated graphene, the electric conductivity of sulfonated graphene is obtained sufficiently
It plays while guaranteeing that lithium titanate can be uniformly scattered on conducting base sulfonated graphene when later period synthesis, CTAB passes through high temperature
After calcining, conductive carbon layer is formed in LTO particle surface, improves the electron conduction of LTO material, to sum up CTAB-S-GNS@
The high rate performance of LTO is best.
Claims (8)
1. sulfonated graphite alkenyl carbon coating lithium titanate composite material, it is characterised in that: composite material is by lithium titanate, carbon and sulfonation stone
Black alkene forms, wherein Li4Ti5O12It is 92~98% in the mass content on composite material, sulfonated graphene and carbon are in composite wood
Mass content in material is 2~8%, and the mass ratio of sulfonated graphene and carbon is (2~4): 1, carbon-coated lithium titanate attachment
In on sulfonated graphene.
2. sulfonated graphite alkenyl carbon coating lithium titanate composite material according to claim 1, it is characterised in that: described compound
Material is prepared as follows,
(1) be 5:(4~5 in titanium elements and elemental lithium the mass ratio of the material) ratio weigh titanium source and lithium source, be dissolved in distilled water
In, wherein lithium source is that one of lithium carbonate, lithium acetate and lithium hydroxide or two kinds or more mix；Titanium source be butyl titanate,
One of butyl titanate or tetra-n-butyl titanate or two kinds or more mix；
(2) sulfonated graphene is dispersed in water, ultrasonic 0.1-1h；
(3) solution that step (2) obtains is added to the aqueous solution containing the surfactant that mass fraction is 0.2-0.8wt%,
It stirs and heats simultaneously, time 10-25h, temperature is 25-60 DEG C, wherein the quality of sulfonated graphene and surfactant
Than for (1.5~3): 1；
(3) solution that step (1) obtains is added in the solution in step (3), after stirring 2-5h, is gone to reaction kettle
In, and 10-25h is reacted at 100-200 DEG C；The white precipitate obtained after centrifugation dry 6~12h at 60~120 DEG C；Finally
Under reducing atmosphere, temperature calcines 3~12h under conditions of being 500~800 DEG C, obtains sulfonated graphite alkenyl carbon coating lithium titanate
Composite material.
3. a kind of preparation method of sulfonated graphite alkenyl carbon coating lithium titanate composite material of any of claims 1 or 2, feature
It is, the preparation of sulfonated graphite alkenyl carbon coating lithium titanate composite material sequentially includes the following steps:
(1) be 5:(4~5 in titanium elements and elemental lithium the mass ratio of the material) ratio weigh titanium source and lithium source, be dissolved in distilled water
In, wherein lithium source is that one of lithium carbonate, lithium acetate and lithium hydroxide or two kinds or more mix；Titanium source be butyl titanate,
One of butyl titanate or tetra-n-butyl titanate or two kinds or more mix；
(2) it disperses sulfonated graphene in distilled water, ultrasonic 0.1-1h；(3) solution that step (2) obtains is added to quality
The aqueous surfactant solution of score 0.2-0.8wt%, while stirring and heating, time 10-25h, temperature 25-60
℃；
(3) solution that step (1) obtains is added in the solution in step (3), is stirred while adding, it, will after stirring 2-5h
It goes in reaction kettle, and reacts 10-25h at 100-200 DEG C；The white precipitate obtained after centrifugation is done at 60~120 DEG C
Dry 6~12h；Finally under reducing atmosphere, temperature calcines 3~12h under conditions of being 500~800 DEG C, obtains sulfonated graphite alkenyl
Carbon coating lithium titanate composite material.
4. the preparation method of sulfonated graphite alkenyl carbon coating lithium titanate composite material according to claim 3, feature exist
In: mass concentration of the lithium source in solvent in step (1) is 10-80g/L, and sulfonated graphene quality accounts for solvent in step (2)
The 1-5g/L of volume.
5. the preparation method of sulfonated graphite alkenyl carbon coating lithium titanate composite material according to claim 3, feature exist
In: in step (2), ultrasonic power is 200~700W, and the speed stirred in step (3) is 100~400rpm.
6. the preparation method of sulfonated graphite alkenyl carbon coating lithium titanate composite material according to claim 3, feature exist
In: reducing atmosphere described in step (3) is H2With the gaseous mixture of inert atmosphere gases, wherein the volume of the total gaseous mixture of hydrogen Zhan is dense
Degree is 1%~10%, and inert atmosphere gases are one or more of argon gas, helium or nitrogen.
7. the preparation method of sulfonated graphite alkenyl carbon coating lithium titanate composite material according to claim 3, feature exist
In: surfactant is dodecyl trimethyl ammonium bromide (DTAB), Cetyltrimethylammonium bromide (STAB), cetyl
Trimethylammonium bromide (CTAB), tetradecyltrimethylammonium bromide (TTAB), in dioctadecyl dimethyl ammonium chloride (DDAC)
One or more.
8. a kind of application of sulfonated graphite alkenyl carbon coating lithium titanate composite material as claimed in claim 1 or 2, it is characterised in that:
The sulfonated graphite alkenyl carbon coating lithium titanate composite material is as active material for the cathode in lithium ion super capacitor.
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