CN107275614A - MoS2CNT lithium titanate composite anode material and its preparation and lithium battery - Google Patents
MoS2CNT lithium titanate composite anode material and its preparation and lithium battery Download PDFInfo
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- CN107275614A CN107275614A CN201710494620.9A CN201710494620A CN107275614A CN 107275614 A CN107275614 A CN 107275614A CN 201710494620 A CN201710494620 A CN 201710494620A CN 107275614 A CN107275614 A CN 107275614A
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of MoS2CNT lithium titanate composite anode material, including CNT lithium titanate composite material, and enveloped carbon nanometer tube lithium titanate composite material MoS2.The invention also discloses a kind of MoS2The preparation method of CNT lithium titanate composite anode material, including lithium source, titanium source, CNT be added to the water scattered, obtain solution A；Added into molybdate solution after sulphur source, it is ultrasonically treated to add solution A, obtains solution B；Solution B is handled using liquid phase method, dries, obtains presoma；It will be calcined in presoma protective atmosphere, cooling obtains MoS2CNT lithium titanate composite anode material.The invention also discloses one kind application MoS of the present invention in addition2The lithium ion battery of CNT lithium titanate composite anode material.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, more particularly to MoS2CNT lithium titanate Compound Negative
Pole material and its preparation and lithium battery.
Background technology
At present, electric automobile has turned into alleviation consumption of petroleum and has solved one of effective means of environmental pollution.And develop electricity
The core of motor-car is then safe and efficient secondary battery.At present, in electric car or hybrid electric vehicle it is main using plumbic acid and
Ni-MH battery, because service life is short, easily pollutes environment, is progressively replaced by safe and efficient lithium ion battery.Lithium-ion electric
Pond is a kind of novel secondary energy-storage battery grown up 1990s.Due to high-energy, the long-life, low energy consumption,
The advantages of nuisanceless, memory-less effect and self discharge are small, internal resistance is small, cost performance is high, pollution is few, is widely used in mobile electricity
The fields such as words, notebook computer, video camera, digital camera, electric automobile.
The major obstacle that lithium-ion-power cell is applied to electric automobile is that the security, energy density, power of battery are close
Degree and high power charge-discharge performance, and the key factor for restricting above-mentioned performance is electrode material used in battery.Mesh
Preceding studied lithium-ion-power cell is generally using LiFePO4, nickel-cobalt-manganese ternary material, LiMn2O4 as positive electrode, carbon material
For negative material, although the security performance of above-mentioned three kinds of positive electrodes in itself is preferable, but when battery abnormal condition is used
With electrolyte vigorous reaction can occur for embedding lithium carbon negative pole material, release substantial amounts of heat and imflammable gas, cause battery failure, very
To blast.Never had and obtained effectively with the safety problem for the large-capacity high-power type lithium-ion-power cell that carbon material is negative pole
Solve, its application on electric automobile is seriously constrained, so how to solve the safety issue of lithium-ion-power cell
Through being also the key issue for hindering electric vehicle industrialization as the fundamental issue for perplexing its industrialized development.
Solve the problems, such as the key of security of lithium-ion-power cell with safer, smaller with electrolyte reactivity
Negative material substitutes carbon negative pole material.Lithium titanate (Li4Ti5O12) has lot of advantages as a kind of novel anode material：Zero should
Become, cycle performance is excellent；Higher oxidation-reduction potential (1.5VvsLi), does not react, security is good with conventional electrolyte；
It is environment-friendly, easily prepare, cost is low.But the electrical conductivity of lithium titanate is low, cause that its high rate capability is poor, this is greatly constrained
It is promoted with application, the field especially attracted attention in this whole world of electrokinetic cell, and the high magnification working characteristics of material is to determine its energy
One of key factor of no large-scale commercial application, therefore the high rate capability of lithium titanate is improved as current researcher concern
One of core topic.
The content of the invention
The present invention proposes a kind of MoS2CNT lithium titanate composite anode material and its preparation and lithium battery, it is described multiple
Close negative material high power forthright good, it is ensured that material can fully carry out discharge and recharge under high magnification.
A kind of MoS proposed by the present invention2CNT lithium titanate composite anode material, including CNT lithium titanate are compound
Material, and enveloped carbon nanometer tube lithium titanate composite material MoS2。
Wherein, MoS2As a typical stratiform transient metal sulfide, with high-ratio surface, flexibility of structure etc.
Unique physical and chemical performance, the concern obtained in many fields is greatly increased.The present invention is first by stratiform MoS2It is used as cladding
Materials application passes through first principle in modified carbon nano-tube lithium titanate composite material：Due to stratiform MoS2Cladding, pole
The earth improves the high rate capability of the stability of material interface, effectively enhancing CNT lithium titanate composite material.
First principle is the principle and its basic exercise rule according to atomic nucleus and electronics interaction, with quantum force
Principle is learned, from specific requirement, the algorithm of direct solution Schrodinger equation after some approximate processings, first principle is
Ab iitio, it is not necessary to any parameter, it is only necessary to some basic physical constants, it is possible to obtain the fundamental property of system ground state
Principle.
Preferably, the MoS2In MoS2Shared ratio is 0.5- in CNT lithium titanate composite anode material
5wt%.
A kind of this also disclosed MoS2The preparation method of CNT lithium titanate composite anode material, comprises the following steps：
S1, lithium source, titanium source, CNT be added to the water scattered, obtain solution A；
S2, add after sulphur source into molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；
S3, by solution B using liquid phase method handle, dry, obtain presoma；
S4, will in presoma protective atmosphere calcine, cooling, obtain MoS2CNT lithium titanate composite anode material.
Preferably, in S1, dispersion process is stirred using high-speed mixer, and wherein mixing speed is 1400-1500rpm,
The dispersed with stirring time is 3-5min.
Preferably, in S1, lithium source is lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium phosphate, one kind of lithium hydroxide
Or it is a variety of, titanium source is butyl titanate, tetraisopropyl titanate, tetraethyl titanate, metatitanic acid methyl esters, metatitanic acid, anatase titanium dioxide
One or more in titanium；
Preferably, in S1, the mol ratio of the Ti in Li and titanium source in lithium source is 0.80-0.86：1.
Preferably, in S1, CNT is double-walled carbon nano-tube, multi-walled carbon nanotube, many walls of vacuum high-temperature processing
CNT or graphitized carbon nano pipe；
Preferably, in S1, CNT is in MoS2Proportion is in CNT lithium titanate composite anode material
0.5-3wt%.
Preferably, in S2, molybdate is sodium molybdate or ammonium molybdate, and sulphur source is Cys, thiocarbamide or thioacetyl
Amine；
Preferably, in S2, the concentration of molybdate solution is 0.02-0.07molL；
Preferably, in S2, the amount ratio of the material of sulphur source and molybdate is 5-10：1.
Preferably, in S3, ultrasonic time is 1-2h.
Preferably, in S3, liquid phase method is sol-gel, water (solvent) thermal response or microwave method；
Preferably, in S3, the temperature of sol-gel process is 40-120 DEG C；
Preferably, in S3, the temperature of hydro-thermal reaction is 100-350 DEG C；
Preferably, in S3, the microwave reaction time is 10-90min.
Preferably, in S3, drying means is that heated at constant temperature is dried, rotary evaporation is dried, is spray-dried or is freeze-dried.
Preferably, in S4, calcining heat is 600-900 DEG C, and calcination time is 6-12h；
Preferably, in S4, protective atmosphere is more than one or both of argon gas, nitrogen, helium.
Invention additionally discloses a kind of lithium ion battery, including negative pole, the negative pole includes the MoS2 CNTs titanium
Sour lithium composite negative pole material.
Compared with prior art, the advantage of the invention is that：
1) by CNT lithium titanate composite material Surface coating MoS2, not only increase CNT lithium titanate and answer
The stability of condensation material, and composite negative pole material can be protected not to be corroded, enhance high rate capability.
2) MoS is prepared by In-situ reaction2CNT lithium titanate composite anode material, not only realizes CNT in titanium
Being uniformly distributed in sour lithium material, also achieves MoS2Uniform cladding in CNT lithium titanate, so as to improve metatitanic acid
The high rate capability of lithium.
3) MoS that the present invention is prepared using liquid phase method2CNT lithium titanate composite anode material, preparation process is simple,
Flow is short, and energy consumption is low, and production cost is low.The present invention is by controlling CNT consumption and MoS2Covering amount control composite wood
The quality of each component in material, causes each component is formed on crystalline size to be uniformly distributed by liquid phase method low-temperature treatment presoma,
Reduce material internal intermediate ion and the crystal boundary resistance of electric transmission.
4) MoS of the invention2CNT lithium titanate composite anode material is during high power charging-discharging is carried out, and carbon is received
Mitron provides preferable electronic conduction environment for lithium titanate, improves material high-rate charge-discharge capability；Outer layer stratiform MoS2Uniformly
Clad, on the one hand provides protective layer for CNT lithium titanate composite material, makes what electrode material was not volatilized by electrolyte
HF corrodes, and being on the other hand continuously lithium titanate material by the stability feature of itself provides electronics, it is ensured that material is in high magnification
Under can fully carry out discharge and recharge.
In summary, the present invention is first by stratiform MoS2Surface coating improves the interface performance of lithium titanate, prepares nucleocapsid
Structure MoS2CNT lithium titanate composite material.Stratiform MoS is prepared by In-situ reaction2Enveloped carbon nanometer tube lithium titanate material,
Make stratiform MoS2, CNT and lithium titanate particle three combine closely, fully contact forms more closely knit nucleocapsid knot
Structure, make composite negative pole material high rate capability be improved significantly.Core shell structure MoS prepared by the present invention2CNT metatitanic acid
The method of lithium composite negative pole material, it is easy to form the material that outer layer is uniformly coated, material surface particle and intergranular ion and
The crystal boundary resistance of electric transmission greatly reduces, and composite negative pole material chemical property especially high rate capability is substantially carried
It is high.
Brief description of the drawings
Fig. 1 is MoS proposed by the present invention2The x-ray diffraction pattern of CNT lithium titanate composite anode material.
Fig. 2 is MoS proposed by the present invention2Discharge and recharge of the CNT lithium titanate composite anode material under different multiplying is bent
Line chart.
Embodiment
As shown in Figure 1, 2, Fig. 1 is MoS proposed by the present invention2The X-ray of CNT lithium titanate composite anode material is spread out
Figure is penetrated, Fig. 2 is MoS proposed by the present invention2Charging and discharging curve of the CNT lithium titanate composite anode material under different multiplying
Figure.
Below, technical scheme is described in detail by specific embodiment.
A kind of MoS that the present invention is provided2CNT lithium titanate composite anode material, including CNT lithium titanate are compound
Material, and enveloped carbon nanometer tube lithium titanate composite material MoS2。
The MoS2The preparation method of/CNT/lithium titanate composite anode material, is carried out as follows：
S1 by lithium source, titanium source, CNT mixed dissolution in water, with 1400-5000rpm speed in high-speed mixer
Spend high-speed stirred and disperse 3-5min, obtain solution A；
Wherein, lithium source is one or both of lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium phosphate, lithium hydroxide
More than；Titanium source is butyl titanate, tetraisopropyl titanate, tetraethyl titanate, metatitanic acid methyl esters, metatitanic acid, anatase titania
One or both of more than；CNT is double-walled carbon nano-tube, many wall carbon of multi-walled carbon nanotube, vacuum high-temperature processing are received
It is more than one or both of mitron or graphitized carbon nano pipe；CNT ratio shared in composite negative pole material is
0.5-3wt%.
S2, concentration for 0.02-0.07mol/L molybdate solution in plus sulphur source, sulphur source be Cys, thiocarbamide,
Thioacetamide, molybdate is sodium molybdate or ammonium molybdate, adds solution A, the amount ratio of the wherein material of sulphur source and molybdate is
5-10：1, ultrasonically treated 1-2h is carried out, mixture solution B is obtained；
S3, by solution B using liquid phase method processing after, by drying, obtain presoma；
S4, presoma calcined 6-12 hours in protective atmosphere, cool down, obtain MoS2CNT lithium titanate Compound Negative
Pole material；Wherein, MoS2Shared ratio is 0.5-5wt% in composite negative pole material；Protective atmosphere is argon gas, nitrogen, helium
One or more in gas.
A kind of lithium ion battery that the present invention is provided, including negative pole, the negative pole include the MoS2 CNTs metatitanic acid
Lithium composite negative pole material.
Embodiment 1
A kind of MoS2CNT lithium titanate composite anode material, it is characterised in that compound including CNT lithium titanate
Material, and enveloped carbon nanometer tube lithium titanate composite material MoS2。
Embodiment 2
A kind of MoS2CNT lithium titanate composite anode material, it is characterised in that compound including CNT lithium titanate
Material, and enveloped carbon nanometer tube lithium titanate composite material MoS2.The MoS2In MoS2CNT lithium titanate composite negative pole material
Shared ratio is 0.5-5wt% in material.
Embodiment 3
A kind of MoS2The preparation method of CNT lithium titanate composite anode material, comprises the following steps：
S1, lithium source, titanium source, CNT be added to the water scattered, obtain solution A；
S2, add after sulphur source into molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；
S3, by solution B using liquid phase method handle, dry, obtain presoma；
S4, will in presoma protective atmosphere calcine, cooling, obtain MoS2CNT lithium titanate composite anode material.
Embodiment 4
A kind of MoS2The preparation method of CNT lithium titanate composite anode material, comprises the following steps：
S1, lithium carbonate, butyl titanate, graphitized carbon nano pipe be added to the water scattered, obtain solution A；In lithium source
The mol ratio of Ti in Li and titanium source is 0.80：1, graphitized carbon nano pipe is in MoS2 CNT lithium titanate composite anode materials
Middle proportion is 2.8wt%；
S2, add after Cys into sodium molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；Molybdic acid
The concentration of sodium solution is 0.02molL, and the amount ratio of the material of Cys and sodium molybdate is 10：1；
S3, solution B uses to sol-gel process, treatment temperature is 110 DEG C, and heated at constant temperature is dried, and obtains presoma；
S4, will in presoma blanket of nitrogen calcine, calcining heat be 600 DEG C, calcination time is 12h, cooling, obtain MoS2Carbon
Nanotubed titanic acid lithium composite negative pole material.
Embodiment 5
A kind of MoS2The preparation method of CNT lithium titanate composite anode material, comprises the following steps：
S1, many wall CNTs for handling lithium carbonate, lithium nitrate, tetraisopropyl titanate, tetraethyl titanate, vacuum high-temperature
It is added to the water scattered, obtains solution A；The mol ratio of the Ti in Li and titanium source in lithium source is 0.86：1；Vacuum high-temperature processing
Many wall CNTs are in MoS2Proportion is 1wt% in CNT lithium titanate composite anode material；
S2, add after thioacetamide into ammonium molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；Molybdic acid
The concentration of ammonium salt solution is 0.07molL, and the amount ratio of the material of thioacetamide and ammonium molybdate is 5：1；
S3, by solution B using hydro-thermal reaction handle, reaction temperature be 100 DEG C, rotary evaporation dry, obtain presoma；
S4, will in presoma helium-atmosphere calcine, calcining heat be 900 DEG C, calcination time is 6h, cooling, obtain MoS2Carbon
Nanotubed titanic acid lithium composite negative pole material.
Embodiment 6
A kind of MoS2The preparation method of CNT lithium titanate composite anode material, comprises the following steps：
S1, lithium acetate, tetraethyl titanate, metatitanic acid methyl esters, metatitanic acid, anatase titania, double-walled carbon nano-tube added
Enter in water and disperse, obtain solution A；The mol ratio of the Ti in Li and titanium source in lithium source is 0.82：1；Double-walled carbon nano-tube exists
MoS2Proportion is 3wt% in CNT lithium titanate composite anode material；
S2, add after thiocarbamide into ammonium molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；Ammonium molybdate solution
Concentration be 0.04molL, the amount ratio of the material of thiocarbamide and ammonium molybdate is 6：1；
S3, by solution B using microwave method handle 80min, spray drying, obtain presoma；
S4, will in presoma blanket of nitrogen calcine, calcining heat be 700 DEG C, calcination time is 8h, cooling, obtain MoS2Carbon
Nanotubed titanic acid lithium composite negative pole material.
Embodiment 7
A kind of MoS2The preparation method of CNT lithium titanate composite anode material, comprises the following steps：
S1, lithium phosphate, lithium hydroxide, metatitanic acid methyl esters, multi-walled carbon nanotube be added to the water scattered, obtain solution A；Lithium source
In Li and titanium source in Ti mol ratio be 0.84：1；Multi-walled carbon nanotube is in MoS2CNT lithium titanate composite negative pole material
Proportion is 0.5wt% in material；
S2, add after Cys into sodium molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；Molybdic acid
The concentration of sodium solution is 0.06molL, and the amount ratio of the material of Cys and sodium molybdate is 8：1；
S3, by solution B using solvent thermal reaction handle, reaction temperature be 300 DEG C, freeze-drying, obtain presoma；
S4, will in presoma argon atmospher calcine, calcining heat be 800 DEG C, calcination time is 10h, cooling, obtain MoS2Carbon
Nanotubed titanic acid lithium composite negative pole material.
Embodiment 8
A kind of MoS2CNT lithium titanate composite anode material, including CNT lithium titanate composite material, and cladding
The MoS of CNT lithium titanate composite material2, preparation method comprises the following steps：
S1, by lithium hydroxide, titanium dioxide, multi-walled carbon nanotube mixed dissolution in water, in high-speed mixer with
4000rpm speed high-speed stirred disperses 3min, obtains solution A, wherein elemental lithium and titanium elements molar ratio are 0.82:1, carbon
Ratio of the nanotube in composite negative pole material is 0.5wt%.
S2, concentration for 0.05mol/L sodium molybdate solution in add Cys, add solution A, wherein, L-
The amount ratio of the material of cysteine and sodium molybdate is 5：1, ultrasonically treated 1h, obtain solution B, MoS2 institutes in composite negative pole material
The ratio accounted for is 0.5wt%；
S3, solution B poured into the stainless steel cauldron that 50mL polytetrafluoroethylene (PTFE) is inner bag, be placed in after sealing in micro-wave oven
180 DEG C of insulation 30min, obtain presoma.
S4, by presoma through centrifugation, washing, heated at constant temperature dry, obtained compound is 700 DEG C in blanket of nitrogen
Calcining 8 hours, cooling, obtains MoS2CNT lithium titanate composite anode material.
A kind of lithium ion battery, including negative pole, the negative pole include above-mentioned MoS2CNT lithium titanate composite negative pole material
Material.
The a curves of reference picture 1, XRD structured testings show that this composite negative pole material is pure phase spinel type lithium titanate.Ginseng
Show according to Fig. 2 high rate performance test results, 0.2C charge specific capacities are 169.3mAh/g, 1C charge specific capacities are 166.1mAh/
G, 5C charge specific capacity are 153.6mAh/g, and 8C charge specific capacities are 135.8mAh/g, show excellent high rate performance.
Embodiment 9
A kind of MoS2CNT lithium titanate composite anode material, including CNT lithium titanate composite material, and cladding
The MoS of CNT lithium titanate composite material2, preparation method comprises the following steps：
S1, by lithium nitrate, metatitanic acid, multi-walled carbon nanotube mixed dissolution in water, with 3000rpm in high-speed mixer
Speed high-speed stirred disperse 5min, obtain solution A, wherein elemental lithium and titanium elements molar ratio are 0.84:1, CNT
Ratio in the composite is 0.5wt%.
S2, concentration for 0.06mol/L sodium molybdate solution in add Cys, add solution A, wherein, L-
The amount ratio of the material of cysteine and sodium molybdate is 5：1, ultrasonically treated 1h, obtain solution B, MoS2 institutes in composite negative pole material
The ratio accounted for is 1.5wt%；
S3, solution B poured into the stainless steel cauldron that 50mL polytetrafluoroethylene (PTFE) is inner bag, forced air drying is placed in after sealing
In case, reacted 2 hours under the conditions of 120 DEG C, obtain presoma；
S4, presoma naturally cooled to after room temperature, by centrifuging, washing, be freeze-dried in temperature 50 C, will
To compound in nitrogen 700 DEG C calcine 7 hours, cooling, obtain MoS2CNT lithium titanate composite anode material.
A kind of lithium ion battery, including negative pole, the negative pole include above-mentioned MoS2CNT lithium titanate composite negative pole material
Material.
The b curves of reference picture 1, XRD structured testings show that this composite negative pole material is pure phase spinel type lithium titanate.Times
Rate the performance test results show that 0.2C charge specific capacities are 170.3mAh/g, and 1C charge specific capacities are 167.1mAh/g, 5C chargings
Specific capacity is 153.9mAh/g, and 8C charge specific capacities are 136.8mAh/g, show excellent high rate performance.
Embodiment 10
A kind of MoS2CNT lithium titanate composite anode material, including CNT lithium titanate composite material, and cladding
The MoS of CNT lithium titanate composite material2, preparation method comprises the following steps：
S1, by lithium acetate, tetraethyl titanate, double-walled carbon nano-tube mixed dissolution in water, in high-speed mixer with
4500rpm speed high-speed stirred disperses 5min, obtains solution A, wherein elemental lithium and titanium elements molar ratio are 0.85:1, carbon
The ratio of nanotube in the composite is 0.5wt%.
S2, concentration for 0.05mol/L ammonium molybdate solution in add Cys, add solution A, wherein, L-
The amount ratio of the material of cysteine and ammonium molybdate is 7：1, ultrasonically treated 1h, obtain solution B, MoS2 institutes in composite negative pole material
The ratio accounted for is 0.5wt%；
S3, with ammoniacal liquor by the pH value of solution B regulation to 5.6, stirred 2 hours at 30 DEG C, then heat to 90 DEG C, stirring is extremely
Gel, wet gel is changed into xerogel presoma by drying；
S4, by xerogel presoma in nitrogen 750 DEG C calcine 8 hours, cooling, obtain MoS2CNT lithium titanate is answered
Close negative material.
A kind of lithium ion battery, including negative pole, the negative pole include above-mentioned MoS2CNT lithium titanate composite negative pole material
Material.
The c curves of reference picture 1, XRD structured testings show that this composite negative pole material is pure phase spinel type lithium titanate.Times
Rate the performance test results show that 0.2C charge specific capacities are 169.8mAh/g, and 1C charge specific capacities are 166.9mAh/g, 5C chargings
Specific capacity is 154.2mAh/g, and 8C charge specific capacities are 135.1mAh/g, show excellent high rate performance.
Embodiment 11
A kind of MoS2CNT lithium titanate composite anode material, including CNT lithium titanate composite material, and cladding
The MoS of CNT lithium titanate composite material2, preparation method comprises the following steps：
S1, by lithium hydroxide, metatitanic acid methyl esters, double-walled carbon nano-tube mixed dissolution in water, in high-speed mixer with
3500rpm speed high-speed stirred disperses 5min, obtains solution A, wherein elemental lithium and titanium elements molar ratio are 0.84:1, carbon
Nanotube ratio shared in composite negative pole material is 1.5wt%；
S2, in concentration 0.06mol/L ammonium molybdate solution Cys are added, add solution A, wherein, L- half
The amount ratio of the material of cystine and ammonium molybdate is 8：1, ultrasonically treated 2h, obtain solution B, and MoS2 is shared in composite negative pole material
Ratio be 0.5wt%；
S3, solution B poured into 50mL using polytetrafluoroethylene (PTFE) as the stainless steel cauldron of inner bag, micro-wave oven is placed in after sealing
In 180 DEG C be incubated 15 minutes, obtain presoma；
S4, by presoma through centrifugation, washing, heated at constant temperature dry, by obtained compound 850 DEG C in argon gas
Calcining 7 hours, cooling, obtains MoS2CNT lithium titanate composite anode material.
A kind of lithium ion battery, including negative pole, the negative pole include above-mentioned MoS2CNT lithium titanate composite negative pole material
Material.
The d curve XRD structured testings of reference picture 1 show that this composite negative pole material is pure phase spinel type lithium titanate.Multiplying power
The performance test results show that 0.2C charge specific capacities are 170.8mAh/g, and 1C charge specific capacities are 167.6mAh/g, 5C charge ratios
Capacity is 153.9mAh/g, and 8C charge specific capacities are 135.7mAh/g, show excellent high rate performance.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of MoS2CNT lithium titanate composite anode material, it is characterised in that including CNT metatitanic acid lithium composite
Material, and enveloped carbon nanometer tube lithium titanate composite material MoS2。
2. MoS according to claim 12CNT lithium titanate composite anode material, it is characterised in that the MoS2
MoS2Shared ratio is 0.5-5wt% in CNT lithium titanate composite anode material.
3. a kind of MoS according to claim 1 or 22The preparation method of CNT lithium titanate composite anode material, it is special
Levy and be, comprise the following steps：
S1, lithium source, titanium source, CNT be added to the water scattered, obtain solution A；
S2, add after sulphur source into molybdate solution, it is ultrasonically treated to add solution A, obtains solution B；
S3, by solution B using liquid phase method handle, dry, obtain presoma；
S4, will in presoma protective atmosphere calcine, cooling, obtain MoS2CNT lithium titanate composite anode material.
4. MoS according to claim 32The preparation method of CNT lithium titanate composite anode material, it is characterised in that
In S1, lithium source is lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium phosphate, the one or more of lithium hydroxide, and titanium source is titanium
Sour four butyl esters, tetraisopropyl titanate, tetraethyl titanate, metatitanic acid methyl esters, metatitanic acid, one kind in anatase titania or many
Kind；Preferably, the mol ratio of the Ti in the Li and titanium source in lithium source is 0.80-0.86：1.
5. MoS according to claim 32The preparation method of CNT lithium titanate composite anode material, it is characterised in that
In S1, CNT is double-walled carbon nano-tube, multi-walled carbon nanotube, many wall CNTs of vacuum high-temperature processing or graphitization
CNT；Preferably, CNT is in MoS2Proportion is 0.5- in CNT lithium titanate composite anode material
3wt%.
6. MoS according to claim 32The preparation method of CNT lithium titanate composite anode material, it is characterised in that
In S2, molybdate is sodium molybdate or ammonium molybdate, and sulphur source is Cys, thiocarbamide or thioacetamide；Preferably, molybdate
The concentration of solution is 0.02-0.07molL；Preferably, the amount ratio of the material of sulphur source and molybdate is 5-10：1.
7. MoS according to claim 32The preparation method of CNT lithium titanate composite anode material, it is characterised in that
In S3, liquid phase method is sol-gel, water (solvent) thermal response or microwave method；Preferably, the temperature of sol-gel process is 40-
120℃；Preferably, the temperature of hydro-thermal reaction is 100-350 DEG C；Preferably, the microwave reaction time is 10-90min.
8. MoS according to claim 32The preparation method of CNT lithium titanate composite anode material, it is characterised in that
In S3, drying means is that heated at constant temperature is dried, rotary evaporation is dried, is spray-dried or is freeze-dried.
9. MoS according to claim 32The preparation method of CNT lithium titanate composite anode material, it is characterised in that
In S4, calcining heat is 600-900 DEG C, and calcination time is 6-12h；Preferably, protective atmosphere is in argon gas, nitrogen, helium
One or more.
10. a kind of lithium ion battery, including negative pole, it is characterised in that the negative pole includes the MoS described in claim 12Carbon is received
Mitron lithium titanate composite anode material.
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Application publication date: 20171020 |