CN109980223A - A kind of lithium titanate/carbon/carbon nano tube composite material and preparation method and application - Google Patents
A kind of lithium titanate/carbon/carbon nano tube composite material and preparation method and application Download PDFInfo
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- CN109980223A CN109980223A CN201711453113.7A CN201711453113A CN109980223A CN 109980223 A CN109980223 A CN 109980223A CN 201711453113 A CN201711453113 A CN 201711453113A CN 109980223 A CN109980223 A CN 109980223A
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation methods of lithium titanate/carbon/carbon nano tube composite material; lithium titanate is added in Catalyst precursor solutions; mixture is dried to obtain at 50 ~ 120 DEG C after mixing; by the mixture first under air atmosphere in 400 ~ 800 DEG C of 1 ~ 4h of calcining; then 30 ~ 240min is heated at 500 ~ 800 DEG C in reducing atmosphere; carbon-source gas and isothermal reaction 1 ~ for 24 hours are passed through at 700 ~ 1200 DEG C again; then it cools down under inert gas protection, removal catalyst obtains the lithium titanate/carbon/carbon nano tube composite material.Lithium titanate/carbon nano tube composite cathode material prepared by the present invention, reduce the internal resistance of material, it improves the electric conductivity of material and then improves its fast charging and discharging ability and cyclical stability under high current, lay a good foundation for lithium titanate anode material in the practical application of lithium ion battery.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of lithium titanate/carbon/carbon nano tube composite material and its preparation
Methods and applications.
Background technique
Lithium ion battery electrode material has become the research hotspot of whole world battery circle.Negative electrode material is as lithium-ion electric
The important component in pond, the superiority and inferiority of performance directly influence the superiority and inferiority of battery overall performance.In recent years, for lithium-ion electric
The research of pond negative electrode material is mainly concentrated in the energy density for improving material, and is effectively reduced in first charge-discharge not
Reversible capacity loss and the cyclical stability for improving material, and reduce production cost.
Currently, carbon material is still the main source of commercial lithium-ion batteries negative electrode material.But carbon material is steady in circulation
There are still many defects for qualitative, security performance etc.: insert lithium after carbon negative pole material current potential and lithium metal current potential very close to,
It easily forms Li dendrite and causes short circuit;Many electrolyte are unstable under this current potential, can decompose and produce flammable in battery charging
Property gas etc..As the hot spot of current cell materials research, spinel lithium titanate (Li4Ti5O12) not only have in charge and discharge
The characteristic of " zero strain " in journey, also as its spinel structure can provide the three-dimensional channel that lithium ion quickly moves, and has
It is at low cost, potential plateau is wide, intercalation potential is high (1.55V vs Li/Li), have extended cycle life, that surface does not form passivating film etc. is excellent
Point is ideal lithium ion battery negative material.But Li4Ti5O12Conductive capability it is very poor, belong to typical insulator
(electronic conductivity < 10-13 Scm-1), the serious polarization in high current charge-discharge, or even amount of heat is generated, capacity attenuation is fast,
And become the one of the major reasons for hindering it to be widely used.Improve spinelle Li4Ti5O12Electronic conductivity improves its multiplying power
Performance becomes Li4Ti5O12The key of practicalization, becomes to Li4Ti5O12The main flow direction of research.It is forthright again usually to improve it
There are three types of the method for energy is usual: first is that synthesis has the Li of special construction or nano-scale4Ti5O12;Second is that by Li4Ti5O12
Doping improves its conductive capability;Third is that coating highly conductor phase on its surface.
Carbon nanotube is by graphite atomic monolayer around the hollow pipe being coaxially entwined.The outermost electronics of carbon atom passes through
SP2 hydridization and three adjacent carbon atoms form stable key, and remaining one electronically forms the big pi bond of delocalization.Thus carbon nanometer
There are a large amount of free electrons in tube wall, have good electric conductivity, are a kind of good conductive agents.Chinese patent is (open
Number: CN1770515A) disclose a kind of method with carbon nanotube directly as lithium ion battery plus-negative plate material conductive agent.But
Be this method in actual application, carbon nanotube is difficult to disperse, reunite it is very serious.Chinese patent (publication number:
CN101714627A a kind of method with ball milling) is disclosed by the carbon nano tube-doped method to positive electrode surface.This side
In the composite material of method preparation, the contact defective tightness between carbon nanotube and material of main part, carbon nanotube is in bulk material surface
Dispersion it is uneven, the excellent electric conductivity of carbon nanotube cannot be played.
Application publication number CN106207132A discloses a kind of lithium titanate/carbon fiber/carbon nanotube/graphene quaternary composite wood
The preparation method of material comprising following preparation step:
1) lithium carbonate load carbon fiber and carbon nano-tube catalyst: by the carbon nano-tube catalyst of 1 parts by weight and 100 ~ 500 weight
The mass fraction of part is solution of 5 ~ 20% citric acid solutions mixing as carbon nano-tube catalyst precursor, by 5 ~ 20 parts by weight
Carbon fiber impregnates 1 ~ 3h in the above solution, and the carbonic acid powder for lithium that 50 ~ 500 parts by weight are then added impregnates 1 ~ 3h, later 200
1 ~ 5h is kept the temperature under the conditions of ~ 500 DEG C, obtains the lithium titanate that load has carbon fiber and carbon nano-tube catalyst precursor;
2) the resulting load of step 1) chemical vapor infiltration in-situ preparation carbon nanotube: there are into carbon fiber and carbon nanometer pipe catalytic
The lithium titanate of agent precursor heats up 600 ~ 1200 DEG C in atmosphere of inert gases, keeps temperature-resistant, is passed through 60 ~ 300min of hydrogen, with
Afterwards at 600 ~ 1200 DEG C, keeps temperature-resistant, be passed through 60 ~ 300min of carbon-source gas, then cool down under inert gas protection
To room temperature, lithium titanate/carbon fiber/carbon nanotube trielement composite material is obtained;
3) in-situ reducing graphene oxide: lithium titanate prepared by step 2/carbon fiber/carbon nanotube trielement composite material is used
Graphene oxide solution impregnates 1 ~ 3h, takes out lithium titanate/carbon fiber/carbon nanotube trielement composite material after impregnating, in 200 ~
300 DEG C, 1 ~ 5h is kept the temperature under inert gas shielding, be cooled to room temperature, lithium carbonate/carbon fiber/carbon of graphene oxide must be loaded
Nanotube trielement composite material;Above-mentioned load is had to the trielement composite material of graphene oxide, in 800 ~ 1200 DEG C, inert gas
Heat preservation is lower to keep the temperature 1 ~ 5h, is finally cooled to room temperature, obtains lithium titanate/carbon fiber/carbon nanotube/graphene quaternary composite material.
But lithium titanate is dissolved in the patent using citric acid solution, and citric acid solution is aqueous solution, metatitanic acid
Lithium stability in aqueous solution is poor.In addition, the quaternary composite material prepare it is relatively complicated, although compared with the carbon coating one of multilayer
The tap density determined the electric conductivity that material can be improved in degree, but will affect lithium titanate material itself, and then reduce the energy of material
Metric density;The material with charge-discharge magnification be 2.0C/2.0C carry out 2000 times circulation, test capacity conservation rate be 92.7 ~
93.4%。
Summary of the invention
It is all good technical problem to be solved by the invention is to provide a kind of high rate performance and cycle performance and preparation method is simple
Single lithium titanate/carbon/carbon nano tube composite material and preparation method and application.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
It is an object of the present invention to provide a kind of preparation methods of lithium titanate/carbon/carbon nano tube composite material, and lithium titanate is added
In Catalyst precursor solutions, it is dried to obtain mixture at 50 ~ 120 DEG C after mixing, by the mixture first in air atmosphere
In 400 ~ 800 DEG C of 1 ~ 4h of calcining under enclosing, 30 ~ 240min is then heated at 500 ~ 800 DEG C in reducing atmosphere, then 700 ~
It is passed through carbon-source gas and isothermal reaction 1 ~ for 24 hours at 1200 DEG C, then cools down under inert gas protection, removal catalyst obtains institute
The lithium titanate/carbon/carbon nano tube composite material stated.
Preferably, the catalyst precursor in the Catalyst precursor solutions be the nitrate of iron, iron acetate,
The sulfate of iron, other salt of iron, ferrous nitrate, ferrous acetate, ferrous sulfate, other ferrous salt, cobalt
Nitrate, the acetate of cobalt, the sulfate of cobalt, other salt of cobalt, the nitrate of nickel, the acetate of nickel, the sulfate of nickel, nickel
One of other salt or a variety of.
Preferably, the solvent in the Catalyst precursor solutions is methanol, ethyl alcohol or other alcohols.
Preferably, the lithium titanate is according to the mass ratio of titanium and catalyst with the Catalyst precursor solutions
10:0.1 ~ 1 feeds intake, further preferably 10:0.5 ~ 1, more preferably 10:0.8 ~ 1.
Wherein, which refers to iron, ferrous iron, cobalt or nickel.
Preferably, the crystal habit of the lithium titanate is positive octahedral spinel structure.
Preferably, the lithium titanate is one or more of powder, particle, tubulose, fiber, rodlike, sheet, microballoon
Mixing.
Preferably, the reducibility gas is hydrogen or carbon monoxide, and the carbon-source gas is methane, ethane, second
One or more of alkynes, aromatic hydrocarbon.
Preferably, the inert atmosphere is one or more of nitrogen, argon gas, helium.
Preferably, the heating rate for controlling 5 ~ 20 DEG C/min is warming up to 800 ~ 1200 DEG C.
Preferably, the flow velocity that is passed through for controlling the carbon-source gas is 10 ~ 200 mL/min, be passed through the time be 10 ~
240min。
It is further preferred that the carbon-source gas be passed through flow velocity be 60 ~ 80 mL/min, be passed through the time be 30 ~
60min。
Preferably, the mixed specific method is 20 ~ 40min of first ultrasonic disperse, then stirs 1 ~ 2h.
Preferably, the temperature being dried is 80 ~ 100 DEG C.
Preferably, drying time is 1 ~ 48h, further preferably 5 ~ for 24 hours, more preferably 10 ~ 14h.
Preferably, the reactant after drying grinds 30 ~ 60min and obtains the mixture.
Preferably, the temperature for carrying out the calcining is 400 ~ 600 DEG C.
Preferably, it is identical as the temperature of calcining is carried out to be passed through the temperature that the reducing atmosphere is reacted.
Preferably, being passed through the carbon-source gas and carrying out the temperature of isothermal reaction is 700 ~ 800 DEG C.
It is a further object to provide lithium titanate/carbon/carbon nano tube composite woods made from the preparation method described in one kind
Material.
Third object of the present invention is to provide the lithium titanate/carbon/carbon nano tube composite materials described in one kind in lithium ion battery
Cathode in application.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
The present invention forms solution using catalyst precursor, and then lithium titanate is added in solution, dries after mixing;It is this
Hybrid mode is directly added into metal simple-substance catalyst more evenly than common, and the carbon nanotube distribution of subsequent growth is also more uniform;
Catalyst-loaded using lithium titanate, the mode of situ catalytic growth introduces carbon nanotube, than the carbon nanotube directly adulterated
Have the characteristics that be uniformly mixed and binding force is strong;
It is controlled by the global optimization of preparation process, the carbon nanotube of lithium titanate material surface growth forms the netted of intersection, has
Beneficial to improving the electric conductivity of material entirety and the stability of structure;And carbon nanotube has excellent heating conduction, promotes battery
Heat dissipation in use process enhances battery security;
Lithium titanate/carbon nano tube composite cathode material prepared by the present invention reduces the internal resistance of material, improves the conduction of material
Property so improve its fast charging and discharging ability and cyclical stability under high current, be lithium titanate anode material in lithium ion
The practical application of battery is laid a good foundation.
Detailed description of the invention
Fig. 1 is the TEM figure of comparative example blank lithium titanate powder of the present invention.
Fig. 2 is the TEM figure of composite negative pole material prepared by the embodiment of the present invention 1.
Fig. 3 is the half of composite negative pole material (LTO & CNT) He Yichun lithium titanate (LTO) prepared by the embodiment of the present invention 1
The 3C cycle performance figure of battery;
Fig. 4 is composite negative pole material (B is marked in figure) He Yichun lithium titanate prepared by the embodiment of the present invention 2 (A is marked in figure)
Half-cell 10C cycle performance figure;
Fig. 5 is composite negative pole material (B is marked in figure) He Yichun lithium titanate prepared by the embodiment of the present invention 2 (A is marked in figure)
Half-cell 3C cycle performance figure;
Fig. 6 is composite negative pole material (B is marked in figure) He Yichun lithium titanate prepared by the embodiment of the present invention 2 (A is marked in figure)
Half-cell cyclic voltammetry curve figure;
Fig. 7 is composite negative pole material (B is marked in figure) He Yichun lithium titanate prepared by the embodiment of the present invention 2 (A is marked in figure)
Half-cell ac impedance spectroscopy.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.If not special herein
Illustrate, " % " representation quality percentage.
Comparative example
Fig. 1 is shown in blank lithium titanate powder material, no modification.
Embodiment 1
Lithium titanate/carbon nano tube composite cathode material is prepared by the following method in the present embodiment, specific steps are as follows:
(1) a certain amount of ferrous nitrate is weighed according to the amount of mass ratio Ti:Fe=10:1, is placed it in and is dissolved in ethyl alcohol in beaker
In solvent, solution is formed;The graininess lithium titanate powder for weighing metering ratio pours into solution, and ultrasonic disperse stirred 1- after 30 minutes
Mixed liquor is put into baking oven in 80 DEG C of dry 12h by 2h.
(2) step (1) obtained dried powder is put into hand-ground 30 minutes to 60 minutes in mortar, makes it sufficiently
It is uniformly mixed;It is placed in tube furnace after 600 DEG C of calcining 2h, is passed through hydrogen reducing;Then with 60 mL/min stream at 800 DEG C
Speed is passed through acetylene gas 1h, keeps the temperature 6h under an argon atmosphere, takes out after being cooled to room temperature, with being washed with water after pickling, drying and grinding
After obtain lithium titanate/carbon nano tube composite cathode material.The electron microscope of composite material is shown in Fig. 2.It can be seen from the figure that being grown in
The carbon nanotube on lithium titanate particle surface forms a close conductive network across;With blank LTO at 3C loop test
As can be seen that composite property is obviously improved (Fig. 3).
Embodiment 2
Lithium titanate/carbon nano tube composite cathode material is prepared by the following method in the present embodiment, specific steps are as follows:
(1) a certain amount of nickel acetate is weighed according to the amount of mass ratio Ti:Ni=10:1, places it in beaker that be dissolved in ethyl alcohol molten
In agent, green transparent solution is formed;The lithium titanate powder for weighing metering ratio pours into solution, and ultrasonic disperse stirred 1- after 30 minutes
Mixed liquor is put into baking oven in 100 DEG C of dry 12h by 2h.
(2) step (1) obtained dried powder is put into hand-ground 30 minutes to 60 minutes in mortar, makes it sufficiently
It is uniformly mixed;It is placed in tube furnace and is passed through hydrogen reducing after 400 DEG C of calcining 2h;Then with 80 mL/min flow velocitys at 700 DEG C
6h is kept the temperature under an argon atmosphere after being passed through acetylene gas 30min, is taken out after being cooled to room temperature, and lithium titanate/carbon is obtained after drying and grinding
Nanotube composite negative pole material.
(3) button half-cell is made in above-mentioned sample as follows: with negative electrode material: acetylene black: PVDF=8:1:1's
Quality compares mix.Gained ingredient mixed pulp in N-Methyl pyrrolidone solvent, after film, drying, tabletting and punching
It is put into glove box and assembles, be to electrode assembling into 2032 type button cells with metal lithium sheet.
It is recycled within 2500 weeks under blue electric battery testing instrument blank testing sample and composite material 10C discharge performance and 3C;Electricity
The cyclic voltammetry curve and ac impedance spectroscopy for the half-cell that chem workstation measures.
Test result is shown, compared with pure lithium titanate, 10C discharge capacity composite material is obviously excellent;3C multiplying power 2500
After all long circulatings, composite material capacity still has 93% or so conservation rate;Cyclic voltammetry curve can be seen that composite material polarizes
Reduce, peak area increase has corresponded to the increase of capacity;Ac impedance spectroscopy can be seen that the internal resistance of composite material reduces, electric conductivity
It is improved significantly, has established its fast charging and discharging ability and cyclical stability as well as lithium-ion electric under high current
The practicability of pond negative electrode material.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium titanate/carbon/carbon nano tube composite material, it is characterised in that: complex catalyst precursor is added in lithium titanate
In liquid solution, be dried to obtain mixture at 50 ~ 120 DEG C after mixing, by the mixture first under air atmosphere in 400 ~
Then 800 DEG C of 1 ~ 4h of calcining heat 30 ~ 240min at 500 ~ 800 DEG C in reducing atmosphere, then lead at 700 ~ 1200 DEG C
Enter carbon-source gas and isothermal reaction 1 ~ for 24 hours, then cools down under inert gas protection, removal catalyst obtains the metatitanic acid
Lithium/carbon nano tube compound material.
2. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to claim 1, it is characterised in that: described
Catalyst precursor in Catalyst precursor solutions be the nitrate of iron, the acetate of iron, the sulfate of iron, iron other
Salt, ferrous nitrate, ferrous acetate, ferrous sulfate, other ferrous salt, the nitrate of cobalt, cobalt acetate,
The sulfate of cobalt, other salt of cobalt, the nitrate of nickel, the acetate of nickel, the sulfate of nickel, nickel one of other salt or more
Kind.
3. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to claim 1, it is characterised in that: described
Solvent in Catalyst precursor solutions is methanol, ethyl alcohol or other alcohols.
4. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to any one of claim 1 to 3, feature
Be: the lithium titanate is the progress of 10:0.1 ~ 1 according to the mass ratio of titanium and catalyst with the Catalyst precursor solutions
It feeds intake.
5. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to claim 1, it is characterised in that: described
The crystal habit of lithium titanate is positive octahedral spinel structure, and the lithium titanate is powder, particle, tubulose, fiber, stick
The mixing of one or more of shape, sheet, microballoon.
6. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to claim 1, it is characterised in that: described
Reducibility gas is hydrogen or carbon monoxide, and the carbon-source gas is one of methane, ethane, acetylene, aromatic hydrocarbon or several
Kind, the inert atmosphere is one or more of nitrogen, argon gas, helium.
7. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to claim 1, it is characterised in that: control 5 ~
The heating rate of 20 DEG C/min is warming up to 800 ~ 1200 DEG C.
8. the preparation method of lithium titanate/carbon/carbon nano tube composite material according to claim 1, it is characterised in that: control institute
The flow velocity that is passed through for the carbon-source gas stated is 10 ~ 200 mL/min, and being passed through the time is 10 ~ 240min.
9. a kind of lithium titanate/carbon/carbon nano tube composite material as made from preparation method described in any item of the claim 1 to 8.
10. a kind of lithium titanate/carbon/carbon nano tube composite material answering in the cathode of lithium ion battery as claimed in claim 9
With.
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CN110416537B (en) * | 2019-08-02 | 2022-05-31 | 广东东岛新能源股份有限公司 | Lithium titanate composite negative electrode material, preparation method thereof and lithium ion battery |
CN110429324A (en) * | 2019-08-05 | 2019-11-08 | 安徽相源新能源有限公司 | A kind of preparation method of the modified compound lithium cell of high capacity |
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