CN106784693A - A kind of surface has the preparation method of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating layer - Google Patents
A kind of surface has the preparation method of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating layer Download PDFInfo
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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
- 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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/48—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
There is the new method of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating layer the invention discloses a kind of surface.The method comprises the following steps：By nano-TiO2Complete wetting is in the easy volatile solvent dissolved with oxidant；The TiO of attachment oxidant is obtained after separation2Powder is placed in that the TiO that polypyrrole is coated is obtained in pyrroles's steam2Solid powder；Above-mentioned powder is sufficiently mixed with lithium salts and required doped metal salt in proportion carries out the high temperature anneal under protective atmosphere, that is, the nano lithium titanate electrode material of richness nitrogen surface substantially uniformity carbon coating is obtained.This method is by gas-phase polymerization combination high-temperature roasting, TiO2Surface polypyrrole is coated completely, and fired carbonization forms porous carbon film, intercepts the growth of lithium titanate particle diameter, forms the uniform nano lithium titanate electrode material for coating of minimum particle diameter, thickness of thin and carbon.The material shows excellent electrochemistry high rate performance, and Processes and apparatus requirement is simple, and low cost is adapted to large-scale production.
Description
Technical field
The present invention relates to the preparation method of battery electrode material, the rich nitrogen nano lithium titanate of particularly a kind of uniform carbon coating
The preparation method of electrode material, belongs to battery material technical field.
Background technology
Under current fossil energy crisis and the increasingly serious background of environmental pollution, reproducible clean energy resource meet the tendency of and
It is raw, also drive developing rapidly for electrochemical energy storage technology simultaneously.In electrochemical storage device, lithium ion battery is because with height
Energy density (120~200Whkg-1), long circulation life, the advantage such as memory-less effect, have been widely used and set in portable electronic
In standby, and it is expected to break through material bottleneck, improves high rate performance and security performance, applies in electronic (or hybrid power) automobile, newly
The fields such as energy energy storage.Therefore the security and high power performance of battery material turn into the most critical of electrochemical energy storing device development
Factor.In battery material, spinel-type Li-Ti-O ternary system compound-materials, particularly nLi/nTi=4/5's
Li4Ti5O12Material, because of its unique structure and performance, it is considered to be the outstanding time of current alternative graphite mould carbon negative pole material
Select one of negative material.Additionally, unit cell volume has almost no change during the insertion and deintercalation of lithium, therefore with excellent
Cycle performance.But, micron or submicron order Li that traditional high-temperature solid phase reaction method is obtained4Ti5O12Lithium ion diffusion speed
Rate (~10-9cm2s-1) and electronic conductivity (~10-13Scm-1) all very low, which prevent Li4Ti5O12In high-power electrochemical storage
Application in energy system.
Reduce Li4Ti5O12Particle diameter is nanoscale, can improve lithium ion conduction dynamics so as to improve lithium ion and expand calculation
Speed, coating method by metal-doped or conductive material (such as conductive carbon material) can improve its electric conductivity.But research
Show to reduce Li simply4Ti5O12Particle diameter a series of problem occurs in actual applications to nanoscale, such as it is increased
Specific surface area can strengthen the side reaction with electrolyte, have a strong impact on cycle life；Additionally, Li4Ti5O12Li insertion extraction current potential ratio
(relative to lithium metal 1.5V) higher, electrolyte is not easy to decompose production SEI diaphragms under this current potential, causes metatitanic acid lithium dimer
With electrolyte directly contact, wherein Ti transition metal atoms to electrolyte have decompose catalytic action cause flatulence.Lithium titanate
Electrode flatulence problem also turns into industrial quarters difficult point urgently to be resolved hurrily.Research shows that lithium titanate coated with carbon bed can play obstruct
The effect of lithium titanate and electrolyte directly contact, so that effectively suppress flatulence produce, but, carbon coating layer needs completely, uniformly
Thickness is moderate, this requirement lithium titanate it is industrially prepared on be very big challenge.
The present invention proposes a kind of preparation side of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating based on above-mentioned consideration
Method.The method can be good at controlling the thickness of carbon coating layer, and because be using the gas-phase polymerization principle of gas molecule, bag
The uniformity of coating is also very high.It is emphasized that using the polypyrrole of high nitrogen content as carbon source, synthesizing in pyrolytic
Cheng Zhong, N atom are combined with C and Ti atoms, formed electron cloud, so as to get uniform carbon coating rich nitrogen nano barium titanate lithium electrode
Show extraordinary high rate capability.
The rich nitrogen nano lithium titanate combination electrode material of uniform carbon coating is prepared using gas-phase polymerization combination high―temperature nuclei process
The method of material has no report.
The content of the invention
A kind of method preparation easy to operate, low cost is proposed it is an object of the invention to be directed to above-mentioned technical barrier uniformly
The rich nitrogen nano lithium titanate combination electrode material of carbon coating.The method is by gas-phase polymerization combination high-temperature roasting, TiO2Gather on surface
Pyrroles's cladding is complete, and fired carbonization forms porous carbon film, intercepts the growth of lithium titanate particle diameter, and formation particle diameter is minimum, thickness of thin
The nano lithium titanate electrode material uniformly coated with carbon.The material shows excellent electrochemistry high rate performance.
Concrete technical scheme of the invention is as follows：
A kind of surface has the preparation method of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating layer, its specific steps
For：
(1) by nano-TiO2Solid powder is fully infiltrated in the solvent dissolved with oxidant；
(2) by above-mentioned TiO2Separate, one layer of TiO of oxidant film of attachment is obtained after solvent volatilization2Powder；
(3) above-mentioned powder is placed in 10min~24h in pyrroles's steam, pyrrole monomer is polymerized with the oxidant on its surface
Generation polypyrrole, obtains；
(4) TiO for coating the polypyrrole2Solid powder is massaged with the compound of the Li of solid-state, the compound of metal M
You compare Li：M：Ti=w：x：Y carries out mechanical mixture, wherein 0 ＜ w≤8；0≤x ＜ 5；0 ＜ y≤6；1/2≤w:y≤2；
(5) mixed powder is placed in high temperature furnace, is passed through protective gas, 500~1100 DEG C carry out the high temperature anneal, protected
1~24h of temperature, makes polypyrrole be carbonized, while LiwMxTiyOzMaterial crystalline formation, wherein 1≤z≤12, obtain after natural cooling
The rich nitrogen nano lithium titanate electrode material of surface substantially uniformity carbon coating.
Preferably, the oxidant includes chloride, P- toluene fulfonates, benzene sulfonate, 4- ethyl groups benzene sulfonate, 4-
N- octyl benzene sulfonic acids salt, dodecyl benzene sulfonate, 1,3,3- tri-methyl p-toluenesulfonates salt, m- dimethylbenzene -4- sulfonate, tetrem
Ammonium-P- toluenesulfonates and thiosulfate, its mass fraction in a solvent are 5~90%.
Preferably, solvent described in includes water, methyl alcohol, ethanol, ethylene glycol, acetonitrile, ether and n-butanol.
Preferably, the nano-TiO2For rutile-type, Detitanium-ore-type, brookite type, it is unformed in one or two
Mixing above, particle diameter is less than 100nm.
Preferably, the separation method includes filtering, decompression suction filtration and centrifugation.
Preferably, the metal M be Mg, Al, Fe, Ni, Cr, Ga, La and Ag in one or more.
Preferably, the compound of the Li is lithium nitrate, lithium carbonate, lithia, lithium chloride, lithium sulfide, lithium acetate, hydrogen-oxygen
Change lithium；Or solid-state Organic Alcohol, sour or ester type compound containing lithium.
Preferably, the compound of metal M described in the step (4) be the solid-state nitrate containing M, carbonate, oxide,
Chloride, sulfide, acetate, hydroxide；Or solid-state Organic Alcohol, acid, ester type compound containing metal M.
Preferably, protective gas is argon gas, nitrogen or helium in the step (5), or argon gas and hydrogen mixed gas,
Or the mixed gas of nitrogen and hydrogen, the percent by volume of hydrogen is 1~40% in the mixed gas.
Compared with prior art, the present invention has the advantages that：
It is raw material that the present invention uses inexpensive titanium oxide, reduces production cost, it is not necessary to use special installation, process letter
It is single, easily operation and amplification.The present invention is due to being that the uniformity of clad is very using the gas-phase polymerization principle of gas molecule
Height, and can be good at controlling the thickness of carbon coating layer.In high-temperature calcination process, the N atoms in polypyrrole are former with C and Ti
Son is combined, so as to get lithium titanate electrode material show extraordinary high rate capability.And polypyrrole is in high-temperature roasting
During iris action is provided, limit the growth of lithium titanate particle diameter, so as to shorten the diffusion length of lithium ion, increase and nanometer electricity
The contact area of pole material, reduces polarization resistance；The carbon coating layer that polypyrrole is formed after high temperature cabonization simultaneously provides good
Conductive network, so as to overcome LiwMxTiyOzMaterial electronicses conductance and the low shortcoming of ionic conductivity, improve chemical property.
The rich nitrogen nano lithium titanate electrode material preparation method preparation method of the uniform carbon coating that the present invention is provided is environment-friendly, easy to be easy
OK, yield is high, and controllability is good, is adapted to large-scale industrial production.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of the polypyrrole cladding titanium dioxide particle of synthesis in embodiment 1；Wherein (a) is low
The imaging of times transmission electron microscope；B () is that titanium dioxide and polypyrrole edge high-resolution-ration transmission electric-lens are imaged.
Fig. 2 is the X-ray diffraction spectra figure of the carbon coating lithium titanate electrode material of synthesis in embodiment 1；
Fig. 3 is the carbon coating lithium titanate electrode material charging and discharging curve of synthesis in embodiment 1；
Fig. 4 is the transmission electron microscope photo of the carbon coating lithium titanate electrode material of synthesis in embodiment 2；
Fig. 5 is to apply material X-ray photoelectron spectroscopic analysis (XPS) collection of illustrative plates synthesized in example 2；
Fig. 6 is the material circulation curve of synthesis in embodiment 2.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but the present invention is not limited to following examples.
Embodiment 1
0.005mol carbon coatings richness nitrogen nanometer Li4Ti5O12The synthesis of composite, the test of structure and its it is assembled into Li
The electrochemical property test of simulated battery.
It is dissolved in n-butanol according to the ratio that mass fraction is 40% as oxidant using P- toluenesulfonic acids iron, will
1.9970g anatase titanias (average grain diameter 30nm) is dipped in oxidizing agent solution, ultrasonic disperse 15min, is treated just after suction filtration
Butanol volatilizees completely, in TiO2Particle surface forms one layer of P- toluenesulfonic acid iron film.The TiO of P- toluenesulfonic acid iron films will be adhered to2Put
20min is stood in pyrroles's steam, pyrrole monomer is aggregated in TiO2 particle surfaces, form uniform complete polypyrrole film.Again
It is placed in ethanol solution and washs 3 times, add 1.3788g lithium nitrates and grind uniform, 700 DEG C is calcined 5h in an ar atmosphere,
The rich nitrogen lithium titanate with the uniform carbon coating in surface is obtained.
The TiO of Surface coating polypyrrole2Transmission electron microscope photo as shown in figure 1, surface coated poly- as can be seen from Figure 1
Pyrroles's film is uniform and complete, thickness average out to 10nm.The nanometer Li obtained after roasting4Ti5O12The X-ray diffraction light of composite
Spectrum as shown in Fig. 2 figure it is seen that the position of each diffraction maximum of the XRD of synthetic product and relative intensity and Li4Ti5O12
Standard JCPDS cards (49-0207) matches, and shows that product is single-phase spinel-type Li4Ti5O12Electrode material, Li4Ti5O12's
Crystallization degree is very high.
Composite obtained in embodiment 1 is assembled into half-cell as steps described below：The material that will be prepared is viscous with 7wt%
(solid content is 0.02g ml for the butadiene-styrene rubber-sodium carboxymethylcellulose emulsion or concentration of 2wt% for knot agent-1Kynoar
1-METHYLPYRROLIDONE solution) and 8wt% conductive agent (Super P conductive carbon blacks) mixing, be coated in copper after stirring
On paper tinsel, it is put into baking oven in 60~80 DEG C of drying.Pole piece is washed into the drift of 12~16mm of diameter again, is put into vacuum drying oven
4~12h is dried at 60~120 DEG C, is then transferred into the glove box full of argon gas.It is to electrode, ENTEK with metal lithium sheet
PE perforated membranes are barrier film, 1molL-1The ethylene carbonate of lithium hexafluoro phosphate and dimethyl carbonate (volume ratio 1:1) mixed solution
It is electrolyte, is assembled into CR2016 button cells, on LAND battery test system (offer of Wuhan Jin Nuo Electronics Co., Ltd.s)
Constant current charge-discharge performance test is carried out, discharge and recharge blanking voltage is relative to Li/Li+It is 1~3V.Charge-discharge test under 1C multiplying powers
As shown in figure 3, charge/discharge capacity reaches 170mAh g under 1C multiplying powers (the discharge and recharge time is respectively 1h)-1, close to theoretical capacity
175mAh g-1。
Embodiment 2
0.005mol carbon coatings richness nitrogen nanometer Li4Al0.15Ti4.85O12The synthesis of composite, the test of structure and its and Li
It is assembled into the electrochemical property test of simulated battery.
4- ethyl group benzene sulfonic acid iron is dissolved in ethanol with the ratio that mass fraction is 50%, by 1.9371g rutile-types
Titanium dioxide (average grain diameter 20nm) is dipped in oxidizing agent solution, ultrasonic disperse 10min, and taking precipitate is centrifuged, and treats that ethanol is complete
Volatilization, to put the precipitate in and stand 1h in pyrroles's steam, pyrrole monomer is aggregated in TiO2Particle surface, forms uniform complete
Polypyrrole film.It is placed on again in ethanol solution and washs 3 times, adds 0.1597g aluminum nitrates (analysis is pure), 1.3198g lithium acetates
(analysis is pure) and grind uniform, be then placed in high temperature furnace, be passed through nitrogen, being warming up to 850 DEG C carries out the high temperature anneal,
Insulation 8h, then naturally cools to room temperature, and obtaining Surface coating has the rich nitrogen nanometer Li of uniform carbon-coating4Al0.15Ti4.85O12It is compound
Material, its transmission electron microscope picture is as shown in Figure 4.From fig. 4, it can be seen that because there is the protective effect of carbon film, by 850 DEG C of roastings
Afterwards, Li4Al0.15Ti4.85O12Grain diameter is not grown up significantly, keeps 20-30nm or so, and there is uniform carbon-coating bag on surface
Wrap up in.Fig. 5 is carbon coating Li4Al0.15Ti4.85O12Composite material surface XPS collection of illustrative plates, can be seen that N1s peaks, and N from XPS collection of illustrative plates
Shared atomicity ratio is 4.7% in C/N surface coating layers.
Obtained composite is assembled into battery according to the method for the assembling half-cell of embodiment 1, is carried out under different multiplying
Discharge and recharge and loop test, as shown in fig. 6, material multiplying power and cycle performance are good 20C (the discharge and recharge time is respectively 2min)
Under charge-discharge magnification, capacity still keeps 110mAh g-1, and Reversible Cycle is functional.
3~embodiment of embodiment 5
Method by above experiment parameter with reference to embodiment 1 or example 2 can respectively obtain the corresponding uniform carbons of 0.005mol
The rich nitrogen nano lithium titanate electrode material of cladding.
In sum, the present invention uses gas-phase polymerization combination high―temperature nuclei process, obtains the richness with uniform carbon coating layer
Nitrogen nano lithium titanate electrode material, the composite carbon coating layer uniformity for obtaining is very high, and can be good at controlling carbon
The thickness of clad.The structure of rich nitrogen causes that lithium titanate electrode material shows extraordinary high rate capability.And polypyrrole
Iris action is provided in high-temperature calcination process, the growth of lithium titanate particle diameter is limited, so as to shorten the diffusion length of lithium ion, is increased
Greatly with the contact area of nano-electrode material, reduce polarization resistance；The carbon coating layer that polypyrrole is formed after high temperature cabonization simultaneously
There is provided good conductive network, so as to overcome LiwMxTiyOzMaterial electronicses conductance and the low shortcoming of ionic conductivity, improve electricity
Chemical property.The rich nitrogen nano lithium titanate electrode material preparation method preparation method environment friend of the uniform carbon coating that the present invention is provided
Good, simple and easy to do, yield is high, and controllability is good, is adapted to large-scale industrial production.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.
Claims (9)
1. a kind of surface has the preparation method of the rich nitrogen nano lithium titanate electrode material of uniform carbon coating layer, it is characterised in that
It is concretely comprised the following steps：
(1) by nano-TiO2Solid powder is fully infiltrated in the solvent dissolved with oxidant；
(2) by above-mentioned TiO2Separate, one layer of TiO of oxidant film of attachment is obtained after solvent volatilization2Powder；
(3) above-mentioned powder is placed in 10min~24h in pyrroles's steam, pyrrole monomer is polymerized with the oxidant on its surface generation
Polypyrrole, obtains the TiO of polypyrrole cladding2Solid powder；
(4) TiO for coating the polypyrrole2The compound of the Li of solid powder and solid-state, the compound of metal M are in molar ratio
Li：M：Ti=w：x：Y carries out mechanical mixture, wherein 0 ＜ w≤8；0≤x ＜ 5；0 ＜ y≤6；1/2≤w:y≤2；
(5) mixed powder is placed in high temperature furnace, is passed through protective gas, 500~1100 DEG C carry out the high temperature anneal, insulation 1
~24h, makes polypyrrole be carbonized, while LiwMxTiyOzMaterial crystalline formation, wherein 1≤z≤12, obtain table after natural cooling
The rich nitrogen nano lithium titanate electrode material of face substantially uniformity carbon coating.
2. method according to claim 1, it is characterised in that oxidant described in step (1) includes chloride, P- toluene
Sulfonate, benzene sulfonate, 4- ethyl groups benzene sulfonate, 4-N- octyl benzene sulfonic acids salt, dodecyl benzene sulfonate, 1,3,3- front threes
Base benzene sulfonate, m- dimethylbenzene -4- sulfonate, etamon-P- toluenesulfonates and thiosulfate, its matter in a solvent
Amount fraction is 5~90%.
3. method according to claim 1, it is characterised in that solvent described in step (1) includes water, methyl alcohol, ethanol, second
Glycol, acetonitrile, ether and n-butanol.
4. method according to claim 1, it is characterised in that nano-TiO described in step (1)2It is rutile-type, sharp titanium
Ore deposit type, brookite type, it is unformed in one or more mixing, particle diameter be less than 100nm.
5. method according to claim 1, it is characterised in that separation method described in step (2) includes that filtering, decompression are taken out
Filter and centrifugation.
6. method according to claim 1, it is characterised in that metal M described in step (4) be Mg, Al, Fe, Ni, Cr,
One or more in Ga, La and Ag.
7. method according to claim 1, it is characterised in that the compound of Li described in step (4) is lithium nitrate, carbonic acid
Lithium, lithia, lithium chloride, lithium sulfide, lithium acetate, lithium hydroxide；Or solid-state Organic Alcohol, sour or esters chemical combination containing lithium
Thing.
8. method according to claim 1, it is characterised in that the compound of metal M is consolidating containing M described in step (4)
State nitrate, carbonate, oxide, chloride, sulfide, acetate, hydroxide；Or solid-state containing metal M is organic
Alcohol, acid, ester type compound.
9. method according to claim 1, it is characterised in that protective gas described in step (5) is argon gas, nitrogen or helium
Gas, or argon gas and hydrogen mixed gas, or nitrogen and hydrogen mixed gas, the volume basis of hydrogen in the mixed gas
Than being 1~40%.
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| CN108539143A (en) * | 2018-03-08 | 2018-09-14 | 上海理工大学 | A method of quickly preparing high-capacity lithium ion cell silicon based anode material |
| CN110571423A (en) * | 2019-09-17 | 2019-12-13 | 上海理工大学 | Preparation method of nitrogen-carbon-coated nano titanium niobate electrode material |
| CN114388749A (en) * | 2020-10-21 | 2022-04-22 | 湖南中科星城石墨有限公司 | Silicon-based negative electrode material and preparation method and application thereof |
| CN114388749B (en) * | 2020-10-21 | 2024-02-27 | 湖南中科星城石墨有限公司 | Silicon-based anode material and preparation method and application thereof |
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