CN102544468A - Carbon-coated mesoporous lithium titanate anode material of lithium ion battery and method for preparing carbon-coated mesoporous lithium titanate anode material - Google Patents
Carbon-coated mesoporous lithium titanate anode material of lithium ion battery and method for preparing carbon-coated mesoporous lithium titanate anode material Download PDFInfo
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Abstract
The invention discloses a carbon-coated mesoporous lithium titanate anode material of a lithium ion battery and a method for preparing the carbon-coated mesoporous lithium titanate anode material. A particle aggregate with the diameter of 0.1 to 10 mu m is formed by self-assembling nano-crystals with the diameter of 5 to 150 nm. The material has a mesoporous structure, the average pore diameter of the material is 2 to 6 nm, and the carbon content of the material is 0.5 to 5 percent. A lithium titanate sample can serve as an anode material of the lithium ion battery.
Description
Technical field
The present invention relates to the mesoporous lithium titanate lithium ion battery cathode material and its preparation method that a kind of carbon in the lithium ion battery field coats.
Background technology
Along with the continuous deterioration of global resources aggravation in short supply and environment, the exploitation of green renewable new forms of energy obtains people's attention gradually, and the cleaning energy storage device receives the concern energetically of countries in the world.Lithium ion battery has that high voltage, high power capacity, volume are little, light weight, memoryless function, have extended cycle life, advantage such as security performance is good; Pollute little; Become the first-selected object that can fill the formula power supply again of current portable type electronic product; And have broad application prospects in fields such as electric automobile, space technologies, be the energy storage device that present various countries endeavour to develop.Though the graphite-like carbon negative pole of extensive use at present has with low cost; Reversible doff lithium functional; But the volume energy density of traditional graphite cathode material is lower, and irreversible capacity loss is bigger, has restricted the application of high energy density cells; Therefore seek to have that fail safe is good, reliability is high, the new type lithium ion battery negative material of advantages such as long-life and high power receives scientific research personnel's attention always, also being needs the guardian technique problem that breaks through.
Lithium titanate is one of lithium ion battery of new generation negative pole candidate material the most likely, and its voltage platform is about 1.5V, and the Theoretical Mass specific capacity is 175mAhg
-1, this material has the following advantages simultaneously: (1) can not change by recurring structure in charge and discharge process, is described as " zero strain material "; (2) with respect to Li
+The discharge voltage of/Li is higher, does not react with electrolyte and is difficult for causing that lithium metal separates out, and fail safe is secure; (3) the lithium ion diffusion coefficient (2 * 10
-8Cm
2/ s) than the high one magnitude of carbon negative pole; (4) coulombic efficiency height, advantages of nontoxic raw materials, inexpensive are fit to environmental protection and large-scale development; (5) chemical stability is good, preparation is simple, is the negative level of a kind of very promising lithium ion battery material, estimates aspect electrokinetic cell, can accomplish something.Yet the conductivity of this material own is very poor, causes the high power charging-discharging capacity very low, has limited its commercialization and has used.People are devoted to improve the conductivity research of this material always, and even as be devoted to the nano level Li with meso-hole structure of tiny particle diameter from the preparation method
4Ti
5O
12Study on the synthesis in the hope of shortening the migration path of lithium ion, improves high rate performance; Start with like carbon coated raising conductivity from coating technology; Other metallic elements or with the Ti in the lithium titanate mix
4+Partial reduction becomes Ti
3+, improve conductivity to improve high rate performance etc.Though these methods are to Li
4Ti
5O
12High rate performance make moderate progress, but its performance still can not practical requirement.The invention provides a kind of mesoporous lithium titanate anode material with high-rate charge-discharge capability and preparation method thereof, this material has excellent high-rate charge-discharge capability, simultaneously its preparation method simple, controlled, be easy to large-scale production.
Summary of the invention
The purpose of this invention is to provide mesoporous lithium titanate lithium ion battery material of a kind of carbon coating and preparation method thereof.
The mesoporous lithium titanate lithium ion battery negative material that carbon provided by the present invention coats; It is characterized in that this material forms the cluster of grains aggressiveness that diameter is 0.1～10 μ m by the nanocrystalline self assembly of 5～150nm; Have meso-hole structure, average pore size is 2～6nm, and carbon content is 0.5～5%.
This mesoporous lithium titanate anode material can prepare according to the method that comprises the steps:
(1) gets the additive of 0.02～2g, it is added in organic solution, directly use or get its suspension and use;
(2) in the solution that step (1) obtains, add the titanium source, making its concentration is 0.02～0.5mol/L, after the stirring, presses Li: Ti=4: 5 add lithium-containing compound, stir;
(3) solution of step (2) gained is packed in the agitated reactor, compactedness 50～80% is heat-treated in baking oven, and heat treatment obtains white depositions after finishing, washing, drying;
(4) dried sample is placed protective atmosphere, and under different temperatures, calcine certain hour, obtain the lithium titanate with meso-hole structure of different-grain diameter at last, this lithium titanate sample can be used as lithium ion battery negative material.
In the above-mentioned steps (1) the additive that uses be in glycine, lysine, alanine, glutamic acid, the monoethanolamine one or more.
Employed titanium source is one or more in butyl titanate, isopropyl titanate, tetraethyl titanate, the titanium tetrachloride in the above-mentioned steps (2); Lithium-containing compound is one or more in lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, the lithium sulfate.
Heat treatment temperature in the above-mentioned steps (3) is 150 ℃～240 ℃, and the reaction time is 8～72 hours.
Protective atmosphere in the above-mentioned steps (4) is the mist of argon gas, nitrogen, argon gas or nitrogen and hydrogen; Calcining heat is 300～900 ℃, and calcination time is 0.5～72 hour.
The present invention utilizes the process characteristic of solvent thermal, and through optimizing technological parameter, adjustment reactant and solvent species through Overheating Treatment, obtain the mesoporous lithium titanate that carbon coats, and this lithium titanate have the part titanous.In the present invention preparation, additive plays following three effects: (1) additive id reaction or produce water with solvent reaction helps the hydrolysis in titanium source; (2) additive id reaction or produce organic substance with solvent reaction is adsorbed on the surface of lithium titanate particle, prevents particle agglomeration; (3) in reducing atmosphere, during heat treatment, be adsorbed on the organic carbon of particle surface, simultaneously the Ti in the lithium titanate
4+Partial reduction becomes Ti
3+The present invention's preparation has the mesoporous lithium titanate that carbon coats, the chemical composition homogeneous, and specific area is big; Carbon coating and part titanous help the migration of lithium ion and electronics; Its charge/discharge capacity under high magnification is higher, and enclosed pasture efficient shows excellent chemical property near 100%.Through the addition of control additive, the conditioned reaction temperature and time can be controlled the grain diameter scope (0.1～10 μ m) of the mesoporous lithium titanate that carbon coats and the content (0.5～5%) of carbon.Technical process is simple, and preparation parameter is easy to control, and good reproducibility can synthesize in scale.
The mesoporous lithium titanate material that carbon of the present invention coats can be used as the negative material of lithium ion battery.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the mesoporous lithium titanate that carbon coats among the embodiment 1.
Fig. 2 is the stereoscan photograph of the whole pattern of mesoporous lithium titanate that carbon coats among the embodiment 1.
Fig. 3 is the graph of pore diameter distribution of the mesoporous lithium titanate that carbon coats among the embodiment 1.
Fig. 4 is the electron paramagnetic resonance spectrum of the mesoporous lithium titanate that carbon coats among the embodiment 1.
Fig. 5 is the charging and discharging curve of mesoporous lithium titanate when 2C that carbon coats among the embodiment 1.
Fig. 6 is the charging and discharging curve of mesoporous lithium titanate when 20C that carbon coats among the embodiment 1.
Embodiment
Main implementation process of the present invention is:
(1) get certain quantity of additive, it is dissolved in the organic solution, the amount of additive is 0.02～2g, directly uses or get its suspension use;
(2) in the solution that obtains, add a certain amount of titanium source, making its concentration is 0.02～0.5mol/L, after the stirring, presses Li: Ti=4: 5 add lithium-containing compound, stir a period of time;
(3) solution of gained is packed in the agitated reactor, compactedness is 50～80%, in baking oven, heat-treats, and the control temperature is between 150 ℃～240 ℃, and successive reaction is 8～72 hours, and heat treatment obtains white look sediment after finishing, washing, drying;
(4) with dried sample respectively under the protection of the mixed atmosphere of argon gas, nitrogen, argon gas or nitrogen and hydrogen; Between 300～900 ℃, calcined 0.5～72 hour; Obtain the mesoporous lithium titanate of the carbon coating of different-grain diameter at last, this lithium titanate sample can be used as lithium ion battery negative material.
Below further illustrate characteristics of the present invention through embodiment, but be not limited to embodiment.
Experimental technique among the following embodiment if no special instructions, is conventional method.
Embodiment 1:
Under agitation the 1.2g glycine is joined in the 60mL absolute ethyl alcohol, stir 1h, leave standstill 20min subsequently, remove deposition, it is subsequent use to get upper strata suspension.Under agitation the butyl titanate with 3ml adds in the suspension, stirs 1h, adds the 0.2961g lithium hydroxide again, stirs 2h.The solution that obtains is poured in the agitated reactor that capacity is 100ml, and compactedness is 60%, in baking oven, reacts 20h in 200 ℃.After the question response still is reduced to room temperature, collect product, and product is used the ethanol centrifuge washing, the product after will washing is at last put into baking oven, promptly gets the former crystalline substance of lithium titanate after the drying.With the former crystalline substance of the lithium titanate of gained 500 ℃ of calcining 2h under nitrogen atmosphere, promptly get grey lithium titanate powder.Its Fig. 1 is the X-ray diffracting spectrum of the lithium titanate powdery of embodiment preparation for this reason, can find out that from collection of illustrative plates its thing is that the lithium titanate crystallinity of cubic spinel structure is good mutually.Through elementary analysis, getting its phosphorus content is 0.78%.Fig. 2 is the photo of the whole pattern of powder under JEOL JSM-6700 type field emission scanning electron microscope for this reason, can find out that this powder granule varies, and granule is approximately about 100nm, and bulky grain is about about 1～3 μ m, by the nanocrystalline composition about 20nm.Fig. 3 is the graph of pore diameter distribution of gained sample, and by finding out that sample is a meso-hole structure among the figure, pore-size distribution is between 3～5nm.Fig. 4 is the electron paramagnetic resonance spectrum of gained sample, can find out that by figure sample has oxygen room and Ti
3+Signal.It is even that this powder, conductive carbon black and binding agent PVDF (Kynoar) are pressed 7: 1.5: 1.5 mixed grindings of mass ratio; Add an amount of solvent NMP (N-methyl pyrrolidone) then; Evenly be coated on the Copper Foil after mixing well pulping, 100 ℃ of following vacuum dryings obtain pole piece.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with constant current density, the charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mAg
-1(2C).Fig. 5 and Fig. 6 are the charge-discharge test curve that obtains, and as can be seen from the figure, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is 173.3mAhg
-1, the charge ratio capacity is 171.0mAhg
-1, very near its theoretical capacity 175mAhg
-1After discharging and recharging through 200 times, its specific discharge capacity remains 163.3mAhg
-1When charging and discharging currents density is 3350mAg
-1In the time of (20C), its first discharge specific capacity is 146mAhg
-1, the charge ratio capacity is 138.2mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 135.2mAhg
-1
Embodiment 2:
Under agitation the 1.2g glycine is joined in the 60mL absolute ethyl alcohol, stir 1h, leave standstill 20min subsequently, remove deposition, it is subsequent use to get upper strata suspension.Under agitation the butyl titanate with 3ml adds in the suspension, stirs 1h, adds the 0.2961g lithium hydroxide again, stirs 2h.The solution that obtains is poured in the agitated reactor that capacity is 100ml, and compactedness is 60%, in baking oven, reacts 20h in 200 ℃.After the question response still is reduced to room temperature, collect product, and product is used the ethanol centrifuge washing, be drying to obtain the former crystalline substance of lithium titanate.With the former crystalline substance of the lithium titanate of gained 300 ℃ of calcining 0.5h under nitrogen atmosphere, promptly get grey lithium titanate powder.X-ray diffracting spectrum is the result show, its thing is the lithium titanate of cubic spinel structure mutually.Through elementary analysis, getting its phosphorus content is 0.8%.Through electron paramagnetic resonance spectrum, can find out that sample has oxygen room and Ti
3+Signal.Scanning electron microscopic observation is the result show, particle is more even, and particle is approximately about 100nm, by the nanocrystalline composition about 5nm.The graph of pore diameter distribution of gained sample shows that sample is a meso-hole structure, and pore-size distribution is between 3～6nm.It is even that this powder, conductive carbon black and binding agent PVDF (Kynoar) are pressed 7: 1.5: 1.5 mixed grindings of mass ratio; Add an amount of solvent NMP (N-methyl pyrrolidone) then; Evenly be coated on the Copper Foil after mixing well pulping, 100 ℃ of following vacuum dryings obtain pole piece.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with constant current density, the charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mAg
-1(2C).The charge-discharge test result, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is 174.2mAhg
-1, the charge ratio capacity is 165.4mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 151.2mAhg
-1When charging and discharging currents density is 3350mAg
-1In the time of (20C), its first discharge specific capacity is 139.2mAhg
-1, the charge ratio capacity is 132.4mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 115.6mAhg
-1
Embodiment 3:
Under agitation 0.02g lysine is joined in the 60mL isopropyl alcohol, stir 1h, under agitation the butyl titanate with 1.5ml slowly dropwise adds in the suspension, stirs 1h, adds the 0.2432g lithium nitrate again, stirs 2h.The solution that obtains is poured in the agitated reactor that capacity is 100ml, and compactedness is 80%, in baking oven, reacts 72h in 150 ℃.After the question response still is reduced to room temperature, collect product, and product is used the ethanol centrifuge washing, promptly get the former crystalline substance of lithium titanate after the drying.With the former crystalline substance of the lithium titanate of gained 900 ℃ of calcining 72h under nitrogen atmosphere, promptly get grey lithium titanate powder.X-ray diffracting spectrum is the result show, its thing is the lithium titanate of cubic spinel structure mutually.Through elementary analysis, getting its phosphorus content is 0.5%.Through electron paramagnetic resonance spectrum, can find out that sample has oxygen room and Ti
3+Signal.Scanning electron microscopic observation is the result show, this powder granule size is between 7～10 μ m, by nanocrystalline composition the about 150nm.The graph of pore diameter distribution of gained sample shows that sample is a meso-hole structure, and pore-size distribution is between 2～3nm.It is even that this powder, conductive carbon black and binding agent PVDF (Kynoar) are pressed 7: 1.5: 1.5 mixed grindings of mass ratio; Add an amount of solvent NMP (N-methyl pyrrolidone) then; Evenly be coated on the Copper Foil after mixing well pulping, 100 ℃ of following vacuum dryings obtain pole piece.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt the LANDCT2001A battery test system, carry out charge-discharge test with constant current density, the charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mAg
-1(2C).The charge-discharge test result, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is 159.4mAhg
-1, the charge ratio capacity is 158.1mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 154.6mAhg
-1When charging and discharging currents density is 3350mAg
-1In the time of (20C), its first discharge specific capacity is 129.5mAhg
-1, the charge ratio capacity is 124.3mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 120.6mAhg
-1
Embodiment 4:
Under agitation the 2g alanine is joined in the 60mL ethylene glycol, stir 1h, under agitation the tetraisopropyl titanate with 9ml slowly dropwise adds in the suspension, stirs down to add the 3.0710g lithium sulfate, stirs 2h.The solution that obtains is poured in the agitated reactor that capacity is 100ml, and compactedness is 70%, in baking oven, reacts 8h in 240 ℃.After the question response still is reduced to room temperature, collect product, and product is used the ethanol centrifuge washing, promptly get the former crystalline substance of lithium titanate after the drying.With the former crystalline substance of the lithium titanate of gained 800 ℃ of calcining 4h under argon gas atmosphere, promptly get grey lithium titanate powder.X-ray diffracting spectrum is the result show, its thing is the lithium titanate of cubic spinel structure mutually.Through elementary analysis, getting its carbon content is 5%.Through electron paramagnetic resonance spectrum, can find out that sample has oxygen room and Ti
3+Signal.Scanning electron microscopic observation is the result show, this powder granule varies, and granule is approximately about 300nm, and bulky grain is about about 4～5 μ m, by the nanocrystalline composition about 35nm.The graph of pore diameter distribution of gained sample shows that sample is a meso-hole structure; Pore-size distribution is pressed 7: 1.5: 1.5 mixed grindings of mass ratio with this powder, conductive carbon black and binding agent PVDF (Kynoar) between 2～4nm even; Add an amount of solvent NMP (N-methyl pyrrolidone) then; Evenly be coated on the Copper Foil after mixing well pulping, 100 ℃ of following vacuum dryings obtain pole piece.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with constant current density, the charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mAg
-1(2C).The charge-discharge test result, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is 170.1mAhg
-1, the charge ratio capacity is 169.3mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 163.6mAhg
-1When charging and discharging currents density is 3350mAg
-1In the time of (20C), its first discharge specific capacity is 140.2mAhg
-1, the charge ratio capacity is 135mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 130.4mAhg
-1
Embodiment 5:
Under agitation 1.2g glutamic acid is joined in the 60mL ethylene glycol, stir 1h, under agitation the tetraethyl titanate with 0.27ml is added dropwise in the suspension, stirs down to add the 0.1228g lithium sulfate, stirs 2h.The solution that obtains is poured in the agitated reactor that capacity is 100ml, and compactedness is 70%, in baking oven, reacts 36h in 200 ℃.After the question response still is reduced to room temperature, collect product, and product is used the ethanol centrifuge washing, promptly get the former crystalline substance of lithium titanate after the drying.With the former crystalline substance of the lithium titanate of gained 600 ℃ of calcining 3h under the gaseous mixture atmosphere of argon gas and hydrogen, promptly get grey lithium titanate powder.X-ray diffracting spectrum is the result show, its thing is the lithium titanate of cubic spinel structure mutually.Through elementary analysis, getting its phosphorus content is 3.3%.Through electron paramagnetic resonance spectrum, can find out that sample has oxygen room and Ti
3+Signal.Scanning electron microscopic observation is the result show, this powder granule varies, and granule is approximately about 100nm, and bulky grain is about about 2～4 μ m, by the nanocrystalline composition about 25nm.The graph of pore diameter distribution of gained sample shows that sample is a meso-hole structure; Pore-size distribution is pressed 7: 1.5: 1.5 mixed grindings of mass ratio with this powder, conductive carbon black and binding agent PVDF (Kynoar) between 2.5～4.5nm even; Add an amount of solvent NMP (N-methyl pyrrolidone) then; Evenly be coated on the Copper Foil after mixing well pulping, 100 ℃ of following vacuum dryings obtain pole piece.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with constant current density, the charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mAg
-1(2C).The charge-discharge test result, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is 170.4mAhg
-1, the charge ratio capacity is 168.5mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 161.7mAhg
-1When charging and discharging currents density is 3350mAg
-1In the time of (20C), its first discharge specific capacity is 139mAhg
-1, the charge ratio capacity is 134.2mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 128.6mAhg
-1
Embodiment 6:
Under agitation the 0.3g monoethanolamine is joined in the 60mL isopropyl alcohol, stir 1h, under agitation the titanium tetrachloride with 3.3ml adds in the solution, stirs 1h, adds the 1.4498g lithium chloride again, stirs 2h.The solution that obtains is poured in the agitated reactor that capacity is 100ml, and compactedness is 50%, in baking oven, reacts 20h in 200 ℃.After the question response still is reduced to room temperature, collect product, and product is used the ethanol centrifuge washing, promptly get the former crystalline substance of lithium titanate after the drying.With the former crystalline substance of the lithium titanate of gained 400 ℃ of calcining 8h under the gaseous mixture atmosphere of nitrogen and hydrogen, promptly get grey lithium titanate powder.X-ray diffracting spectrum is the result show, its thing is the lithium titanate of cubic spinel structure mutually.Through elementary analysis, getting its carbon content is 2.1%.Through electron paramagnetic resonance spectrum, can find out that sample has oxygen room and Ti
3+Signal.Scanning electron microscopic observation is the result show, this powder granule varies, and granule is approximately about 100nm, and bulky grain is about about 1 μ m, by the nanocrystalline composition about 12nm.The graph of pore diameter distribution of gained sample shows that sample is a meso-hole structure; Pore-size distribution is pressed 7: 1.5: 1.5 mixed grindings of mass ratio with this powder, conductive carbon black and binding agent PVDF (Kynoar) between 3～5.5nm even; Add an amount of solvent NMP (N-methyl pyrrolidone) then; Evenly be coated on the Copper Foil after mixing well pulping, 100 ℃ of following vacuum dryings obtain pole piece.With metal lithium sheet is to the utmost point, 1molL
-1LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolyte, and polypropylene material is a barrier film, in being full of the glove box of argon gas, is assembled into 2025 type button cells.Adopt LAND CT2001A battery test system, carry out charge-discharge test with constant current density, the charging/discharging voltage scope is between 1～3V, and charging and discharging currents density is 335mAg
-1(2C).The charge-discharge test result, this material shows excellent chemical property during as the negative pole of lithium ion battery, and its first discharge specific capacity is 171.6mAhg
-1, the charge ratio capacity is 167.4mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 160.2mAhg
-1When charging and discharging currents density is 3350mAg
-1In the time of (20C), its first discharge specific capacity is 143mAhg
-1, the charge ratio capacity is 136.5mAhg
-1, after discharging and recharging through 200 times, its specific discharge capacity remains 130.4mAhg
-1
Claims (6)
1. the mesoporous lithium titanate lithium ion battery negative material that coats of a carbon, this material forms the cluster of grains aggressiveness that diameter is 0.1～10 μ m by the nanocrystalline self assembly of 5～150nm, has meso-hole structure, and average pore size is 2～6nm, and carbon content is 0.5～5%.
2. method for preparing the mesoporous lithium titanate lithium ion battery negative material that the described carbon of claim 1 coats may further comprise the steps:
(1) gets the additive of 0.02～2g, it is dissolved in the organic solution, directly use or get its suspension and use;
(2) in the solution that step (1) obtains, add the titanium source, making its concentration is 0.02～0.5mol/L, presses Li: Ti=4: 5 add lithium-containing compound, stir;
(3) solution of step (2) gained is packed in the agitated reactor, compactedness 50～80% is heat-treated in baking oven, and heat treatment obtains white depositions after finishing, washing, drying;
(4) dried sample is placed protective atmosphere, and under different temperatures, calcine certain hour, obtain the lithium titanate of the carbon coating with meso-hole structure of different-grain diameter at last, this lithium titanate sample can be used as lithium ion battery negative material.
3. the preparation method of the mesoporous lithium titanate lithium ion battery negative material that carbon according to claim 2 coats is characterized in that: in the said step (1) the additive that uses be in glycine, lysine, alanine, glutamic acid, the monoethanolamine one or more.
4. the preparation method of the mesoporous lithium titanate lithium ion battery negative material that carbon according to claim 2 coats, it is characterized in that: employed titanium source is one or more in butyl titanate, isopropyl titanate, tetraethyl titanate, the titanium tetrachloride in the said step (2); Lithium-containing compound is one or more in lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, the lithium sulfate.
5. the preparation method of the mesoporous lithium titanate lithium ion battery negative material that carbon according to claim 2 coats, it is characterized in that: the heat treatment temperature in the said step (3) is 150 ℃～240 ℃, and the reaction time is 8～72 hours.
6. the preparation method of the mesoporous lithium titanate lithium ion battery negative material that carbon according to claim 2 coats, it is characterized in that: the protective atmosphere in the said step (4) is the mist of argon gas, nitrogen, argon gas or nitrogen and hydrogen; Calcining heat is 300～900 ℃, and calcination time is 0.5～72 hour.
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Cited By (4)
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| CN104409712A (en) * | 2014-09-19 | 2015-03-11 | 四川省有色冶金研究院有限公司 | Preparation method of carbon and nitrogen coated lithium titanate material |
| CN106450255A (en) * | 2016-11-05 | 2017-02-22 | 中南大学 | NiTiO3/C cathode material of sodium-ion battery, preparation and application |
| WO2018132992A1 (en) * | 2017-01-19 | 2018-07-26 | GM Global Technology Operations LLC | Hybrid active materials for batteries and capacitors |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102969493A (en) * | 2012-12-12 | 2013-03-13 | 苏州大学 | Cathode material for non-aqueous secondary battery and preparation method thereof as well as non-aqueous secondary battery cathode and non-aqueous secondary battery |
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| CN104409712A (en) * | 2014-09-19 | 2015-03-11 | 四川省有色冶金研究院有限公司 | Preparation method of carbon and nitrogen coated lithium titanate material |
| CN106450255A (en) * | 2016-11-05 | 2017-02-22 | 中南大学 | NiTiO3/C cathode material of sodium-ion battery, preparation and application |
| WO2018132992A1 (en) * | 2017-01-19 | 2018-07-26 | GM Global Technology Operations LLC | Hybrid active materials for batteries and capacitors |
| CN110140237A (en) * | 2017-01-19 | 2019-08-16 | 通用汽车环球科技运作有限责任公司 | Hydridization active material for battery pack and capacitor |
| CN110140237B (en) * | 2017-01-19 | 2022-09-27 | 通用汽车环球科技运作有限责任公司 | Hybrid active materials for batteries and capacitors |
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