CN103730649A - Method for preparing carbon-coated lithium titanate negative electrode material for lithium battery - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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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Abstract
The invention discloses a method for preparing a carbon-coated lithium titanate negative electrode material for a lithium battery. The method comprises the following steps: preparing a polymer with controllable molecular weight by adopting living polymerization, performing ball milling and mixing with raw materials of lithium titanate, and sintering to obtain a lithium titanate material coated with a conductive carbon layer. The adopted polymerization method has the advantages that range of optional monomers is wide, polymers of different carbon chain lengths can be obtained by adjusting the raw material ratio, the carbon chain length distribution is uniform, and the finally obtained carbon-coated lithium titanate material is uniform and stable in performance. Moreover, the initial charge specific capacity of the obtained lithium titanate material reaches over 160mAh/g under the rate of 1C (1C=175mA/g), and the capacity is kept over 90 percent due to cycle of 800 times.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, relate in particular to the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery.
Background technology
Lithium ion battery is a kind of novel rechargeable battery, and its volumetric specific energy and specific energy are high, can fill and pollution-free, is referred to as by " the most promising chemical power source " by people, develops very fast.Lithium ion battery has been widely used in the portable type electronic product power supplys such as mobile phone, laptop computer and video camera, and is applied to gradually hybrid electric vehicle, pure electric vehicle and regenerative resource power station as electrokinetic cell and accumulation power supply.Commercial lithium ion battery negative material is mainly graphitized carbon material at present, but has the poor problem of fail safe.
Spinel type lithium titanate (Li
4ti
5o
12) with its outstanding security feature and long circulation life, become the lithium ion battery negative material that has Commercial Prospect.Li
4ti
5o
12as negative material, lithium ion de-/embedding process in, crystal structure can keep the stability of height, and makes it have good cycle performance and discharge voltage stably; There is relatively high electrode potential, this electrode material can be used in the electrolytical burning voltage of most liquid interval, thereby avoided the generation of electrolyte decomposition phenomenon or diaphragm; Raw materials (TiO
2, Li
2cO
3or LiOHH
2o etc.) source is also abundanter.But this material intrinsic conductivity is low, become the key factor of its development of restriction.
Li
4ti
5o
12electron conduction is very poor, belongs to typical insulator, in electrochemical reaction process, will cause serious polarization, even produces amount of heat, very unfavorable to electrode performance.Certainly, by doping/coated grade Li
4ti
5o
12modification, leads performance to raising electrode significant.
Guerfi etc. take polymer as carbon source, take acetone and water and carry out wet mixing as solvent, prepared the lithium titanate of doping carbon, obtain good chemical property (A. Guerfi, P. Charest, Power Sources 2004,126,163-168.).And disclosing employing several kinds of carbon source, US Patent No. 2004/0202934A1 comprises that carbon black, polyol, polyethylene glycol etc. are to lithium titanate modification.But adopt living polymerization to prepare carbon source the method for lithium titanate modification is had no to report.
CN 102593444A discloses preparation method and the product thereof of the coated lithium titanate of a kind of carbon.First it be dispersed in deionized water water with lithium titanate and softex kw, add again resorcinol, formaldehyde and sodium carbonate, the washing of reflow treatment afterproduct, the dry presoma that obtains, finally presoma is calcined under inert atmosphere and obtained the coated lithium titanate of carbon, improved the conductivity of lithium titanate, its circulation and high rate performance are all greatly improved.
CN 102569767A discloses a kind of polymer composite lithium titanate electrode and preparation method thereof.First this invention prepares oxidizing agent solution A, the Bronsted acid solution B of prepared polymer monomer; Again lithium titanate powder is joined in solution B, then solution A is progressively added drop-wise in solution B, after dispersed with stirring reacts, obtain product polymer composite lithium titanate electrode.
In above-mentioned two pieces of patents, the method for modifying of lithium titanate material is all adopted and adds polymer to improve the conductivity of lithium titanate, but the type of polymer that method therefor obtains is single, its strand length is uncontrollable and different in size, cannot stable performance improves the effect of conductivity in the modified lithium titanate material finally obtaining for the conductive materials of modification.Meanwhile, the preparation method for the polymer of modification in above-mentioned two pieces of patents is higher to equipment and environmental requirement, and CN 102593444A polymerization used adopts reflux, and reactor is more complicated, needs use backflow tower reactor; CN 102569767A polymerization used adopts monomer only for conducting polymer monomer, and need protonic acid doping, and slowly drips oxidant, and operation is more complicated, is difficult to industrialization and produces continuously.
Summary of the invention
The invention provides the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery, this method adopts living polymerization to prepare the controlled polymer of molecular weight, and carry out after ball milling mixes firing with the raw material of lithium titanate, obtain the lithium titanate material of coated with conductive carbon-coating, the optional monomer of polymerization that the present invention adopts is in extensive range, by regulating raw material proportioning can obtain the polymer of different carbon chain lengths, and carbon chain length distribution is even, the coated too sour lithium material performance stable homogeneous of carbon finally obtaining.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, is characterized in that: comprise the following steps:
(1) polymer monomer, azo-initiator and trithiocarbonate are dissolved in to oxolane and are mixed with solution, 70-90 in nitrogen atmosphere
oat C temperature, react 5-10 hour, obtain mixed solution, wherein, polymer monomer: azo-initiator: the mol ratio of trithiocarbonate is 100:0.5-1:0.01-1, the volume ratio of polymer monomer and oxolane is 1:1-2;
(2) mixed solution step (1) being obtained precipitates and obtains polymer carbon source in precipitation reagent;
(3) press lithium ion and titanium ion mol ratio Li
+: Ti
+=0.8:1 takes lithium-containing compound and titanium-containing oxide, and take by the 5%-20% of the mass fraction of lithium-containing compound and titanium-containing oxide total weight the polymer carbon source that step (2) obtains, adding deionized water is dispersant ball milling 4-8 hour in ball grinder, obtains the mixed slurry mixing;
(4) mixed slurry step (3) being obtained, is delivered to spray dryer and carries out granulating and drying, obtains dry mixed powder;
(5) by the presoma powder of step (4) granulating and drying under inert gas environment high-temperature roasting 8-16 hour, obtain the coated spinel type lithium titanate material Li of carbon
4ti
5o
12.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, roasting process two steps in preferred steps (5) are carried out, first according to 1-10
othe programming rate of C/min, is elevated to 400 from room temperature
oc-600
oc, and keep 4-8 hour; Then according to the programming rate of 1-10 ℃/min, temperature is elevated to 700
oc-900
oc, and keep 4-8 hour.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, preferably azo-initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, preferred polymers monomer is any one in acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, EMA, styrene.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, preferably precipitation reagent is any one in methyl alcohol, ethanol, benzinum.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, preferably lithium-containing compound comprise in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, preferably titanium-containing oxide comprise in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, in step (4), described granulating and drying is specially: the dry inlet temperature of spraying is 150
oC-250
oC, outlet temperature is 100
oC-150
oC, charging rate is 0.01-0.1L/min.
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, preferably inert gas comprise in helium, argon gas, nitrogen one or several arbitrarily than mixture.
The present invention has the following advantages:
Compared with prior art, the manufacture method of the coated lithium titanate material of carbon of the present invention has following beneficial effect:
1, the present invention obtains polymer carbon source by living polymerization, only need to replace polymer monomer just can obtain different carbon sources, and polymer molecular weight is controlled, and molecular weight distribution is little, and the coated lithium titanate material surface carbon chain length homogeneous of the carbon of acquisition is controlled.
2, the carbon that uses of the present invention is coated to lithium titanate material modification, and the lithium titanate material of acquisition is at 1C(1C=175mA/g) more than initial charge specific capacity reaches 160mAh/g under multiplying power, through 500 circulation volumes, keep more than 90%.And lithium titanate material prepared by existing method is at 1C(1C=175mA/g) initial charge specific capacity only reaches 150mAh/g conventionally under multiplying power, through 500 circulation volumes, conventionally keeps less than 80%.
3, the present invention adopts two-stage roasting technique, and lithium titanate crystallite dimension is little, and energy resource consumption is few, low for equipment requirements, easily realizes suitability for industrialized production.
4, the present invention adopts closed reactor, and polymer monomer is without using protonic acid doping, and technique is relatively simple, is applicable to industrialization and produces continuously.
Accompanying drawing explanation
Fig. 1 is 800 cycle charge-discharge curves of lithium battery graphite-doping lithium titanate anode material 1C multiplying power of the present invention.
Embodiment
Embodiment 1
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1) polymer monomer methacrylic acid, azo-initiator azo-bis-isobutyl cyanide and trithiocarbonate are dissolved in to oxolane and are mixed with mixed solution, 70-90 in nitrogen atmosphere
oat C temperature, react 5-10 hour, this course of reaction is carried out in closed reactor.Wherein the mol ratio of each mixture is, methacrylic acid: azo-bis-isobutyl cyanide: trithiocarbonate=100:0.5-1:0.01-1, and the volume ratio of polymer monomer and solvent is, polymer monomer: oxolane=1:1-2; Polymerization rate described in this step raises and accelerates with reaction temperature; Made polymer molecular weight increases and reduces with the content of trithiocarbonate in reaction raw materials, with the increase in reaction time, reduces; Solvent for use preferably can dissolve the minimum of added solid matter completely.
2) solution step 1) being obtained precipitates in methyl alcohol, and then filtration drying obtains polymer.
3) press lithium ion and titanium ion mol ratio Li
+: Ti
+=0.8:1 takes lithium-containing compound lithium carbonate and titanium-containing oxide anatase titanium dioxide, and take by the 5%-20% of the mass fraction of lithium carbonate and anatase titanium dioxide total weight the polymer that (step 2) obtains, adding deionized water is dispersant ball milling 4-8 hour in ball grinder, obtains the mixed slurry mixing; Lithium ion in this step and titanium ion mol ratio convert with lithium, titanium mol ratio in product lithium titanate; Lithium titanate material conductivity increases with polymer content, and specific capacity increases and reduces with polymer content; Described Ball-milling Time be take mixture becomes uniform sizing material as benchmark, and those skilled in the art can select described Ball-milling Time voluntarily according to this area knowledge.
4) mixed slurry step 3) being obtained, mixed slurry is delivered to spray dryer and carries out granulating and drying, obtains dry mixed powder;
5) by the presoma powder of step 4) granulating and drying under nitrogen environment at 400-900
oc roasting temperature 8-16 hour, obtain the coated spinel type lithium titanate material Li of carbon
4ti
5o
12.The perfect crystalline degree of the lithium titanate material in this step improves with the rising of sintering temperature, with the increase of roasting time, improves; The granular size of described lithium titanate material increases with the rising of temperature, with the increase of roasting time, increases.
Embodiment 2
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1) polymer monomer methacrylic acid, azo-initiator 2,2'-Azobis(2,4-dimethylvaleronitrile) and trithiocarbonate are dissolved in to oxolane and are mixed with mixed solution, in nitrogen atmosphere 80
oat C temperature, react 5 hours, this course of reaction is carried out in closed reactor.Wherein the mol ratio of each mixture is, methacrylic acid: azo-bis-isobutyl cyanide: trithiocarbonate=100:1:0.5, and the volume ratio of polymer monomer and solvent is, polymer monomer: oxolane=1:2;
2) solution step 1) being obtained precipitates in methyl alcohol, and then filtration drying obtains polymer.
3) press lithium ion and titanium ion mol ratio Li
+: Ti
+=0.8:1 takes lithium-containing compound lithium carbonate and titanium-containing oxide anatase titanium dioxide, and take by 5% of the mass fraction of lithium carbonate and anatase titanium dioxide total weight the polymer that (step 2) obtains, adding deionized water is dispersant ball milling 4 hours in ball grinder, obtains the mixed slurry mixing;
4) mixed slurry step 3) being obtained is delivered to spray dryer, and the dry inlet temperature of spraying is 150
oC-250
oC, outlet temperature is 100
oC-150
oC, charging rate is 0.01-0.1L/min, carries out granulating and drying; Inlet temperature and the charging rate of this step are greater than 100 with outlet temperature
oc is criterion, and those skilled in the art can select with reference to the viscosity of described slurry voluntarily according to this area knowledge.
5), by presoma powder high-temperature roasting under nitrogen environment of step 4) granulating and drying, roasting process adopts two-stage roasting.First according to 1-10
othe programming rate of C/min, is elevated to 400 from room temperature
oc-600
oc, and keep 4-8 hour; Then according to the programming rate of 1-10 ℃/min, temperature is elevated to 700
oc-900
oc, and keep 4-8 hour; The coated spinel type lithium titanate material Li of carbon obtaining
4ti
5o
12.Two-stage roasting in this step completes in same high temperature reaction stove, and first paragraph roasting makes lithium-containing compound form oxide, and second segment roasting forms lithium titanate crystallization, adopt two-stage roasting technique, lithium titanate crystallite dimension is little, and energy resource consumption is few, low for equipment requirements, easily realize suitability for industrialized production.
Embodiment 3
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1) polymer monomer methyl methacrylate, initator azo-bis-isobutyl cyanide and trithiocarbonate are dissolved in to oxolane and are mixed with solution, in nitrogen atmosphere 70
oat C temperature, react 10 hours.Wherein mol ratio is, methyl methacrylate: azo-bis-isobutyl cyanide: trithiocarbonate=100:0.5:0.1, methyl methacrylate: oxolane=1:1.5;
2) solution step 1) being obtained precipitates in methyl alcohol, and then filtration drying obtains polymer;
3) press lithium ion and titanium ion mol ratio Li
+: Ti
+=0.8:1 takes lithium-containing compound lithium hydroxide and titanium-containing oxide rutile titanium dioxide, and take by 10% of the mass fraction of lithium-containing compound and titanium-containing oxide total weight the polymer that (step 2) obtains, adding deionized water is dispersant ball milling 6 hours in ball grinder, obtains the mixed slurry mixing;
4) mixed slurry step 3) being obtained, is delivered to spray dryer, and the dry inlet temperature of spraying is 200
oC, outlet temperature is 125
oC, charging rate is 0.1L/min, carries out granulating and drying;
5), by presoma powder high-temperature roasting under nitrogen environment of step 4) granulating and drying, roasting process adopts two-stage roasting, first according to 5
othe programming rate of C/min, is elevated to 450 from room temperature
oc, and keep 5 hours; Then according to the programming rate of 5 ℃/min, temperature is elevated to 850
oc, and keep 7 hours; The coated spinel type lithium titanate material Li of carbon obtaining
4ti
5o
12.
Embodiment 4
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1) polymer monomer styrene, initator azo-bis-isobutyl cyanide and trithiocarbonate are dissolved in to oxolane and are mixed with solution, in nitrogen atmosphere 90
oat C temperature, react 8 hours.Wherein mol ratio is monomer: initator: trithiocarbonate=100:0.5:1, and the volume ratio of monomer and solvent is monomer: oxolane=1:1;
2) solution step 1) being obtained precipitates in methyl alcohol, and then filtration drying obtains polymer;
3) press lithium ion and titanium ion mol ratio Li
+: Ti
+=0.8:1 takes lithium-containing compound lithium acetate and titanium-containing oxide anatase titanium dioxide, and take by 15% of the mass fraction of lithium-containing compound and titanium-containing oxide total weight the polymer that (step 2) obtains, adding deionized water is dispersant ball milling 8 hours in ball grinder, obtains the mixed slurry mixing;
4) mixed slurry step 3) being obtained, is delivered to spray dryer, and the dry inlet temperature of spraying is 150
oC, outlet temperature is 100
oC, charging rate is 0.01L/min, carries out granulating and drying;
5), by presoma powder high-temperature roasting under nitrogen environment of step 4) granulating and drying, roasting process adopts two-stage roasting.First according to 1
othe programming rate of C/min, is elevated to 550 from room temperature
oc, and keep 4 hours; Then according to the programming rate of 1 ℃/min, temperature is elevated to 750
oc, and keep 6 hours; The coated spinel type lithium titanate material Li of carbon obtaining
4ti
5o
12.
Embodiment 5
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1mol ethyl acrylate, 0.005mol initator azo-bis-isobutyl cyanide and 0.01mol trithiocarbonate are dissolved in to 100ml oxolane and are mixed with solution, in nitrogen atmosphere 80
oat C temperature, react 8 hours, the solution obtaining precipitates and obtains polymer in benzinum.Take 1mol lithium carbonate and 2.5mol anatase titanium dioxide, the polymer 13.68g that adds step (2) to obtain, adding deionized water is dispersant ball milling 8 hours in ball grinder, obtains the mixed slurry mixing and is delivered to spray dryer.The dry inlet temperature of spraying is 150
oC, outlet temperature is 100
oC, charging rate is 0.05L/min, the high-temperature roasting under nitrogen environment of the powder of granulating and drying.First according to 10
othe programming rate of C/min, is elevated to 550 from room temperature
oc, and keep 4 hours; Then according to the programming rate of 10 ℃/min, temperature is elevated to 750
oc, and keep 6 hours; The coated spinel type lithium titanate material Li of carbon obtaining
4ti
5o
12.
Embodiment 6
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1mol acrylic acid, 0.005mol initator azo-bis-isobutyl cyanide and 0.001mol trithiocarbonate are dissolved in to 80ml oxolane and are mixed with solution, in nitrogen atmosphere 85
oat C temperature, react 10 hours, the solution obtaining precipitates and obtains polymer in methyl alcohol.Take 1mol lithium hydroxide and 1.25mol anatase titanium dioxide, the polymer 12.38g that adds step (2) to obtain, adding deionized water is dispersant ball milling 6 hours in ball grinder, obtains the mixed slurry mixing and is delivered to spray dryer.The dry inlet temperature of spraying is 150
oC, outlet temperature is 100
oC, charging rate is 0.1L/min, the high-temperature roasting under nitrogen environment of the powder of granulating and drying.First according to 3
othe programming rate of C/min, is elevated to 500 from room temperature
oc, and keep 5 hours; Then according to the programming rate of 3 ℃/min, temperature is elevated to 900
oc, and keep 5 hours; The coated spinel type lithium titanate material Li of carbon obtaining
4ti
5o
12.
Embodiment 7
A preparation method for the coated lithium titanate anode material of carbon for lithium battery, prepares by following steps:
1mol EMA, 0.005mol initator azo-bis-isobutyl cyanide and 0.05mol trithiocarbonate are dissolved in to 100ml oxolane and are mixed with solution, in nitrogen atmosphere 90
oat C temperature, react 6 hours, the solution obtaining precipitates and obtains polymer in ethanol.Take 1mol lithium acetate and 1.25mol anatase titanium dioxide, the polymer 30.28g that adds step (2) to obtain, adding deionized water is dispersant ball milling 5 hours in ball grinder, obtains the mixed slurry mixing and is delivered to spray dryer.The dry inlet temperature of spraying is 200
oC, outlet temperature is 125
oC, charging rate is 0.1L/min, the high-temperature roasting under nitrogen environment of the powder of granulating and drying.First according to 3
othe programming rate of C/min, is elevated to 550 from room temperature
oc, and keep 5 hours; Then according to the programming rate of 3 ℃/min, temperature is elevated to 850
oc, and keep 5 hours; The coated spinel type lithium titanate material Li of carbon obtaining
4ti
5o
12.
By the 8:1:1 mixing in mass ratio of electrode material, conductive agent carbon black and the bonding agent Kynoar (PVDF) of embodiment 3 preparations, add 1-METHYLPYRROLIDONE (NMP) to be modulated into slurry, and be evenly coated on Copper Foil, 100
oCin vacuum, be dried after 12 hours, with tablet press machine, pole piece compacting evenly obtained to pole piece to be measured.Take lithium sheet as to electrode, and electrolyte is 1mol/L concentration LiPF
6the solution of ethyl carbonate ester (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), barrier film adopts the battery diaphragm that model is celgard2325, is assembled into CR2032 type button cell in the glove box of argon gas atmosphere.The battery that the negative material of example 2 preparations fills is done constant current charge-discharge test in 1-2.5V voltage range, at 1C(175mA/g) under multiplying power, first discharge specific capacity is 163.8mAh/g, and initial charge specific capacity is 160.2mAh/g, and first charge-discharge efficiency is 97.8%; Its specific discharge capacity after 800 times that circulates is 147.4mAh/g, and charge ratio capacity is 147.3mAh/g.
Embodiment 9
The electrode material that embodiment 5 is prepared is assembled into button heart test battery according to method described in example 7, in 1-2.5V voltage range, do constant current charge-discharge test, at 1C(175mA/g) under multiplying power, its first charge-discharge curve as shown in Figure 1, first discharge specific capacity is 164.8mAh/g, initial charge specific capacity is 153.8mAh/g, and first charge-discharge efficiency is 93.3%; Its specific discharge capacity after 800 times that circulates is 163.4mAh/g, and charge ratio capacity is 163.3mAh/g.
Claims (9)
1. a preparation method for the coated lithium titanate anode material of carbon for lithium battery, is characterized in that: comprise the following steps:
(1) polymer monomer, azo-initiator and trithiocarbonate are dissolved in to oxolane and are mixed with solution, 70-90 in nitrogen atmosphere
oat C temperature, react 5-10 hour, obtain mixed solution, wherein, polymer monomer: azo-initiator: the mol ratio of trithiocarbonate is 100:0.5-1:0.01-1, the volume ratio of polymer monomer and oxolane is 1:1-2;
(2) mixed solution step (1) being obtained precipitates and obtains polymer carbon source in precipitation reagent;
(3) press lithium ion and titanium ion mol ratio Li
+: Ti
+=0.8:1 takes lithium-containing compound and titanium-containing oxide, and take by the 5%-20% of the mass fraction of lithium-containing compound and titanium-containing oxide total weight the polymer carbon source that step (2) obtains, adding deionized water is dispersant ball milling 4-8 hour in ball grinder, obtains the mixed slurry mixing;
(4) mixed slurry step (3) being obtained is delivered to spray dryer and carries out granulating and drying, obtains dry mixed powder;
(5) by the presoma powder of step (4) granulating and drying under inert gas environment, at 400-900
oc roasting temperature 8-16 hour, the coated spinel type lithium titanate material Li of carbon of acquisition
4ti
5o
12.
2. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1, is characterized in that: roasting process two steps in described step (5), and first according to 1-10
othe programming rate of C/min, is elevated to 400 from room temperature
oc-600
oc, and keep 4-8 hour; Then according to the programming rate of 1-10 ℃/min, temperature is elevated to 700
oc-900
oc, and keep 4-8 hour.
3. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: described azo-initiator is azo-bis-isobutyl cyanide or 2,2'-Azobis(2,4-dimethylvaleronitrile).
4. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: described polymer monomer is any one in acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, EMA, styrene.
5. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: described precipitation reagent is any one in methyl alcohol, ethanol, benzinum.
6. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: described lithium-containing compound comprise in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate one or several arbitrarily than mixture.
7. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: described titanium-containing oxide comprise in rutile titanium dioxide, anatase titanium dioxide one or several arbitrarily than mixture.
8. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: in step (4), described granulating and drying is specially: the dry inlet temperature of spraying is 150
oC-250
oC, outlet temperature is 100
oC-150
oC, charging rate is 0.01-0.1L/min.
9. the preparation method of the coated lithium titanate anode material of carbon for a kind of lithium battery according to claim 1 and 2, is characterized in that: described inert gas comprise in helium, argon gas, nitrogen one or several arbitrarily than mixture.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104505502A (en) * | 2014-12-26 | 2015-04-08 | 宁夏共享新能源材料有限公司 | Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material |
| CN104600280A (en) * | 2015-01-27 | 2015-05-06 | 中国东方电气集团有限公司 | Method for preparing carbon-coated lithium titanate |
| CN104733699A (en) * | 2015-03-20 | 2015-06-24 | 常州大学 | Method for preparing molybdenum dioxide coated lithium titanate negative electrode material |
| CN108336341A (en) * | 2018-02-28 | 2018-07-27 | 江苏金阳光新能源科技有限公司 | A kind of preparation method of high performance lithium ionic cell cathode material |
| CN108520953A (en) * | 2018-04-17 | 2018-09-11 | 吉林大学 | A kind of carbon coating lithium titanate negative material and preparation method thereof |
| CN109004196A (en) * | 2018-07-24 | 2018-12-14 | 大连理工大学 | A kind of preparation method of cotton cladding lithium titanate anode material |
| DE112018000205T5 (en) | 2017-02-21 | 2019-08-14 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | A METHOD FOR PRODUCING A POWERFUL LITHIUM TITANATE ANODE MATERIAL FOR APPLICATIONS OF LITHIUM-ION ACCUMULATORS |
| CN112290012A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Preparation method of ternary cathode material of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104505502A (en) * | 2014-12-26 | 2015-04-08 | 宁夏共享新能源材料有限公司 | Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material |
| US9923199B2 (en) * | 2015-01-27 | 2018-03-20 | Dongfang Electric Corporation | Method for preparing carbon-coated lithium titanate |
| CN104600280A (en) * | 2015-01-27 | 2015-05-06 | 中国东方电气集团有限公司 | Method for preparing carbon-coated lithium titanate |
| US20160218355A1 (en) * | 2015-01-27 | 2016-07-28 | Dongfang Electric Corporation | Method for Preparing Carbon-Coated Lithium Titanate |
| CN104733699A (en) * | 2015-03-20 | 2015-06-24 | 常州大学 | Method for preparing molybdenum dioxide coated lithium titanate negative electrode material |
| CN104733699B (en) * | 2015-03-20 | 2017-02-01 | 常州大学 | Method for preparing molybdenum dioxide coated lithium titanate negative electrode material |
| DE112018000205T5 (en) | 2017-02-21 | 2019-08-14 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | A METHOD FOR PRODUCING A POWERFUL LITHIUM TITANATE ANODE MATERIAL FOR APPLICATIONS OF LITHIUM-ION ACCUMULATORS |
| US11001506B2 (en) | 2017-02-21 | 2021-05-11 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | Method of producing high performance lithium titanate anode material for lithium ion battery applications |
| CN108336341A (en) * | 2018-02-28 | 2018-07-27 | 江苏金阳光新能源科技有限公司 | A kind of preparation method of high performance lithium ionic cell cathode material |
| CN108520953A (en) * | 2018-04-17 | 2018-09-11 | 吉林大学 | A kind of carbon coating lithium titanate negative material and preparation method thereof |
| CN109004196A (en) * | 2018-07-24 | 2018-12-14 | 大连理工大学 | A kind of preparation method of cotton cladding lithium titanate anode material |
| CN112290012A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Preparation method of ternary cathode material of lithium ion battery |
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