CN102637851A - Preparation method of carbon-doped magniferous lithium titanate for lithium ion battery - Google Patents
Preparation method of carbon-doped magniferous lithium titanate for lithium ion battery Download PDFInfo
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- CN102637851A CN102637851A CN2012101281751A CN201210128175A CN102637851A CN 102637851 A CN102637851 A CN 102637851A CN 2012101281751 A CN2012101281751 A CN 2012101281751A CN 201210128175 A CN201210128175 A CN 201210128175A CN 102637851 A CN102637851 A CN 102637851A
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- lithium
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- lithium titanate
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of carbon-doped magniferous lithium titanate Li4-xMgTi5O12/C for a lithium ion battery. In the formula Li4-xMgTi5O12/C, x is more than or equal to 0.05 and is less than or equal to 0.5. The preparation method comprises the following steps: weighing a lithium source, titanium dioxide and a magnesium source in the molar ratio of (3.5-3.95):5.0:(0.05-0.5); adding acetylene black or activated carbon the weigh of which is 2.0-10.0% of that of the mixture obtained in the former step and carrying out ball milling for 0.5-4 hours; calcining the mixture subjected to ball milling at the argon atmosphere; carrying out heat preservation at the temperature of 550-650DEG C for 6-12 hours; then carrying out heat preservation at the temperature of 800-950DEG C for 2-6 hours; and cooling to room temperature along with a furnace to obtain carbon-doped magniferous lithium titanate Li4-xMgTi5O12/C. The preparation method has the biggest advantages that Li4-xMgTi5O12/C shows high discharge specific capacity and excellent circulating stability under the condition of high multiplying power, especially 10C discharging while high reversible specific capacity is obtained. The method is simple and safe in technical process and low in cost, and industrial production is easy to realize.
Description
Technical field
The invention belongs to the energy and material preparation method, particularly a kind of carbon dope contains magnesium lithium titanate Li
4-xMg
xTi
5O
12The preparation method of/C.
Background technology
Lithium ion battery has obtained extensive use owing to have advantages such as high-energy-density, high voltage and environmental friendliness in portable type electronic product, and electrode material wherein is the key factor of restriction battery industry development.At present, commercial negative material with lithium ion battery mainly is various carbon/graphite type material with embedding lithium characteristic, causes internal short-circuit but this battery is prone to form Li dendrite in carbon electrodes when high power pulse charges, and has serious potential safety hazard.Secondly, material with carbon element can produce volumetric expansion to a certain degree in the cycle charge discharge electric process, so that cause the electrode material structural deterioration, reversible capacity is significantly decayed.Therefore, seek safe and reliable and can realize that the novel negative material that high power discharges and recharges is the key that addresses the above problem.
Than traditional carbon negative pole material, spinelle Li
4Ti
5O
12Be a kind of constitutionally stable " zero strain " embedded material, have excellent cyclical stability.In addition, in charge and discharge process, show height and voltage platform (1.55V vs.Li/Li stably
+), with the electrolyte reaction, the fail safe that has improved battery does not prepare Li simultaneously
4Ti
5O
12Raw material cheap and easy to get.Therefore, Li
4Ti
5O
12Receive pursuing of lot of domestic and foreign researcher.But, Li
4Ti
5O
12Structure itself has determined ionic conductivity and the electron conduction that it is low, has influenced the performance of reversible specific capacity and high rate performance like this, thereby limits its practical application.In order to overcome this technical bottleneck, people have done number of research projects: particle size nanometerization, thereby the diffusion length of shortening lithium ion increase and take off/the embedding lithium degree of depth; Carry out carbon through the organic substance thermal decomposition at particle surface and coat the formation conductive network, can improve the reversible specific capacity of material; Another kind of approach is exactly to mix through different valence metal ion, such as Zr
4+, Al
3+, V
5+Deng, increase Ti mixed valence Ti
3+/ Ti
4+Quantity, the conductance of material and high rate capability thereof are improved.In order to obtain nano particle, adopt sol-gel process usually, but that this method prepares process is loaded down with trivial details, the higher and product of cost is unfavorable for electrode processing, the suitability for industrialized production difficulty is bigger; Although carbon coats the reversible specific capacity that can improve material, the inhomogeneous unstable properties that causes material that coats produces the security requirement that a large amount of gas will improve equipment in the course of reaction simultaneously; And the different valence metal ion that mixes has improved the high rate capability of material to a certain extent; But not obvious to the effect that improves reversible specific capacity, even reduce reversible specific capacity, most of doped chemicals belong to rare metal simultaneously; Cost an arm and a leg, be difficult to satisfy the wilderness demand of energy field.The lithium titanate material of modification is not at present taken into account on reversible specific capacity and high rate capability simultaneously; Even the lithium titanate material after some modification can keep better electrochemical performance under low range; But the chemical property under high magnification is then not ideal enough, only is confined to the application on the low-power equipment.So, explore and a kind ofly can improve the simple method for preparing that reversible specific capacity can improve high rate capability again and seem particularly important.Magnesium metal and simple substance carbon have advantages such as excellent conductivity and low price, and the employing carbon dope is mixed the method for magnesium again to improve between the material granule and the electronic conduction ability of crystals, improves reversible specific capacity then and improves the high current charge-discharge high rate performance.
(" power technology " 2010,34 (8) 793-796) introduced a kind of solid phase synthesis magnesium Li doped to Yin Yanhong etc.
4Ti
5O
12The preparation method of/C composite material is with Li
2CO
3And TiO
2Be dissolved in the absolute ethyl alcohol after weighing at 4: 5 by mass ratio, add 9% and 1% glucose and magnesium lactate respectively as carbon source and Mg ion doping source, under nitrogen atmosphere, 600～800 ℃ of sintering form.This method is through organic substance thermal decomposition to take place in high-temperature reaction process to carry out the carbon coating, is difficult to guarantee the uniformity of carbon coating layer like this, cause material property unstable, and the magnesium that adds seldom, and is not obvious to the improvement effect of electronic conductivity.When this material uses as lithium ion battery negative, under the C/3 multiplying power its for the second time specific discharge capacity can reach 162.0mAh/g, but cycle performance is poor, specific discharge capacity is 150.0mAh/g after 30 charge and discharge cycles, the specific capacity retention is merely 92.6%.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion battery and contain magnesium lithium titanate Li with carbon dope
4-xMg
xTi
5O
12/ C, the preparation method of 0.05≤x≤0.5 to overcome the defective on the prior art, solves the problem that existing lithium titanate reversible specific capacity and high-rate charge-discharge capability can not be taken into account simultaneously.
Method of the present invention is made up of following steps: (1) takes by weighing lithium source, titanium dioxide and magnesium source in molar ratio at 3.5～3.95: 5.0: 0.05～0.5, presses 2.0～10.0% of said mixture mass percent and adds acetylene black or activated carbon, ball milling 0.5～4 hour; (2) mixture behind step (1) ball milling is placed under the argon gas atmosphere calcine, 550～650 ℃ of insulations 6～12 hours down are then 800～950 ℃ of insulations 2～6 hours down; (3) cool to room temperature with the furnace, obtain carbon dope and contain magnesium lithium titanate Li
4-xMg
xTi
5O
12/ C.
Said titanium dioxide is micron or nano-scale anatase titanium dioxide.
Said lithium source is lithium carbonate or lithium hydroxide.
Said magnesium source is magnesium acetate, magnesium carbonate or magnesium hydroxide.
Lithium ion battery of the present invention is used Li
4-xMg
xTi
5O
12The preparation method of/C replaces the back in order to keep whole charge balance, part Ti owing to the part lithium ion of tetrahedron 8a position in the magnesium-doped replacement crystal structure
4+Convert high conductive Ti into
3+, and number of cavities also increases thereupon, help the raising of material electronics conductance and ionic conductivity, thereby the high rate performance of material and cycle performance improves.Simultaneously directly add carbon in the batch mixing process; Can increase the uniformity coefficient of raw materials mix, carbon can suppress the growth of product particle effectively in course of reaction, can obtain the particle of the little and good dispersion of particle diameter; And between particle, form conductive network; Improve the electronic conductivity of material, reduce polarization, increase reversible specific capacity.Mix magnesium and the carbon dope acting in conjunction makes Li
4-xMg
xTi
5O
12The conductance of/C negative material is significantly improved, and reversible specific capacity and high magnification cyclical stability are taken into account simultaneously.
Lithium ion battery of the present invention contains magnesium lithium titanate Li with carbon dope
4-xMg
xTi
5O
12/ C, in the general formula when x greater than 0.5 the time, too much magnesium can not get in the crystal structure, but with the impurity phase segregation in crystallite at the interface, has hindered the migration of lithium ion like this, reduces the purity of lithium titanate, has a strong impact on the performance of specific capacity; And when x less than 0.05 the time, in ion replacement process, but can not produce the mixed valence Ti of sufficient amount
3+/ Ti
4+, do not have the effect of improving conductivity.Could obtain the high rate performance that high reversible specific capacity is become reconciled when having only value as x suitable.Equally, when the addition of carbon during greater than 10.0wt%, the actual active material of participating in electrode reaction just reduces and the migration of lithium ion is formed obstacle, and reversible specific capacity is lower.And the addition of carbon is when being lower than 2.0wt%, and the electron transport ability of material is not enough, and degree of polarization increases the weight of.So the addition of carbon also must be controlled at a comparatively suitable scope, material could obtain high reversible specific capacity.
Biggest advantage of the present invention is Li
4-xMg
xTi
5O
12/ C is when obtaining higher reversible specific capacity, and high magnification especially also shows high specific discharge capacity and good cyclical stability under the 10C discharging condition.This method technical process is simple, safety, and cost is low, is prone to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the Li of embodiment 9
4-xMg
xTi
5O
12/ CX diffracting spectrum;
Fig. 2 is the Li of embodiment 9
4-xMg
xTi
5O
12/ C charging and discharging curve for the second time under the C/3 multiplying power;
Fig. 3 is the Li of embodiment 9
4-xMg
xTi
5O
12/ C is preceding 50 times cycle performance curve under C/3,10C multiplying power respectively.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but the present invention is not limited to following embodiment.
Embodiment 1
Took by weighing lithium carbonate, nano-scale anatase titanium dioxide and magnesium carbonate in 3.95: 5.0: 0.05 in molar ratio, add the activated carbon of said mixture mass percent 10.0% then, ball milling 3.5 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 12 hours down, then 800 ℃ of insulations 6 hours at 500 ℃; Cool to room temperature with the furnace, obtain Li
3.95Mg
0.05Ti
5O
12/ C.
Embodiment 2
Took by weighing lithium carbonate, micron order anatase titanium dioxide and magnesium acetate in 3.5: 5.0: 0.5 in molar ratio, add the acetylene black of said mixture mass percent 2.0% then, ball milling 3 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 8 hours down, then 850 ℃ of insulations 4 hours at 550 ℃; Cool to room temperature with the furnace, obtain Li
3.5Mg
0.5Ti
5O
12/ C.
Took by weighing lithium hydroxide, nano-scale anatase titanium dioxide and magnesium carbonate in 3.9: 5.0: 0.1 in molar ratio, add the activated carbon of said mixture mass percent 4.0% then, ball milling 3.5 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 10 hours down, then 900 ℃ of insulations 2 hours at 600 ℃; Cool to room temperature with the furnace, obtain Li
3.9Mg
0.1Ti
5O
12/ C.
Embodiment 4
Took by weighing lithium carbonate, micron order anatase titanium dioxide and magnesium carbonate in 3.7: 5.0: 0.3 in molar ratio, add the activated carbon of said mixture mass percent 4.0% then, ball milling 2 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 6 hours down, then 950 ℃ of insulations 4 hours at 650 ℃; Cool to room temperature with the furnace, obtain Li
3.7Mg
0.3Ti
5O
12/ C.
Embodiment 5
Took by weighing lithium carbonate, micron order anatase titanium dioxide and magnesium acetate in 3.8: 5.0: 0.2 in molar ratio, add the activated carbon of said mixture mass percent 6.0% then, ball milling 1.5 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 8 hours down, then 900 ℃ of insulations 4 hours at 650 ℃; Cool to room temperature with the furnace, obtain Li
3.8Mg
0.2Ti
5O
12/ C.
Embodiment 6
Took by weighing lithium carbonate, micron order anatase titanium dioxide and magnesium hydroxide in 3.9: 5.0: 0.1 in molar ratio, add the acetylene black of said mixture mass percent 6.0% then, ball milling 0.5 hour; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 8 hours down, then 900 ℃ of insulations 6 hours at 600 ℃; Cool to room temperature with the furnace, obtain Li
3.9Mg
0.1Ti
5O
12/ C.
Embodiment 7
Took by weighing lithium hydroxide, micron order anatase titanium dioxide and magnesium acetate in 3.5: 5.0: 0.5 in molar ratio, add the activated carbon of said mixture mass percent 10.0% then, ball milling 1 hour; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 12 hours down, then 850 ℃ of insulations 4 hours at 500 ℃; Cool to room temperature with the furnace, obtain Li
3.5Mg
0.5Ti
5O
12/ C.
Embodiment 8
Took by weighing lithium carbonate, nano-scale anatase titanium dioxide and magnesium carbonate in 3.7: 5.0: 0.3 in molar ratio, add the acetylene black of said mixture mass percent 2.0% then, ball milling 2.5 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 10 hours down, then 950 ℃ of insulations 2 hours at 550 ℃; Cool to room temperature with the furnace, obtain Li
3.7Mg
0.3Ti
5O
12/ C.
Embodiment 9
Took by weighing lithium carbonate, nano-scale anatase titanium dioxide and magnesium acetate in 3.8: 5.0: 0.2 in molar ratio, add the acetylene black of said mixture mass percent 6.0% then, ball milling 4 hours; Place the argon gas atmosphere stove to calcine in the mixture behind the ball milling, be incubated 8 hours down, then 900 ℃ of insulations 4 hours at 650 ℃; Cool to room temperature with the furnace, obtain Li
3.8Mg
0.2Ti
5O
12/ C.
Electrochemical property test: with embodiment 1～9 prepared Li
4-xMg
xTi
5O
12/ C, polyvinylidene fluoride (PVDF) and acetylene black are fully mixed the line number hour grinding of going forward side by side by mass ratio at 80: 10: 10, are solvent with N-methyl pyrrolidone (NMP), stir fast and form slurry.Slurry is coated on the Al paper tinsel disk that 20 μ m are thick, diameter is 14mm equably processes wet electrode; Place wet electrode then and carry out drying under 60 ℃, treat baking after half-dried, use tablet press machine compacting electrode; At 120 ℃ of following vacuumize 12h, make work electrode subsequently.In being full of the vacuum glove box of argon gas with work electrode, metal lithium sheet, Celgard2400 barrier film, 1mol/L LiPF
6EC+DEC (volume ratio 1: 1) electrolyte be assembled into 2032 type button cells, button cell leaves standstill and carries out electric performance test, test result such as table 1 after 24 hours.
The performance of table 1 embodiment sample relatively
Carry out the constant current charge-discharge test respectively with C/3, voltage range is 1.0～3.0V, and the charging and discharging curve second time of test implementation example 9 gained samples is as shown in Figure 2, and its reversible specific capacity is 160.0mAh/g.With embodiment 9 prepared Li
3.8Mg
0.2Ti
5O
12/ C dresses up button cell and under C/3,10C multiplying power, carries out preceding 50 cycle charge-discharges respectively, and test result is as shown in Figure 3.With C/3 rate charge-discharge circulation time, the specific capacity retention after 50 circulations is up to 98.9%.Li of the present invention
3.8Mg
0.2Ti
5O
12Specific discharge capacity can be up to 118.1mAh/g for the second time under the 10C multiplying power for/C, still keeps higher specific capacity after 50 circulations, and its retention is 97.6%, shows good high magnification cyclical stability.
Claims (4)
1. a lithium ion battery contains magnesium lithium titanate Li with carbon dope
4-xMg
xTi
5O
12/ C; 0.05 the preparation method of≤x≤0.5; It is characterized in that being made up of following steps: (1) takes by weighing lithium source, titanium dioxide and magnesium source in molar ratio at 3.5～3.95: 5.0: 0.05～0.5; Press 2.0～10.0% of said mixture mass percent and add acetylene black or activated carbon, ball milling 0.5～4 hour; (2) mixture behind step (1) ball milling is placed under the argon gas atmosphere calcine, 550～650 ℃ of insulations 6～12 hours down are then 800～950 ℃ of insulations 2～6 hours down; (3) cool to room temperature with the furnace, obtain carbon dope and contain magnesium lithium titanate Li
4-xMg
xTi
5O
12/ C.
2. carbon dope according to claim 1 contains magnesium lithium titanate Li
4-xMg
xTi
5O
12The preparation method of/C is characterized in that described titanium dioxide is micron or nano-scale anatase titanium dioxide.
3. carbon dope according to claim 1 contains magnesium lithium titanate Li
4-xMg
xTi
5O
12The preparation method of/C is characterized in that described lithium source is lithium carbonate or lithium hydroxide.
4. carbon dope according to claim 1 contains magnesium lithium titanate Li
4-xMg
xTi
5O
12The preparation method of/C is characterized in that described magnesium source is magnesium acetate, magnesium carbonate or magnesium hydroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107403927A (en) * | 2017-07-11 | 2017-11-28 | 大连理工大学 | A kind of preparation method of Mg doped titanic acids lithium titanate cathode material |
| CN109301236A (en) * | 2018-08-17 | 2019-02-01 | 中北润良新能源汽车(徐州)股份有限公司 | A kind of solid reaction process improving 1.55V lithium titanate battery capacity |
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| CN1837057A (en) * | 2006-04-13 | 2006-09-27 | 复旦大学 | Li4Ti5O12 materials with spinel structure and preparation process and use thereof |
| CN101630732A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium titanate compound and preparation method thereof |
| CN101764207A (en) * | 2009-09-25 | 2010-06-30 | 合肥工业大学 | Lithium titanate for lithium ion battery negative electrode material and preparation method thereof |
| CN101777644A (en) * | 2010-02-05 | 2010-07-14 | 中国科学院新疆理化技术研究所 | Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate |
-
2012
- 2012-04-26 CN CN2012101281751A patent/CN102637851A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837057A (en) * | 2006-04-13 | 2006-09-27 | 复旦大学 | Li4Ti5O12 materials with spinel structure and preparation process and use thereof |
| CN101630732A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium titanate compound and preparation method thereof |
| CN101764207A (en) * | 2009-09-25 | 2010-06-30 | 合肥工业大学 | Lithium titanate for lithium ion battery negative electrode material and preparation method thereof |
| CN101777644A (en) * | 2010-02-05 | 2010-07-14 | 中国科学院新疆理化技术研究所 | Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107403927A (en) * | 2017-07-11 | 2017-11-28 | 大连理工大学 | A kind of preparation method of Mg doped titanic acids lithium titanate cathode material |
| CN109301236A (en) * | 2018-08-17 | 2019-02-01 | 中北润良新能源汽车(徐州)股份有限公司 | A kind of solid reaction process improving 1.55V lithium titanate battery capacity |
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Application publication date: 20120815 |