CN103346310A - Preparation method of carbon-clad holmium-doped lithium titanate composite negative material - Google Patents
Preparation method of carbon-clad holmium-doped lithium titanate composite negative material Download PDFInfo
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- CN103346310A CN103346310A CN2013102895416A CN201310289541A CN103346310A CN 103346310 A CN103346310 A CN 103346310A CN 2013102895416 A CN2013102895416 A CN 2013102895416A CN 201310289541 A CN201310289541 A CN 201310289541A CN 103346310 A CN103346310 A CN 103346310A
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- holmium
- doped lithium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 relates to a preparation method of a carbon-clad holmium-doped lithium titanate composite negative material. The preparation method comprises the following steps of: (1) preparing carbon particles for the cladding; (2) mixing lithium hydrogencarbonate, titanium dioxide and holmium oxide serving as raw materials, adding the carbon particles for the cladding accounting for 3 to 5 percent by weight of the general weight of the three raw materials, adding an acetone dispersing agent, carrying out ball milling on a ball milling machine, and carrying out vacuum drying on the mixture to obtain a carbon-clad holmium-doped lithium titanate precursor; (3) sintering the dried carbon-clad holmium-doped lithium titanate precursor under a helium atmosphere to obtain a product. According to the carbon-clad holmium-doped lithium titanate composite negative material for a lithium ion battery, the conductive performance of the lithium titanate is improved by doping the holmium with the lithium titanate, and the conductivity and cycling stability of the battery can be further improved by cladding the lithium titanate with the carbon particles which are prepared through a specific process and has a hollow structure.
Description
Affiliated technical field
The present invention relates to the preparation method that a kind of carbon coats holmium doped lithium titanate composite negative pole material.
Background technology
The world today, petroleum resources are day by day nervous, and environmental pollution is on the rise, and forces various countries to strive to find the novel energy of sustainable development.Along with Aero-Space, defence and military, communications and transportation, electronic information and instrument and meter, especially practical application such as electric automobile is urgent day by day to the demand of high power density, wide temperature range energy storage system, is the focus that the environmental protection energy storage device of representative has become current concern with lithium ion battery, ultracapacitor or super capacitance cell.The performance of electrode material and preparation technology are determining the performance of energy storage device to a great extent, so the research of battery material is particularly important.
Lithium ion battery has advantages such as high-energy-density, high working voltage, memory-less effect, is expected to one of major impetus source that becomes by electric automobile.At present, though the graphite-like carbon negative pole material successfully is applied in the lithium ion battery, because the current potential of the current potential of carbon electrode and lithium metal is very approaching, easily the precipitating metal lithium forms dendrite, has potential safety hazard; Lithium ion embeds repeatedly and deviates from simultaneously, and material structure can be damaged and cause capacity attenuation.Lithium titanate (Li with spinel structure
4Ti
5O
12) be considered to that one of negative material of application prospect is arranged most.In lithium ion embedding and subtractive process, the lithium titanate with spinel structure unit cell volume is constant substantially, thereby is called as " zero strain " material.Lithium titanate with spinel structure is as the cathode of lithium battery of a new generation, and structure and physico-chemical property are stable, not with electrolyte reaction, good cycle.Because its stability of structure becomes safety and extended-life lithium ion battery negative material; Spinelle Li
4Ti
5O
12Chemical diffusion coefficient at normal temperatures is 2 * 10
-8Cm
2/ s, than big 1 order of magnitude of carbon negative pole material, the speed that discharges and recharges is faster.But as lithium ion battery negative material, the intrinsic conductivity of lithium titanate is 10
-9S/cm belongs to typical insulator, poorly conductive, and heavy-current discharge performance is poor.
Summary of the invention
For overcoming above-mentioned deficiency, the invention provides the preparation method that a kind of carbon coats holmium doped lithium titanate composite negative pole material, use the negative material of this method preparation, have higher capacity and excellent conducting performance and cyclical stability.
To achieve these goals, a kind of carbon provided by the invention coats the preparation method of holmium doped lithium titanate composite negative pole material, comprises the steps:
(1) preparation coats and uses carbon particle
As oil-phase component, the monomer divinylbenzene of 100 weight portions, the hollow agent pentane of 100-150 weight portion, the nano silica fume of 5-10 weight portion, the acetone dispersant of 7-10 weight portion are mixed, after ultrasonic wave disperses, and then add organic peroxide as polymerization initiator, make monomer mixture, in addition, as water-phase component, the deionized water of 500 weight portions, the POLYPROPYLENE GLYCOL as dispersant of 10-20 weight portion are mixed;
The oil-phase component and the water-phase component that obtain are mixed, disperse with ultrasonic wave, make suspension, with the suspension that obtains under helium flow, temperature 90-95 ℃ stirs down, keeps 8-10h, with polymerization and particle clean drying, obtain resin particle, with the resin particle that obtains under air atmosphere, temperature 400-450 ℃ following heat treatment 1-2h, under helium atmosphere, temperature 1200-1350 ℃ following sintering 4-5h, obtain coating and use carbon particle;
(2) preparation carbon coats holmium doped lithium titanate precursor
Selecting lithium bicarbonate, titanium dioxide and holimium oxide for use is raw material, wherein the mol ratio of lithium bicarbonate and titanium dioxide is 0.805-0.82: 1, holimium oxide accounts for the 0.5-1.5wt% of three kinds of raw material gross weights, after three kinds of raw materials mixing, add the above-mentioned coating carbon particle that accounts for above-mentioned three kinds of raw material gross weight 3-5wt%, add the acetone dispersant, on ball mill, with rotating speed 300-400r/min ball milling 8-10h, get carbon after the vacuumize and coat holmium doped lithium titanate precursor;
(3) sintering
Coat holmium doped lithium titanate precursor sintering under helium atmosphere with getting carbon after the drying, heat up with 5-10 ℃/min speed, at temperature 800-900 ℃ of constant temperature sintering 10-15h, with 10-15 ℃/min cooling, prepare product.
The lithium ion battery of the present invention's preparation coats holmium doped lithium titanate composite negative pole material with carbon, by holmium lithium titanate is mixed to improve the electric conductivity of lithium titanate earlier, the carbon particle with hollow structure by the special process preparation coats then, further improves its conductivity and cyclical stability.Therefore this composite material has charge-discharge velocity and long useful life faster when being used for lithium ion battery.
Embodiment
Embodiment one
As oil-phase component, the monomer divinylbenzene of 100 weight portions, the hollow agent pentane of 100-150 weight portion, the nano silica fume of 5-10 weight portion, the acetone dispersant of 7-10 weight portion are mixed, after ultrasonic wave disperses, and then add organic peroxide as polymerization initiator, make monomer mixture, in addition, as water-phase component, the deionized water of 500 weight portions, the POLYPROPYLENE GLYCOL as dispersant of 10-20 weight portion are mixed.
The oil-phase component and the water-phase component that obtain are mixed, disperse with ultrasonic wave, make suspension, with the suspension that obtains under helium flow, 90 ℃ of temperature stir down, keep 10h, with polymerization and particle clean drying, obtain resin particle, with the resin particle that obtains under air atmosphere, 400 ℃ of following heat treatment 2h of temperature, under helium atmosphere, 1200 ℃ of following sintering 5h of temperature, obtain coating and use carbon particle.
Selecting lithium bicarbonate, titanium dioxide and holimium oxide for use is raw material, wherein the mol ratio of lithium bicarbonate and titanium dioxide is 0.805: 1, holimium oxide accounts for the 0.5wt% of three kinds of raw material gross weights, after three kinds of raw materials mixing, add the above-mentioned coating carbon particle that accounts for above-mentioned three kinds of raw material gross weight 3wt%, add the acetone dispersant, on ball mill, with rotating speed 300r/min ball milling 10h, get carbon after the vacuumize and coat holmium doped lithium titanate precursor.
Coat holmium doped lithium titanate precursor sintering under helium atmosphere with getting carbon after the drying, heat up with 5 ℃/min speed, at 800 ℃ of constant temperature sintering of temperature 15h, with 10 ℃/min cooling, prepare product.
Embodiment two
As oil-phase component, the monomer divinylbenzene of 100 weight portions, the hollow agent pentane of 150 weight portions, the nano silica fume of 10 weight portions, the acetone dispersant of 10 weight portions are mixed, after ultrasonic wave disperses, and then add organic peroxide as polymerization initiator, make monomer mixture, in addition, as water-phase component, the deionized water of 500 weight portions, the POLYPROPYLENE GLYCOL as dispersant of 20 weight portions are mixed.
The oil-phase component and the water-phase component that obtain are mixed, disperse with ultrasonic wave, make suspension, with the suspension that obtains under helium flow, 95 ℃ of temperature stir down, keep 8h, with polymerization and particle clean drying, obtain resin particle, with the resin particle that obtains under air atmosphere, 450 ℃ of following heat treatment 1h of temperature, under helium atmosphere, 1350 ℃ of following sintering 4h of temperature, obtain coating and use carbon particle.
Selecting lithium bicarbonate, titanium dioxide and holimium oxide for use is raw material, wherein the mol ratio of lithium bicarbonate and titanium dioxide is 0.82: 1, holimium oxide accounts for the 1.5wt% of three kinds of raw material gross weights, after three kinds of raw materials mixing, add the above-mentioned coating carbon particle that accounts for above-mentioned three kinds of raw material gross weight 5wt%, add the acetone dispersant, on ball mill, with rotating speed 400r/min ball milling 8h, get carbon after the vacuumize and coat holmium doped lithium titanate precursor.
Coat holmium doped lithium titanate precursor sintering under helium atmosphere with getting carbon after the drying, heat up with 10 ℃/min speed, at 900 ℃ of constant temperature sintering of temperature 10h, with 15 ℃/min cooling, prepare product.
Comparative example
Take by weighing 7.62g and analyze pure Li
2CO
3, then by Li: Ti=4.12: 5 take by weighing the 20.00g rutile TiO
2, both being mixed the back add in the PTFE ball grinder, ball milling mixing 2h in anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.
In being positioned in the high temperature resistance furnace with the crucible splendid attire, carry out the pre-burning reaction under the air conditions, the control heating rate is 5 ℃/min, is warming up to 650 ℃ of insulation 6h, cools to room temperature with the furnace and obtains middle phase product.
Press Li
4Ti
5O
12The target carbon content is that 2wt% adds starch 0.46g respectively in the/C composite material, and ball milling mixing 2h in the anhydrous ethanol medium puts into 120 ℃ of dry 8h of vacuum drying chamber then.Dry back in atmosphere furnace at N
2Be warming up to 800 ℃ of insulation 6h under the protective atmosphere, cool off with stove then.Products therefrom is Li
4Ti
5O
12/ C combination electrode material.
With above-described embodiment one, two and comparative example in product be assembled into the CR2016 button cell respectively, (Φ=16 purity＞99.9%) is to electrode with the lithium sheet, be barrier film with polypropylene porous film (Φ=18), (VEC: VDMC=1: mixed solution 1) is as electrolyte, and the CR2016 battery is to finish in being full of the glove box of argon gas with the ethylene carbonate (EC) of LiPF6 and dimethyl carbonate (DMC).Negative pole is to form with the The tape casting membrane, and used slurry is that the active material of 80% (mass percent), 10% PVDF solution, 10% conductive black, 1-Methyl-2-Pyrrolidone (NMP) mix, and the substrate of electrode film is metal copper foil.Be to carry out electric performance test under 25 ℃ at probe temperature, after tested this embodiment one with two material compare with the product of comparative example, first charge-discharge speed has improved 35-40%, improves useful life more than 1.3 times.
Claims (1)
1. the preparation method of a carbon coating holmium doped lithium titanate composite negative pole material comprises the steps:
(1) preparation coats and uses carbon particle
As oil-phase component, the monomer divinylbenzene of 100 weight portions, the hollow agent pentane of 100-150 weight portion, the nano silica fume of 5-10 weight portion, the acetone dispersant of 7-10 weight portion are mixed, after ultrasonic wave disperses, and then add organic peroxide as polymerization initiator, make monomer mixture, in addition, as water-phase component, the deionized water of 500 weight portions, the POLYPROPYLENE GLYCOL as dispersant of 10-20 weight portion are mixed;
The oil-phase component and the water-phase component that obtain are mixed, disperse with ultrasonic wave, make suspension, with the suspension that obtains under helium flow, temperature 90-95 ℃ stirs down, keeps 8-10h, with polymerization and particle clean drying, obtain resin particle, with the resin particle that obtains under air atmosphere, temperature 400-450 ℃ following heat treatment 1-2h, under helium atmosphere, temperature 1200-1350 ℃ following sintering 4-5h, obtain coating and use carbon particle;
(2) preparation carbon coats holmium doped lithium titanate precursor
Selecting lithium bicarbonate, titanium dioxide and holimium oxide for use is raw material, wherein the mol ratio of lithium bicarbonate and titanium dioxide is 0.805-0.82: 1, holimium oxide accounts for the 0.5-1.5wt% of three kinds of raw material gross weights, after three kinds of raw materials mixing, add the above-mentioned coating carbon particle that accounts for above-mentioned three kinds of raw material gross weight 3-5wt%, add the acetone dispersant, on ball mill, with rotating speed 300-400r/min ball milling 8-10h, get carbon after the vacuumize and coat holmium doped lithium titanate precursor;
(3) sintering
Coat holmium doped lithium titanate precursor sintering under helium atmosphere with getting carbon after the drying, heat up with 5-10 ℃/min speed, at temperature 800-900 ℃ of constant temperature sintering 10-15h, with 10-15 ℃/min cooling, prepare product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331869A (en) * | 2017-01-21 | 2017-11-07 | 深圳市瑞能达科技有限公司 | It is a kind of to lift the compound additive of lithium titanate electric material cryogenic property |
Citations (3)
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|---|---|---|---|---|
| CN101456581A (en) * | 2009-01-05 | 2009-06-17 | 中信国安盟固利新能源科技有限公司 | Method for preparing lithium ion secondary battery cathode material lithium titanate containing rare-earth element |
| WO2010074243A1 (en) * | 2008-12-26 | 2010-07-01 | 積水化学工業株式会社 | Process for producing carbon particles for electrode, carbon particles for electrode, and negative-electrode material for lithium-ion secondary battery |
| CN102054963A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Titanium acid lithium battery cathode material containing rare metal elements |
-
2013
- 2013-07-11 CN CN2013102895416A patent/CN103346310A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010074243A1 (en) * | 2008-12-26 | 2010-07-01 | 積水化学工業株式会社 | Process for producing carbon particles for electrode, carbon particles for electrode, and negative-electrode material for lithium-ion secondary battery |
| CN101456581A (en) * | 2009-01-05 | 2009-06-17 | 中信国安盟固利新能源科技有限公司 | Method for preparing lithium ion secondary battery cathode material lithium titanate containing rare-earth element |
| CN102054963A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Titanium acid lithium battery cathode material containing rare metal elements |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107331869A (en) * | 2017-01-21 | 2017-11-07 | 深圳市瑞能达科技有限公司 | It is a kind of to lift the compound additive of lithium titanate electric material cryogenic property |
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Application publication date: 20131009 |