CN1812168A - Modified method for lithium ion cell negative electrode material - Google Patents
Modified method for lithium ion cell negative electrode material Download PDFInfo
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- CN1812168A CN1812168A CNA2005100457696A CN200510045769A CN1812168A CN 1812168 A CN1812168 A CN 1812168A CN A2005100457696 A CNA2005100457696 A CN A2005100457696A CN 200510045769 A CN200510045769 A CN 200510045769A CN 1812168 A CN1812168 A CN 1812168A
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- 239000003575 carbonaceous material Substances 0.000 claims description 4
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
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- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
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- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000428 dust Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000002296 pyrolytic carbon Substances 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
This invention relates to a kind of improving method of lithium ionic cell cathode materials. The cathode materials in need of improving are mixed evenly with catalyst which has 0.1%-10% weight percent of cathode materials. The materials are then put into reaction furnace, which uses hydrocarbon as carbon source. The cathode materials are mixed with buffer gas according to 1: (0-10) volume ratio. Then the mixture are reacted in reaction furnace at 600-1300DEG C for 1-900 minutes. A kind of improved composite cathode materials, at the surface of which in-situ grows nanometer carbon fibrin/ carbon tube, are gained. The improved materials have good cell kinetic ability, circulating ability, charge-discharge capacity and consistency with electrolyte.
Description
Technical field
The present invention relates to chargeable secondary lithium battery negative material technology, be specially a kind of method of modifying of lithium ion battery negative material, can significantly improve performances such as the cycle performance of chargeable secondary lithium battery and capacity.
Background technology
Voltage height, discharge time are long because of having for the charging secondary lithium battery, energy density greatly, light weight, memory-less effect and advantage such as pollution-free, become the focus of battery industry in recent years.The application of lithium ion battery enlarges rapidly: be widely used in portable type electronic product (as the supporting power supply of mobile phone, notebook computer, digital camera etc.); The electric automobile industry; The military equipment field; Space industry etc.Especially in recent years along with at the application need aspect the electric automobile power battery, need further to improve the performance of lithium ion battery.And the raising of lithium ion battery performance is decided by the performance improvement of electrode material to a great extent, high-energy-density: the high power capacity lithium storage materials needs electrode material to have high power density, long service life, high performance-price ratio and high security, these require still to have very big challenge.
The lithium ion battery negative material of broad research mainly contains various traditional raw material of wood-charcoal material, transition metal oxide, fluoride, tinbase and silicon-base oxide, nitride, lithium alloy etc. at present.On capacity and cycle performance, these materials often all can not get both simultaneously.And the negative material of current widely used commercialization lithium ion battery mainly adopts carbonaceous materials such as MCMB, modified graphite, all exists charge-discharge magnification low, can not adapt to the requirement of great current power battery, and while cyclicity and capacity be defectiveness also.
Summary of the invention
The object of the present invention is to provide the method that improves the lithium ion battery negative material performance.Be used as chargeable secondary lithium battery through the negative material after the present invention's processing, have higher battery power and learn performance, higher cycle performance of battery, higher charge/discharge capacity and the compatibility good with electrolyte.
Technical scheme of the present invention is:
To need the modification negative material evenly to mix by suitable chemical treatment (removal impurity) and interpolation catalyst (percentage by weight that catalyst accounts for the modification negative material is 0.1%-10%), the material that disposes is put into reacting furnace, do carbon source with hydrocarbon, mix by a certain percentage with buffer gas, the volume ratio of hydrocarbon and buffer gas is 1: (0-10), wherein buffer gas can not add yet, feed temperature in (600-1300 ℃) reacting furnace, through after 1-900 minute the reaction, obtain a kind of modification composite negative pole material of the nano carbon fiber/magnetic tube of growth in situ from the teeth outwards.
In a kind of method of modifying that improves the lithium ion battery negative material performance provided by the invention, needing the modification negative material can be carbonaceous materials such as native graphite, modified graphite, MCMB (MCMB), amorphous carbon, hard charcoal, pyrolytic carbon, petroleum coke, transition metal oxide (TiO, TiO
2, VO
2, V
2O
3, Cr
2O
3, MoO
3, RuO
2, FeO, NiO, CoO, Co
3O
4, Cu
2O etc.) and fluoride (TiF
3, VF
3, MnF
2, FeF
2, CoF
2, NiF
2, CuF
2, CaF
2, BaF
2Deng), tinbase and silicon-base oxide (SnO, SnO
2, SiO, SiO
2Deng) one or more of material.
Catalyst among the present invention can be Fe, Co, Ni, Mo, V metal dust and oxide thereof, nitrate, halate, sulfate etc. one or more;
Hydrocarbon as carbon source can be: methane, ethane, propane, ethene, acetylene, benzene, toluene, dimethylbenzene, cyclohexane, carbon monoxide, water-gas etc. one or more;
Buffer gas can be: hydrogen, argon gas, nitrogen etc. one or more;
In the method for modifying of lithium ion battery negative material provided by the invention, the modification composite negative pole material behind growth in situ nano carbon fiber/carbon pipe also can pass through high temperature graphitization, slight oxidation, chemical treatment etc. again, to obtain better performance.
Beneficial effect of the present invention is as follows:
1, the present invention proposes the method at existing negative material surface in situ growing nano charcoal fiber/carbon pipe, pass through chemical reaction, at existing negative material surface in situ growing nano charcoal fiber/carbon pipe, finished the modification of anticathode material, make its have good battery power learn performance, cycle performance, charge/discharge capacity and with the compatibility of electrolyte, be the lithium ion battery performance of negative material thereby improved with this material.
2, the nano carbon fiber/carbon pipe of surface in situ growth of the present invention because draw ratio is big, specific strength is high, can suppress volumetric expansion and efflorescence effect that lithium ion brings when embedding and deviating from basic negative material, thereby improves the cycle performance of negative pole.
3, the nano carbon fiber/carbon pipe of surface in situ growth of the present invention has good electrical conductivity and big L/D ratio, helps forming three-dimensional conductive network in the negative pole body, can increase substantially the conductive capability of electrode, and is more obvious to transition metal oxide especially.The raising of conductivity can make the electrochemical polarization of battery alleviate and the reduction of internal resistance dividing potential drop, and the high power that helps battery discharges and recharges.
4, surface in situ growing nano charcoal fiber of the present invention/carbon pipe greatly reduces the degree that basic negative material directly contacts with electrolyte, can improve the compatibility of electrode and electrolyte like this, enlarges the range of choice of electrolyte.
5, studies show that at present, the solid-state diffusion of lithium ion in electrode is the controlled step that embeds and deviate from, because nano carbon fiber/carbon pipe has nanoscale, lithium ion embed and the stroke deviate from than traditional electrode material much shorter, the diffusion of lithium ion becomes easily, can make battery adapt to the requirement of high power charging-discharging like this.
6, surface in situ growing nano charcoal fiber of the present invention/carbon pipe can well solve the direct difficult homodisperse problem that the interpolation nano carbon fiber/the carbon pipe is brought, and because growth in situ, the combination between basic negative material and the nano carbon fiber is also more far better than direct interpolation.
In sum, the present invention improves the method for lithium ion battery negative material performance, by surface in situ growing nano charcoal fiber/carbon pipe, development NEW TYPE OF COMPOSITE negative material, thereby improve lithium ion battery dynamic performance, cycle performance, charge/discharge capacity and with the compatibility of electrolyte.
Experimental results demonstrate, cycle life, charge-discharge magnification, the capacity of the lithium ion battery negative after the carbon fiber modified processing of surface in situ growing nano, all obtain raising with the technical indicators such as compatibility of electrolyte, thereby effectively improved the performance of lithium ion battery.
Description of drawings
Fig. 1 a-b is that natural graphite nodule and the present invention obtain the graphite nodule stereoscan photograph after modification is handled; Wherein, Fig. 1 a is a natural graphite nodule; Fig. 1 b handles back graphite nodule stereoscan photograph for the inventive method modification.
Fig. 2 primary sample (comparative example 1) and the cycle performance that utilizes the inventive method (embodiment 1) modification to handle the back sample compare.
Embodiment
The present invention will be described below in conjunction with embodiment:
Embodiment 1
(Fig. 1 a), adding the Fe powder is catalyst (quality 0.046g), evenly mixes, and uses C to select average diameter 20 μ m natural graphite nodules (quality 2g) for use
2H
4Do 1: 1 by volume mixed of carbon source and Ar, feed temperature in 1000 ℃ of reacting furnaces, after 100 minutes reaction, obtain the modification composite negative pole material (Fig. 1 b) of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.Be used as lithium ion battery negative material.Show by conventional lithium ion battery negative evaluation method testing result, under the same loop number of times, capacity and cycle performance all be greatly improved (Fig. 2).
Comparative Examples 1
With not processed average diameter 20 μ m natural graphite nodules, be used as lithium ion battery negative material.Show that by conventional lithium ion battery negative evaluation method testing result under the same loop number of times, capacity and cycle performance are than embodiments of the invention 1 poor (referring to Fig. 2) far away.
Embodiment 2
Select average diameter 20 μ m natural graphite nodules (quality 2g) for use, add Fe (NO
3)
3Be catalyst (quality 0.198g), natural graphite nodule can be added Fe (NO
3)
3After evenly mixing in the solution, CH is used in oven dry
4Be carbon source and N
22: 1 by volume mixed feed temperature in 700 ℃ of reacting furnaces, after 60 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.Be used as lithium ion battery negative material.Show that by conventional lithium ion battery negative evaluation method testing result under the same loop number of times, capacity and cycle performance all are greatly improved.
Embodiment 3
Select average diameter 20 μ m natural graphite nodules (quality 2g) for use, add Fe (NO
3)
3Be catalyst (quality 0.084g), natural graphite nodule can be added Fe (NO
3)
3After evenly mixing in the solution, CH is used in oven dry
4Be carbon source and N
29: 1 by volume mixed feed temperature in 700 ℃ of reacting furnaces, after 240 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.Be used as lithium ion battery negative material.Show that by conventional lithium ion battery negative evaluation method testing result under the same loop number of times, capacity and cycle performance all are greatly improved.
Embodiment 4
Select average diameter 20 μ m MCMB (quality 2g) for use, add Fe (NO
3)
3Be catalyst (quality 0.102g), MCMB can be added Fe (NO
3)
3After evenly mixing in the solution, CH is used in oven dry
4Be carbon source and N
25: 1 by volume mixed feed temperature in 800 ℃ of reacting furnaces, after 600 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.Be used as lithium ion battery negative material.Show that by conventional lithium ion battery negative evaluation method testing result under the same loop number of times, capacity and cycle performance all are greatly improved.
Embodiment 5
Select the hard charcoal ball (quality 1g) of average diameter 10 μ m for use, add FeCl
2Be catalyst (quality 0.052g), the hard carbon ball can be added FeCl
2After evenly mixing in the solution, C is used in oven dry
2H
6Be carbon source and H
22: 1 by volume mixed feed temperature in 1100 ℃ of reacting furnaces, after 30 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.After this method modification is handled, be used as lithium ion battery negative material.Conventional lithium ion battery negative evaluation method testing result shows that under the same loop number of times, capacity improves 70% after the modification, and performance is better stable.
Embodiment 6
Select the hard charcoal ball (quality 1g) of average diameter 10 μ m for use, add NiSO
4Be catalyst (quality 0.061g), the hard carbon ball can be added NiSO
4After evenly mixing in the solution, C is used in oven dry
6H
6Do 3: 1 by volume mixed of carbon source and Ar, feed temperature in 1200 ℃ of reacting furnaces, after 45 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.After this method modification is handled, be used as lithium ion battery negative material.Conventional lithium ion battery negative evaluation method testing result shows that under the same loop number of times, capacity improves 70% after the modification, and performance is better stable.
Embodiment 7
Selecting average particle size particle size for use is the Cr of 1 μ m
2O
3Powder (quality 2g) adds Co
2O
3Be catalyst (quality 0.065g), evenly mix, the reacting furnace of putting into that disposes, do carbon source with CO, feed temperature in 900 ℃ of reacting furnaces, after 30 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe.After this method modification was handled, capacity was compared with Comparative Examples 2 to improve and is reached and 145% under the same loop number of times, and cycle performance is also greatly improved.
Comparative Examples 2
Selecting average particle size particle size for use is the Cr of 1 μ m
2O
3Powder is used as lithium ion battery negative material, and conventional lithium ion battery negative evaluation method testing result shows that its capacity attenuation is very fast, and cycle performance is very poor.
Embodiment 8
Select the modified graphite ball (quality 2g) of average diameter 20 μ m for use, add Ni (NO
3)
2Be catalyst (quality O.15g), the modified graphite ball can be added Ni (NO
3)
2After evenly mixing in the solution, C is used in oven dry
2H
4Do carbon source, with H
21: 1 by volume mixed, feed temperature in 750 ℃ of reacting furnaces, after 100 minutes reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe, be used as lithium ion battery negative material, discharge and recharge under the 1.5C multiplying power, capacity reaches 101.6mAh/g, and charge-discharge performance is significantly improved under the high magnification.
Comparative Examples 3
Select the modified graphite ball of average diameter 20 μ m for use, be used as lithium ion battery negative material, adopt and embodiment six same test processes, discharge and recharge under the 1.5C multiplying power, capacity is 65.5mAh/g.
Claims (3)
1, a kind of modified method for lithium ion cell negative electrode material, it is characterized in that: needs modification negative material is added catalyst evenly mix, the percentage by weight that catalyst accounts for the modification negative material is 0.1%-10%, the material that disposes is put into reacting furnace, do carbon source with hydrocarbon, mix in proportion with buffer gas, the volume ratio of hydrocarbon and buffer gas is 1: (0-10), feed temperature in 600-1300 ℃ of reacting furnace, through after 1-900 minute the reaction, obtain the modification composite negative pole material of a kind of nano carbon fiber of growth in situ from the teeth outwards/carbon pipe; Described modification negative material is one or more in carbonaceous material, transition metal oxide, fluoride, tinbase and the silicon-base oxide; Described catalyst is Fe, Co, Ni, Mo, one or more in V metal dust and oxide thereof, nitrate, halate, the sulfate; Described buffer gas is a hydrogen, argon gas, one or more in the nitrogen.
2, according to the described modified method for lithium ion cell negative electrode material of claim 1, it is characterized in that: described carbonaceous material is native graphite, modified graphite, MCMB, amorphous carbon, hard charcoal, pyrolytic carbon, petroleum coke; Described transition metal oxide is TiO, TiO
2, VO
2, V
2O
3, Cr
2O
3, MoO
3, RuO
2, FeO, NiO, CoO, Co
3O
4, Cu
2O; Described fluoride TiF
3, VF
3, MnF
2, FeF
2, CoF
2, NiF
2, CuF
2, CaF
2, BaF
2Described tinbase and silicon-base oxide are SnO, SnO
2, SiO, SiO
2
3, according to the described modified method for lithium ion cell negative electrode material of claim 1, it is characterized in that: described hydrocarbon as carbon source is a methane, ethane, propane, ethene, acetylene, benzene, toluene, dimethylbenzene, cyclohexane, carbon monoxide, one or more in the water-gas.
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CN100565980C (en) * | 2008-05-30 | 2009-12-02 | 成都中科来方能源科技有限公司 | A kind of composite cathode material for lithium ion cell and preparation method thereof |
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CN102169984A (en) * | 2011-03-30 | 2011-08-31 | 深圳市翔丰华科技有限公司 | Method for preparing lithium-ion battery cathode material with gas phase deposition |
WO2013029212A1 (en) * | 2011-09-03 | 2013-03-07 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium-ion battery negative electrode material, preparation method therefor, and lithium-ion battery |
CN103367716A (en) * | 2013-06-13 | 2013-10-23 | 浙江南博电源科技有限公司 | Preparation method of anode material by growing carbon nano tube on surface of titanium dioxide |
CN103682282A (en) * | 2012-09-22 | 2014-03-26 | 微宏动力系统(湖州)有限公司 | Graphite negative electrode material for lithium ion battery and preparation method of graphite negative electrode material |
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