CN1305236A - Process for preparing C/C composition used for negative electrode of lithium ion bettery - Google Patents
Process for preparing C/C composition used for negative electrode of lithium ion bettery Download PDFInfo
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- CN1305236A CN1305236A CN00118577A CN00118577A CN1305236A CN 1305236 A CN1305236 A CN 1305236A CN 00118577 A CN00118577 A CN 00118577A CN 00118577 A CN00118577 A CN 00118577A CN 1305236 A CN1305236 A CN 1305236A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
A composite carbon/carbon material used as the negative electrode of Li-ion battery is prepared through dissolving phenolic resin and hexamethine tetramine in methanol to obtain 2-40% methanol solution, pouring it into a sealed vacuum system containing powder graphite, reflux stirring for 1-10 hr, thermal filtering, solidifying and carbonization. Its advantages are high reversible capacity, high charge-discharge efficiency for first time, and stable cycle performance.
Description
The invention belongs to a kind of preparation method of C/C composition used for negative electrode of lithium ion bettery.
Charcoal element (Carbon), 2000 the 38th volumes, 183～197 pages: introduce lithium ion battery in " lithium ion battery with the progress of raw material of wood-charcoal material " literary composition owing to have advantage such as high-energy-density, high working voltage (about 3.6 volts), excellent cycle performance (cycle-index is greater than 500 times), memoryless property, safety and environmental nonpollution extremely common people favor nearly 4,000,000,000 dollars/year of its output value.Current further miniaturization and aerospace special requirement along with power consumption equipment, lithium ion battery is being still waiting further raising aspect energy density, efficiency for charge-discharge and the cycle performance, and the raising of carbon cathode material performance is depended in the raising of lithium ion battery performance to a great extent.
Used as negative electrode of Li-ion battery graphite has lower discharge platform, big, the slotting lithium capacity height of real density, initial charge discharging efficiency height, but charge-discharge performance is poor.The hard raw material of wood-charcoal material of used as negative electrode of Li-ion battery has the higher quality specific capacity, good with the compatibility of electrolyte, but its initial charge efficient is low, real density is little, and the charge-discharge performance of hard raw material of wood-charcoal material and the source of raw material and heat-treat condition relation are greatly, this makes its charging performance alter a great deal, and these factors are unfavorable for that hard raw material of wood-charcoal material is as lithium cell negative electrode material.
In order to obtain high performance lithium battery cathode raw material of wood-charcoal material, United States Patent (USP) patent No. .5908715, date, 1999, disclosed a kind of surface on June 1 and coated last layer epoxy resin charcoal at graphite, the method of polyparaphenylene's charcoal, the characteristics of its method are that the building-up process of resin is carried out simultaneously with coating, but the method repeatability difficulty is big, also some residual gass of graphite inside are not removed before coating in addition, the composite material that this method makes is still poor at the cycle performance that carries out high current charge-discharge: its highest reversible capacity first is 400mAhg
-1, then reduce to 235mAhg after the 20 circulation
-1
The compound raw material of wood-charcoal material that the preparation method who the purpose of this invention is to provide a kind of C/C composition used for negative electrode of lithium ion bettery of easy repetition, this method make carries out the stable cycle performance of high current charge-discharge as lithium ion battery negative.
Step of the present invention is as follows:
1. by weight phenolic resins: hexamethylenetetramine=100: (1.7～53) are dissolved in phenolic resins and hexamethylenetetramine in the methyl alcohol, are configured to weight percent concentration and are 2～40% methanol solution;
2. powdered graphite is placed in the closed system, closed system is vacuumized, by weight graphite: methyl alcohol=100: (150～800) add the methanol solution of above-mentioned preparation to closed system, reflux, stir 1～10 hour, at last mixed liquor are carried out heat filtering and get filter cake;
3. with filter cake hot curing 1～15 hour between 120～300 ℃, composite material through solidifying is under inert gas shielding, programming rate with 1～20 ℃/decomposition is warming up to 600～1600 ℃ of charings 0.5～15 hour, obtains the compound raw material of wood-charcoal material of phenolic resin carbon/graphite at last;
Described inert gas is nitrogen, argon gas.
The composite material that this method makes is as the advantage of taking off embedding current potential low (with respect to lithium metal), stable cycle performance of lithium ion battery negative reversible capacity height, first charge-discharge efficiency height, lithium ion.
It is as follows that the composite material of the present invention's preparation carries out the charge-discharge performance test process:
1. the preparation of carbon resistance rod: ptfe emulsion and compound raw material of wood-charcoal material mixed roll on Copper Foil, carbon membrane thickness is 0.08～0.12 millimeter.Then carbon membrane is carried out drying and remove solvent.
2. prepare three electrode Experimental cells: as work electrode, the lithium metal conduct is to electrode and auxiliary electrode with carbon membrane.Electrolyte is the organic electrolyte that contains lithium ion.
3. Experimental cell is carried out the charge-discharge performance test: charging and discharging currents density is 15mAg
-1, 50mAg
-1, 100mAg
-1The charging/discharging voltage excursion is 0.001～2.000 volt (with respect to lithium metal).
The result shows:
The compound raw material of wood-charcoal material of phenolic resin carbon/graphite that this method makes is with 15mAg
-1, 50mAg
-1, 100mAg
-1Charging or discharging current density discharge and recharge, the reversible capacity best result Wei 351mAhg first
-1, 335mAhg
-1, 325mAhg
-1, the reversible capacity of the 20 circulation is respectively 342mAhg
-1, 325mAhg
-1, 320mAhg
-1
Comparative Examples:
With graphite with 15mAg
-1, 50mAg
-1, 100mAg
-1Charging or discharging current density discharge and recharge, the reversible capacity best result Wei 377mAhg first
-1, 224mAhg
-1, 163mAhg
-1, the reversible capacity of the 20 circulation is respectively 281mAhg
-1, 204mAhg
-1, 148mAhg
-1
Embodiment 1
Methyl alcohol and the phenolic resins of 6.05 grams and the hexamethylenetetramine (phenolic resins: reflux stirring hexamethylenetetramine=100: 1.7 weight ratios) of 0.10 gram with 123 grams, phenolic resins and hexamethylenetetramine are fully dissolved, be mixed with 5% the phenolic resins and the methanol solution of hexamethylenetetramine.19.2 gram powdered graphites are placed in the closed system, closed system is vacuumized, the methanol solution that adds above-mentioned preparation then (by weight, graphite: methanol solution=100: 672), reflux, stirring 1 hour, at last mixed liquor is carried out heat filtering, the gained filter cake was heating and curing under 120 ℃ 15 hours in vacuum drying chamber.Cured product programming rate with 1 ℃/minute under inert atmosphere is warming up to 900 ℃, and charing made compound raw material of wood-charcoal material A in 0.5 hour.Composite A is carried out the constant current charge-discharge performance test.Compound raw material of wood-charcoal material A is with 15mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of current density be 322mAhg
-1, 302mAhg
-1, 271mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 65%, 68%, 71%, the two ten circulation is 305mAhg
-1, 289mAhg
-1, 268mAhg
-1
Embodiment 2
(phenolic resins: concentration of methanol solution hexamethylenetetramine=100: 1.7) is 2% with the phenolic resins among the embodiment 1 and hexamethylenetetramine, graphite and methanol solution weight ratio become 100: 800, reflux, mixing time become 10 hours, and other process is with embodiment 1.The compound raw material of wood-charcoal material of gained B is with 15mAg
-1The reversible capacity first that discharges and recharges of current density be 345mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 65%, the two ten circulation is 302mAhg
-1
Embodiment 3
The concentration of methanol solution of phenolic resins among the embodiment 1 and hexamethylenetetramine is become 25%, and graphite and methanol solution weight ratio are 100: 150, and other process is with embodiment 1.The compound raw material of wood-charcoal material of gained C is with 15mAg
-1, 50mAg
-1, 100mAg
-1The reversible capacity first that discharges and recharges of current density be 351mAhg
-1, 335mAhg
-1, 309mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 65%, 73%, 79%, the two ten circulation is 345mAhg
-1, 325mAhg
-1, 315mAhg
-1
Embodiment 4
Phenolic resins among the embodiment 1 and hexamethylenetetramine concentration of methanol solution are become 40%, and other process is with embodiment 1.The compound raw material of wood-charcoal material of gained D is with 15mAg
-1The reversible capacity first that discharges and recharges of current density be 350mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 62%, the two ten circulation is 315mAhg
-1
Embodiment 5
Heat curing temperature among the embodiment 1 is become 300 ℃, and thermal curing time is 1 hour, and the carbonization temperature of cured product becomes 600 ℃, and carbonization time becomes 15 hours, and other process is with embodiment 1.The compound raw material of wood-charcoal material of gained E is with 15mAg
-1The reversible capacity first that discharges and recharges of current density be 345mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 60%, the two ten circulation is 340mAhg
-1
Embodiment 6
With cured product among the embodiment 1 carbonization temperature become 1600 ℃, carbonization time is 0.5 hour, other process is with embodiment 1.The compound raw material of wood-charcoal material of gained F is with 100mAg
-1The reversible capacity first that discharges and recharges of current density be 325mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 82%, the two ten circulation is 320mAhg
-1
Embodiment 7
(phenolic resins: hexamethylenetetramine=100: 53) be mixed with 5% phenolic resins and hexamethylenetetramine methanol solution, other process is with embodiment 1 to add 3.35 gram phenolic resins and 2.6 gram hexamethylenetetramines in the methyl alcohol of 123 grams.The compound raw material of wood-charcoal material of gained G is with 100mAg
-1The reversible capacity first that discharges and recharges of current density be 302mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 75%, the two ten circulation is 296mAhg
-1
Embodiment 8
The charing programming rate of cured product among the embodiment 1 is become 20 ℃/minute, and other process is with embodiment 1.The compound raw material of wood-charcoal material of gained H is with 100mAg
-1The reversible capacity first that discharges and recharges of current density be 290mAhg
-1, first charge-discharge efficiency is that the reversible capacity of 82%, the two ten circulation is 284mAhg
-1
Claims (2)
1. the preparation method of a C/C composition used for negative electrode of lithium ion bettery is characterized in that:
(1) by weight phenolic resins: hexamethylenetetramine=100: (1.7～53) are dissolved in phenolic resins and hexamethylenetetramine in the methyl alcohol, are configured to weight percent concentration and are 2～40% methanol solution;
(2) powdered graphite is placed in the closed system, closed system is vacuumized, by weight graphite: methyl alcohol=100: (150～800) add the methanol solution of above-mentioned preparation to closed system, reflux, stir 1-10 hour, at last mixed liquor are carried out heat filtering and get filter cake;
(3) with filter cake between 120～300 ℃ hot curing 1-15 hour; composite material through solidifying is under inert gas shielding; programming rate with 1～20 ℃/decomposition is warming up to 600～1600 ℃ of charings 0.5～15 hour, obtains the compound raw material of wood-charcoal material of phenolic resin carbon/graphite at last.
2. the preparation method of a kind of C/C composition used for negative electrode of lithium ion bettery as claimed in claim 1 is characterized in that described inert gas is nitrogen, argon gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00118577A CN1129194C (en) | 2000-07-07 | 2000-07-07 | Process for preparing C/C composition used for negative electrode of lithium ion bettery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00118577A CN1129194C (en) | 2000-07-07 | 2000-07-07 | Process for preparing C/C composition used for negative electrode of lithium ion bettery |
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| CN1305236A true CN1305236A (en) | 2001-07-25 |
| CN1129194C CN1129194C (en) | 2003-11-26 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305150C (en) * | 2003-08-16 | 2007-03-14 | 比亚迪股份有限公司 | Modified graphite and its preparing method |
| CN100400415C (en) * | 2002-12-31 | 2008-07-09 | 中国人民解放军63971部队 | Preparation method of nano-pore glassy carbon |
| CN101157451B (en) * | 2007-09-16 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Method for preparing resin-based ball charcoal |
-
2000
- 2000-07-07 CN CN00118577A patent/CN1129194C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400415C (en) * | 2002-12-31 | 2008-07-09 | 中国人民解放军63971部队 | Preparation method of nano-pore glassy carbon |
| CN1305150C (en) * | 2003-08-16 | 2007-03-14 | 比亚迪股份有限公司 | Modified graphite and its preparing method |
| CN101157451B (en) * | 2007-09-16 | 2011-04-06 | 中国科学院山西煤炭化学研究所 | Method for preparing resin-based ball charcoal |
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| CN1129194C (en) | 2003-11-26 |
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