CN105244473A - Post-processing method for improving electrochemical performance of lithium ion battery carbon anode material - Google Patents
Post-processing method for improving electrochemical performance of lithium ion battery carbon anode material Download PDFInfo
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- CN105244473A CN105244473A CN201410326677.4A CN201410326677A CN105244473A CN 105244473 A CN105244473 A CN 105244473A CN 201410326677 A CN201410326677 A CN 201410326677A CN 105244473 A CN105244473 A CN 105244473A
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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
The invention relates to a post-processing method for improving electrochemical performance of a lithium ion battery carbon anode material. The post-processing method comprises the following concrete steps: mixing oxidizing acid with distilled water at the volume ratio of 1: 0.1 to 1: 10 to obtain an acid solution; carrying out stirring treatment on the carbon material with the average diameter of 1-50 microns in the acid solution for 1-24 h at room temperature, washing with deionized water until the carbon material is neutral, and drying to obtain an acid-treated carbon material; carrying out air oxidation treatment on the acid-treated carbon material for 1-12 h at 100-500 DEG C to obtain a carbon material of air oxidation carbon; and directly taking the air oxidation product as the lithium ion battery anode material to show high electrochemical performance.
Description
Technical field
The present invention relates to the hard negative material technology of lithium ion battery, refer more particularly to a kind of post-processing approach improving carbon negative electrode material of lithium ion cell chemical property.
Background technology
The energy is that the important substance of human society high speed development ensures.Nowadays, tellurian coal, natural gas and oil etc. can not reduce and fossil energy problem of environmental pollution day by day in raw fossil energy, force the mankind to find clean energy resource that is clean, sustainable development, as the clean energy resource such as wind energy, solar energy substitutes fossil energy.
Lithium ion battery is the new forms of energy of novel, the sustainable development produced under this historical background.Lithium ion battery has the advantages such as operating voltage is high, specific energy is high, good cycle, memory-less effect and is used to mancarried device energy-storage battery, as computer, communication, consumption electronic product etc.Along with improving constantly of technology, the performance of people to lithium ion battery is had higher requirement.The performance of lithium ion battery is determined by battery electrode material to a great extent, therefore improves the performance of battery electrode material, obtains high-energy-density, emphasis and focus that long-life, lithium ion battery that fail safe is good are research at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of post-processing approach improving carbon negative electrode material of lithium ion cell chemical property.
The invention provides a kind of post-processing approach improving carbon negative electrode material of lithium ion cell chemical property, it is characterized in that, comprise the following steps:
A) acid and distilled water being mixed to get acid solution according to volume ratio 1: 0.1 ~ 1: 10, is 1 ~ 50um Carbon Materials acid solution stirring at room temperature process, 1 ~ 24h by diameter, extremely neutral and dry through deionized water washing, obtains acid treatment Carbon Materials;
B) by acid treatment charcoal 100 DEG C ~ 500 DEG C airoxidation 1 ~ 12h in Muffle furnace, air oxidation Carbon Materials is obtained;
C) air oxidation Carbon Materials is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property;
Preferably, it is characterized in that, described acid solution is selected from the volume ratio 1: 0.5 ~ 1: 2 of acid and distilled water.One or more in concentrated hydrochloric acid, red fuming nitric acid (RFNA), the concentrated sulfuric acid, perchloric acid.
Preferably, described steps A) in charcoal be phenolic resin carbon, coke, mesophase pitch carbon microspheres, asphalt carbon, charcoal, bamboo charcoal etc., its average diameter is 1-10um.
Preferably, described steps A) in time of acid solution room temperature treatment Carbon Materials be 6 ~ 12h.
Preferably, described step B) in air oxidation temperature be 250 DEG C ~ 450 DEG C.
Preferably, described step B) in the air oxidation time be 3 ~ 6h.
Advantage of the present invention:
Compared with existing invention, the present invention first by Carbon Materials with certain density acid in room temperature treatment, and then the charcoal after acid treatment is placed in airoxidation certain hour under uniform temperature, is conducive to Carbon Materials like this and can be sufficiently oxidized, etches.After this kind of method process Carbon Materials, charcoal shows to become coarse from smooth, and containing abundant oxygen-containing functional group, the chemical property of Carbon Materials is obviously promoted simultaneously.
When hard charcoal charcoal ball is without any process, when discharge current density is 50mA/g, its first discharge specific capacity is 600mAh/g, coulombic efficiency is that after 42%, 50 circulations, specific discharge capacity is 200mAh/g first, and through the hard charcoal charcoal ball of reprocessing, it is same when discharge current density is 50mA/g, its first discharge specific capacity is 1400mAh/g, and coulombic efficiency is that after 70%, 50 circulations, specific discharge capacity is 500mAh/g first.Chemical property before and after the process of harder charcoal charcoal ball is known, and after process, the first discharge specific capacity of charcoal ball improves 130%, and after coulombic efficiency improves 66.67%, 50 circulations first, specific discharge capacity improves 150%.
Accompanying drawing explanation
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of hard charcoal charcoal ball after acid treatment in embodiment 1;
Accompanying drawing 2 is hard charcoal charcoal ball scanning electron microscope (SEM) photograph after oxidation processes in embodiment 1;
Accompanying drawing 3 is the discharge curve cycle performance figure without charcoal ball in the hard charcoal charcoal ball of any process and embodiment 1.
Embodiment
Embodiment 1
The distilled water of red fuming nitric acid (RFNA) (67%) and 20mL that acid and distilled water are measured 20mL according to volume ratio 1: 1 puts into the glass beaker of 250mL, the average diameter taking 0.5g is afterwards that beaker put into by 2um phenolic resin carbon ball, stirring at room temperature process 12h, hard charcoal charcoal ball through acid solution process is washed with distilled water to neutrality, drying, obtains acid treatment charcoal ball.
By acid treatment carbon microspheres 450 DEG C of airoxidation 3h in Muffle furnace, obtain air oxidation carbon microspheres.
Air oxidation carbon microspheres is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.
Through obtaining the discharge curve cycle performance map analysis of charcoal ball in without the hard charcoal charcoal ball of any process and embodiment 1, after lithium ion battery first discharge specific capacity improves 130%, 50 circulations, capacity still improves 150%.
Scanning electron microscopy is utilized to analyze before and after the hard charcoal charcoal ball air oxidation in embodiment 1, obtain the electromicroscopic photograph before and after 450 DEG C of airoxidation 3h, as depicted in figs. 1 and 2, Fig. 1 is electromicroscopic photograph before air oxidation, and Fig. 2 is electromicroscopic photograph after air oxidation.
Accompanying drawing 3 is the discharge curve cycle performance figure without charcoal ball in the hard charcoal charcoal ball of any process and embodiment 1.Shown by Fig. 4 electrochemical property test result, without the hard charcoal charcoal ball of any process, under 50mA/g current density, first discharge specific capacity is 650mAh/g, and coulombic efficiency is that after 42%, 50 circulations, specific discharge capacity is 200mAh/g first.And the hard charcoal charcoal ball in treated i.e. embodiment 1 is under 50mA/g current density, its first discharge specific capacity is 1400mAh/g, and coulombic efficiency is that after 70%, 50 circulations, specific discharge capacity is 500mAh/g first.
Embodiment 2
The distilled water of red fuming nitric acid (RFNA) (67%) and 4mL that acid and distilled water are measured 40mL according to volume ratio 1: 0.1 puts into the glass beaker of 250mL, the average diameter taking 0.5g is afterwards that the mesophase pitch carbon microspheres of 5um puts into beaker, stirring at room temperature process 1h, charcoal ball through acid solution process is washed with distilled water to neutrality, drying, obtains acid treatment charcoal ball.
By acid treatment carbon microspheres 450 DEG C of airoxidation 3h in Muffle furnace, obtain air oxidation carbon microspheres.
Air oxidation carbon microspheres is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.Find that its capacity can up to 720mAh/g, after comparatively raw material microballoon improves 200%, 50 circulations, capacity still improves 130%.
Embodiment 3
The distilled water of red fuming nitric acid (RFNA) (67%) and 25mL that acid and distilled water are measured 5mL according to volume ratio 1: 9 puts into the glass beaker of 250mL, the average grain diameter taking 0.5g is afterwards that the coke powder of 20um puts into beaker, stirring at room temperature process 24h, hard charcoal charcoal ball through acid solution process is washed with distilled water to neutrality, drying, obtains acid treatment powdered carbon.
By acid treatment powdered carbon 100 DEG C of airoxidation 12h in Muffle furnace, obtain air oxidation powdered carbon.
Air oxidation powdered carbon is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.Find that lithium ion battery first discharge specific capacity improves the rear capacity of 70%, 50 circulations and still improves 5%.
Embodiment 4
The distilled water of red fuming nitric acid (RFNA) (67%) and 40mL that acid and distilled water are measured 20mL according to volume ratio 1: 2 puts into the glass beaker of 250mL, the average diameter taking 0.5g is afterwards that the charcoal powdered carbon of 50um puts into beaker, stirring at room temperature process 6h, hard charcoal charcoal ball through acid solution process is washed with distilled water to neutrality, drying, obtains acid treatment charcoal ball.
By acid treatment carbon microspheres 450 DEG C of airoxidation 1h in Muffle furnace, obtain air oxidation powdered carbon.
Air oxidation powdered carbon is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.Lithium ion battery first discharge specific capacity improves 130%, reaches 450mAh/g, and after 50 circulations, capacity still improves 100%.
Embodiment 5
The distilled water of the concentrated sulfuric acid (98%) and 40mL that acid and distilled water are measured 20mL according to volume ratio 1: 2 puts into the glass beaker of 250mL, the average diameter taking 0.5g is afterwards that beaker put into by the hard charcoal charcoal ball of 50um, stirring at room temperature process 6h, hard charcoal charcoal ball through acid solution process is washed with distilled water to neutrality, drying, obtains acid treatment charcoal ball.
By acid treatment carbon microspheres 500 DEG C of airoxidation 1h in Muffle furnace, obtain air oxidation carbon microspheres.
Air oxidation carbon microspheres is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.Find that lithium ion battery first discharge specific capacity improves the rear capacity of 25%, 50 circulations and still improves 5%.
Embodiment 6
The distilled water of red fuming nitric acid (RFNA) (67%) and 40mL that acid and distilled water are measured 10mL according to volume ratio 1: 4 puts into the glass beaker of 250mL, the average diameter taking 0.5g is afterwards that the bamboo charcoal powder of 10um puts into beaker, stirring at room temperature process 16h, hard charcoal charcoal ball through acid solution process is washed with distilled water to neutrality, drying, obtains acid treatment charcoal ball.
By acid treatment carbon microspheres 400 DEG C of airoxidation 3h in Muffle furnace, obtain air oxidation powdered carbon.
Air oxidation powdered carbon is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.Find that lithium ion battery first discharge specific capacity improves the rear capacity of 70%, 50 circulations and still improves 120%.
Below concrete comparative descriptions has been carried out to preferred embodiment of the present invention, thus the advantage of the chemical property of checking the present invention to the reprocessing of hard charcoal charcoal ball and as lithium ion battery negative material.But the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all equivalent modification or replacement under the prerequisite without prejudice to spirit of the present invention, and these equivalent modification or replacement are all included in the application's claim limited range.
Claims (8)
1. one kind is improved the post-processing approach of carbon negative electrode material of lithium ion cell chemical property, it is characterized in that: when the Carbon Materials of reprocessing is used as the negative material of lithium ion battery, electrode first discharge specific capacity can improve 10 ~ 200%, and after 50 circulations, capacity still can improve 5 ~ 150%.
2. prepare a method for carbon cathode material reprocessing described in claim 1, it is characterized in that, comprise the following steps:
A) acid and distilled water are mixed to get acid solution according to volume ratio 1: 0.1 ~ 1: 10, taking a certain amount of diameter is 1 ~ 50um powdered carbon material stirring at room temperature process 1 ~ 24h in an acidic solution, extremely neutral and dry by deionized water washing, obtain acid treatment Carbon Materials;
B) by acid treatment Carbon Materials in 100 DEG C ~ 500 DEG C airoxidation 1 ~ 12h, obtain air oxidation Carbon Materials;
C) air oxidation Carbon Materials is directly used as lithium ion battery negative material, prepares lithium ion battery and test its chemical property.
3. the method according to claim 1 and 2, it is characterized in that, described Carbon Materials is hard charcoal through 500-1500 process and soft charcoal material, and comprise coke, mesophase pitch carbon microspheres, phenolic resin carbon, asphalt carbon, charcoal, bamboo charcoal, its particle diameter is 1-10um.
4. method according to claim 2, is characterized in that, described acid solution is selected from one or more in concentrated hydrochloric acid, red fuming nitric acid (RFNA), the concentrated sulfuric acid, perchloric acid.
5. method according to claim 2, is characterized in that, described steps A) in acid and the volume ratio 1: 0.5 ~ 1: 2 of distilled water.
6. method according to claim 2, is characterized in that, described steps A) in time of acid solution room temperature treatment Carbon Materials be 6 ~ 12h.
7. method according to claim 2, is characterized in that, described step B) in air oxidation temperature be 250 DEG C ~ 450 DEG C.
8. method according to claim 2, is characterized in that, described step B) in the air oxidation time be 3 ~ 6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170986A (en) * | 2017-05-11 | 2017-09-15 | 华南农业大学 | A kind of preparation method of lithium ion battery bamboo charcoal negative material |
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| CN1387268A (en) * | 2001-05-22 | 2002-12-25 | 中国科学院金属研究所 | Electrode of rechargeable battery and its preparing process |
| CN1688046A (en) * | 2005-04-06 | 2005-10-26 | 清华大学 | Method for increasing electrochemical lithium storage content of nano-carbon tube |
| CN1785510A (en) * | 2005-11-10 | 2006-06-14 | 上海交通大学 | Preparation method of carbon nano-cage loaded metal platinum nano-particle electrode catalyst |
| WO2007114849A2 (en) * | 2005-11-04 | 2007-10-11 | Meadwestvaco Corporation | Activated carbon from carbohydrate |
| TW201221473A (en) * | 2010-10-12 | 2012-06-01 | Aquion Energy Inc | Activated carbon with surface modified chemistry |
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- 2014-07-10 CN CN201410326677.4A patent/CN105244473A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387268A (en) * | 2001-05-22 | 2002-12-25 | 中国科学院金属研究所 | Electrode of rechargeable battery and its preparing process |
| CN1688046A (en) * | 2005-04-06 | 2005-10-26 | 清华大学 | Method for increasing electrochemical lithium storage content of nano-carbon tube |
| WO2007114849A2 (en) * | 2005-11-04 | 2007-10-11 | Meadwestvaco Corporation | Activated carbon from carbohydrate |
| CN1785510A (en) * | 2005-11-10 | 2006-06-14 | 上海交通大学 | Preparation method of carbon nano-cage loaded metal platinum nano-particle electrode catalyst |
| TW201221473A (en) * | 2010-10-12 | 2012-06-01 | Aquion Energy Inc | Activated carbon with surface modified chemistry |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170986A (en) * | 2017-05-11 | 2017-09-15 | 华南农业大学 | A kind of preparation method of lithium ion battery bamboo charcoal negative material |
| CN107170986B (en) * | 2017-05-11 | 2019-10-22 | 华南农业大学 | A kind of preparation method of lithium ion battery bamboo charcoal negative electrode material |
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