CN101214952A - Modified method of natural graphite material for lithium ion battery - Google Patents
Modified method of natural graphite material for lithium ion battery Download PDFInfo
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- CN101214952A CN101214952A CNA2007103080794A CN200710308079A CN101214952A CN 101214952 A CN101214952 A CN 101214952A CN A2007103080794 A CNA2007103080794 A CN A2007103080794A CN 200710308079 A CN200710308079 A CN 200710308079A CN 101214952 A CN101214952 A CN 101214952A
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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
Abstract
Disclosed is a modification method for native graphite materials used for lithium ion batteries. The method comprises the following steps that native graphite powders are placed into an autoclave, dense oxidizing acid, oxidizing salt and hydrochloric acid are used for oxidation treatment, wherein the oxidation treatment proceeds at a temperature ranging from 180 to 250 DEC G, the native graphite materials which are washed or not are centrifugalized, then native graphite materials which are centrifugalized are calcined, semi-modified native graphite materials are gained, silanization film forming treatment is completed on the semi-modified native graphite materials, then tetrahydrofuran is used to wash and dry the native graphite materials, thereby obtaining modified native graphite materials. The modified native graphite materials are capable of satisfying the application of the lithium ion batteries, have the advantages of high cost performance, low costs, large specific capacity, perfect circulative property and higher initial charge and discharge efficiency, and simultaneously are adapted to the negative pole application of high-current charge and discharge lithium ion batteries.
Description
Technical field
The present invention relates to a kind of preparation method of natural graphite material for lithium ion battery, refer to a kind of method of modifying of natural graphite material for lithium ion battery especially.
Background technology
Lithium ion battery is the novel high-energy secondary cell that twentieth century begins practicability the nineties, have that voltage height, energy density are big, outstanding advantages such as good cycle, self-discharge are little, memory-less effect, be widely used in field of portable electronic apparatus such as mobile telephone, notebook computer, digital product, power tool.Lithium ion battery all is with a wide range of applications as the electrical source of power of electromobile and hybrid vehicle and at numerous areas such as military equipment, aerospace.
In the lithium ion battery one of the most vital material be negative material.At present the negative material of research has graphitized carbon, graphite, RESEARCH OF PYROCARBON, and the oxide compound of non-carbon material such as metal alloy, tin, nitride etc.Although non-carbon material has a clear superiority at some aspect of performances, there is bigger deficiency, can't be as the negative pole of commercial li-ion battery.The negative material that is widely used in lithium ion battery now remains carbon material, as electrographite, natural graphite, carbonaceous mesophase spherules (MCMB), refinery coke etc., and in these commercial lithium ion battery negative materials, the synthetic graphite circulation volume has reversible capacity problem on the low side (as MCMB, refinery coke), though can reach 300～330mAhg
-1Between, need ultra high temp (3000 ℃) to handle during owing to preparation, therefore, it costs an arm and a leg; Though and the natural graphite theoretical capacity can reach 372mAh g
-1, but cycle performance is undesirable, and irreversible capacity is bigger first, and first charge-discharge efficiency is low.Therefore, in order to obtain the lithium ion battery negative material of better cost performance, it is a kind of method of having very much potentiality that natural graphite is carried out modification.
Because the place of production and subsequent machining technology is different, there is very big-difference in the natural graphite of China on structure and performance.The producer of some advanced technology is obtaining breakthrough aspect the Physical Processing moulding of crystalline flake graphite, and the main physical and chemical index of the spherical graphite of acquisition is close with synthetic graphite.Disclose with high-speed rotating impeller bump method as patent CN1330419A, made grain breakage or slightly be folded into almost circular and pancake graphite granule at its circumference place through the graphite granule after the sorting.But as the negative material of lithium ion battery, but show defectives such as reversible capacity is on the low side, performance degradation is too fast, can not directly use, still need further modification.
Natural graphite has low embedding lithium current potential and is suitable for the laminate structure that lithium ion embeds and deviates from, and should be good lithium ion battery negative material.Therefore, for many years, it is a lot of both at home and abroad modifying natural graphite to be done the research of lithium ion battery negative material, and has obtained certain achievement.For example manyly discover employing, can both make the natural graphite chemical property after the modification obtain certain improvement less than gas phase and liquid phase oxidation technique under 150 ℃ of normal temperature or the low temperature.Oxidizing process " repairing " fragment of natural graphite, isoreactivity site, sword limit.By with high molecular polymer natural graphite being coated processing, its physicals and chemical property also can be improved.Yet the result of above achievement and patent shows, still has the following technical problem that waits to solve:
Though 1, discover that employing can make the natural graphite chemical property after the modification have some improvement less than the gas phase under 150 ℃ of normal temperature or the low temperature and liquid oxidation technology, but the interlamellar spacing of natural graphite does not change, be unfavorable for the deep layer reparation of intercalator to natural graphite, it is less than normal that still there is interlamellar spacing in the material of Chu Liing like this, the problem that high rate during charging-discharging is relatively poor; And because oxidising process thoroughly (oxygenant can not be deep into graphite layers effectively) causes the defective of graphite layers profound level can not obtain " repairing ", thereby, cause the improvement degree of chemical property of the graphite after its modification limited.
2, natural graphite is after acid or salt processing, certainly will be at the natural graphite remained on surface some influence the ionic group of the acid of natural graphite cathode performance and salt etc., the existence of these groups can influence the generation quality of SEI film in the graphite cathode material charge and discharge process, is unfavorable for the raising and the material stable circulation subsequently of first charge-discharge efficiency.
3, natural graphite has certain activity, even adsorbed moisture content and hydroxyl also are difficult to eliminate fully by drying or subzero treatment.Their existence can cause electrolyte decomposition, increases the consumption of lithium ion, worsens the performance of electrolytic solution simultaneously.
Described technical problem can cause that the natural graphite material cycle performance is relatively poor, first charge-discharge efficiency is lower.
Summary of the invention
Purpose of the present invention is exactly the method for modifying of a kind of natural graphite material for lithium ion battery that will provide, and makes natural graphite material have excellent cycle performance and higher first charge-discharge efficiency.Technical problem to be solved is: 1, be beneficial to intercalator easy intercalation characteristic to natural graphite under comparatively high temps and suitably increase the interlamellar spacing of natural graphite and graphite layers is carried out the deep layer reparation, with large current density problem and perfect " repairing " degree to graphite that solves graphite material; 2, removing some that remain in the natural graphite surface after acid or salt are handled influence the organic and inorganic group of natural graphite cathode performance, so that make the SEI film that forms in the material electrochemistry circulation afterwards fine and close and firm, makes stable cycle performance; 3, utilize moisture content and the hydroxyl reaction of silane coupling agent with the absorption of natural graphite, generation can be eliminated moisture content and hydroxyl can strengthen silane film with the affinity and the penetrance of electrolytic solution again, improves the stability and the stability of the SEI film that forms in the charge and discharge process.
For solving described technical problem, the present invention adopts following technical scheme: the method for modifying of the natural graphite material for lithium ion battery that is provided, this method may further comprise the steps: A, put into the natural graphite powder in reactor, carry out the deep layer oxide treatment with intercalator, described intercalator is meant dense oxidizing acid, oxidisability salt, hydrochloric acid; Described dense oxidizing acid is the vitriol oil, concentrated nitric acid or their combination; Described oxidisability salt is meant cerous sulfate.B, to without the washing or after washing natural powdered graphite carry out centrifugation; C, the natural graphite powder after centrifugation is calcined, half modified natural graphite powder, the natural graphite powder is in calcination process, calcining temperature is at 600～1000 ℃; D, double modified natural graphite powder carry out film forming and handle; E, the natural graphite powder is cleaned with tetrahydrofuran (THF); F, drying.In steps A, described oxide treatment is to carry out 180～250 ℃ of temperature ranges; Described oxide treatment also can be carried out in 200～230 ℃ of temperature ranges.The used time of described oxide treatment is 5～48 hours.In step D, double modified natural graphite powder carries out the silanization film forming to be handled.It is to carry out under silane couplent that the silanization film forming of described half modified natural graphite powder is handled.It is to carry out in the presence of one or more combinations in glycidyl ether oxygen propyl trimethoxy silicane, hexamethyldisilazane, trimethylchlorosilane that the silanization of described half modified natural graphite powder is handled.It is 1～30 minute that the silanization of described half modified natural graphite powder is handled the used time.Natural graphite powder drying temperature behind the silanization is 100～180 ℃.
The present invention selects for use dense oxidizing acid or salt and combination thereof as intercalator, and select for use the intrusion layer characteristic of under higher temperature, utilizing dense oxidizing acid or salt and combination thereof that the natural graphite powder is carried out the deep layer oxide treatment, produce by high-temperature calcination then that to have height carbon active and have the half modified natural graphite powder on " totally " surface, thus the natural graphite product after in silylation technology subsequently, obtaining also finally to obtain modification evenly and in conjunction with firm silane film.Because silane film has outstanding organic feature, organic electrolyte is not only had affinity and it is passed, thereby make in battery charging process at natural graphite powder surface and the good SEI film (solid electrolyte interface film) of this intermembranous formation; Simultaneously since silanization eliminated the harmful water impurity of natural graphite powder surface adsorption and hydroxyl, the surface chemistry that has changed graphite and form fully and provide more firm anchor point for the SEI film, thereby can make the SEI film more firm, this obtains excellent cycle performance for natural graphite material and high first charge-discharge efficiency provides assurance.
Having the following advantages of natural graphite powder after the modification that the present invention obtains: can satisfy the application of lithium ion battery negative by the modified natural graphite powder, the cost performance height, with low cost, specific storage is big, have excellent cycle performance and higher first charge-discharge efficiency.Also be applicable to simultaneously the application of the charging-discharging lithium ion battery negative pole of big electric current.
Embodiment
Introduce embodiments of the invention below:
Embodiment one. and 5 gram spherical natural graphite powder are put into the vitriol oil, the concentrated nitric acid that contains 80mL, and about 10: 1 of its volume ratio is in the reactor of the mixing solutions of composition, slowly heating under suitable stirring, after temperature reaches 180 ℃, keep constant temperature, oxidation treatment time is 10 hours.After centrifuging; the natural graphite powder that filters out is promptly put into heat treatment furnace under the situation without washing calcine under protection of inert gas; be heated to 600 ℃～1000 ℃ by certain heating curve during calcining, be incubated 1～5 hour, naturally cool to room temperature again and obtain half modified graphite.With half modified graphite powder join glycidyl ether oxygen propyl trimethoxy silicane and hexamethyldisilazane by a certain percentage in the blended silane coupling agent agitation as appropriate carry out silanization and handle, time is 5 minutes, take out then, use tetrahydrofuran (THF) (THF) to clean for several times again, be evaporated to and put into 100 ℃ of loft drier drying treatment after doing, obtain the natural graphite product of modification after cooling down.This product can be used as the lithium ion battery negative material.The modified natural graphite negative material of this method preparation has bigger specific storage, and the initial charge capacity is at 370mAh g
-1More than, reversible capacity remains on 360mAh g
-1About, first charge-discharge efficiency is greater than 90%.
Embodiment two. and the ball grinder of 5 gram flakey natural graphite powder being put into the concentrated sulfuric acid solution of the 95-98% that contains 100mL carries out ball milling 5-16h, pour in the reactor then, inside adds concentrated nitric acid and hydrochloric acid again, slowly heating under suitable stirring, reach 230 ℃ up to temperature, keep constant temperature, oxidation treatment time is 36 hours.Natural graphite powder after the centrifugation is promptly put into heat treatment furnace under protection of inert gas, calcine under the situation without washing, be heated to 800 ℃ by certain heating curve during calcining, be incubated 3.5 hours, naturally cool to room temperature again and obtain half modified graphite.With half modified graphite powder join hexamethyldisilazane and trimethylchlorosilane by a certain percentage in the blended silane coupling agent agitation as appropriate carry out silanization and handle, treatment time is 30 minutes, after the taking-up, use tetrahydrofuran (THF) (THF) to clean for several times again, be evaporated to and put into loft drier after doing, 150 ℃ of temperature dryings obtain the natural graphite product of modification after cooling down.This product can be used as the lithium ion battery negative material.
Embodiment three. 5 gram spherical natural graphite powder are put into the vitriol oil and the reactor of hydrochloric acid mixed solution that contains 60mL, and slowly heating under suitable stirring, after temperature surpassed 210 ℃, maintenance constant temperature carried out oxide treatment 20 hours.After centrifuging, with the graphite that filters out with washed with de-ionized water for several times and through centrifugation, putting into heat treatment furnace then calcines in the presence of air, be heated to 900 ℃ by certain heating curve during calcining, be incubated 2 hours, half modified graphite powder is joined glycidyl ether oxygen propyl trimethoxy silicane, hexamethyldisilazane and trimethylchlorosilane are by a certain percentage in the blended silane coupling agent, agitation as appropriate is carried out silanization and is handled, 15 minutes times spent, take out, use tetrahydrofuran (THF) (THF) to clean for several times again, be evaporated to put into after doing loft drier 180 ℃ dry down, obtain the natural graphite product of modification after cooling down.This product can be used as the lithium ion battery negative material.
Embodiment four. and 5 gram spherical natural graphite powder are put into the reactor of the concentrated nitric acid, the vitriol oil or the cerous sulfate solution that contain 120mL, and slowly heating under suitable stirring after temperature surpasses 180 ℃, keeps constant temperature, oxide treatment 5 hours.After centrifuging, with the graphite that filters out with washed with de-ionized water for several times and through centrifugation, putting into heat treatment furnace then calcines in the presence of air, be heated to 1000 ℃ by certain heating curve during calcining, be incubated 1 hour, half modified graphite powder is joined hexamethyldisilazane and trimethylchlorosilane agitation as appropriate in the blended silane coupling agent by a certain percentage, carrying out silanization handles, treatment time is 1 minute, take out, use tetrahydrofuran (THF) (THF) to clean for several times again, be evaporated to that to put into loft drier after doing dry 120 ℃ of temperature, obtain the natural graphite product of modification after cooling down.This product can be used as the lithium ion battery negative material.
Embodiment five. and the ball grinder of 5 gram flakey natural graphites being put into the concentrated sulfuric acid solution of the 95-98% that contains 80mL carried out spheroidal graphite 6 hours, pour in the reactor then, inside adds cerous sulfate again, slowly heating under suitable stirring, when temperature reaches 200 ℃, keeping constant temperature, oxide treatment 30 hours.After centrifuging, with the graphite that filters out with washed with de-ionized water for several times and through centrifugation, put into heat treatment furnace then and under vacuum state, calcine, be heated to 800 ℃ by certain heating curve during calcining, be incubated 2 hours, naturally cool to room temperature again and obtain half modified graphite.Half modified graphite powder is joined agitation as appropriate in the silane coupling agent glycidyl ether oxygen propyl trimethoxy silicane, carrying out silanization handles, 3 minutes times spent, take out half modified graphite powder, use tetrahydrofuran (THF) (THF) to clean for several times again, be evaporated to do after, it is dry under 150 ℃ of temperature to put into loft drier, obtains the natural graphite product of modification after cooling down.This product can be used as the lithium ion battery negative material.
Embodiment six. and the horizontal pulverizing mill of 5 gram flakey natural graphites being put into the concentrated sulfuric acid solution that contains 20mL carried out nodularization graphite 3 hours, pour in the reactor then, inside adds concentrated nitric acid or cerous sulfate again, slowly heating under suitable stirring, reach 190 ℃ up to temperature, keep constant temperature, carried out oxide treatment 5 hours.After centrifuging; with the graphite that filters out with washed with de-ionized water for several times and through centrifugation, put into heat treatment furnace then and under protection of inert gas, calcine, be heated to 800 ℃ by certain heating curve during calcining; be incubated 3 hours, naturally cool to room temperature again and obtain half modified graphite.Half modified graphite powder is joined glycidyl ether oxygen propyl trimethoxy silicane, hexamethyldisilazane and trimethylchlorosilane agitation as appropriate in the blended silane coupling agent by a certain percentage, carrying out silanization handles, 20 minutes times spent, take out half modified natural graphite powder, use tetrahydrofuran (THF) (THF) to clean for several times again, be evaporated to put into after doing loft drier 130 ℃ dry down, obtain the natural graphite product of modification after cooling down.This product can be used as the lithium ion battery negative material.
Claims (10)
1. the method for modifying of a natural graphite material for lithium ion battery, this method may further comprise the steps: A, put into the natural graphite powder in reactor, carry out oxide treatment with dense oxidizing acid, oxidisability salt, hydrochloric acid; B, to without the washing or after washing natural powdered graphite carry out centrifugation; C, the natural graphite powder after centrifugation is calcined, half modified natural graphite powder; D, double modified natural graphite powder carry out film forming and handle; E, the natural graphite powder is cleaned with tetrahydrofuran (THF); F, drying; It is characterized in that: in steps A, described oxide treatment is to carry out 180～250 ℃ of temperature ranges; In step D, double modified natural graphite powder carries out the silanization film forming to be handled.
2. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1 is characterized in that: it is to carry out under silane couplent that the silanization film forming of described half modified natural graphite powder is handled.
3. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1 or 2 is characterized in that: it is to carry out in the presence of one or more combinations in glycidyl ether oxygen propyl trimethoxy silicane, hexamethyldisilazane, trimethylchlorosilane that the silanization of described half modified natural graphite powder is handled.
4. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1 or 2, it is characterized in that: it is 1～30 minute that the silanization of described half modified natural graphite powder is handled the used time.
5. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 3, it is characterized in that: it is 1～30 minute that the silanization of described half modified natural graphite powder is handled the used time.
6. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1, it is characterized in that: the natural graphite powder drying temperature behind the silanization is 100～180 ℃.
7. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1, it is characterized in that: described dense oxidizing acid is the vitriol oil, concentrated nitric acid or their combination; Described oxidisability salt is meant cerous sulfate.
8. as the method for modifying of claim 1 or 7 described natural graphite material for lithium ion battery, it is characterized in that: described oxide treatment is to carry out in 180～230 ℃ of temperature ranges.
9. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1, it is characterized in that: described natural graphite powder is in calcination process, and calcining temperature is at 600～1000 ℃.
10. the method for modifying of natural graphite material for lithium ion battery as claimed in claim 1, it is characterized in that: the used time of described oxide treatment is 5～48 hours.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110274982A1 (en) * | 2009-01-23 | 2011-11-10 | Nec Energy Devices, Ltd. | Lithium ion battery |
| CN102916168A (en) * | 2012-11-09 | 2013-02-06 | 中国海洋石油总公司 | Modification method of artificial graphite |
| CN102931407A (en) * | 2012-11-01 | 2013-02-13 | 无锡东恒新能源材料有限公司 | Method for modifying natural graphite |
| WO2013068297A1 (en) | 2011-11-10 | 2013-05-16 | Basf Se | Process for producing expandable styrene polymers containing hydrophobicized carbon particles |
| US20130302680A1 (en) * | 2012-04-18 | 2013-11-14 | Lg Chem, Ltd. | Anode active material and the secondary battery comprising the same |
| CN104798228A (en) * | 2012-11-20 | 2015-07-22 | 昭和电工株式会社 | Method for producing negative electrode material for lithium ion batteries |
| CN105098163A (en) * | 2014-05-16 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Preparation method of coated electrode material |
| CN105633370A (en) * | 2016-01-06 | 2016-06-01 | 上海第二工业大学 | Modified natural graphite and preparation method and application thereof |
| CN108751187A (en) * | 2018-04-23 | 2018-11-06 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of acid modified spherical natural graphite negative electrode material |
| CN108987687A (en) * | 2018-06-22 | 2018-12-11 | 中南大学 | A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof |
| CN110745819A (en) * | 2019-10-25 | 2020-02-04 | 哈尔滨工业大学 | Method for modifying surface of graphite material by using silane coupling agent, lithium ion battery cathode and preparation method thereof |
| CN112599741A (en) * | 2020-12-15 | 2021-04-02 | 广东凯金新能源科技股份有限公司 | Preparation method of modified graphite electrode material |
-
2007
- 2007-12-31 CN CNA2007103080794A patent/CN101214952A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9343740B2 (en) | 2009-01-23 | 2016-05-17 | Nec Energy Devices, Ltd. | Lithium ion battery |
| CN102292856A (en) * | 2009-01-23 | 2011-12-21 | Nec能源元器件株式会社 | Lithium ion battery |
| CN102292856B (en) * | 2009-01-23 | 2014-04-09 | Nec能源元器件株式会社 | Lithium ion battery |
| US20110274982A1 (en) * | 2009-01-23 | 2011-11-10 | Nec Energy Devices, Ltd. | Lithium ion battery |
| WO2013068297A1 (en) | 2011-11-10 | 2013-05-16 | Basf Se | Process for producing expandable styrene polymers containing hydrophobicized carbon particles |
| US20130302680A1 (en) * | 2012-04-18 | 2013-11-14 | Lg Chem, Ltd. | Anode active material and the secondary battery comprising the same |
| CN102931407A (en) * | 2012-11-01 | 2013-02-13 | 无锡东恒新能源材料有限公司 | Method for modifying natural graphite |
| CN102916168A (en) * | 2012-11-09 | 2013-02-06 | 中国海洋石油总公司 | Modification method of artificial graphite |
| CN104798228B (en) * | 2012-11-20 | 2017-10-20 | 昭和电工株式会社 | The manufacture method of cathode material of lithium ion battery |
| CN104798228A (en) * | 2012-11-20 | 2015-07-22 | 昭和电工株式会社 | Method for producing negative electrode material for lithium ion batteries |
| CN105098163A (en) * | 2014-05-16 | 2015-11-25 | 微宏动力***（湖州）有限公司 | Preparation method of coated electrode material |
| CN105098163B (en) * | 2014-05-16 | 2017-09-29 | 微宏动力***（湖州）有限公司 | A kind of preparation method of cladded type electrode material |
| CN105633370A (en) * | 2016-01-06 | 2016-06-01 | 上海第二工业大学 | Modified natural graphite and preparation method and application thereof |
| CN108751187A (en) * | 2018-04-23 | 2018-11-06 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of acid modified spherical natural graphite negative electrode material |
| CN108987687A (en) * | 2018-06-22 | 2018-12-11 | 中南大学 | A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof |
| CN110745819A (en) * | 2019-10-25 | 2020-02-04 | 哈尔滨工业大学 | Method for modifying surface of graphite material by using silane coupling agent, lithium ion battery cathode and preparation method thereof |
| CN110745819B (en) * | 2019-10-25 | 2022-02-18 | 哈尔滨工业大学 | Method for modifying surface of graphite material by using silane coupling agent, lithium ion battery cathode and preparation method thereof |
| CN112599741A (en) * | 2020-12-15 | 2021-04-02 | 广东凯金新能源科技股份有限公司 | Preparation method of modified graphite electrode material |
| CN112599741B (en) * | 2020-12-15 | 2021-09-24 | 广东凯金新能源科技股份有限公司 | Preparation method of modified graphite electrode material |
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Application publication date: 20080709 |