CN1343017A - Carbon material as negative electrode of Li-ion battery and its preparing process and application - Google Patents
Carbon material as negative electrode of Li-ion battery and its preparing process and application Download PDFInfo
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- CN1343017A CN1343017A CN00124727A CN00124727A CN1343017A CN 1343017 A CN1343017 A CN 1343017A CN 00124727 A CN00124727 A CN 00124727A CN 00124727 A CN00124727 A CN 00124727A CN 1343017 A CN1343017 A CN 1343017A
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- lithium ion
- negative electrode
- graphite
- ion cell
- slaine
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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
A carbon material used as negative electrode of Li-ion battery is a nm-class millipore graphite material, which is prepared through preparing solution of metal salt (KNO3, NiNO3, NaNO3, RbNO3, or CsNO3) in hydrochloric acid, by adding natural graphite, heating at 20-120 deg.C for 1-48 hr, and calcining at 200-1200 deg.C.
Description
The present invention relates to a kind of lithium ion battery material, particularly a kind of carbon negative electrode material of lithium ion cell and preparation method thereof
Since nineteen ninety, Sony corporation of Japan was released firstling, lithium ion battery had obtained developing rapidly and has been widely used in fields such as telecommunications, Aero-Space.Compare with traditional nickel-cadmium cell, Ni-MH battery have high voltage, the advantage of high-energy-density, and be full green power supply.
Therefore carbon negative pole material has attracted people's interest because it has considerable influence to the lithium ion battery charge-discharge performance.Natural graphite material has obtained broad research in recent years because it is cheap, the source is abundant.These researchs mainly concentrate on modification and two aspects of mixing.But the interlamellar spacing of natural graphite material is 3.35 , embeds in the process at lithium ion, and its interlamellar spacing can be expanded as 3.5-3.7 .The enlarged meeting of interlamellar spacing causes the expansion of graphite volume in the charge and discharge process and peeling off of graphite flake layer, influence chemical property, the little interlamellar spacing quick embedding that can influence lithium ion is simultaneously deviate from, if therefore enlargement layer spacing effectively just can be improved the performance of graphite material well
J.Electrochem.Soc, Vo1.144,2968-2973 (1997) have reported and have utilized strong acid such as persulfuric acid that graphite is carried out surface oxidation treatment, and this method can improve the first charge-discharge capacity of graphite material.Its principle is by oxidation, can form imitative SEI film (Solid Electrolyte Interface-solid electrolyte intermediate coat) at graphite surface, has reduced the lithium ion capacity loss of first charge-discharge.But, only maintain 3.35 because the method when oxidation, do not add other material, so interlamellar spacing is less.J.Electrochem.Soc, Vo1.144,186-192 (1997) has reported and has utilized KC
8During as the negative material of lithium ion battery, can effectively improve chemical property.After its principle is that K inserts graphite linings, can be effectively with the graphite linings pitch enlargement, thus the passage that makes lithium ion embed graphite linings becomes big.But the method is at preparation KC
8During electrode, need 400-500 ℃ of high temperature and vacuumizing, complicated condition is wayward.
The object of the invention has been to overcome the shortcoming that the graphite cathode material interlamellar spacing is less and reversible capacity is low in the prior art, and a kind of method that makes a kind of carbon negative electrode material of lithium ion cell by the oxidation intercalation is provided.
Carbon negative electrode material of lithium ion cell of the present invention is a slaine intercalated graphite material, and it is based on native graphite, and interlayer mixes KNO
3, LiNO
3, NaNO
3, RbNO
3Or CsNO
3Molecules of salt, its surface distributed is nanometer level microporous.KNO
3, LiNO
3, NaNO
3, RbNO
3Or CsNO
3Molecules of salt is that with hydrone, micromolecule such as acid ion together insert graphite layers when utilizing nitration mixture oxidation native graphite, then at a certain temperature, burns and removes volatile small molecule, and interlayer only keeps KNO
3LiNO
3, NaNO
3, RbNO
3, CsNO
3Equimolecular supports molecule as skeleton.The particle diameter of wherein prepared carbon negative electrode material of lithium ion cell is 10-30um, and specific area is 9.87m
2/ g, the graphite material interlamellar spacing is 3.35-3.40 , plasma emission spectrum confirms K, Li, Na, Rb, the content of Cs is 0.05%-5% by wt%.
Carbon negative electrode material of lithium ion cell of the present invention carries out according to the following steps:
1. with KNO
3, LiNO
3, NaNO
3, RbNO
3Or CsNO
3The recrystallization drying.
2. get 5%-50%KNO
3, LiNO
3, NaNO
3, RbNO
3Or CsNO
3Salt is dissolved in the inorganic acid that concentration is 30%-98%, as H
2SO
4, HNO
3Or in the nitration mixture, make acid solution, and above-mentioned acid solution is joined in the native graphite, heated 1-48 hour down at 20-120 ℃ then, obtain the slaine intercalated graphite.
3. above-mentioned slaine intercalated graphite is put into the sintering furnace of inert atmosphere, under 200-1200 ℃, burnt 2-48 hour, obtain oxidation layer expansion graphite negative material.
It is that 2% Kynoar N-N-methyl-2-2-pyrrolidone N-solution fully grinds and becomes even pulpous state viscous fluid that the purposes of a kind of carbon negative electrode material of lithium ion cell of the present invention is above-mentioned carbon cathode material powder and concentration, and wherein Kynoar accounts for 10% of raw material of wood-charcoal material powder weight; On Copper Foil, be coated with into the carbon membrane that thickness is 0.1～0.2mm with scraper then, treat under 1MPa pressure, to carry out after the solvent evaporates roll extrusion and handle, be placed on afterwards in 120 ℃ of vacuum drying ovens dry 24 hours, with this work electrode as lithium ion battery.
Be filled with argon gas, relative humidity is controlled in the glove box below 2%, and as to electrode and auxiliary electrode, electrolyte is 1mol/LLiPF with metallic lithium foil
6+ ethylene carbonate/diethyl carbonate (volume ratio is 1: 1) is made barrier film with the capillary polypropylene permeable membrane, is assembled into Experimental cell with the work electrode of above-mentioned preparation.The charge-discharge performance test of battery is carried out on the constant current charge-discharge instrument.Charging/discharging voltage scope: 0.010V～2.500V.
Adopt lithium ion battery negative of the present invention to obtain following invention achievement (1).The graphite linings pitch enlargement has increased storage lithium space, improved electrochemistry capacitance, has reduced lithium ion and has embedded the activation energy deviate from, has quickened electrode reaction speed, has improved the cycle performance of graphite material.(2) graphite surface has generated a large amount of nanoscale holes, has increased the passage of embedding lithium, has improved charge/discharge capacity.(3) preparation technology of carbon negative electrode material of lithium ion cell of the present invention is simple, does not need the high-temperature vacuum operation.(4) interlamellar spacing of the carbon negative electrode material of lithium ion cell of the present invention's preparation is measured by xrd method, and specific area is measured by the BET method, K, and Li, Na, Rb, Cs content is measured by plasma emission spectrometry, and surface state detects with SEM and STM method.The carbon negative electrode material of lithium ion cell of the present invention's preparation has big charge/discharge capacity and excellent cycle performance (seeing Table).
The chemical property of table .KNO3 intercalation graphite oxide
| Sample | Initial charge capacity (mAh/g) | Discharge capacity (mAh/g) first | Capacity (mAh/g) after 20 times circulates | Interlamellar spacing () |
| Comparative example | ????376 | ????305 | ????150 | ?3.3533 |
| Embodiment 1 | ????412 | ????241 | ????250 | ?3.3533 |
| Embodiment 2 | ????385 | ????276 | ????296 | ?3.3733 |
| Embodiment 3 | ????392 | ????310 | ????332 | ?3.3783 |
| Embodiment 4 | ????378 | ????265 | ????273 | ?3.3658 |
| Embodiment 5 | ????380 | ????270 | ????277 | ?3.3683 |
Embodiment 1 (Comparative Examples)
Take by weighing the 5g native graphite, add concentration and be 98% the 120ml concentrated sulfuric acid and concentration and be in the nitration mixture that 67% 40ml red fuming nitric acid (RFNA) forms, 110 ℃ of following stirring and refluxing 6 hours.Suction filtration washs to filter liquor Ph=6.5, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 500 ℃, and the time is 12 hours.Naturally cool to room temperature, obtain graphite oxide.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 2
Take by weighing 2.15 gram KNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120m198% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 8 hours.Suction filtration washs to filter liquor Ph=2, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 600 ℃, and the time is 10 hours.Naturally cool to room temperature, obtain KNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 3
Take by weighing 8.60 gram KNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 12 hours.Suction filtration washs to filter liquor Ph=2, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 700 ℃, and the time is 12 hours.Naturally cool to room temperature, obtain KNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 4
Take by weighing 8.60 gram KNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 24 hours.Suction filtration washs to filter liquor Ph=3, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 800 ℃, and the time is 16 hours.Naturally cool to room temperature, obtain KNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 5
Take by weighing 8.60 gram KNO3 and be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 48 hours.Suction filtration washs to filter liquor Ph=4, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 800 ℃, and the time is 24 hours.Naturally cool to room temperature, obtain KNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 6
Take by weighing 2.15 gram LiNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 8 hours.Suction filtration washs to filter liquor Ph=2, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 500 ℃, and the time is 10 hours.Naturally cool to room temperature, obtain LiNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 7
Take by weighing 4.30 gram NaNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 8 hours.Suction filtration washs to filter liquor Ph=2, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 500 ℃, and the time is 10 hours.Naturally cool to room temperature, obtain NaNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 8
Take by weighing 4.3 gram RbNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 8 hours.Suction filtration washs to filter liquor Ph=2, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 500 ℃, and the time is 10 hours.Naturally cool to room temperature, obtain RbNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Embodiment 9
Take by weighing 6.45 gram CsNO
3Be dissolved in the 40ml red fuming nitric acid (RFNA) and the 5g native graphite mixes, add the 120ml98% concentrated sulfuric acid again, 110 ℃ of following stirring and refluxing 8 hours.Suction filtration washs to filter liquor Ph=2, oven dry.Above-mentioned material is placed the tube furnace sintering of argon shield, and temperature is 500 ℃, and the time is 10 hours.Naturally cool to room temperature, obtain CsNO
3The graphite oxide of intercalation.The material that makes is made electrode slice and be assembled into its charge-discharge performance of battery testing.
Comparative example
Take by weighing 0.5 gram native graphite powder, adding 1.75 gram concentration is 2% Kynoar N-N-methyl-2-2-pyrrolidone N-solution, fully grind and become even pulpous state viscous fluid, on Copper Foil, be coated with into the carbon membrane that thickness is 0.1～0.2mm with scraper then, treat under 1MPa pressure, to carry out the roll extrusion processing after the solvent evaporates, be placed on afterwards in 120 ℃ of vacuum drying ovens dry 24 hours, and, carried out the charge-discharge performance test after being assembled into battery with this work electrode as lithium ion battery.
Claims (6)
1. a carbon negative electrode material of lithium ion cell is characterized in that described carbon cathode material is that particle diameter is 10-30um, the slaine intercalated graphite material that surface distributed is nanometer level microporous, and described slaine is the KNO of 0.05-5%
3, LiNO
3, NaNO
3, RbNO
3, or CsNO
3
2. a kind of carbon negative electrode material of lithium ion cell according to claim 1 is characterized in that described graphite material interlamellar spacing is 3.35-3.40 .
3. the preparation method of a kind of carbon negative electrode material of lithium ion cell according to claim 1, it is characterized in that following these steps to carry out: (1) is with the KNO of 5-50% through recrystallization
3, LiNO
3, NaNO
3, RbNO
3, or CsNO
3Slaine is dissolved in the inorganic acid of 30-98%; make acid solution; (2) above-mentioned acid solution is added in the native graphite; 20-120 ℃ of heating 1-48 hour; make the slaine intercalated graphite; (3) above-mentioned slaine intercalated graphite is put into the sintering furnace of argon shield, burnt 2-48 hour, make oxidation layer expansion graphite negative material at 200-1200 ℃.
4. the preparation method of a kind of carbon negative electrode material of lithium ion cell according to claim 3 is characterized in that described inorganic acid is sulfuric acid, nitric acid or nitration mixture.
5. the purposes of a kind of carbon negative electrode material of lithium ion cell according to claim 1 is characterized in that making the work electrode of lithium ion battery.
6. the purposes of a kind of carbon negative electrode material of lithium ion cell according to claim 6, it is characterized in that carbon cathode material and Kynoar N-N-methyl-2-2-pyrrolidone N-solution are developed into the pulpous state viscous fluid, through filming, roll, drying makes the work electrode of lithium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001247271A CN1141746C (en) | 2000-09-13 | 2000-09-13 | Carbon material as negative electrode of Li-ion battery and its preparing process and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001247271A CN1141746C (en) | 2000-09-13 | 2000-09-13 | Carbon material as negative electrode of Li-ion battery and its preparing process and application |
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|---|---|
| CN1343017A true CN1343017A (en) | 2002-04-03 |
| CN1141746C CN1141746C (en) | 2004-03-10 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005043652A1 (en) * | 2003-11-04 | 2005-05-12 | Shanghai Shanshan Tech Co., Ltd. | The preparation method of carbon negative electrode material for lithium ion battery |
| WO2014082296A1 (en) * | 2012-11-30 | 2014-06-05 | Shanghai Jiaotong University | Cathode material for a li-s battery and the method for preparing the same, a cathode made of the cathode material and a li-s battery comprising the cathode |
| CN108217640A (en) * | 2018-01-09 | 2018-06-29 | 江西理工大学 | A kind of preparation method of the cathode of lithium ion battery available for quick charge |
| CN109742356A (en) * | 2018-12-29 | 2019-05-10 | 湖南中科星城石墨有限公司 | A kind of preparation method of graphite cathode material |
| CN110707323A (en) * | 2019-09-27 | 2020-01-17 | 太原理工大学 | Anion layer-expanding carbon material and preparation method and application thereof |
| CN113611855A (en) * | 2021-07-30 | 2021-11-05 | 山东大学 | Water-soluble inorganic salt modified graphite material and preparation method and application thereof |
| CN114156440A (en) * | 2021-11-18 | 2022-03-08 | 杭州电子科技大学 | Method for preparing sodium electrode based on sodium salt boiling method |
-
2000
- 2000-09-13 CN CNB001247271A patent/CN1141746C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005043652A1 (en) * | 2003-11-04 | 2005-05-12 | Shanghai Shanshan Tech Co., Ltd. | The preparation method of carbon negative electrode material for lithium ion battery |
| WO2014082296A1 (en) * | 2012-11-30 | 2014-06-05 | Shanghai Jiaotong University | Cathode material for a li-s battery and the method for preparing the same, a cathode made of the cathode material and a li-s battery comprising the cathode |
| CN104904040A (en) * | 2012-11-30 | 2015-09-09 | 上海交通大学 | Cathode material for a li-s battery and the method for preparing the same, a cathode made of the cathode material and a li-s battery comprising the cathode |
| US9773581B2 (en) | 2012-11-30 | 2017-09-26 | Robert Bosch Gmbh | Cathode material for a Li—S battery and the method for preparing the same, a cathode made of the cathode material and a Li—S battery comprising the cathode |
| CN108217640A (en) * | 2018-01-09 | 2018-06-29 | 江西理工大学 | A kind of preparation method of the cathode of lithium ion battery available for quick charge |
| CN109742356A (en) * | 2018-12-29 | 2019-05-10 | 湖南中科星城石墨有限公司 | A kind of preparation method of graphite cathode material |
| CN110707323A (en) * | 2019-09-27 | 2020-01-17 | 太原理工大学 | Anion layer-expanding carbon material and preparation method and application thereof |
| CN113611855A (en) * | 2021-07-30 | 2021-11-05 | 山东大学 | Water-soluble inorganic salt modified graphite material and preparation method and application thereof |
| CN114156440A (en) * | 2021-11-18 | 2022-03-08 | 杭州电子科技大学 | Method for preparing sodium electrode based on sodium salt boiling method |
| CN114156440B (en) * | 2021-11-18 | 2023-12-01 | 杭州电子科技大学 | Method for preparing sodium electrode based on sodium salt boiling method |
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| Publication number | Publication date |
|---|---|
| CN1141746C (en) | 2004-03-10 |
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