CN1241824A - Preparation of negative pole graphite powder for secondary lithium battery - Google Patents
Preparation of negative pole graphite powder for secondary lithium battery Download PDFInfo
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- CN1241824A CN1241824A CN99111156A CN99111156A CN1241824A CN 1241824 A CN1241824 A CN 1241824A CN 99111156 A CN99111156 A CN 99111156A CN 99111156 A CN99111156 A CN 99111156A CN 1241824 A CN1241824 A CN 1241824A
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- graphite powder
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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
China-made high-purity graphite powder as material is first molded and extruded to form and then graphitized for the second time, and the formed graphite after the secondary graphitizing is finally crushed mechanically to obtain granular graphite powder with large amount of defects in the interior and the exterior. The graphite powder product has excellent Li+ embedding and relieving performance and its average specific capacity of the first 11 discharges in the charge and discharge circulation is as high as 341 mA.hr/g.
Description
The invention belongs to energy technology field, particularly about the preparation process of graphite powder.The graphite powder that utilizes this method to make can be used as lithium secondary battery cathode material.
Lithium secondary battery is the high-performance secondary cell of latest generation, compares with metal hydride battery with other secondary cell commonly used such as plumbic acid, cadmium nickel, and its energy density is the highest; Simultaneously, it also have the voltage height, in light weight, security performance good, have extended cycle life and advantage such as non-environmental-pollution, thereby is a kind of very promising novel battery.The positive and negative pole material that is used for this kind battery all requirement can reversibly take off the absorption lithium ion.Graphite can satisfy this requirement well.
Graphite is 372mAh/g as the theoretical capacity of lithium secondary battery anode, but owing to reasons such as manufacturing process, reality generally only reaches 200～300mAh/g.The graphite powder that adopts the present invention's preparation is as negative material, with the LiCoO of Japanese Osaka Gas Chemicals CO.LTD production
2As positive electrode, be assembled into the average size that 10 circulations of button cell test obtain and reach 341mAh/g.
The purpose of this invention is to provide a kind of preparation method who is used for negative pole graphite powder for secondary lithium battery, the average graphite powder capacity that makes with this method can reach 341mAh/g.
Preparation method of the present invention carries out according to the following steps:
(1) homemade high-purity graphite powder is mixed with binding agent;
(2) mold pressing or extrusion modling;
(3) secondary graphitizing is handled and is obtained the graphitization formed body;
(4) the graphitization formed body is pulverized with following three kinds of possible mechanical means: scraping (cutting), bump or grinding, sieve to obtain graphite powder.
Below by example, the good embedding lithium performance of the graphite powder that the inventive method is made is further described.Wherein, example 1 is the raw material graphite powder, the graphite powder that example 2 makes for control methods, the graphite powder that example 3 makes for the inventive method, the commercialization secondary lithium batteries graphite powder that example 4 is produced for prior art.
Example 1
Use commercially available homemade graphite powder G0 (order of spectrum is pure, crosses 280 mesh sieves) to be prepared into electrode, and be assembled into the Swagelock simulated battery.Battery is a metallic potassium to electrode, and electrolyte is 1MLiPF
61: 1 ethylene carbonate (EC)-diethyl carbonate (DEC) solution, barrier film is the Cellgard2500 micro-pore septum.Test condition is: constant current charge-discharge, current density are 0.25mA/cm
2, cut-ff voltage is 0.005～2.5V.
Example 2
Raw material graphite powder in the example 1 is mixed with binding agent, and mold pressing or extrusion modling are handled through secondary graphitizing and are obtained the graphitization formed body; With ball mill this formed body is pulverized, crossed 280 mesh sieves, obtain graphite powder G1.Use this powder to be prepared into electrode and be assembled into the Swagelock simulated battery.Other composition of battery is identical with example 1 with the formula of survey condition.
Example 3
Raw material graphite powder in the example 1 is mixed with binding agent, and mold pressing or extrusion modling are handled through secondary graphitizing and are obtained the graphitization formed body; This formed body of scraping (cutting) obtains graphite powder G2, crosses 280 mesh sieves.Use this powder to be prepared into electrode and be assembled into the Swagelock simulated battery.Other composition of battery is identical with example 1 with test condition.
Example 4
Use is prepared into electrode and is assembled into the Swagelock simulated battery from the commercialization secondary lithium batteries graphite powder MCMB28 of Japanese Osaka Gas Chemicals CO.LTD import.Other composition of battery is identical with example 1 with test condition.
Table l lists the test result of above-mentioned 4 examples, as seen the graphite powder G2 that adopts the inventive method to make not only is far superior to raw material graphite powder G0 on embedding lithium performance index such as efficiency for charge-discharge, average discharge capacity, and is better than the graphite powder MCMB28 that Japan produces.
The embedding lithium performance (simulated battery) of the various graphite powders of table 1
| Graphite powder | ????G0 | ????G1 | ????G2 | ??MCMB28 |
| Charging capacity (mAh/g) for the first time | ????517 | ????491 | ????442 | ????358 |
| Discharge capacity (mAh/g) for the first time | ????298 | ????293 | ????368 | ????254 |
| First charge-discharge efficiency (%) | ????58 | ????60 | ????83 | ????71 |
| Charging capacity (mAh/g) for the second time | ????300 | ????322 | ????371 | ????264 |
| Discharge capacity (mAh/g) for the second time | ????279 | ????291 | ????358 | ????240 |
| Efficiency for charge-discharge (%) for the second time | ????93 | ????90 | ????96 | ????91 |
| Charging capacity (mAh/g) for the third time | ????279 | ????303 | ????361 | ????249 |
| Discharge capacity (mAh/g) for the third time | ????268 | ????282 | ????355 | ????240 |
| Efficiency for charge-discharge (%) for the third time | ????96 | ????93 | ????98 | ????96 |
| The 4th charging capacity (mAh/g) | ????254 | ????287 | ????369 | ????244 |
| The 4th discharge capacity (mAh/g) | ????246 | ????276 | ????339 | ????236 |
| The 4th efficiency for charge-discharge (%) | ????97 | ????96 | ????92 | ????96 |
| The 5th charging capacity (mAh/g) | ????247 | ????287 | ????341 | ????237 |
| The 5th discharge capacity (mAh/g) | ????236 | ????281 | ????337 | ????233 |
| The 5th efficiency for charge-discharge (%) | ????96 | ????98 | ????99 | ????98 |
| Average discharge capacity (mAh/g) | ????265 | ????285 | ????352 | ????241 |
The graphite powder G2 that uses the inventive method to make is assembled into button cell as negative material and further tests its cycle performance.Anode is the commercialization secondary lithium batteries LiCoO that Japanese Osaka Gas Chemicals CO.LTD produces
2, electrolyte is 1MLiPF
61: 1 ethylene carbonate (EC)-diethyl carbonate (DEC) solution, barrier film is the Cellgard2500 micro-pore septum.Test condition is: constant current charge-discharge, current density are 0.33mA/cm
2, cut-ff voltage is 2.5～4.1V.Test result as shown in Figure 1, its preceding ten once circulation discharge average size be 341mAh/g, as seen the embedding lithium cycle performance of this powder is also fairly good.
The graphite powder that the inventive method makes has following architectural feature: the XRD diffracting spectrum turns out to be typical graphite-structure, and the diffraction maximum of (002) face is sharp-pointed, and interplanar distance is between 3.36～3.38, and crystallite size is about 200～300.It is 4～50 that ESEM records granulometric range.BET specific area＜=20m
2/ g.The max architecture difference of this graphite powder and general commercially available graphite powder is: its granule interior has a large amount of holes (micro-crack) thereby fluffy, and appearance is uneven; Regular graphite laminate is piled up and densification (seeing Fig. 2 stereoscan photograph) and the latter's particle presents.
Beneficial effect of the present invention:
(1) the graphite powder average size of the inventive method preparation can reach 314mAh/g;
(2) function admirable is suitable is applied to China's lithium secondary battery and commercially produces.
Description of drawings:
Graphite powder cycle performance (button cell) curve that Fig. 1 makes for the inventive method;
Fig. 2 (a) is the stereoscan photograph of raw material graphite powder;
(b) stereoscan photograph of the graphite powder that makes for the present invention.
Claims (1)
1. the preparation method of a negative pole graphite powder for secondary lithium battery is characterized in that:
(1) homemade high-purity graphite powder is mixed with binding agent;
(2) mold pressing or extrusion modling;
(3) carry out secondary graphitizing;
(4) pulverize, sieve in the mode of scraping (cutting), bump or grinding handle the formed body that obtains through secondary graphitizing to obtain graphite powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99111156A CN1241824A (en) | 1999-07-28 | 1999-07-28 | Preparation of negative pole graphite powder for secondary lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99111156A CN1241824A (en) | 1999-07-28 | 1999-07-28 | Preparation of negative pole graphite powder for secondary lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1241824A true CN1241824A (en) | 2000-01-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99111156A Pending CN1241824A (en) | 1999-07-28 | 1999-07-28 | Preparation of negative pole graphite powder for secondary lithium battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326266C (en) * | 2003-12-26 | 2007-07-11 | 比亚迪股份有限公司 | A negative electrode graphite material for lithium-ion secondary battery and preparation method thereof |
| CN109509873A (en) * | 2017-09-14 | 2019-03-22 | 丰田自动车株式会社 | The cathode graphite material and its manufacturing method of lithium ion secondary battery |
-
1999
- 1999-07-28 CN CN99111156A patent/CN1241824A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326266C (en) * | 2003-12-26 | 2007-07-11 | 比亚迪股份有限公司 | A negative electrode graphite material for lithium-ion secondary battery and preparation method thereof |
| CN109509873A (en) * | 2017-09-14 | 2019-03-22 | 丰田自动车株式会社 | The cathode graphite material and its manufacturing method of lithium ion secondary battery |
| CN109509873B (en) * | 2017-09-14 | 2022-03-11 | 丰田自动车株式会社 | Graphite material for negative electrode of lithium ion secondary battery and method for producing same |
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Owner name: BODA BATTERY CO., LTD. Free format text: FORMER OWNER: DALU TAIJI BATTERY CO., LTD., BEIJING Effective date: 20021204 |
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Effective date of registration: 20021204 Address after: 100081, 30 Whitehead Road, Beijing, Haidian District Applicant after: Boda Battery Co Ltd Address before: 100081, 30 Whitehead Road, Beijing, Haidian District Applicant before: Dalu Taiji Battery Co., Ltd., Beijing |
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