CN1645651A - Production of positive active material of lithium battery - Google Patents
Production of positive active material of lithium battery Download PDFInfo
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- CN1645651A CN1645651A CNA2004100510161A CN200410051016A CN1645651A CN 1645651 A CN1645651 A CN 1645651A CN A2004100510161 A CNA2004100510161 A CN A2004100510161A CN 200410051016 A CN200410051016 A CN 200410051016A CN 1645651 A CN1645651 A CN 1645651A
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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
The method includes selecting pyrite: purity is 90-99.44%; sulfur content is 48.1-53.15%; iron content is 42.09-46.50. Impurity content: Sio <0.1-1%; Mgo is less than or equal to 0.1-1%; Al2O3<0.15-1%; Cao is less than or equal to 0.1-1%; acid soluble iron 0.38-1%. The selected pyrite is through breaking, screen sizing (75% passes through 200 mesh screen, 25% passes through 325 mesh screen). Then it will be heat treated at certain condition. After heat treatment it will be cooled until it is below 80deg.C.
Description
Technical field
The invention belongs to the battery technology field, particularly a kind of preparation method of the ferrous disulfide as lithium battery anode active material.
Background technology
Battery of lithium-iron disulphide is to be positive active material with the ferrous disulfide, and lithium metal is the lithium battery of negative electrode active material.Barrier film between both positive and negative polarity adopts such as polypropylene and polyethylene composite film (being called for short the PP film), and electrolyte adopts non-aqueous system, and electrolyte has LiClO
4, LiPF
6, LiCF
3SO
3, plus plate current-collecting body adopts the metallic aluminium net, and negative current collector adopts nickel plated steel strip, and shell adopts the nickel plating box hat.FeS
2Theoretical capacity be 890mAh g
-1, in positive electrode than higher; And the theoretical capacity of Li is 3860mAh g
-1, in negative material than higher, so the theoretical weight specific energy height of battery of lithium-iron disulphide.
The open circuit voltage of battery of lithium-iron disulphide is greater than 1.7V, and operating voltage is 1.5V, is complementary with general household electrical appliance, can directly replace standard water solution battery.
But directly as the prepared battery of lithium-iron disulphide of positive active material, its open circuit voltage is too high and actual capacity is very low and shelving performance is very poor without the pyrite of any processing.
To the phenomenon of open circuit overtension, a lot of researchs have been carried out in the past.
Kronenberg; The negative electrode that the battery that Marvin L mentions in U.S.Pat.No.4163829 is made up of anode, organic electrolyte and active material constitutes.Lead, carbon and a spot of reducing agent have been formed the active material of negative electrode, the interpolation of reducing agent can effectively reduce some impurity or other possible electrode potentials than higher material, even now, the current potential of these impurity or high electrode current potential material reduces, but some do not wish that the material of seeing will exist, thereby have caused high open circuit voltage.
For eliminate or weaken battery the discharge initial stage high-voltage value, Jumel; Yves; Gabano; Jean-Paul has provided suggestion in U.S.Pat.No.4018970, Pb or the C in the negative electrode removed in suggestion, and other material such as the elemental metals such as Sn, Co of perhaps mixing join positive pole and close in the powder material, can weaken the too high problem of battery open circuit voltage.
The quantity that adds the metallic reducing agent of negative electrode is according to Kronenberg; The U.S.Pat.No.4163829 of Marvin L draws, and it requires the quantity of metallic reducing agent must the material Restore All higher than cathode material current potential be come out.
Summary of the invention
But said method improves not quite for the capacity and the shelving performance of battery, and the present invention is exactly by the pyrite (be ferrous disulfide) of suitable processing system to natural output, handles, to improve discharge performance, the shelving performance of battery.
Selected pyrite, the general requirement to purity is 90～99.44%, sulfur content is 48.10～53.15%, iron-holder is 42.09～46.50%.It is SiO that its impurity content requires
2Content is less than 0.1～1%, and MgO content is not more than 0.1～1%, Al
2O
3Content is less than 0.15～1%, and CaO content is not more than 0.1～1%, sour molten iron content 0.38～1%.
Pyrite will be through broken, screening, and 75% crosses 200 mesh sieves (particle diameter is not more than 0.076mm), and 25% crosses 325 mesh sieves (particle diameter is not more than 0.044mm).
Its heat treatment mode can adopt two kinds of different processing modes, a kind of is the static treatment mode, be about to pyrite and be tiled in the stainless steel pallet, from top to bottom stack successively in the high temperature oven and heat-treat under 350～400 ℃ of temperature, the processing time is 7～10 hours.Heat treated atmosphere is to carry out under the atmosphere of nitrogen or argon gas, requires that relative humidity is lower than 10% in the gas, gas flow be not less than 0.2～0.4 cumulative volume/hour; Another kind is the dynamic process mode, being about to pyrite puts into revolving burner and heat-treats, heat treated temperature range is 300～400 ℃, time is 7～10 hours, heat treated atmosphere is to carry out under the atmosphere of nitrogen or argon gas, require that relative humidity is lower than 10% in the gas, gas flow be not less than 0.2～0.4 cumulative volume/hour.
The type of cooling after the heat treatment is the type of cooling at a slow speed, promptly under the condition that continues logical protective gas cooling below 50～80 ℃.Take out then, in air, be cooled to room temperature.Its preserving type is stored in shady and cool dry place for after will sealing in the bag of packing into through heat treated pyrite.
Description of drawings
Fig. 1 is that the treated pyrite prepared cell of A group employing is shelved the discharge curve after 1 year;
Fig. 2 is the discharge characteristic curve of A Battery pack;
Fig. 3 is the discharge characteristic curve of the untreated pyrite prepared cell of B group.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments:
Selected pyrite in the present embodiment will be through broken, screening, and 75% crosses 200 mesh sieves (particle diameter is not more than 0.076mm), and 25% crosses 325 mesh sieves (particle diameter is not more than 0.044mm).Purity is 99.44%, and sulfur content is 53.15%, and iron-holder is 46.50%.Its impurity content is SiO
2Content is less than 0.1, and MgO content is not more than 0.1%, Al
2O
3Content is less than 0.15%, and CaO content is not more than 0.1%, sour molten iron content 0.38%.
Its heat treatment mode adopts dynamic process mode, is about to pyrite and puts into revolving burner and heat-treat.
Adopt internal-heated rotary furnace that pyrite dynamically and in the static alternation is being heated.Concrete operation method is: pyrite is put into internal-heated rotary furnace, and pyrite accounts for 1/3 of body of heater cumulative volume in the body of heater, and heating and temperature control is at 320 ℃.Rotary furnace can rotate, and the pyrite in the body of heater is also with movement therewith, and the control rotary furnace rotated 20 minutes, rotating speed can be controlled at about 10 commentaries on classics/min, and static 2 hours, under batch (-type) rotation condition, circulation needs 9 hours altogether successively, and pyrite dynamically and in the static alternation is being heated like this.Heat treated atmosphere is to carry out under the atmosphere of nitrogen or argon gas, requires that humidity is lower than 1% in the gas, gas flow be not less than 0.4 cumulative volume/hour.
Pyrite after Overheating Treatment is cooled to below 80 ℃ under the condition that continues logical protective gas.Take out then, in air, be cooled to room temperature.Its preserving type is stored in shady and cool dry place for after will sealing in the bag of packing into through heat treated pyrite.
Pyrite with above-mentioned processing method obtains is prepared into battery of lithium-iron disulphide.Prove that through discharge test the discharge capacity of AA type can reach 2900mAh above (discharge system: 200mA constant-current discharge, cut-ff voltage are 1.0V), the shelving performance excellence is seen accompanying drawing 1.
The battery of preparation, i.e. the battery made of A Battery pack and untreated pyrite, promptly the B Battery pack compares, and discharge performance is relatively seen accompanying drawing 2,3 (discharge system: 200mA constant-current discharge, cut-ff voltage are 1.0V).
Claims (5)
1. the preparation method of a lithium battery anode active material, this positive electrode active materials is a ferrous disulfide, it is characterized in that: described preparation method comprises and selects pyrite, requirement is 90～99.44% for purity, sulfur content is 48.10～53.15%, iron-holder is 42.09～46.50%, and it is SiO that its impurity content requires
2Content is less than 0.1～1%, and MgO content is not more than 0.1～1%, Al
2O
3Content is less than 0.15～1%, and CaO content is not more than 0.1～1%, sour molten iron content 0.38～1%.
2, preparation method as claimed in claim 1 is characterized in that: may further comprise the steps:
A. broken, screening pyrite, it 75% crosses 200 mesh sieves, and 25% crosses 325 mesh sieves;
B. heat treatment, its heat-treatment temperature range is 300～400 ℃, and its heat treated atmosphere is to carry out under the atmosphere of nitrogen or argon gas, requires that relative humidity is lower than 10% in the gas, gas flow be not less than 0.2～0.4 cumulative volume/hour, its heat treatment time is 7～10 hours;
C. cooling.
3, positive electrode active materials as claimed in claim 2 is characterized in that: described heat treatment method is the static treatment mode, and soon pyrite is tiled in the stainless steel pallet and puts into high temperature oven.
4, positive electrode active materials as claimed in claim 2 is characterized in that: described heat treatment method is the dynamic process mode, is about to pyrite and puts into revolving burner and heat-treat.
5, positive electrode active materials as claimed in claim 2 is characterized in that: the type of cooling after described its heat treatment is the type of cooling at a slow speed, promptly under the condition that continues logical protective gas cooling below 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100510161A CN100372155C (en) | 2004-08-09 | 2004-08-09 | Production of positive active material of lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100510161A CN100372155C (en) | 2004-08-09 | 2004-08-09 | Production of positive active material of lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1645651A true CN1645651A (en) | 2005-07-27 |
| CN100372155C CN100372155C (en) | 2008-02-27 |
Family
ID=34868710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100510161A Expired - Fee Related CN100372155C (en) | 2004-08-09 | 2004-08-09 | Production of positive active material of lithium battery |
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|---|---|
| CN (1) | CN100372155C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386907C (en) * | 2006-06-23 | 2008-05-07 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| CN102157736A (en) * | 2011-03-23 | 2011-08-17 | 中银（宁波）电池有限公司 | Ferrous disulfide/carbon composite cathode material of primary lithium battery and preparation method and application thereof |
| US8119286B2 (en) | 2009-11-24 | 2012-02-21 | The Gillette Company | Electrochemical cells with improved separator and electrolyte |
| US8349493B2 (en) | 2009-11-24 | 2013-01-08 | The Gillette Company | Electrochemical cells with improved separator and electrolyte |
| US8460403B2 (en) | 2007-09-14 | 2013-06-11 | The Gillette Company | Method of storing iron disulfide (FeS2) particles |
| CN103972502A (en) * | 2014-04-02 | 2014-08-06 | 芜湖浙鑫新能源有限公司 | Modified cathode material for lithium battery |
| US8920969B2 (en) | 2012-12-05 | 2014-12-30 | The Gillette Company | Alkaline electrochemical cells with separator and electrolyte combination |
| CN105355918A (en) * | 2015-10-21 | 2016-02-24 | 山东精工电子科技有限公司 | Natural ferrous disulfide acid-treatment positive electrode material and preparation method thereof |
| CN106044867A (en) * | 2016-06-24 | 2016-10-26 | 中国科学院地球化学研究所 | Preparation method of pyrite electrode |
| US10008748B2 (en) | 2012-12-05 | 2018-06-26 | Duracell U.S. Operations, Inc. | Alkaline electrochemical cells with separator and electrolyte combination |
| CN109065865A (en) * | 2018-08-02 | 2018-12-21 | 广州鹏辉能源科技股份有限公司 | Iron disulfide microspheres and preparation method thereof, cell positive material and battery |
| US11081721B2 (en) | 2009-11-24 | 2021-08-03 | Duracell U.S. Operations, Inc. | Secondary electrochemical cells with separator and electrolyte combination |
| CN115954479A (en) * | 2023-03-10 | 2023-04-11 | 四川新能源汽车创新中心有限公司 | Positive electrode material, preparation method thereof and solid-state battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5776758A (en) * | 1980-10-31 | 1982-05-13 | Toshiba Corp | Production of positive electrode for organic solvent battery |
| JPS5840773A (en) * | 1981-09-03 | 1983-03-09 | Toshiba Corp | Positive pole of organic electrolyte battery |
| JPS6113570A (en) * | 1984-06-27 | 1986-01-21 | Japan Storage Battery Co Ltd | Thermal battery |
| CN1043042A (en) * | 1988-11-29 | 1990-06-13 | 国营梅岭化工厂 | The thermal cell group of no crest voltage |
-
2004
- 2004-08-09 CN CNB2004100510161A patent/CN100372155C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386907C (en) * | 2006-06-23 | 2008-05-07 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| US8460403B2 (en) | 2007-09-14 | 2013-06-11 | The Gillette Company | Method of storing iron disulfide (FeS2) particles |
| US8119286B2 (en) | 2009-11-24 | 2012-02-21 | The Gillette Company | Electrochemical cells with improved separator and electrolyte |
| US8349493B2 (en) | 2009-11-24 | 2013-01-08 | The Gillette Company | Electrochemical cells with improved separator and electrolyte |
| US11817545B2 (en) | 2009-11-24 | 2023-11-14 | Duracell U.S. Operations, Inc. | Secondary electrochemical cells with separator and electrolyte combination |
| US11081721B2 (en) | 2009-11-24 | 2021-08-03 | Duracell U.S. Operations, Inc. | Secondary electrochemical cells with separator and electrolyte combination |
| CN102157736A (en) * | 2011-03-23 | 2011-08-17 | 中银（宁波）电池有限公司 | Ferrous disulfide/carbon composite cathode material of primary lithium battery and preparation method and application thereof |
| US10008748B2 (en) | 2012-12-05 | 2018-06-26 | Duracell U.S. Operations, Inc. | Alkaline electrochemical cells with separator and electrolyte combination |
| US8920969B2 (en) | 2012-12-05 | 2014-12-30 | The Gillette Company | Alkaline electrochemical cells with separator and electrolyte combination |
| CN103972502B (en) * | 2014-04-02 | 2016-05-11 | 芜湖浙鑫新能源有限公司 | A kind of lithium battery modified anode material |
| CN103972502A (en) * | 2014-04-02 | 2014-08-06 | 芜湖浙鑫新能源有限公司 | Modified cathode material for lithium battery |
| CN105355918A (en) * | 2015-10-21 | 2016-02-24 | 山东精工电子科技有限公司 | Natural ferrous disulfide acid-treatment positive electrode material and preparation method thereof |
| CN106044867A (en) * | 2016-06-24 | 2016-10-26 | 中国科学院地球化学研究所 | Preparation method of pyrite electrode |
| CN109065865A (en) * | 2018-08-02 | 2018-12-21 | 广州鹏辉能源科技股份有限公司 | Iron disulfide microspheres and preparation method thereof, cell positive material and battery |
| CN109065865B (en) * | 2018-08-02 | 2020-09-25 | 广州鹏辉能源科技股份有限公司 | Ferrous disulfide microspheres and preparation method thereof, battery positive electrode material and battery |
| CN115954479A (en) * | 2023-03-10 | 2023-04-11 | 四川新能源汽车创新中心有限公司 | Positive electrode material, preparation method thereof and solid-state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100372155C (en) | 2008-02-27 |
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Owner name: HUIZHOU DESAI LITHIUM ELECTRICAL TECHNOLOGY CO., Free format text: FORMER OWNER: DESAI ENERGY SCIENCE AND TECHNOLOGY CO., LTD., HUIZHOU Effective date: 20081114 |
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Effective date of registration: 20081114 Address after: B District No. 48 in Guangdong province Huizhou City Zhongkai road Pingnan Industrial Zone Patentee after: Huizhou Desay Battery Technology Co., Ltd. Address before: No. 2, Gu Tong industrial area, Huizhou, Guangdong Patentee before: Desai Energy Science and Technology Co., Ltd., Huizhou |
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Owner name: HUIZHOU HUIDERUI LITHIUM BATTERY TECHNOLOGY CO., L Free format text: FORMER OWNER: HUIZHOU DESAY LITHIUM BATTERY SCI-TECH CO., LTD. Effective date: 20120627 |
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Effective date of registration: 20120627 Address after: 516006 Guangdong province Huizhou City Zhongkai high tech Zone and three West Road No. 67 Patentee after: Huizhou Huiderui Lithium Electrode Technology Co., Ltd. Address before: No. 48 B District 516006 in Guangdong province Huizhou City Zhongkai road Pingnan Industrial Zone Patentee before: Huizhou Desay Battery Technology Co., Ltd. |
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Owner name: HUIZHOU DESAY LITHIUM BATTERY SCI-TECH CO., LTD. Free format text: FORMER OWNER: HUIZHOU HUIDERUI LITHIUM ELECTRODE TECHNOLOGY CO., LTD. Effective date: 20150209 |
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Effective date of registration: 20150209 Address after: 516006 Guangdong province Huizhou City Zhongkai Pingnan new material technology park 48B District No. Patentee after: Huizhou Desay Battery Technology Co., Ltd. Address before: 516006 Guangdong province Huizhou City Zhongkai high tech Zone and three West Road No. 67 Patentee before: Huizhou Huiderui Lithium Electrode Technology Co., Ltd. |
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