CN102354744A - Method for improving stability in batch production of lithium iron phosphate - Google Patents
Method for improving stability in batch production of lithium iron phosphate Download PDFInfo
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- CN102354744A CN102354744A CN2011102993119A CN201110299311A CN102354744A CN 102354744 A CN102354744 A CN 102354744A CN 2011102993119 A CN2011102993119 A CN 2011102993119A CN 201110299311 A CN201110299311 A CN 201110299311A CN 102354744 A CN102354744 A CN 102354744A
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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
The invention relates to a method for improving stability in batch production of lithium iron phosphate. A precursor of the lithium iron phosphate is fed into a kiln body of a rotary kiln which is used as a furnace body through a vacuum feeder and a multidirectional screw conveyer, and the discharge end of the furnace body is manually adjusted to be 5-20cm lower than the feed end of the furnace body, so that the furnace body is tilted; and the precursor is automatically moved forward through an embedded shoveling plate of the kiln body, six different temperature zones are arranged in the kiln body, the precursor stays for 2-5h at each temperature zone to be sintered, and finally the precursor is fed into a cooling zone to be cooled and is discharged automatically. According to the invention, through the regulation of the obliquity of the furnace body, and the arrangement of the rate of feed, automatic rotation of the embedded shoveling plate of the kiln body and the temperature of the temperature zones, the average thickness, the moving speed and the staying time in the high-temperature zones of the precursor are effectively controlled, the stability in batch production of the lithium iron phosphate is greatly improved, frequent homogenate and proportioning adjustment and frequent test are not needed, the production cost of products is reduced, and the method is very suitable for large-scale industrialized production.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries technical field, especially relate to a kind of method that LiFePO4 is produced stability in batches that improves.
Background technology
A.K.Padhi in 1997 and J.B.Goodenough at first propose the positive electrode that LiFePO4 can be used as lithium ion battery, and have carried out synthetic and chemical property assessment, and the most original LiFePO4 patent is grasped in the J.B.Goodenough hand.The Chung of MIT in 2002 and Yet-Ming Chiang have delivered high valence ion doped iron phosphate lithium on the Nature publication, improved the 4-6 one magnitude through this conductivity of electrolyte materials of mixing, and should technology also apply for patent simultaneously.And the another one technological approaches that improves conductivity is the carbon coating, and this technology is proposed by Frenchman doctor M.Armand.More than three LiFePO4 technology constituted the core technology that present LiFePO4 is produced.In addition, also there are the patent protection of relevant ferric phosphate lithium cell in Japanese NTT and Sony Corporation.The patent relevant with LiFePO4 mainly concentrates on process route innovation, electric conductivity raising, electrode preparation and battery assembling aspect at present, and purpose is the preparation high-performance, has the LiFePO 4 material of excellent machinability and prepare ferric phosphate lithium cell.And the performance of LiFePO 4 material height can be applied to different class series batteries, but batch stability of large-scale production will have influence on the quality of each class battery.
Agglomerating plant crucial in the present known LiFePO4 batch production process adopts pushed bat kiln or box type furnace mostly; Pushed bat kiln is for to place ferric lithium phosphate precursor in the saggar; Saggar places in the long kiln of 30-40m, is provided with different warm areas in the kiln, and saggar advances under the hydraulic push rod effect; Every warm area stops official hour, discharging after getting into temperature descending section.When originally meaning as far as possible near step heat treatment mode, realizes this kind sintering method the continous way input and output material; But because presoma is static heat treatment in the process in saggar; Residing difference position heating status is different; The manually-operated intervention of input and output material in addition makes the batch LiFePO4 properties of product of producing with stove differ greatly, and finally has influence on the quality of battery.
Another kind of LiFePO4 agglomerating plant in batches is a rotary kiln; Ferric lithium phosphate precursor gets into the kiln body through vacuum feeder and multidirectional conveying worm; The kiln body rotates voluntarily and utilizes built-in flight to realize that presoma advances automatically, after different warm areas stop official hour, gets into temperature descending section and self-emptying.The application of rotary kiln has remedied the following defective of pushed bat kiln sintering: 1. with artificial involvement level reduce to minimum, 2. the atmosphere protection oxygen content can reach the ppm magnitude, 3. the kiln body length shortened more than 50%, 4. power and inert gas consumption reduces significantly, 5. without firepot wear and tear expense expenditure etc.But; Owing to almost be in level during body of heater work, the LiFePO 4 material specific capacity extreme difference value range that this method is prepared does not still have thoroughly to solve the batch LiFePO 4 material consistency of performance problem of preparing with stove all greater than the standard value of 3mAh/g; When therefore adopting this material preparation battery; Often need adjustment homogenate proportioning and often test, increased labour cost, improved product cost.
Summary of the invention
The present invention provides a kind of method that LiFePO4 is produced stability in batches that improves for solving the technical problem that exists in the known technology; The LiFePO 4 material specific capacity extreme difference value range that this method is prepared is all less than the standard value of 3mAh/g; Solved the problem of the batch LiFePO 4 material consistency of performance of preparing with stove; In the large-scale production battery, need not additional operations, directly utilize the material of this method preparation; Can prepare a batch stable lithium iron phosphate storage battery, reduce product cost.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is:
A kind of LiFePO4 that improves is produced stable method in batches; Through vacuum feeder and multidirectional conveying worm, the feed rate of the ferric lithium phosphate precursor for preparing with 5-30kg/h got in the kiln body of rotary kiln as body of heater, through the built-in flight of kiln body said presoma is advanced automatically; Different warm areas is arranged in the kiln body; The every warm area of said presoma stops 2-5h, and said presoma is carried out sintering, gets into cooling area cooling back self-emptying at last; Be characterized in: (1) to being lower than body of heater feed end 5-20cm, makes tilting furnace with the discharge end manual adjustments of said body of heater; (2) rotating speed of the built-in flight of kiln body being arranged to 0.1-1rpm rotates voluntarily; (3) warm area in the kiln body is set to 6, and the first five warm area rises to 300-400 ℃, 400-500 ℃, 500-600 ℃ gradually from low-temperature space 200-300 ℃, and to high-temperature region 600-800 ℃, last warm area is a cooling area.
The present invention can also adopt following technical measures:
Said cooling area is a water-cooled cooling.
Advantage and good effect that the present invention has are:
The present invention is through the gradient of regulation and control body of heater; Feed rate, the built-in flight of kiln body rotate voluntarily and the setting of warm area temperature under; Control average thickness, travel rate and the high-temperature region time of staying of presoma effectively, increased substantially batch stability of LiFePO4, need not often to adjust homogenate proportioning and often test; Reduce the production cost, be fit to very much large-scale industrial production.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, the following examples of giving an example now specify as follows:
Embodiment 1
Through vacuum feeder and multidirectional conveying worm, the ferric lithium phosphate precursor for preparing is got in the kiln body of rotary kiln as body of heater with the feed rate of 10kg/h, with the discharge end manual adjustments of body of heater to being lower than body of heater feed end 10cm; Make tilting furnace; The rotating speed of the kiln body being arranged to 0.1rpm rotates voluntarily, through the built-in flight of kiln body said presoma is advanced automatically, and said presoma is carried out sintering; 6 different warm areas are arranged in the kiln body; The first five warm area rises to high-temperature region 600-800 ℃ gradually from low-temperature space 200-300 ℃, and last warm area is a cooling area, and the every warm area of said presoma stops 2-5h; Self-emptying after cooling area passes through water-cooled cooling is promptly prepared and is produced the high LiFePO 4 material of stability in batches at last.Product is stablized after the discharging every at a distance from 20kg sampling preparation half-cell, and the extreme difference of investigating the gram specific capacity is 2.1mAh/g, satisfies the instructions for use of the high ferric phosphate lithium cell of preparation stability.
Embodiment 2
Through vacuum feeder and multidirectional conveying worm, the ferric lithium phosphate precursor for preparing is got in the kiln body of rotary kiln as body of heater with the feed rate of 10kg/h, with the discharge end manual adjustments of body of heater to being lower than body of heater feed end 10cm; Make tilting furnace; The rotating speed of the kiln body being arranged to 0.5rpm rotates voluntarily, through the built-in flight of kiln body said presoma is advanced automatically, and said presoma is carried out sintering; 6 different warm areas are arranged in the kiln body; The first five warm area rises to high-temperature region 600-800 ℃ gradually from low-temperature space 200-300 ℃, and last warm area is a cooling area, and the every warm area of said presoma stops 2-5h; Self-emptying after cooling area passes through water-cooled cooling is promptly prepared and is produced the high LiFePO 4 material of stability in batches at last.Product is stablized after the discharging every at a distance from 20kg sampling preparation half-cell, and the extreme difference of investigating the gram specific capacity is 1.2mAh/g, satisfies the instructions for use of the high ferric phosphate lithium cell of preparation stability.
Embodiment 3
Through vacuum feeder and multidirectional conveying worm, the ferric lithium phosphate precursor for preparing is got in the kiln body of rotary kiln as body of heater with the feed rate of 30kg/h, with the discharge end manual adjustments of body of heater to being lower than body of heater feed end 10cm; Make tilting furnace; The rotating speed of the kiln body being arranged to 0.1rpm rotates voluntarily, through the built-in flight of kiln body said presoma is advanced automatically, and said presoma is carried out sintering; 6 different warm areas are arranged in the kiln body; The first five warm area rises to high-temperature region 600-800 ℃ gradually from low-temperature space 200-300 ℃, and last warm area is a cooling area, and the every warm area of said presoma stops 2-5h; Self-emptying after cooling area passes through water-cooled cooling is promptly prepared and is produced the high LiFePO 4 material of stability in batches at last.Product is stablized after the discharging every at a distance from 20kg sampling preparation half-cell, and the extreme difference of investigating the gram specific capacity is 1.2mAh/g, satisfies the instructions for use of the high ferric phosphate lithium cell of preparation stability.
Comparative example 1
Rotary furnace technology: with the mode charging of presoma with vacuum material loading and helical feed, charging rate 30kg/h, body of heater rotating speed 0.1rpm, the high-temperature region stops 10h, and cooling obtains the LiFePO4 product.The every sampling at a distance from 20kg prepared half-cell after product was stablized discharging, and the extreme difference of investigating the gram specific capacity is 4.3mAh/g, when adopting this material preparation battery, needed frequent adjust homogenate proportioning and often test.
Comparative example 2
Pusher furnace technology: presoma identical among the embodiment is placed saggar (2kg/ saggar), and push rod starts frequency and guarantees that material stopped 15 hours in the high-temperature region, and cooling obtains the LiFePO4 product.The every sampling at a distance from 20kg prepared half-cell after product was stablized discharging, and the extreme difference of investigating the gram specific capacity is 3.3mAh/g, when adopting this material preparation battery, needed frequent adjust homogenate proportioning and often test.
Comparative example 3
Batch (-type) tank type testing furnaceman skill: in the stove diverse location with highly place 5 saggars, the following 6 ℃/min of inert atmosphere is warmed up to 700 ℃, high temperature sintering 15h, lowering the temperature obtains the LiFePO4 product.The every sampling at a distance from 20kg prepared half-cell after product was stablized discharging, and the extreme difference of investigating the gram specific capacity is 3.3mAh/g, when adopting this material preparation battery, needed frequent adjust homogenate proportioning and often test.
The performance that table 1 has been listed the LiFePO 4 material that different embodiment and comparative example sintering go out relatively.
The performance of the LiFePO 4 material that different embodiment of table 1 and comparative example sintering go out relatively
Can find out from the result of table 1; The LiFePO 4 material mean range of the present invention's preparation has solved the problem of the batch LiFePO 4 material consistency of performance of preparing with stove all less than the critical field value of 3mAh/g, in the extensive battery production; Need not additional operations; Directly utilize the material of this method preparation, can prepare a batch stable lithium iron phosphate storage battery, reduced product cost.
Claims (2)
1. one kind is improved the method that LiFePO4 is produced stability in batches; Through vacuum feeder and multidirectional conveying worm, the feed rate of the ferric lithium phosphate precursor for preparing with 5-30kg/h got in the kiln body of rotary kiln as body of heater, through the built-in flight of kiln body said presoma is advanced automatically; Different warm areas is arranged in the kiln body; The every warm area of said presoma stops 2-5h, and said presoma is carried out sintering, gets into cooling area cooling back self-emptying at last; It is characterized in that: (1) to being lower than body of heater feed end 5-20cm, makes tilting furnace with the discharge end manual adjustments of said body of heater; (2) rotating speed of the built-in flight of kiln body being arranged to 0.1-1rpm rotates voluntarily; (3) warm area in the kiln body is set to 6, and the first five warm area rises to 300-400 ℃, 400-500 ℃, 500-600 ℃ gradually from low-temperature space 200-300 ℃, and to high-temperature region 600-800 ℃, last warm area is a cooling area.
2. the uniform ferric lithium phosphate precursor preparation method of composition according to claim 1 is characterized in that: said cooling area is a water-cooled cooling.
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| CN2011102993119A CN102354744A (en) | 2011-10-08 | 2011-10-08 | Method for improving stability in batch production of lithium iron phosphate |
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Citations (11)
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| CN1177728A (en) * | 1996-09-24 | 1998-04-01 | 夏重力 | Ferrite prefiring material rotary kiln |
| JPH11139829A (en) * | 1997-11-04 | 1999-05-25 | Nikki Chemcal Co Ltd | Production of positive electrode material for lithium ion secondary cell |
| US20030022035A1 (en) * | 1997-11-07 | 2003-01-30 | Galloway Terry R. | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
| CN1473784A (en) * | 2003-08-08 | 2004-02-11 | 余世华 | Large tilt rotary kiln cement calcining process and rotary kiln |
| US20040115492A1 (en) * | 2002-06-27 | 2004-06-17 | Galloway Terry R | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
| CN201053814Y (en) * | 2007-06-22 | 2008-04-30 | 咸阳陶瓷研究设计院 | Heat-tolerant metal furnace tube continuous external heating type protective atmosphere converter |
| CN201057457Y (en) * | 2007-07-13 | 2008-05-07 | 中国恩菲工程技术有限公司 | Shoveling plate drum type counterflow burning rotary kiln |
| CN101186289A (en) * | 2006-11-17 | 2008-05-28 | 喻维杰 | Method for producing lithium iron phosphate material by vacuum rotary kiln |
| CN101279728A (en) * | 2008-05-28 | 2008-10-08 | 天津大学 | Method for preparing lithium iron phosphate cathode material by three-stage high-temperature solid phase calcination |
| CN201411432Y (en) * | 2009-03-10 | 2010-02-24 | 北京有色金属研究总院 | Continuous dynamic reduction equipment for fluorescent powder |
| CN101671012A (en) * | 2009-10-13 | 2010-03-17 | 恒正科技（苏州）有限公司 | Method of producing electrochemical active material |
-
2011
- 2011-10-08 CN CN2011102993119A patent/CN102354744A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177728A (en) * | 1996-09-24 | 1998-04-01 | 夏重力 | Ferrite prefiring material rotary kiln |
| JPH11139829A (en) * | 1997-11-04 | 1999-05-25 | Nikki Chemcal Co Ltd | Production of positive electrode material for lithium ion secondary cell |
| US20030022035A1 (en) * | 1997-11-07 | 2003-01-30 | Galloway Terry R. | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
| US20040115492A1 (en) * | 2002-06-27 | 2004-06-17 | Galloway Terry R | Process and system for converting carbonaceous feedstocks into energy without greenhouse gas emissions |
| CN1473784A (en) * | 2003-08-08 | 2004-02-11 | 余世华 | Large tilt rotary kiln cement calcining process and rotary kiln |
| CN101186289A (en) * | 2006-11-17 | 2008-05-28 | 喻维杰 | Method for producing lithium iron phosphate material by vacuum rotary kiln |
| CN201053814Y (en) * | 2007-06-22 | 2008-04-30 | 咸阳陶瓷研究设计院 | Heat-tolerant metal furnace tube continuous external heating type protective atmosphere converter |
| CN201057457Y (en) * | 2007-07-13 | 2008-05-07 | 中国恩菲工程技术有限公司 | Shoveling plate drum type counterflow burning rotary kiln |
| CN101279728A (en) * | 2008-05-28 | 2008-10-08 | 天津大学 | Method for preparing lithium iron phosphate cathode material by three-stage high-temperature solid phase calcination |
| CN201411432Y (en) * | 2009-03-10 | 2010-02-24 | 北京有色金属研究总院 | Continuous dynamic reduction equipment for fluorescent powder |
| CN101671012A (en) * | 2009-10-13 | 2010-03-17 | 恒正科技（苏州）有限公司 | Method of producing electrochemical active material |
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Application publication date: 20120215 |