CN101582526A - Reparative regeneration method of inactive ferrous phosphate lithium battery anode material - Google Patents
Reparative regeneration method of inactive ferrous phosphate lithium battery anode material Download PDFInfo
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- CN101582526A CN101582526A CNA2009100537843A CN200910053784A CN101582526A CN 101582526 A CN101582526 A CN 101582526A CN A2009100537843 A CNA2009100537843 A CN A2009100537843A CN 200910053784 A CN200910053784 A CN 200910053784A CN 101582526 A CN101582526 A CN 101582526A
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- ball milling
- lithium
- ferrous phosphate
- lithium battery
- phosphate lithium
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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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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention belongs to the technical field of lithium battery anode material, and in particular relates to a reparative regeneration method of inactive ferrous phosphate lithium battery anode material; the method comprises the following steps: remixing ferrous phosphate lithium waste material by ball milling method; then carrying out high-temperature calcinations and removing remaining water content in the material so as to restore electroconductibility and specific capacity of the material. In the invention, the solid phase method is used to regenerate ferrous phosphate lithium battery waste material with very low activity for manufacturing lithium ion battery with characteristics such as high specific capacity, fine safety performance, long cycle period and the like. The obtained lithium ion battery can be charged and discharged at a speed of 0.5C and has a capacity more than 140mAh/g; charging or discharging for more 50 times shows no sign of attenuation of the capacity.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries technical field, be specifically related to the Regeneration and Repair method of the synthetic middle waste material of a kind of lithium iron phosphate cathode material.
Background technology
Since the influencing factor of aspects such as cyclicity, price, fail safe, specific energy, LiFePO 4 (LiFePO
4) becoming the up-and-coming youngster of anode material for lithium-ion batteries.Have that Stability Analysis of Structures, raw material sources are abundant, environmental friendliness and cost are cheap and have the theoretical capacity of 170mAh/g, many advantages such as steady discharge platform of 3.5V, particularly its security performance and cycle life be other material can't compare, make LiFePO 4 become the most attracting positive electrode now.These performances are the most important technical indicator of electrokinetic cell especially: it 1 hour (1C) charges and discharge cycle life and reaches 2000 times.Single battery overcharged voltage 30V does not burn, do not explode, puncture is not exploded yet, lithium iron phosphate positive material is done the easier use of connecting of high capacity lithium ion battery, so be considered to candidate material important in the lithium ion battery of future generation, the positive electrode of big capacity, middle high-power lithium ion electrokinetic cell first-selection during it is just becoming.Ferric phosphate lithium cell is as the power type power supply, and what will become series batteries such as plumbic acid, ni-mh and manganese, cobalt has the prospect substitute most.
Generally acknowledge pure LiFePO at present
4Conductive capability poor especially, every centimetre is had only 10
-8Siemens, the conductivity that therefore improves it is crucial, is the emphasis of preparation research.Report all thinks there is not the LiFePO of conductive doped material at present
4Positive electrode is poor electric conductivity not only, and specific capacity is also low.To LiFePO
4Study on the modification mainly improves its conductivity, mainly contains and directly mixes the conduction charcoal, metallic cover and metal ion mixing etc.So far, all increase LiFePO 4 conductivity by adding other species.
In synthetic preparation, often because of misoperation, as gas leakage, draining not to the utmost, or air do not eliminate etc., although mixed conductive materials, still can cause ferrousphosphate lithium material may not have conductivity, perhaps ties lump, specific capacity can be very low like this, loses use value.To such LiFePO 4 waste material, also there is not effective reparative regeneration method so far.
Summary of the invention
The present invention proposes to come in conjunction with water-eliminating method with ball milling the new ideas of reparative regeneration ferrous phosphate waste material first, the ferrousphosphate lithium material that does not have use value that will in synthetic, obtain exactly, need not add any other species, as long as iron phosphorus lithium three mol ratio is 1: 1: 1, can be through normal temperature ball milling once more, manage to remove water residual in the LiFePO 4 in the high-temperature calcination stage then, it is normal that the result is that conductivity and specific capacity can be recovered.After being assembled into lithium/lithium ion battery, discharge and recharge with 0.5C speed, specific capacity does not have relaxation phenomenon to occur up to 140 above mAh/g substantially more than 50 times.Here, calcination stage is removed the method for water residual in the LiFePO 4, has a lot, draws water suctions such as phosphorus pentoxide, the gas draining that can dewater etc. as vacuum pump.
One of LiFePO 4 synthesis technique of the present invention is,
(1) raw material is made into
Be the LiFePO 4 waste material, analyze the mol ratio of source of iron, lithium source and phosphoric acid root in the LiFePO 4 waste material earlier,, need to replenish the material that correspondence lacks, make three's mol ratio reach 1: 1: 1 substantially if proportioning is not 1: 1: 1.In the practical application, three's ratio can not become.
(2) ball milling
With waste material in common centrifugal ball mill ball milling 10-20 hour, make particle diameter＜5 micron;
(3) drying
Material behind the ball milling is dried 8～12 hours time under 100～110 degree Celsius;
(4) calcining
The dried material of ball milling is placed high temperature process furnances, in inert atmosphere, in common purity nitrogen (＞99.5%) atmosphere, calcined 1～3 hour for 300-400 ℃, 550-650 ℃ of calcining 5～7 hours, manage residual minor amount of water in the ferrous lithium of dephosphorylate this moment again.Gas draining that dewatering can draw water with vacuum pump, the phosphorus pentoxide suction maybe can be dewatered or the like.
Description of drawings
Fig. 1 is the ferrous lithium material sample of the ferric phosphate SEM figure of the inventive method regeneration back (1a) and regeneration preceding (1b).
Fig. 2 discharges and recharges schematic diagram for the room temperature first of lithium ion battery one example that the positive electrode that obtains with the inventive method prepares.
Fig. 3 discharges and recharges schematic diagram for the room temperature of the preprosthetic waste material of material regeneration among Fig. 2.
Embodiment
The processing of embodiment 1 ferrousphosphate lithium material
(1) raw material is prepared
Take by weighing conductivity and be lower than 10
-6Siemens, capacity is lower than the ferrousphosphate lithium material 100g of 50mAh/g
(2) ball milling
With above-mentioned material in common centrifugal ball mill with per minute 500 rotating speed ball millings 10 hours, particle diameter＜5 micron;
(3) drying
The above-mentioned sample that ball milling is good dries by the fire 10 hours down to dry at 108 ℃ in a conventional oven;
(4) calcining
Above-mentioned dried material is placed high temperature process furnances, in inert atmosphere,, calcined 2 hours for 350 ℃, 600 ℃ of calcinings 6 hours, remove residual moisture again as in common purity nitrogen (＞99.5%) atmosphere.
Calcining back material maintains 100g, grey black, and conductivity is higher than every centimetre 0.01 Siemens.
(1) slurry is prepared
Take by weighing ferrousphosphate lithium material: carbon black: PVDF=0.8 through above-mentioned processing: 0.1: 0.1, in agate mortar, add LiFePO 4 and grind, add carbon black, mix after 10 minutes, place baking oven 78 degree Celsius to toast 1 hour down, add PVDF, after adding a certain amount of NMP, stirred 1 hour;
(2) coating
Lithium ion battery special use aluminium foil with 20 micron thickness places on the coating machine smooth flat, flattens then, slurry is poured in the coating machine be coated with, and guarantees slurry smooth distribution on aluminium foil, and thickness is 200 microns;
(3) oven dry
The aluminium foil that has applied lithium iron phosphate cathode material is placed common drying box baking about 10 hours, bone dry;
(4) roll
LiFePO 4 aluminium foil 100 microns gaps on twin rollers of oven dry are pressed solid, gross thickness is 100 microns;
(5) battery assembling
The LiFePO 4 aluminium foil intercepting diameter that rolled is the disk of 12mm, and weighing is placed in the glove box, gets button cell shell negative terminal in the case, put metal lithium sheet, putting barrier film, drip several electrolyte, put the LiFePO4 anode and cover, sealing machine is sealed back taking-up glove box and is got final product.
Attached: one of ferrousphosphate lithium material method of preparation non-activity takes by weighing industrial battery level iron oxalate 114g (99.9%), ammonium dihydrogen phosphate 73g (99.5%), industrial battery level lithium carbonate 24g (99.9%) respectively; These materials are mixed in bulge, add acetone then, with the material volume ratio be 2: 1, be stirred well to no bubble, continue to stir then 2 hours; With dried above-mentioned material in common centrifugal ball mill with per minute 500 rotating speed ball millings 10 hours; The sample that ball milling is good dried by the fire 10 hours down at 108 ℃ in a conventional oven, placed high temperature process furnances again, calcined three hours for 350 ℃ in common purity nitrogen (＞99.5%) atmosphere, calcined six hours for 600 ℃.The ferrousphosphate lithium material conductivity that obtains like this is very low, and capacity is very little.
Claims (1)
1. the reparative regeneration method of the ferrous phosphate lithium battery anode material of a non-activity is characterized in that concrete steps are as follows:
(1) material is made into
Analyze the mol ratio of source of iron, lithium source and phosphoric acid root in the low LiFePO 4 waste material of electro-chemical activity, if proportioning is not 1: 1: 1, the material that additional correspondence lacks makes three's mol ratio reach 1: 1: 1 substantially;
(2) ball milling
With waste material in centrifugal ball mill ball milling 10-20 hour, make particle diameter＜5 micron;
(3) drying
Material behind the ball milling is dried 8～12 hours time under 100～110 degree Celsius;
(4) calcining
The dried material of ball milling is placed high temperature process furnances, calcined 1～3 hour for 300-400 ℃ in inert atmosphere, again 550-650 ℃ of calcining 5～7 hours, residual minor amount of water in the ferrous lithium of dephosphorylate, dewatering for draw water with vacuum pump, phosphorus pentoxide suction maybe can dewater the gas draining.
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| CNA2009100537843A CN101582526A (en) | 2009-06-25 | 2009-06-25 | Reparative regeneration method of inactive ferrous phosphate lithium battery anode material |
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| CNA2009100537843A CN101582526A (en) | 2009-06-25 | 2009-06-25 | Reparative regeneration method of inactive ferrous phosphate lithium battery anode material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011079409A1 (en) * | 2009-12-28 | 2011-07-07 | 深圳市雄韬电源科技股份有限公司 | Method of recycling and reusing spent lithium iron phosphate power battery |
| CN102569798A (en) * | 2012-02-01 | 2012-07-11 | 哈尔滨师范大学 | Regeneration method of lithium iron silicate lithium ion battery anode material |
| CN104466293A (en) * | 2014-12-30 | 2015-03-25 | 兰州理工大学 | Regeneration method of lithium ion battery anode material lithium cobalt oxide waste |
| CN106058353A (en) * | 2016-08-11 | 2016-10-26 | 荆门市格林美新材料有限公司 | Waste battery positive electrode material restoration regeneration method |
| CN108760586A (en) * | 2018-05-23 | 2018-11-06 | 广州能源检测研究院 | A kind of method that overlay material particle size is distributed in detection lithium battery pole slice |
| CN112838205A (en) * | 2021-01-11 | 2021-05-25 | 厦门厦钨新能源材料股份有限公司 | Method for recovering fine powder of lithium ion battery cathode material |
-
2009
- 2009-06-25 CN CNA2009100537843A patent/CN101582526A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011079409A1 (en) * | 2009-12-28 | 2011-07-07 | 深圳市雄韬电源科技股份有限公司 | Method of recycling and reusing spent lithium iron phosphate power battery |
| CN102569798A (en) * | 2012-02-01 | 2012-07-11 | 哈尔滨师范大学 | Regeneration method of lithium iron silicate lithium ion battery anode material |
| CN104466293A (en) * | 2014-12-30 | 2015-03-25 | 兰州理工大学 | Regeneration method of lithium ion battery anode material lithium cobalt oxide waste |
| CN106058353A (en) * | 2016-08-11 | 2016-10-26 | 荆门市格林美新材料有限公司 | Waste battery positive electrode material restoration regeneration method |
| CN106058353B (en) * | 2016-08-11 | 2018-05-25 | 荆门市格林美新材料有限公司 | The reparative regeneration method of old and useless battery positive electrode |
| CN108760586A (en) * | 2018-05-23 | 2018-11-06 | 广州能源检测研究院 | A kind of method that overlay material particle size is distributed in detection lithium battery pole slice |
| CN112838205A (en) * | 2021-01-11 | 2021-05-25 | 厦门厦钨新能源材料股份有限公司 | Method for recovering fine powder of lithium ion battery cathode material |
| CN112838205B (en) * | 2021-01-11 | 2021-11-30 | 厦门厦钨新能源材料股份有限公司 | Method for recovering fine powder of lithium ion battery cathode material |
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Open date: 20091118 |