CN102738539A - Method and apparatus for recovering lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries - Google Patents
Method and apparatus for recovering lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries Download PDFInfo
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Abstract
A method for recovering a lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries comprises the steps: fixing the recovered positive plates of waste lithium iron phosphate batteries in a dedicated supersonic wave vibration pool after the positive plates are baked and dried, applying supersonic wave vibration until the lithium iron phosphate and a conductive agent on the positive plates are removed from current collector aluminium foil, taking out the aluminium foil and carrying out recovery processing for the aluminium foil, adding a certain amount of compounds or/and organic solutions as a lithium source, a phosphorus source or/and an iron source into the dedicated supersonic wave vibration pool, and conducting mixing homogenization and ball-milling for the obtained solution by using a ball mill, spray drying, high-temperature sintering, and crushing processing to obtain the positive electrode material of lithium iron phosphate which is needed and can be directly used for manufacturing lithium iron phosphate batteries. The beneficial effects of the method are that: more than 95% of the lithium iron phosphate material in the positive plates of the lithium iron phosphate batteries can be recovered, the purity of the recovered lithium iron phosphate material is above 99%, and the purpose of reproducing and manufacturing lithium iron phosphate batteries with the recovered material is achieved. The method has the advantages that the technical processes of recovery and processing are simple, the apparatus is general, industrialization is easy to realize, etc.
Description
Technical fieldThe present invention relates to secondary cell, relate in particular to the regeneration of the useful parts of scrap battery, particularly relate to the method that reclaims ferrousphosphate lithium material from waste and old ferrous phosphate lithium battery anode sheet.
Background technologyThe positive electrode that the prior art lithium rechargeable battery uses mainly is stratiform cobalt acid lithium (LiCoO
2), lithium manganate having spinel structure (LiMn
2O
4), and olivine-type LiFePO 4 (LiFePO
4), also have part to adopt nickle cobalt lithium manganate (LiNiCoMnO in addition
2) and other binary/ternary materials.In these positive electrodes; The ferrousphosphate lithium material of olivine-type structure lithium ion leach repeatedly with telescopiny in show good stability; Often behind the battery end of life, the ferrousphosphate lithium material structure in the positive plate is not damaged, and is also very complete; Deal with slightly after the recovery and can continue to use, therefore have good recovery value and prospect.In addition, the pole piece leftover pieces in the ferrous phosphate lithium battery production process also seem very important with the recycling of scrapping pole piece.For these old and useless batterys and pole piece, at present method commonly used is directly to abandon or work as waste disposal at a low price in the production practices, and lithium iron phosphate cathode material accounts for about 30% of battery cost usually.
Ferrous phosphate lithium battery is the chargeable chemical cell of a kind of good comprehensive properties; Have excellent security can, advantages such as environmentally friendly, specific energy and specific power be big, have extended cycle life, memory-less effect; Can be used for fields such as portable dam, mine lamp, energy-storage system, electric bicycle and electric automobile; Be one of major impetus source that most possibly becomes in the present lithium rechargeable battery by following electric automobile, the use amount of battery will become multiple to increase when the time comes.So when the ferrous phosphate lithium battery use amount grows with each passing day, reclaim economic worth height in waste and old ferrous phosphate lithium battery or the pole piece, the ferrousphosphate lithium material that can be recycled is realized energy-saving and emission-reduction, sustainable development, and is significant.One can prevent the pollution of the environment, the material resources of two recyclable preciousnesses.And over past ten years ferrous phosphate lithium battery to commercially produce technical development rapid, the recovery technology research and development of corresponding old and useless battery or pole piece then seems and relatively lags behind.Common positive electrode recycling way is mainly physical separation method and chemolysis method of purification at present; Recovery process is mainly heat-treats after battery or pole piece are disassembled, and with decomposing organic matter matter, carries out crushing and screening again; Then carry out separation and purifying of valuable metal etc.; Exist process complicated, drop into greatlyyer, the not high many shortcomings of purity are difficult to industrialization and commercialization.
In one Chinese patent application 200710129898.2; Following method is proposed in " recovery method of lithium iron phosphate positive material in a kind of lithium ion battery waste material " by name: the lithium ion battery waste material was toasted 2～5 hours down at 450～600 ℃ under inert gas atmosphere; Wherein this method also comprises; With mixing in the ethanolic solution of lithium ion battery waste material adding soluble ferric iron salt, drying; Then under inert gas atmosphere 300～500 ℃ of following roastings 2～5 hours, reclaim and to obtain lithium iron phosphate positive material.
And the method that one Chinese patent application 200710076890.4 " a kind of comprehensive recovering process of positive pole waste tablet from ferric phosphate lithium cell " by name proposes comprises following steps: the anode material waste sheet Mechanical Crushing of collecting is fragmentated; Fragment is placed by the sintering furnace under vacuum atmosphere, inert gas and/or reducing gas and/or the nitrogen protection, under 150～750 ℃ temperature, heat-treat; Fragment after the heat treatment is adopted mechanical separation or ultrasonic oscillation method, the aluminium foil matrix is separated from fragment, obtain the mixture of lithium iron phosphate positive material, conductive agent and adhesive residue thing; With the mixture of lithium iron phosphate positive material, conductive agent and adhesive residue thing, under 80～150 ℃ of temperature, toast 8～24h; With classification behind the mixture abrasive dust after the baking, control powder maximum particle diameter is not more than 20 μ m, and meso-position radius D50 is controlled at 3～10 μ m, promptly gets the iron phosphate lithium positive pole reclaimed materials.
In the one Chinese patent application 20071077245.4 " renovation process of waste lithium ion phosphate positive pole material " by name; A kind of renovation process of waste lithium ion phosphate positive pole material is provided, may further comprise the steps: 1) with waste lithium ion phosphate positive pole material at 80 ℃～200 ℃ dry 0.5h～12.Oh; 2) dried waste lithium ion phosphate positive pole material is pulverized, made granularmetric composition meet the preparation requirement of iron phosphate lithium positive pole slurry.Iron phosphate lithium positive pole reworked material and the regular burden(ing) of handling gained through this method have close chemical property.
A kind of technology advantages of simple, cost recovery is low, added value the is high comprehensive method that reclaims of waste lithium iron phosphate battery have then been proposed in one Chinese patent application 201010148325.6, by name " the comprehensive method that reclaims of a kind of waste lithium iron phosphate battery "; This method is utilized the binding agent on the organic solvent dissolution electricity core fragment; Through screening; Realize that LiFePO 4 material separates with clean aluminium, Copper Foil, wherein aluminium, Copper Foil reclaim through melting; Utilize NaOH solution to remove residual aluminum foil bits in the LiFePO 4 material, remove graphite and remaining binding agent through heat treatment.After LiFePO4 usefulness acid dissolving; Utilize vulcanized sodium to remove copper ion wherein; And utilize NaOH solution or ammoniacal liquor to make iron in the solution, lithium, phosphonium ion generate sediment; And in sediment, add source of iron, lithium source or P source compound mol ratio with adjustment iron, lithium, phosphorus, and adding carbon source at last, calcination obtains new lithium iron phosphate positive material in ball milling, inert atmosphere.After the above-mentioned steps processing, recovery rate of valuable metals is greater than 95% in the battery, and the comprehensive recovery of lithium iron phosphate positive material is greater than 90%.
Present recovery technology is the product through obtaining after the chemical treatment of a series of time-consuming power consumptions often, and purity is also not high, and is in the laboratory research stage mostly, the report of successful industrial applications aspect also seldom, technical elements is still waiting optimization and perfect.The partial monopoly technology has proposed some easy recovery methods, but the part that comes with some shortcomings more or less, as does not propose the device and the equipment of industrialization, and the recycled materials performance is not high, and the material consistency is difficult to guarantee or the like.
Summary of the inventionThe technical problem that the present invention will solve is to avoid the weak point of above-mentioned prior art and provides a kind of and reclaim the method for ferrousphosphate lithium material from waste and old ferrous phosphate lithium battery anode sheet, solve complex process, purity that prior art exists not high and can not industrialization etc. problem.
It is through adopting following technical scheme to realize that the present invention solve the technical problem: put forward a kind of method from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material, implement following steps:
The waste and old ferrous phosphate lithium battery anode sheet that A. will reclaim cures drying.
B. dried each positive plate is fixed in the special-purpose ultrasonic oscillation pond that fills strong polar organic solvent; Apply ultrasonic oscillation; After LiFePO 4 and the conductive agent on the positive plate of waiting breaks away from from the collector aluminium foil, take out said aluminium foil, it is recycled.
C. the ratio of its contained Li:Fe:P of sample analysis from the solution in above-mentioned special-purpose ultrasonic oscillation pond; According to this ratio in said special-purpose ultrasonic oscillation pond, add lithium source, phosphorus source or/and the compound of source of iron or/and organic solution; Make this special use ultrasonic oscillation pond the contained Li:Fe:P ratio of solution near or reach 1:1:1, its solid content is between 10%～50%.
D. under nitrogen or inert gas shielding condition, the solution that uses ball mill that implementation step C is obtained mixes homogenizing and ball-milling treatment, and re-using closed drying equipment, to carry out spray drying treatment be powder.
E. after said powder being carried out high temperature sintering, promptly obtain directly to be used to make the required positive electrode material LiFePO 4 of lithium of ferrous phosphate lithium battery through pulverization process again.
In steps A " the waste and old ferrous phosphate lithium battery anode sheet of recovery " comprise the positive plate that reclaims from waste and old ferrous phosphate lithium battery or/and the LiFePO 4 pond producing leftover pieces and scrap material; Drying mode described in the steps A comprises drying tunnel or vacuum drying, and baking temperature is 80～130 ℃, and stoving time is more than 6 hours.
The described strong polar organic solvent of step C is the organic solution that can dissolve binding agent polyvinylidene fluoride PVDF, comprises N-methyl pyrrolidone NMP, dimethylacetylamide DMAc, dimethyl formamide DMF; The purity of organic solvent is that moisture is less than 0.1% more than 98%.
The duration of ultrasonic oscillation described in the step B is more than 10 minutes.
" ratio of its contained Li:Fe:P of sample analysis from the solution in above-mentioned special-purpose ultrasonic oscillation pond " is to adopt chemical titration or X-ray fluorescence spectra method to measure among the step C; The compound in the said lithium of this step source comprises one or more in lithium carbonate, lithium hydroxide and the lithium acetate; The compound in said phosphorus source comprises in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid and the ferric phosphate one or more; The compound of said source of iron comprises one or more in ferrous oxalate, iron oxide, ferric phosphate and the ferrous sulfate.
The time of said mixing homogenizing of step D and ball-milling treatment is 3h～24h, and described its inlet temperature of closed drying equipment is 120～200 ℃, 70～120 ℃ of outlet temperatures.
Step D also comprises the organic solvent that reclaims with condensing mode, makes said organic solvent purity more than 98% through distillation and rectifying again, and moisture is less than 0.1%, supplies to recycle.
The temperature of high temperature sintering described in the step e is 550～750 ℃, time 4～6h.The discharging-material size meso-position radius D50 of said pulverization process is between 2～4 μ m.
Be to adopt following method to reclaim positive plate among the present invention from waste and old ferrous phosphate lithium battery:
A1. said waste and old ferrous phosphate lithium battery is discharged fully, make that the reversible lithium ion-transfer in the old and useless battery negative pole is extremely anodal, form the higher LiFePO 4 of lithium content at positive pole.
A2. adopt physical method to remove the external packing and the shell of battery, take out the internal electrical core of old and useless battery.
A3. said electric core is immersed in the deionized water, absorbs with sodium carbonate liquor and contain the soak of hydrogen fluoride HF and the HF gas of effusion, reaction finishes back taking-up battery dries.
A4. the physical method of disassembling with machinery intactly splits out positive plate from the electric core of oven dry.
" battery discharges fully " is meant described in the steps A 1, and using discharge-rate is 0.05V～0.15V as 0.05C～3C, final voltage.
Physical method described in the steps A 2 comprises that machinery is disassembled or centrifugal throwing away.
Oven dry described in the steps A 3 is to toast more than the 6h down at 80～130 ℃.
The present invention designs, produces a kind of special-purpose ultrasonic oscillation pond for solveing the technical problem also; Be used for reclaiming the technical process of ferrousphosphate lithium material from waste and old ferrous phosphate lithium battery anode sheet, comprise flute profile the concussion pond, set up a pair of groove row within it and be arranged on its outside ultrasonic generator; Each transducer of said ultrasonic unit lays respectively on each inwall in concussion pond; Said groove row's one side is provided with the holddown groove that is used for fixing pole piece, and groove row be inserted in the described concussion pond parallel to each other, and two grooves row's spacing L will confirm according to the positive plate length of inserting therebetween.
Said each transducer is to be fixed on the front, rear, left and right of said concussion pond inwall and the middle part of bottom surface.
The height H in said concussion pond is than the big slightly 1～10mm of width of said positive plate.The upper edge pool wall in said concussion pond is provided with screw hole, through screw groove is arranged two ends and is fixed in the concussion pond.Said concussion pond is to adopt stainless steel material to process.
The width W of said groove row's pole piece holddown groove is 1.1～3 times of said positive plate thickness; Two grooves row spacing L is than the long slightly 1～10mm of positive plate length that inserts therebetween; Said groove row is provided with the clip of fixing said positive plate.
Compare with prior art; Beneficial effect of the present invention is: adopt method and apparatus of the present invention, and the ferrousphosphate lithium material more than 95% on the recyclable ferrous phosphate lithium battery anode sheet, its purity is more than 99%; Ferrousphosphate lithium material complete in crystal formation, the pattern that is recovered to is good, electrochemistry capacitance is high; 0.1C gram volume can reach more than 155 mAh/g under the multiplying power, gram volume can reach more than 140 mAh/g under the 1C multiplying power, and good product consistency; Can satisfy the positive electrode requirement that electrokinetic cell uses, reach the purpose of producing again and making that can be used for ferrous phosphate lithium battery once more fully.And recovery, treatment process process are simple, and Device-General is easy to advantages such as industrialization.
Description of drawingsFig. 1 is the present invention reclaims the method for ferrousphosphate lithium material from waste and old ferrous phosphate lithium battery anode sheet a preferred embodiment flow chart;
Fig. 2 is that positive plate 1 described in the said preferred embodiment is placed on the axonometric projection sketch map that applies ultrasonic oscillation in the said special-purpose ultrasonic oscillation equipment concussion pond 3;
Fig. 3 is the structural representation in the pond 3 of special-purpose ultrasonic oscillation equipment concussion described in the said preferred embodiment;
Fig. 4 is the A portion enlarged drawing of Fig. 3;
Fig. 5 is the XRD figure that reclaims the ferrousphosphate lithium material that obtains in the preferred embodiment of the present invention;
Fig. 6 is the SEM figure that reclaims the ferrousphosphate lithium material that obtains in the preferred embodiment of the present invention;
Fig. 7 is the electrochemistry capacitance figure that reclaims the ferrousphosphate lithium material that obtains in the preferred embodiment of the present invention.
EmbodimentBelow, further set forth the present invention in conjunction with the preferred embodiment shown in the accompanying drawing.
Referring to Fig. 1 and Fig. 2, the present invention is to implement following steps from the preferred embodiment of the method for waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The waste and old ferrous phosphate lithium battery anode sheet 1 that A. will reclaim adopts modes such as drying tunnel or vacuum drying that positive plate is carried out drying, and 80～130 ℃ of baking temperatures are more than the stoving time 6h.
B. dried positive plate 1 is transferred in the special-purpose ultrasonic oscillation pond 3 of the organic solution 2 that fills strong polarity, the organic solution 2 of said strong polarity can use N-methyl pyrrolidone NMP, dimethylacetylamide DMAc, dimethyl formamide DMF etc. can dissolve the organic solution of binding agent polyvinylidene fluoride PVDF.Carry out then more than the ultrasonic oscillation 10min, treat that lithium iron phosphate cathode material on this positive plate 1, conductive agent and collector aluminium foil break away from after, take out aluminium foil and reclaim separately.
C. take a sample the solution in special-purpose ultrasonic oscillation pond 3, adopt methods analysts such as chemical titration or X-ray fluorescence spectra to measure the Li/Fe/P ratio; Then according to this ratio calculate should add lithium sources, phosphorus source or dosage from Fe source compound to said special-purpose ultrasonic oscillation pond 3 or/and organic solution 2; Make solution in this special use ultrasonic oscillation pond 3 the Li:Fe:P ratio near or reach 1:1:1, solid content is between 10%～50%.Wherein, Li source compound can be in lithium carbonate, lithium hydroxide, the lithium acetate etc. one or more; P source compound can be in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, the ferric phosphate etc. one or more, and Fe source compound can be in ferrous oxalate, iron oxide, ferric phosphate, the ferrous sulfate etc. one or more.
D. under inert gas shielding conditions such as nitrogen or argon gas; Use ball mill to mix homogenizing and ball-milling treatment 3h～24h; Re-use closed drying equipment and carry out the spray drying treatment powdered, 120～200 ℃ of the inlet temperatures of this closed drying equipment, 70～120 ℃ of outlet temperatures; Simultaneously, the organic solvent 2 of condensing and recycling can be recycled after reclaiming through distillation and rectifying, and the organic solvent purity of recovery will be more than 98%, and moisture is less than 0.1%.
E. the powder that spray drying among the step C is drawn is through high temperature sintering; Its temperature should be 550～750 ℃, sintering time 4h～16h; Carrying out air-flow or mechanical disintegration at last handles; Control discharging-material size meso-position radius D50 promptly draws complete in crystal formation, particle is tiny and pattern is good, electrochemistry capacitance is high LiFePO 4, referring to Fig. 5 and Fig. 7 between 2～4 μ m.
The electrochemistry gram volume of the 0.1C of the LiFePO 4 that is recovered among this preferential embodiment reaches more than 155 mAh/g; The gram volume of 1C reaches more than 140 mAh/g; Above-mentioned recovery production procedure is carried out through material production equipment; Thereby ensured and reclaimed the good consistency of preparing of LiFePO 4 product, the industrialization that can directly be used for ferrous phosphate lithium battery is manufactured, thereby realizes the direct recycling of LiFePO 4.
The positive plate that adopts " the waste and old ferrous phosphate lithium battery anode sheet 1 of recovery " in the steps A in the present embodiment to comprise to reclaim from waste and old ferrous phosphate lithium battery is or/and leftover pieces the ferrous phosphate lithium battery production and scrap material, and the positive plate that wherein reclaims from waste and old ferrous phosphate lithium battery is the processing of carrying out following steps earlier:
The waste and old ferrous phosphate lithium battery that A1. will reclaim discharges fully; Discharge-rate is at 0.05C～3C, final voltage 0.05V～0.15V; Make reversible lithium ion-transfer to positive plate 1 in the old and useless battery negative pole, this moment, positive plate 1 formed the higher LiFePO 4 of lithium content.
A2. adopt machinery to disassemble or centrifugally external packing and the shell that physical method is removed said old and useless battery such as throw away, take out the internal electrical core of this old and useless battery.
A3. soak electric core with deionized water; Absorb with sodium carbonate liquor then and contain the soak of hydrogen fluoride HF and the HF gas of effusion (electrolyte LiPF6 and deionized water reaction generate); Reaction finishes the back and takes out battery, adopts 80～130 ℃ of above oven dry of baking 6h battery down.
A4. physical method such as disassembling with machinery intactly removes positive plate from the electric core that deionized water was handled.
With reference to figure 2 and 3; In the preferred enforcement of the present invention; Also design the concussion pond 3 in a kind of special-purpose ultrasonic oscillation pond, special-purpose ultrasonic oscillation pond comprise stainless steel concussion pond 3, be positioned at its a pair of groove row 33 and be arranged on the outside ultrasonic generators composition in this concussion pond 3; Said ultrasonic unit has 5 transducers 32, the front, rear, left and right and the bottom center place of concussion pond 3 inwalls that distribute; Said groove row's 33 one side is provided with pole piece holddown groove 311, and the width W of this pole piece holddown groove 331 is 1.1～3 times of said positive plate 1 thickness; Groove row 33 is inserted in the concussion pond 3 parallel to each other; The height H in this concussion pond 3 is than the wide big slightly 1～10mm of institute pole piece 1.
When said positive plate 1 needs ultrasonic oscillation, adjust the spacing L between this groove row 33, make spacing L insert the big slightly 1～10mm of length of ratio positive plate therebetween; With screw groove being arranged 33 two ends is fixed on the upper edge pool wall that shakes pond 3; Positive plate 1 inserts said groove successively and arranges in the 33 pole piece holddown grooves 331, and is with the clip 312 that is arranged on this groove row 33 that said positive plate 1 is fixing respectively, can implement ultrasonic oscillation after fixing.
Claims (26)
1. the method from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material comprises the steps:
The waste and old ferrous phosphate lithium battery anode sheet (1) that A. will reclaim cures drying;
B. dried each positive plate (1) is fixed in the special-purpose ultrasonic oscillation pond (3) that fills strong polar organic solvent (2); Apply ultrasonic oscillation; After LiFePO 4 and the conductive agent on the positive plate (1) of waiting breaks away from from the collector aluminium foil, take out said aluminium foil, it is recycled;
C. the ratio of its contained Li:Fe:P of sample analysis from the solution in above-mentioned special-purpose ultrasonic oscillation pond (3); According to this ratio in said special-purpose ultrasonic oscillation pond (3), add lithium source, phosphorus source or/and the compound of source of iron or/and organic solution (2); Make should special use ultrasonic oscillation pond (3) the contained Li:Fe:P ratio of solution near or reach 1:1:1, its solid content is between 10%～50%;
D. under nitrogen or inert gas shielding condition, the solution that uses ball mill that implementation step C is obtained mixes homogenizing and ball-milling treatment, and re-using closed drying equipment, to carry out spray drying treatment be powder;
E. after said powder being carried out high temperature sintering, promptly obtain directly to be used to make the required positive electrode material LiFePO 4 of lithium of ferrous phosphate lithium battery through pulverization process again.
2. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
In the steps A " the waste and old ferrous phosphate lithium battery anode sheet (1) of recovery " comprise the positive plate that reclaims from waste and old ferrous phosphate lithium battery or/and the LiFePO 4 pond producing leftover pieces and scrap material.
3. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
Cure dry mode described in the steps A and comprise drying tunnel or vacuum drying, 80～130 ℃ of baking temperatures, stoving time is more than 6 hours.
4. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
Said strong polar organic solvent (2) is the organic solution that can dissolve binding agent polyvinylidene fluoride PVDF, comprises N-methyl pyrrolidone NMP, dimethylacetylamide DMAc, dimethyl formamide DMF; The purity of said organic solvent (2) is that moisture is less than 0.1% more than 98%.
5. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The duration of ultrasonic oscillation described in the step B is more than 10 minutes.
6. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
" ratio of its contained Li:Fe:P of sample analysis from the solution in above-mentioned special-purpose ultrasonic oscillation pond (3) " is to adopt chemical titration or X-ray fluorescence spectra method to measure among the step C.
7. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The compound in said lithium source comprises one or more in lithium carbonate, lithium hydroxide and the lithium acetate.
8. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The compound in the source of phosphorus described in the step C comprises in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid and the ferric phosphate one or more.
9. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The compound of source of iron comprises one or more in ferrous oxalate, iron oxide, ferric phosphate and the ferrous sulfate among the step C.
10. according to the said method of claim 1, it is characterized in that from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The time of mixing homogenizing and ball-milling treatment described in the step D is 3h～24h.
11., it is characterized in that according to the said method of claim 1 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
Its inlet temperature of closed drying equipment described in the step D is 120～200 ℃, 70～120 ℃ of outlet temperatures.
12., it is characterized in that according to the said method of claim 1 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
Step D also comprises the organic solvent (2) that adopts condensing mode to reclaim, and makes said organic solvent (2) purity more than 98% through distillation and rectifying again, and moisture is less than 0.1%, supplies to recycle.
13., it is characterized in that according to the said method of claim 1 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The temperature of high temperature sintering described in the step e is 550～750 ℃, time 4～6h.
14., it is characterized in that according to the said method of claim 1 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The discharging-material size meso-position radius D50 of pulverization process described in the step e is between 2～4 μ m.
15., it is characterized in that according to claim 1 or 2 said methods from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
The waste and old ferrous phosphate lithium battery anode sheet (1) of said recovery is the positive plate that reclaims from waste and old ferrous phosphate lithium battery, comprises the steps:
A1. said waste and old ferrous phosphate lithium battery is discharged fully, make that the reversible lithium ion-transfer in the old and useless battery negative pole is extremely anodal, the anodal higher LiFePO 4 of lithium content that forms;
A2. adopt physical method to remove the external packing and the shell of battery, take out the internal electrical core of old and useless battery;
A3. said electric core is immersed in the deionized water, absorbs with sodium carbonate liquor and contain the soak of hydrogen fluoride HF and the HF gas of effusion, reaction finishes back taking-up battery dries;
A4. the physical method of disassembling with machinery intactly splits out positive plate (1) from the electric core of oven dry.
16., it is characterized in that according to the said method of claim 15 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
" battery discharges fully " is meant described in the steps A 1, and using discharge-rate is 0.05V～0.15V as 0.05C～3C, final voltage.
17., it is characterized in that according to the said method of claim 15 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
Physical method described in the steps A 2 comprises that machinery is disassembled or centrifugal throwing away.
18., it is characterized in that according to the said method of claim 15 from waste and old ferrous phosphate lithium battery anode sheet recovery ferrousphosphate lithium material:
Oven dry described in the steps A 3 is to toast more than the 6h down at 80～130 ℃.
19. a special-purpose ultrasonic oscillation pond is used for it is characterized in that from the technical process of waste and old ferrous phosphate lithium battery anode sheet (1) recovery ferrousphosphate lithium material:
Comprise flute profile concussion pond (31), set up a pair of groove row (33) within it and be arranged on its outside ultrasonic unit; Each transducer (32) of said ultrasonic generator lays respectively on each inwall in concussion pond (31); Said groove row's (33) one side is provided with the holddown groove (331) that is used for fixing pole piece, and groove row (33) is inserted in the described concussion pond (31) parallel to each other, and two grooves rows' (33) spacing L will confirm according to positive plate (1) length of inserting therebetween.
20. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
Said each transducer (32) is to be fixed on the front, rear, left and right of said concussion pond (31) inwall and the middle part of bottom surface.
21. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
The height H in said concussion pond (31) is than the big slightly 1～10mm of width of said positive plate (1).
22. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
The upper edge pool wall in said concussion pond (31) is provided with screw hole, through screw groove row (33) two ends is fixed in the concussion pond (3).
23. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
The width W of said pole piece holddown groove (331) is 1.1～3 times of said positive plate (1) thickness.
24. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
Said two grooves row (33) spacing L is than the long slightly 1～10mm of positive plate (1) length that inserts therebetween.
25. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
Process with stainless steel material in said concussion pond (31).
26. special-purpose ultrasonic oscillation according to claim 19 pond is characterized in that:
Said groove row (33) is provided with the clip (312) of fixing said positive plate.
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