CN101916889A - Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery - Google Patents
Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery Download PDFInfo
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- CN101916889A CN101916889A CN2010102538595A CN201010253859A CN101916889A CN 101916889 A CN101916889 A CN 101916889A CN 2010102538595 A CN2010102538595 A CN 2010102538595A CN 201010253859 A CN201010253859 A CN 201010253859A CN 101916889 A CN101916889 A CN 101916889A
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 11
- 229930006000 Sucrose Natural products 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000001172 regenerating effect Effects 0.000 claims abstract description 9
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 8
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910010710 LiFePO Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 108010064245 urinary gonadotropin fragment Proteins 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000007873 sieving Methods 0.000 abstract description 4
- 230000001680 brushing effect Effects 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 239000011363 dried mixture Substances 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 229960004793 sucrose Drugs 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 12
- 238000011084 recovery Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power batteries, comprising the following steps: 1) cutting and brushing a water-system waste lithium-ion power battery, processing by deionized water, sieving and drying to recover the mixture of an electrode material and a conductive agent; 2) adding inorganic acid to the dried mixture of the electrode material and the conductive agent to process, filtering to obtain acid solution containing Li+, Fe2+ and PO43-; 3) adding lithium salt or iron salt to the acid solution containing Li+, Fe2+ and PO43-, adding ascorbic acid and stirring, controlling the pH value to equal to 3-7, and filtering to obtain precipitation; and 4) adding the crude product LiFePO4 obtained in step 3) to a water solution of cane sugar for ball milling, drying and calcining to obtain a regenerative LiFePO4 material. The method has low cost, simple operation and no secondary pollution.
Description
Technical field
The present invention relates to a kind of method of preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery, belong to waste and old lithium ion battery recovery, recycle utilization field.
Background technology
LiFePO4 is characteristics such as the lithium-ion-power cell of positive electrode is low owing to its cost, cycle performance is good, security performance is good, has been applied in the electric automobile industry widely.The consumption of huge lithium-ion-power cell has brought the surprising refuse battery of number, and these applying waste lithium ionic electrokinetic cells are much directly as garbage disposal, and this is not only a kind of waste of resource, and environment is polluted.Therefore, the recovery of lithium-ion-power cell has great importance.
Traditional lithium iron phosphate dynamic battery adopts PVDF as adhesive usually, and the adhesive of this oiliness not only makes cost increase, and also there is pollution in environment.Recent years, aqueous binder is little with environmental pollution, and advantages such as cost is low, excellent performance have progressively replaced oil binder.But, the recovery method in the industry is primarily aimed at the lithium-ion-power cell of oiliness system, discloses the method for the LiFePO4 recovery that is fit to the oiliness system as Chinese patent CN101383441A and CN101359756A etc.Yet the lithium-ion-power cell of different systems reclaims the characteristic that himself is arranged, and above-mentioned disclosed patent is not the recovery that is applicable to the electrokinetic cell of all systems.And these patents only are to carry out recycling at the waste material and the useless sheet that produce in producing, do not mention the recovery method of lithium iron phosphate dynamic battery integral body.So, how from the water-system waste lithium-ion-power cell, to reclaim the preparation LiFePO4 and just seem most important.
Summary of the invention
The object of the present invention is to provide a kind of water-system waste lithium-ion-power cell to prepare the method for LiFePO4.
For achieving the above object, the method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery provided by the invention, key step is:
1) fractionation of water-system waste lithium-ion-power cell: with the water-system waste lithium ion battery through overdischarge, shell, take out electric core, electric core is carried out shearing-crushing after, handle by deionized water, sieve and reclaim electrode material and conductive agent mixture.
2) separation of positive and negative electrode material: the inorganic acid that the electrode material and the conductive agent mixture of step 1 adds 0.1-5M is after drying handled under 20 ℃-100 ℃, and the solid-to-liquid ratio of mixed liquor is 5-50g/L; Filtration obtains Li
+, Fe
2+, PO
4 3-Acid solution.
3) LiFePO
4Thick product is synthetic: contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 50ml-950ml concentration be lithium salts or the molysite of 1M, mol ratio n
Li+: n
Fe2+: n
PO43-=0.8-1.2: 1: 1, add ascorbic acid 10g-200g, stirred 1 hour-3 hours down at 50 ℃-100 ℃, in whipping process, with ammoniacal liquor control pH value=3-7; Filter, obtain precipitation;
4) LiFePO
4Synthetic: the LiFePO that step 3 is obtained
4Thick product is pressed quality than sucrose: LiFePO
4The ratio of thick product=5%-45% joins carries out ball milling, the LiFePO that drying and calcining obtains regenerating in the aqueous sucrose solution
4Material.
Described method, wherein the deionized water in the step 1 is handled, and is 1g electricity core fragment is added the 30ml-100ml deionized water, and 20 ℃-100 ℃ are stirred down or sonic oscillation 1 hour-3 hours.
Described method, wherein the inorganic acid in the step 2 comprises the mixed solution of hydrochloric acid, sulfuric acid or hydrochloric acid and sulfuric acid.
Described method, wherein the lithium salts in the step 3 is selected from lithium sulfate, lithium hydroxide, lithium chloride or lithium nitrate.
Described method, wherein the molysite in the step 3 is selected from ferrous sulfate, frerrous chloride or ferric nitrate.
Described method, wherein the drying and calcining in the step 4 is at N
2Protection was calcined 1 hour-24 hours in 600 ℃-900 ℃ down.
Method from preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery provided by the invention, effectively reclaim and utilized again electrokinetic cell, not only reclaimed copper, aluminium, and prepared the new LiFePO4 electrode material of lithium again, solved the water system lithium iron phosphate battery and reclaimed problem.Reduced the production cost of battery enterprise, realized the recycling of waste and old water system lithium iron phosphate electrokinetic cell electrode material to a certain extent, effect is obvious, the technology simple possible.
Embodiment
At lacking this present situation of a kind of effective method to reclaim the preparation LiFePO4 from the water-system waste lithium iron phosphate dynamic battery at present, low cost provided by the invention, simple to operate, the waste lithium iron phosphate electrokinetic cell that does not produce secondary pollution reclaims the method for preparing LiFePO4, and concrete steps comprise:
(1) with waste and old lithium ion battery through overdischarge, shell, take out electric core, electric core is carried out shearing-crushing after, handle by deionized water, 1g electricity core fragment adds the 30ml-100ml deionized water, under 20 ℃-100 ℃, stirs or sonic oscillation 1 hour-3 hours.Sieve then and reclaim electrode material and conductive agent mixture.
(2) inorganic acid that adds 0.1-5M after electrode material and the conductive agent mixture drying is handled under 20 ℃-100 ℃, and the solid-to-liquid ratio of mixed liquor is 5-50g/L.Filtration obtains Li
+, Fe
2+, PO
4 3-Acid solution.
(3) contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 50ml-950ml concentration be lithium salts or the molysite of 1M, make n
Li+: n
Fe2+: n
PO43-=0.8-1.2: 1: 1, add ascorbic acid 10g-200g, under 50 ℃-100 ℃, stirred 1 hour-3 hours, in whipping process, with concentration ammoniacal liquor control pH value=3-7.Filter, obtain precipitation.
(4) LiFePO
4Synthetic: the precipitation that previous step is obtained joins in the aqueous sucrose solution, the sucrose quality: precipitation mass ratio=5%-45%.Above-mentioned mixture is carried out ball milling, drying, the powder that obtains is at N
2Under the protection, temperature is 600 ℃-900 ℃ calcinings 1 hour-24 hours, the LiFePO that obtains regenerating
4Electrode material.Calcining, the LiFePO that obtains regenerating
4Material.
Below in conjunction with embodiment the present invention is elaborated
Embodiment 1
Waste and old water system lithium iron phosphate electrokinetic cell is shelled to battery through after the discharge process, take out electric core, carry out Mechanical Crushing, with waste and old lithium ion battery through overdischarge, shell, take out electric core, electric core is carried out shearing-crushing after, take by weighing 200g electricity core fragment, add the 6L deionized water, under 20 ℃, stir and sieved afterwards in 1 hour, sieve top is divided into collector, and the lower part of screen is divided into electrode material and conductive agent mixture.To add the hydrochloric acid of 0.1M after electrode material and the conductive agent mixture drying, the solid-to-liquid ratio of mixed liquor is 50g/L.Stir down at 20 ℃, make it abundant reaction, filter and obtain Li
+, Fe
2+, PO
4 3-Acid solution.Contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 50ml concentration be the LiOH of 1mol/L, make n
Li+: n
Fe2+: n
PO43-=0.8: 1: 1, add ascorbic acid 10g, under 50 ℃, stirred 1 hour, the pH value with ammoniacal liquor is regulated mixed solution makes pH=5.0.Filter, obtain precipitation.Take by weighing 9g sucrose, be dissolved in the deionized water, take by weighing the precipitation 20g that previous step obtains, above-mentioned mixture is carried out ball milling, drying, the powder that obtains is at N
2Under the protection, temperature is 600 ℃ of calcinings 24 hours, the LiFePO that obtains regenerating
4Electrode material.The LiFePO 4 material that reclaims with this method has good electrochemical, is 130mAH/g in the 0.2C discharge capacity, and 50 capability retentions of charge and discharge cycles are 94%.The LiFePO 4 material of regeneration has good crystalline structure.
Embodiment 2
Waste and old water system lithium iron phosphate electrokinetic cell is shelled to battery through after the discharge process, take out electric core, carry out Mechanical Crushing, with waste and old lithium ion battery through overdischarge, shell, take out electric core, after electric core carried out shearing-crushing, take by weighing 100g electricity core fragment, add the 10L deionized water, under 100 ℃, stir the back of sieving afterwards in 3 hours and reclaim electrode material and conductive agent mixture.To add the sulfuric acid of 5M after electrode material and the conductive agent mixture drying, the solid-to-liquid ratio of mixed liquor is 5g/L.Stir down at 100 ℃, make it abundant reaction, filter and obtain Li
+, Fe
2+, PO
4 3-Acid solution.Contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 950ml concentration be the LiOH of 1mol/L, make n
Li+: n
Fe2+: n
PO43-=1.2: 1: 1, add ascorbic acid 200g, under 100 ℃, stirred 1 hour, the pH value with ammoniacal liquor is regulated mixed solution makes pH=6.0.Filter, obtain precipitation.Take by weighing 1.25g sucrose, be dissolved in the deionized water, take by weighing the precipitation 25g that previous step obtains, above-mentioned mixture is carried out ball milling, drying, the powder that obtains is at N
2Under the protection, temperature is 900 ℃ of calcinings 12 hours, the LiFePO that obtains regenerating
4Electrode material.The LiFePO 4 material that reclaims with this method has good electrochemical, is 135mAH/g in the 0.2C discharge capacity, and 50 capability retentions of charge and discharge cycles are 95.6%.
Embodiment 3
Waste and old water system lithium iron phosphate electrokinetic cell is shelled to battery through after the discharge process, take out electric core, carry out Mechanical Crushing, with waste and old lithium ion battery through overdischarge, shell, take out electric core, after electric core carried out shearing-crushing, take by weighing 1Kg electricity core fragment, add the 50L deionized water, under 50 ℃, stir the back of sieving afterwards in 2 hours and reclaim electrode material and conductive agent mixture.To add the sulfuric acid of 3M after electrode material and the conductive agent mixture drying, the solid-to-liquid ratio of mixed liquor is 20g/L.Stir down at 60 ℃, make it abundant reaction, filter and obtain Li
+, Fe
2+, PO
4 3-Acid solution.Contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 500ml concentration be the ferrous sulfate of 2mol/L, make n
Li+: n
Fe2+: n
PO43-=1.2: 1: 1, add ascorbic acid 150g, under 80 ℃, stirred 2 hours, the pH value with ammoniacal liquor is regulated mixed solution makes pH=6.0.Filter, obtain precipitation.Take by weighing 10g sucrose, be dissolved in the deionized water, take by weighing the precipitation 200g that previous step obtains, above-mentioned mixture is carried out ball milling, drying, the powder that obtains is at N
2Under the protection, temperature is 750 ℃ of calcinings 3 hours, the LiFePO that obtains regenerating
4Electrode material.The LiFePO 4 material that reclaims with this method has good electrochemical, is 125mAH/g in the 0.2C discharge capacity, and 50 capability retentions of charge and discharge cycles are 96.7%.
Embodiment 4
Waste and old water system lithium iron phosphate electrokinetic cell is shelled to battery through after the discharge process, take out electric core, carry out Mechanical Crushing, with waste and old lithium ion battery through overdischarge, shell, take out electric core, after electric core carried out shearing-crushing, take by weighing 1.5Kg electricity core fragment, add the 60L deionized water, under 70 ℃, sonic oscillation reclaims electrode material and conductive agent mixture after sieving after 1.5 hours.To add the sulfuric acid of 4M after electrode material and the conductive agent mixture drying, the solid-to-liquid ratio of mixed liquor is 35g/L.Stir down at 55 ℃, make it abundant reaction, filter and obtain Li
+, Fe
2+, PO
4 3-Acid solution.Contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 350ml concentration be the ferrous sulfate of 1mol/L, make n
Li+: n
Fe2+: n
PO43-=1: 1: 1, add ascorbic acid 100g, under 80 ℃, stirred 2 hours, the pH value with ammoniacal liquor is regulated mixed solution makes pH=5.0.Filter, obtain precipitation.Take by weighing 20g sucrose, be dissolved in the deionized water, take by weighing the precipitation 250g that previous step obtains, above-mentioned mixture is carried out ball milling, drying, the powder that obtains is at N
2Under the protection, temperature is 750 ℃ of calcinings 10 hours, the LiFePO that obtains regenerating
4Electrode material.The LiFePO 4 material that reclaims with this method has good electrochemical, is 145mAH/g in the 0.2C discharge capacity, and 50 capability retentions of charge and discharge cycles are 94.7%.
Claims (6)
1. the method for a preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery, key step is:
1) fractionation of water-system waste lithium-ion-power cell: with the water-system waste lithium ion battery through overdischarge, shell, take out electric core, electric core is carried out adding deionized water behind the shearing-crushing handles, sieve and reclaim electrode material and conductive agent mixture;
2) separation of positive and negative electrode material: the inorganic acid that the electrode material and the conductive agent mixture of step 1 adds 0.1-5M is after drying handled under 20 ℃-100 ℃, and the solid-to-liquid ratio of mixed liquor is 5-50g/L; Filtration obtains Li
+, Fe
2+, PO
4 3-Acid solution;
3) LiFePO
4Thick product is synthetic: contain Li to 1L
+, Fe
2+, PO
4 3-Acid solution in to add 50ml-950ml concentration be lithium salts or the molysite of 1M, mol ratio n
Li+: n
Fe2+: n
PO43-=0.8-1.2: 1: 1, add ascorbic acid 10g-200g, stirred 1 hour-3 hours down at 50 ℃-100 ℃, in whipping process, with ammoniacal liquor control pH value=3-7; Filter, obtain precipitation;
4) LiFePO
4Synthetic: the LiFePO that step 3 is obtained
4Thick product is pressed quality than sucrose: LiFePO
4The ratio of thick product=5%-45% joins carries out ball milling, the LiFePO that drying and calcining obtains regenerating in the aqueous sucrose solution
4Material.
2. method according to claim 1, wherein, deionized water in the step 1 is handled, and is 1g electricity core fragment is added the 30ml-100ml deionized water, and 20 ℃-100 ℃ are stirred down or sonic oscillation 1 hour-3 hours.
3. method according to claim 1, wherein, the inorganic acid in the step 2 comprises the mixed solution of hydrochloric acid, sulfuric acid or hydrochloric acid and sulfuric acid.
4. method according to claim 1, wherein, the lithium salts in the step 3 is selected from lithium sulfate, lithium hydroxide, lithium chloride or lithium nitrate.
5. method according to claim 1, wherein, the molysite in the step 3 is selected from ferrous sulfate, frerrous chloride or ferric nitrate.
6. method according to claim 1, wherein, the drying and calcining in the step 4 is at N
2Protection was calcined 1 hour-24 hours in 600 ℃-900 ℃ down.
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|---|---|---|---|
| CN2010102538595A CN101916889B (en) | 2010-08-16 | 2010-08-16 | Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery |
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|---|---|---|---|
| CN2010102538595A CN101916889B (en) | 2010-08-16 | 2010-08-16 | Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery |
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| CN101916889B CN101916889B (en) | 2012-05-30 |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208707A (en) * | 2011-05-12 | 2011-10-05 | 合肥工业大学 | Method for repair and regeneration of waste lithium iron phosphate battery cathode material |
| CN102403554A (en) * | 2011-11-10 | 2012-04-04 | 大连交通大学 | Method for recycling waste lithium iron phosphate ion battery anode material |
| CN102583297A (en) * | 2012-02-15 | 2012-07-18 | 东营昊坤电池有限公司 | Method for recycling lithium ion battery cathode material lithium iron phosphate |
| CN102956936A (en) * | 2011-08-25 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Method for treating lithium iron phosphate cathode material of waste and old power lithium battery of automobile |
| FR2979756A1 (en) * | 2011-09-07 | 2013-03-08 | Commissariat Energie Atomique | PROCESS FOR RECYCLING LITHIUM BATTERIES AND / OR ELECTRODES OF SUCH BATTERIES |
| CN103276406A (en) * | 2013-03-29 | 2013-09-04 | 江西省电力科学研究院 | Electrochemical lithium recovery method |
| US20130313485A1 (en) * | 2012-05-25 | 2013-11-28 | Korea Institute Of Science And Technology | METHOD OF FABRICATING LiFePO4 CATHODE ELECTROACTIVE MATERIAL BY RECYCLING, AND LiFePO4 CATHODE ELECTROACTIVE MATERIAL, LiFePO4 CATHODE, AND LITHIUM SECONDARY BATTERY FABRICATED THEREBY |
| CN103449395A (en) * | 2013-08-28 | 2013-12-18 | 北京科技大学 | Method for recycling positive material from water-system waste lithium iron phosphate battery |
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