CN109346789A - A kind of the reclaiming technique and regeneration positive electrode of lithium iron phosphate positive material - Google Patents
A kind of the reclaiming technique and regeneration positive electrode of lithium iron phosphate positive material Download PDFInfo
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- CN109346789A CN109346789A CN201811002616.7A CN201811002616A CN109346789A CN 109346789 A CN109346789 A CN 109346789A CN 201811002616 A CN201811002616 A CN 201811002616A CN 109346789 A CN109346789 A CN 109346789A
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- Prior art keywords
- lithium
- battery
- source
- iron phosphate
- positive material
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- 239000000463 material Substances 0.000 title claims abstract description 69
- 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 64
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008929 regeneration Effects 0.000 title claims abstract description 21
- 238000011069 regeneration method Methods 0.000 title claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229940062993 ferrous oxalate Drugs 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 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 description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000008103 glucose Substances 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
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 claims 1
- 238000005538 encapsulation Methods 0.000 claims 1
- 229940032958 ferric phosphate Drugs 0.000 claims 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of reclaiming technique of lithium iron phosphate positive material, steps are as follows: removing battery assembly housing disconnects battery pack bus marco port；The power battery not being substantially discharged is substantially discharged, and power battery pack conductive interface is done into insulation-encapsulated；Battery management system dismantling；Removing battery module housing, dismantling battery parlor conduction and connection component, removing battery pack arrangement fixing piece；Lithium iron phosphate battery positive material is isolated from single battery core；After lithium iron phosphate battery positive material is handled, lithium source, source of iron, titanium source, phosphorus source, carbon source is added, obtains precursor；Solvent medium is added in precursor, obtains intermediary after mixing；Under an inert atmosphere, intermediary is handled by calcination, regeneration lithium iron phosphate positive material is made.Regeneration positive electrode prepared by the present invention is applied in lithium ion battery as positive electrode active materials, has excellent electro-chemical activity and cyclical stability.
Description
Technical field
The present invention relates to a kind of reclaiming technique of lithium iron phosphate positive material and regeneration positive electrodes, belong to lithium battery
Technical field.
Background technique
Due to LiFePO4 (LiFePO4) power battery performance stabilization, it is widely used in recent years, following problem
It is the taking back and process of retired lithium battery group, the battery pack of significant proportion also recyclable benefit retired or after scrapping in lithium battery group
With especially lithium iron phosphate positive material has very high recycling benefit, this is relating to battery pack dismantling and LiFePO4 just
The regeneration technology of pole material.
However, there are still following challenges for the reclaiming technique of lithium iron phosphate positive material: on the one hand, retired lithium battery group
Dismantling process need to pay attention to and avoid causing battery itself irreversible damage, and there are safeties poor, dismantling low efficiency,
Disassemble the problems such as lack of standardization；On the other hand, the regeneration technology of existing lithium iron phosphate positive material is only through simple supplement lithium
Positive electrode is repaired with ferro element, but smaller by the discharge capacity of the regenerated lithium iron phosphate positive material of current method, survey
Cycle-index is shorter when examination, and capacity attenuation rate is larger.
Summary of the invention
The technical problem to be solved by the present invention is to solve the reclaiming technique of existing lithium iron phosphate positive material and again
Above-mentioned technical problem existing for raw positive electrode provides the reclaiming technique and regeneration anode of a kind of lithium iron phosphate positive material
Material.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of reclaiming technique of lithium iron phosphate positive material, includes the following steps:
Removing battery assembly housing disconnects battery pack bus marco port；
The power battery not being substantially discharged is substantially discharged, and always just, always negative conductive interface is done by power battery pack
Insulation-encapsulated；
Pretreated battery pack is removed into management system control, the circuit protection plate of detection line and management system, from control mould
Block, main control module obtain battery module；
Removing battery module housing, dismantling battery parlor conduction and connection component, removing battery pack arrangement fixing piece obtain
Obtain single battery core；
Positive plate is isolated from single battery core, separates lithium iron phosphate battery positive material with plus plate current-collecting body, after
Processing obtains recycling lithium iron phosphate battery positive material；
After lithium source, source of iron, titanium source, phosphorus source, carbon source is added in recycling lithium iron phosphate battery positive material, precursor is obtained,
The ferro element in elemental lithium, source of iron in the lithium source, the titanium elements in titanium source, the P elements in phosphorus source molar ratio be 1:
0.9-0.99:0.1-0.01:1, the elemental lithium in the lithium source, the ferro element in source of iron, the titanium elements in titanium source, in phosphorus source
The quality of carbon in P elements, carbon source and the percentage for accounting for precursor mass are 5-25wt%；
Solvent medium is added in precursor, obtains intermediary after mixing；
Under an inert atmosphere, intermediary is handled by calcination, regeneration lithium iron phosphate positive material is made.
Preferably, the elemental lithium in the lithium source, the ferro element in source of iron, the titanium elements in titanium source, the phosphorus member in phosphorus source
The molar ratio of element is 1:x:(1-x): 1, x=0.9-0.99.
Preferably, disconnection battery pack bus marco port are as follows: disconnect battery pack fuse both ends connecting cable and
The total transmission line of signal in battery management system main control module port.
Preferably, the recycling lithium iron phosphate battery positive material obtains by the following method: by positive plate through superheated water
Steam heating, separates lithium iron phosphate battery positive material with plus plate current-collecting body, then by positive electrode through drying, grinding, screening
After obtain.
Preferably, the temperature of the overheated steam is 200-600 DEG C, and the screening was the screening of 200-500 mesh.
The major advantage of high-temperature steam heating are as follows: heated under 1. oxygen free conditions, keep raw material not oxidized to greatest extent.
2. heating under oxygen free condition, plus plate current-collecting body brittleness is good, and lithium iron phosphate battery positive material is easy to peel off.
Preferably, the lithium source is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide or lithium oxalate.
Preferably, the source of iron is the one or more of ferric nitrate, ferrous acetate, ferrous oxalate or iron oxide.
Preferably, phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate or phosphoric acid.
Preferably, the titanium source is one or more of titanium dioxide, butyl titanate, titanium tetrachloride.
Preferably, the carbon source is one or more of starch, citric acid, sucrose, glucose.
Preferably, the hybrid mode of precursor and solvent medium be ball milling, the solvent medium be methanol, ethyl alcohol, isopropanol,
The mass ratio of the one or more of acetone or butanone, the solvent medium and precursor is 1-2:1.
Preferably, the calcination temperature of intermediary calcining is 500-800 DEG C, calcination time 2-12h.
Preferably, the inert atmosphere is the gaseous mixture of argon gas, nitrogen or both.
The present invention also provides a kind of regeneration positive electrodes prepared by above-mentioned technique.
The beneficial effects of the present invention are:
(1) the reclaiming technique of lithium iron phosphate positive material of the present invention, battery pack dismantling is high-efficient, and dismantling specification is kept away
Exempt to damage the person, battery will not be caused to damage or destroy, and the regeneration technology of lithium iron phosphate battery positive material
Simply, it is easy to amplify, is appropriate for the industrial scale reclaiming of discarded lithium iron phosphate battery positive material.
(2) regeneration lithium iron phosphate positive material of the invention is applied in lithium ion battery as positive electrode active materials, tool
There are excellent electro-chemical activity and cyclical stability.
Specific embodiment
The present invention is described in further detail now.
Embodiment 1
The present embodiment provides a kind of reclaiming techniques of lithium iron phosphate positive material, include the following steps:
It is dismantling object with a certain waste lithium cell group, removing battery assembly housing disconnects battery pack bus marco port；
The power battery not being substantially discharged is substantially discharged, and always just, always negative conductive interface is done by power battery pack
Insulation-encapsulated；
Pretreated battery pack is removed into management system control, the circuit protection plate of detection line and management system, from control mould
Block, main control module obtain battery module；
Removing battery module housing, dismantling battery parlor conduction and connection component, removing battery pack arrangement fixing piece obtain
Obtain single battery core；
Positive plate is isolated from single battery core, after positive plate is heated under 400 DEG C of overheated steams, makes LiFePO4
Cell positive material is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, the sieve of 200 meshes excessively
Recycling lithium iron phosphate battery positive material is obtained after point；
In recycling lithium iron phosphate battery positive material in be added lithium carbonate, ferric nitrate, butyl titanate, ammonium dihydrogen phosphate,
After citric acid, obtain precursor, the lithium carbonate, ferric nitrate, butyl titanate, ammonium dihydrogen phosphate molar ratio be 0.5:0.9:
0.1:1, the elemental lithium in the lithium carbonate, the ferro element in ferric nitrate, the titanium elements in butyl titanate, in ammonium dihydrogen phosphate
P elements, the carbon in citric acid and account for precursor mass percentage be 5wt%；
Acetone is added in precursor, ball milling mixing is uniform, obtains intermediary, and the mass ratio of the acetone and precursor is 2:1；
Under high-purity argon gas protection, intermediary is calcined into 10h at 700 DEG C, regeneration lithium iron phosphate positive material is made.
In addition, the present embodiment be also prepared for it is a kind of using regeneration lithium iron phosphate positive material prepare button cell, step is such as
Under:
By the regeneration lithium iron phosphate positive material of the present embodiment, conductive charcoal (carbon) black (Super P), PVDF (polyvinylidene fluoride
Alkene) 85:10:5 in mass ratio ratio mixing, a certain amount of N-Methyl pyrrolidone (NMP) ball milling 1h afterwards is added, during which can be with
The viscosity of appropriate NMP adjusting slurry is added to suitable coating, slurry is made；
The slurry made is coated uniformly on aluminium foil with spreader, with sheet-punching machine round pole piece is made after to be dried, it will
Pole piece 100 DEG C of freeze-day with constant temperature 12h in a vacuum drying oven, are made positive plate；
The assembly that button cell is carried out in the glove box full of dry argon gas, using metal lithium sheet as cathode, diaphragm is beauty
State Celgard 2400, electrolyte are 1.0mol/L LiPF6/EC+DMC+EMC (1:1:1, volume ratio), are assembled into button electricity
Pond.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.2C constant current, then
0.2C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.Test result shows the button
Formula battery 0.2C discharge capacity is 153.1mAh/g, illustrates that regenerating lithium iron phosphate positive material has excellent chemical property.
Button cell is prepared at room temperature 1C charge and discharge cycles 400 weeks using the present embodiment, capacity attenuation rate is 0.0185%/
Illustrate that regenerating lithium iron phosphate positive material has excellent cycle performance in week.
Embodiment 2
The present embodiment provides a kind of reclaiming techniques of lithium iron phosphate positive material, include the following steps:
It is dismantling object with a certain waste lithium cell group, removing battery assembly housing disconnects battery pack bus marco port；
The power battery not being substantially discharged is substantially discharged, and always just, always negative conductive interface is done by power battery pack
Insulation-encapsulated；
Pretreated battery pack is removed into management system control, the circuit protection plate of detection line and management system, from control mould
Block, main control module obtain battery module；
Removing battery module housing, dismantling battery parlor conduction and connection component, removing battery pack arrangement fixing piece obtain
Obtain single battery core；
Positive plate is isolated from single battery core, after positive plate is heated under 200 DEG C of overheated steams, makes LiFePO4
Cell positive material is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, the sieve of 200 meshes excessively
Recycling lithium iron phosphate battery positive material is obtained after point；
Lithium hydroxide, ferrous oxalate, titanium dioxide, phosphoric acid hydrogen two is added in recycling lithium iron phosphate battery positive material
After ammonium, sucrose, obtain precursor, the lithium hydroxide, ferrous oxalate, titanium dioxide, diammonium hydrogen phosphate molar ratio be 1:0.98:
0.02:1, elemental lithium, the ferro element in ferrous oxalate, the titanium elements in titanium dioxide, phosphoric acid hydrogen two in the lithium hydroxide
The quality of the carbon in P elements, sucrose in ammonium and to account for the percentage of precursor mass be respectively 12.5wt%；
Isopropanol is added in precursor, ball milling mixing is uniform, obtains intermediary, and the mass ratio of the isopropanol and precursor is
1.5:1；
Under high pure nitrogen protection, intermediary is calcined into 2h at 800 DEG C, regeneration lithium iron phosphate positive material is made.
In addition, the present embodiment is also prepared for a kind of button cell using regeneration lithium iron phosphate positive material, step is as implemented
Example 1.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.2C constant current, then
0.2C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.Test result shows the button
Formula battery 0.2C discharge capacity is 153.1mAh/g, illustrates that regenerating lithium iron phosphate positive material has excellent chemical property.
Button cell is prepared at room temperature 1C charge and discharge cycles 400 weeks using the present embodiment, capacity attenuation rate is 0.0185%/
Illustrate that regenerating lithium iron phosphate positive material has excellent cycle performance in week.
Embodiment 3
The present embodiment provides a kind of reclaiming techniques of lithium iron phosphate positive material, include the following steps:
It is dismantling object with a certain waste lithium cell group, removing battery assembly housing disconnects battery pack bus marco port；
The power battery not being substantially discharged is substantially discharged, and always just, always negative conductive interface is done by power battery pack
Insulation-encapsulated；
Pretreated battery pack is removed into management system control, the circuit protection plate of detection line and management system, from control mould
Block, main control module obtain battery module；
Removing battery module housing, dismantling battery parlor conduction and connection component, removing battery pack arrangement fixing piece obtain
Obtain single battery core；
Positive plate is isolated from single battery core, after positive plate is heated under 600 DEG C of overheated steams, makes LiFePO4
Cell positive material is separated with plus plate current-collecting body, then by lithium iron phosphate battery positive material through drying, grinding, the sieve of 500 meshes excessively
Recycling lithium iron phosphate battery positive material is obtained after point；
After lithium oxalate, iron oxide, titanium tetrachloride, phosphoric acid, glucose is added in recycling lithium iron phosphate battery positive material,
Obtain precursor, the lithium oxalate, iron oxide, titanium tetrachloride, phosphoric acid molar ratio be 1:0.99:0.01:1, in the lithium oxalate
Elemental lithium, the ferro element in iron oxide, the titanium elements in titanium tetrachloride, the P elements in phosphoric acid, the carbon in glucose
Quality and to account for the percentage of precursor mass be respectively 25wt%；
Dehydrated alcohol is added in precursor, ball milling mixing is uniform, obtains intermediary, the quality of the dehydrated alcohol and precursor
Than for 1:1；
Under high-purity argon gas protection, intermediary is calcined into 12h at 500 DEG C, regeneration lithium iron phosphate positive material is made.
In addition, the present embodiment is also prepared for a kind of button cell using regeneration lithium iron phosphate positive material, step is as implemented
Example 1.
By the button cell of preparation, related charge-discharge test is carried out, battery is charged to 3.8V with 0.2C constant current, then
0.2C constant current is put to 2.7V, cycle charge-discharge, and the gram volume of active material in iron electrode is calculated.Test result shows the button
Formula battery 0.2C discharge capacity is 155.2mAh/g, illustrates that regenerating lithium iron phosphate positive material has excellent chemical property.
Button cell is prepared at room temperature 1C charge and discharge cycles 400 weeks using the present embodiment, capacity attenuation rate is 0.0178%/
Illustrate that regenerating lithium iron phosphate positive material has excellent cycle performance in week.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of reclaiming technique of lithium iron phosphate positive material, which comprises the steps of:
Removing battery assembly housing disconnects battery pack bus marco port；
The power battery not being substantially discharged is substantially discharged, and always just, always negative conductive interface does and insulate by power battery pack
Encapsulation；
Pretreated battery pack is removed into management system control, the circuit protection plate of detection line and management system, from control module, master
Module is controlled, battery module is obtained；
Removing battery module housing, dismantling battery parlor conduction and connection component, removing battery pack arrangement fixing piece, obtain single
Body battery core；
Positive plate is isolated from single battery core, separates lithium iron phosphate battery positive material with plus plate current-collecting body, it is post-treated
Obtain recycling lithium iron phosphate battery positive material；
After lithium source, source of iron, titanium source, phosphorus source, carbon source is added in recycling lithium iron phosphate battery positive material, precursor is obtained, it is described
The ferro element in elemental lithium, source of iron in lithium source, the titanium elements in titanium source, the P elements in phosphorus source molar ratio be 1:0.9-
0.99:0.1-0.01:1, the elemental lithium in the lithium source, the ferro element in source of iron, the titanium elements in titanium source, the phosphorus member in phosphorus source
The quality of carbon plain, in carbon source and the percentage for accounting for precursor mass are 5-25wt%；
Solvent medium is added in precursor, obtains intermediary after mixing；
Under an inert atmosphere, intermediary is handled by calcination, regeneration lithium iron phosphate positive material is made.
2. the reclaiming technique of lithium iron phosphate positive material according to claim 1, which is characterized in that in the lithium source
Elemental lithium, the ferro element in source of iron, the titanium elements in titanium source, the P elements in phosphorus source molar ratio be 1:x:(1-x): 1, x
=0.9-0.99.
3. the reclaiming technique of lithium iron phosphate positive material according to claim 1 or 2, which is characterized in that described disconnected
Open battery pack bus marco port are as follows: disconnect connecting cable and the battery management system main control module end at battery pack fuse both ends
The total transmission line of signal in mouthful.
4. the reclaiming technique of lithium iron phosphate positive material according to claim 1-3, which is characterized in that institute
It states recycling lithium iron phosphate battery positive material to obtain by the following method: positive plate being heated through overheated steam, makes ferric phosphate
Anode material of lithium battery is separated with plus plate current-collecting body, then positive electrode is obtained after drying, grinding, screening.
5. the reclaiming technique of lithium iron phosphate positive material according to claim 4, which is characterized in that the superheated water
The temperature of steam is 200-600 DEG C, and the screening was the screening of 200-500 mesh.
6. the reclaiming technique of lithium iron phosphate positive material according to claim 1-5, which is characterized in that institute
Stating lithium source is one or more of lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide or lithium oxalate, the source of iron be ferric nitrate,
The one or more of ferrous acetate, ferrous oxalate or iron oxide, phosphorus source are ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate
Or one or more of phosphoric acid, the titanium source be one or more of titanium dioxide, butyl titanate, titanium tetrachloride,
The carbon source is one or more of starch, citric acid, sucrose, glucose.
7. the reclaiming technique of lithium iron phosphate positive material according to claim 1-6, which is characterized in that preceding
The hybrid mode of body and solvent medium is ball milling, and the solvent medium is one kind of methanol, ethyl alcohol, isopropanol, acetone or butanone
Or it is several, the mass ratio of the solvent medium and precursor is 1-2:1.
8. the reclaiming technique of lithium iron phosphate positive material according to claim 1-7, which is characterized in that in
Between object calcine calcination temperature be 500-800 DEG C, calcination time 2-12h.
9. the reclaiming technique of lithium iron phosphate positive material according to claim 1-8, which is characterized in that institute
State the gaseous mixture that inert atmosphere is argon gas, nitrogen or both.
10. a kind of regeneration positive electrode of the described in any item technique preparations of claim 1-9.
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