CN104609385A - Method for recycling and preparing lithium iron manganese phosphate from positive electrode materials of waste lithium iron phosphate batteries - Google Patents
Method for recycling and preparing lithium iron manganese phosphate from positive electrode materials of waste lithium iron phosphate batteries Download PDFInfo
- Publication number
- CN104609385A CN104609385A CN201510049888.2A CN201510049888A CN104609385A CN 104609385 A CN104609385 A CN 104609385A CN 201510049888 A CN201510049888 A CN 201510049888A CN 104609385 A CN104609385 A CN 104609385A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- lithium iron
- lithium
- iron phosphate
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 56
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 16
- 238000004064 recycling Methods 0.000 title abstract description 5
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title abstract 3
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims description 23
- 239000005030 aluminium foil Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000007669 thermal treatment Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- -1 polyoxyethylene Polymers 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 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 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000011888 foil Substances 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000005955 Ferric phosphate Substances 0.000 description 5
- 229940032958 ferric phosphate Drugs 0.000 description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910011980 LiFe0.4Mn0.6PO4 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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 recycling and preparing lithium iron manganese phosphate from positive electrode materials of waste lithium iron phosphate batteries. The method comprises the following steps: (1) discharging remnant electric quantities of the waste lithium iron phosphate batteries, disassembling the batteries, taking positive electrode sheets, washing, drying, roasting and separating lithium iron phosphate from aluminum foils; (2) by controlling the addition of acid, carrying out acid leaching on separated lithium iron phosphate, and filtering to separate insoluble iron phosphate and iron oxide to obtain a filtrate; (3) analyzing the filtrate, adjusting the molar ratio of the elements, namely, nLi to (nFe+Mn) to nP to 1: 1: 1 and adding a manganese source and a phosphorus source; and adjusting the pH to obtain a precipitate; drying the precipitate, adding a carbon source and mixing to obtain a pre-sintered material; and (4) carrying out solid sintering treatment on the pre-sintered material under non-oxidizing atmosphere to obtain the lithium iron manganese phosphate serving as the lithium ion battery positive electrode material. The method has the advantages of simplicity in process, environmental friendliness, good product properties and the like.
Description
Technical field
The present invention relates to iron lithium phosphate old and useless battery and reclaim field, be specifically related to a kind of recovery from iron lithium phosphate old and useless battery and prepare the method for lithium ferric manganese phosphate.
Background technology
Along with 3C electronic product, various power tools etc. present explosive type development, the demand of people to secondary cell sharply increases.And lithium-ions battery has environmentally friendly, the feature such as specific energy is high, voltage platform is high, have extended cycle life, good rate capability, self-discharge are little, memory-less effect, be far superior to plumbic acid, Ni-Cd, Ni-MH battery, obtain very widespread use at military, civil area.At present, with iron lithium phosphate be the lithium-ion secondary cell of positive electrode material due to the feature such as cost is low and safety performance is good, started the power cell being widely used in power tool and power truck.Along with the development of electromobile, be widely used using iron lithium phosphate as the power cell of positive electrode material, the quantity of waste and old lithium ion battery also will increase year by year.Therefore, in order to recycling material, cost-saving and protection of the environment, reclaim iron lithium phosphate waste material and become necessary.
Current China is also relatively little about the report reclaiming positive electrode material in iron lithium phosphate old and useless battery.Publication number is the treating method that the Chinese invention patent application of CN101359756A, CN102280673A and CN101394015A then mainly relates to the iron lithium phosphate waste material produced in industrial production, is not suitable for the recycling of ferric phosphate lithium cell waste and old after using.
Publication number is that the Chinese invention patent application of CN102285673A discloses a kind of method reclaiming lithium and iron from electric automobile lithium ferric phosphate power cell, mainly through the mode of hydrometallurgy by lithium, iron, aluminium, reclaim not exclusively, the rate of recovery is not high, and economic benefit is not good.
Publication number is the method that the Chinese invention patent application of CN101916889A discloses preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery, only the old and useless battery of water system viscose glue system is recycled, do not relate to the recycling of the old and useless battery of oil system viscose glue system.
Publication number is the recovery method that the Chinese invention patent application of CN102017276 discloses a kind of lithium iron phosphate dynamic battery, and the method is only simple to be separated positive plate and cleaning, just can directly as positive electrode material.But because the positive plate of original ferric phosphate lithium cell lost efficacy, do not carry out the steps such as process reparation to the iron lithium phosphate be separated, the battery performance that this method is made can existing defects.
In order to overcome prior art, method the rate of recovery not high, reclaim incomplete defect, the present invention removes glue paste by the mode of roasting, makes iron lithium phosphate and aluminium foil be easy to be separated, and is applicable to the ferric phosphate lithium cell that water system and oil are viscose glue system; The iron lithium phosphate that acidleach process is separated, remain the element such as iron, phosphorus of lithium and part, by ultimate analysis, manganese supplement and phosphorus, obtain lithium ferric manganese phosphate by roasting.This reclaiming method, technique are simple, easy to operate; Prepared lithium ferric manganese phosphate material is relative to Li
+the electrode potential of/Li is 4.1V, and lithium ferric manganese phosphate has two voltage platforms simultaneously, and high-voltage platform can improve the voltage of battery, and low voltage platform can well judge the surplus capacity of battery, for cell container management provides a simple scheme.
Summary of the invention
The object of this invention is to provide a kind of positive material of waste lithium iron phosphate and reclaim the method preparing lithium ferric manganese phosphate, comprise the steps:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, at 450 ~ 600 DEG C, after thermal treatment 1 ~ 3h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) iron lithium phosphate after being separated and H is controlled
+mol ratio be 1:(2.5 ~ 3.5), by isolated for previous step iron lithium phosphate and acid-respons, temperature of reaction is 70 ~ 95 DEG C, and the reaction times is after 2 ~ 5h, the tertiary iron phosphate that filtering separation is insoluble and ferric oxide, collects acidleach filter residue and acidleach filtrate respectively;
4) carrying out ultimate analysis to the filtrate of gained, is n according to elemental mole ratios
li: n
fe: n
mn:nP=1:(0.2 ~ 0.8): (0.2 ~ 0.8): 1 wherein n
fe+ n
mn=1, after allocating manganese source and phosphorus source into, under stirring at 60 ~ 90 DEG C, slowly drip ammoniacal liquor and regulate pH=8 ~ 10, after stirring 5-10h, suction filtration, washing obtain solid, then dry;
5) by the solid of drying and 5 ~ 10 wt% carbon source ground and mixed evenly after, under non-oxidizing atmosphere, rise to 300 ~ 400 DEG C with 5 ~ 15 DEG C/min, and after keeping 2 ~ 5h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under non-oxidizing atmosphere, rise to 600 ~ 900 DEG C with 5 ~ 15 DEG C/min, keep 3 ~ 15h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.
Acid described in step 3) is one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid.
Manganese source described in step 4) is one or more the mixture in manganese acetate, manganous carbonate, manganous nitrate.
Phosphorus source described in step 4) is one or more the mixture in primary ammonium phosphate, ammonium hydrogen phosphate, ammonium phosphate.
Carbon source described in step 5) is one or more the mixture in sucrose, glucose, polyoxyethylene glycol.
Rare gas element described in step 5) and step 6) is argon gas, one or more mixture in nitrogen, argon hydrogen gas mixture.
The method preparing lithium ferric manganese phosphate from waste lithium iron phosphate battery recovery provided by the invention, effective recovery has also recycled waste lithium iron phosphate battery, not only reclaim aluminium, and again prepared lithium ferric manganese phosphate electrode materials, solved ferric phosphate lithium cell and reclaim problem.This preparation method's environmental protection, product 0.2C first loading capacity reaches 155.1mAh/g, and after 50 circulations, capacity is 148.0mAh/g.Compared with LiFePO 4 material, improve the operating voltage of synthetic materials and the specific energy of material.
Accompanying drawing explanation
1. Fig. 1 is the embodiment of the present invention 3 product LiFe
0.4mn
0.6pO
4xRD figure spectrum;
2. Fig. 2 is the embodiment of the present invention 3 product LiFe
0.4mn
0.6pO
4discharge cycles graphic representation;
Embodiment
Below with reference to specific embodiment, technical scheme provided by the invention is described in detail, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.In addition, do not have the embodiment described can fully understand to those skilled in the art in this specification sheets, no longer set forth at this.For those skilled in the art, without departing from the spirit and substance in the present invention, various improvement of making obtaining, is also considered as protection scope of the present invention.
Embodiment 1:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 450 DEG C of thermal treatment 3h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 50g previous step and add 199ml 4mol/L hydrochloric acid, oil bath 70 DEG C, stirring reaction is after 5h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 29.3g and filtrate;
4) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.2:0.8:1, adds manganous carbonate solid 27.7g, ammonium hydrogen phosphate 18.6g in the filtrate of gained, and after stirring and dissolving, control temperature is 60 DEG C, drips ammoniacal liquor to pH=8, and after stirring 10h, suction filtration, washing obtain solid dries 54.5g;
5) by the solid of drying and 2.5g polyoxyethylene glycol ground and mixed even, in a nitrogen atmosphere, rise to 300 DEG C with 5 DEG C/min, and after keeping 5h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under argon hydrogen gas mixture atmosphere, rise to 600 DEG C with 5 DEG C/min, keep 15h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 142.7mAh/g at 0.2C discharge capacity after tested.
Embodiment 2:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 500 DEG C of thermal treatment 2h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 50g previous step and add 199ml 4mol/L nitric acid, oil bath 80 DEG C, stirring reaction is after 4h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 24.7g and filtrate;
4) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.3:0.7:1, adds manganous nitrate solid 37.7g, ammonium hydrogen phosphate 16.5g in the filtrate of gained, and after stirring and dissolving, control temperature is 70 DEG C, drips ammoniacal liquor to pH=8, and after stirring 10h, suction filtration, washing obtain solid dries 53.3g;
5) by the solid of drying and 2.5g glucose ground and mixed even, under argon hydrogen gas mixture atmosphere, rise to 300 DEG C with 5 DEG C/min, and after keeping 5h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under argon hydrogen gas mixture atmosphere, rise to 600 DEG C with 7 DEG C/min, keep 15h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 149.5mAh/g at 0.2C discharge capacity after tested.
Embodiment 3:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 600 DEG C of thermal treatment 1h, the iron lithium phosphate after thermal treatment is separated with aluminium foil, and aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 100g previous step and add 113ml 4mol/L sulfuric acid, oil bath 90 DEG C, stirring reaction is after 3h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 40.2g and filtrate;
4) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.4:0.6:1, adds manganous nitrate solid 62.5g, primary ammonium phosphate 18.5g in the filtrate of gained, and after stirring and dissolving, control temperature is 70 DEG C, drips ammoniacal liquor to pH=9, and after stirring 7h, suction filtration, washing obtain solid dries 109.1g;
5) by the solid of drying and 3g sucrose ground and mixed even, under an argon atmosphere, rise to 350 DEG C with 7 DEG C/min, and after keeping 3h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under an argon atmosphere, rise to 700 DEG C with 10 DEG C/min, keep 9h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 155.1mAh/g at 0.2C discharge capacity after tested, and after 50 circulations, capacity is 148.0mAh/g.Its XRD figure stave is levied as shown in Figure 1, and discharge cycles curve as shown in Figure 2.
Embodiment 4:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 600 DEG C of thermal treatment 1h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 50g previous step and add 120ml 4mol/L sulfuric acid, oil bath 90 DEG C, stirring reaction is after 3h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 15.6g and filtrate;
4)) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.5:0.5:1, adds manganese acetate solid 26g, primary ammonium phosphate 5.8g in the filtrate of gained, and after stirring and dissolving, control temperature is 70 DEG C, drips ammoniacal liquor to pH=9, and after stirring 7h, suction filtration, washing obtain solid dries 53.6g;
5) by the solid of drying and 3g sucrose ground and mixed even, in a nitrogen atmosphere, rise to 350 DEG C with 7 DEG C/min, and after keeping 3h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, in a nitrogen atmosphere, rise to 700 DEG C with 10 DEG C/min, keep 9h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 152.6mAh/g at 0.2C discharge capacity after tested.
Embodiment 5:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 500 DEG C of thermal treatment 2h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 50g previous step and add 126.5ml 4mol/L sulfuric acid, oil bath 90 DEG C, stirring reaction is after 3h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 11g and filtrate;
4) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.6:0.4:1, adds manganese acetate solid 20.8g, primary ammonium phosphate 2.3g in the filtrate of gained, and after stirring and dissolving, control temperature is 80 DEG C, drips ammoniacal liquor to pH=9, and after stirring 7h, suction filtration, washing obtain solid dries 53.7g;
5) by the solid of drying and 5g sucrose ground and mixed even, under an argon atmosphere, rise to 350 DEG C with 10 DEG C/min, and after keeping 3h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under an argon atmosphere, rise to 800 DEG C with 10 DEG C/min, keep 9h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 145.6mAh/g at 0.2C discharge capacity after tested.
Embodiment 6:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 450 DEG C of thermal treatment 3h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 50g previous step and add 266.5ml 4mol/L hydrochloric acid, oil bath 95 DEG C, stirring reaction is after 2h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 7.2g and filtrate;
4) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.7:0.3:1, adds manganous carbonate solid 10.47g in the filtrate of gained, and after stirring and dissolving, control temperature is 80 DEG C, drips ammoniacal liquor to pH=9, and after controlling to stir 5h, suction filtration, washing obtain solid dries 52.9g;
5) by the solid of drying and 5g glucose ground and mixed even, in a nitrogen atmosphere, rise to 400 DEG C with 10 DEG C/min, and after keeping 3h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, in a nitrogen atmosphere, rise to 800 DEG C with 10 DEG C/min, keep 5h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 148.5mAh/g at 0.2C discharge capacity after tested.
Embodiment 7:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, in retort furnace after 450 DEG C of thermal treatment 3h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) get the isolated iron lithium phosphate of 50g previous step and add 280ml 4mol/L nitric acid, oil bath 80 DEG C, stirring reaction is after 2h, filtering separation solid-liquid, and suction filtration obtains brick-red precipitation 5g and filtrate;
4) filtrate is analyzed through detecting, and is n according to elemental mole ratios
li: n
fe: n
mn: n
p=1:0.8:0.2:1, adds manganous nitrate solid 10.8g in the filtrate of gained, and after stirring and dissolving, control temperature is 90 DEG C, drips ammoniacal liquor to pH=10, and after stirring 5h, suction filtration, washing obtain solid dries as 53.3g;
5) by the solid of drying and 5g polyoxyethylene glycol ground and mixed even, in a nitrogen atmosphere, rise to 400 DEG C with 15 DEG C/min, and after keeping 2h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under argon hydrogen gas mixture atmosphere, rise to 900 DEG C with 15 DEG C/min, keep 9h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.It can reach 143.5mAh/g at 0.2C discharge capacity after tested.
Claims (6)
1. positive material of waste lithium iron phosphate reclaims the method preparing lithium ferric manganese phosphate, it is characterized in that, comprises following steps:
1) waste lithium iron phosphate battery is discharged remaining capacity, after being disassembled by battery, be separated positive plate, negative plate and barrier film, after positive plate is washed, dry;
2) positive plate of will dry, at 450 ~ 600 DEG C, after thermal treatment 1 ~ 3h, be separated with aluminium foil by the iron lithium phosphate after thermal treatment, aluminium foil is reclaimed by melting;
3) iron lithium phosphate after being separated and H is controlled
+mol ratio be 1:(2.5 ~ 3.5), by isolated for previous step iron lithium phosphate and acid-respons, temperature of reaction is 70 ~ 95 DEG C, and the reaction times is after 2 ~ 5h, the tertiary iron phosphate that filtering separation is insoluble and ferric oxide, collects acidleach filter residue and acidleach filtrate respectively;
4) carrying out ultimate analysis to the filtrate of gained, is n according to elemental mole ratios
li: n
fe: n
mn:nP=1:(0.2 ~ 0.8): (0.2 ~ 0.8): 1 wherein n
fe+ n
mn=1, after allocating manganese source and phosphorus source into, under stirring at 60 ~ 90 DEG C, slowly drip ammoniacal liquor and regulate pH=8 ~ 10, after stirring 5-10h, suction filtration, washing obtain solid, then dry;
5) by the solid of drying and 5 ~ 10 wt% carbon source ground and mixed evenly after, under non-oxidizing atmosphere, rise to 300 ~ 400 DEG C with 5 ~ 15 DEG C/min, and after keeping 2 ~ 5h, furnace cooling, obtains presoma;
6) by cooled presoma, after grinding, under non-oxidizing atmosphere, rise to 600 ~ 900 DEG C with 5 ~ 15 DEG C/min, keep 3 ~ 15h, furnace cooling, namely obtains lithium ferric manganese phosphate positive electrode material.
2. a kind of positive material of waste lithium iron phosphate according to claim 1 reclaims the method preparing lithium ferric manganese phosphate, it is characterized in that: acid described in step 3) is one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid.
3. a kind of positive material of waste lithium iron phosphate according to claim 1 reclaims the method preparing lithium ferric manganese phosphate, it is characterized in that: manganese source described in step 4) is one or more the mixture in manganese acetate, manganous carbonate, manganous nitrate.
4. a kind of positive material of waste lithium iron phosphate according to claim 1 reclaims the method preparing lithium ferric manganese phosphate, it is characterized in that: phosphorus source described in step 4) is one or more the mixture in primary ammonium phosphate, ammonium hydrogen phosphate, ammonium phosphate.
5. a kind of positive material of waste lithium iron phosphate according to claim 1 reclaims the method preparing lithium ferric manganese phosphate, it is characterized in that: carbon source described in step 5) is one or more the mixture in sucrose, glucose, polyoxyethylene glycol.
6. a kind of positive material of waste lithium iron phosphate according to claim 1 reclaims the method preparing lithium ferric manganese phosphate, it is characterized in that: rare gas element described in step 5) and step 6) is argon gas, one or more mixture in nitrogen, argon hydrogen gas mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510049888.2A CN104609385B (en) | 2015-01-30 | 2015-01-30 | A kind of method that lithium ferric manganese phosphate is prepared in positive material of waste lithium iron phosphate recovery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510049888.2A CN104609385B (en) | 2015-01-30 | 2015-01-30 | A kind of method that lithium ferric manganese phosphate is prepared in positive material of waste lithium iron phosphate recovery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104609385A true CN104609385A (en) | 2015-05-13 |
| CN104609385B CN104609385B (en) | 2016-08-31 |
Family
ID=53144086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510049888.2A Active CN104609385B (en) | 2015-01-30 | 2015-01-30 | A kind of method that lithium ferric manganese phosphate is prepared in positive material of waste lithium iron phosphate recovery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104609385B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016205780A1 (en) * | 2015-06-19 | 2016-12-22 | 24M Technologies, Inc. | Methods for electrochemical cell remediation |
| CN106848221A (en) * | 2017-01-18 | 2017-06-13 | 昆明理工大学 | A kind of method that hydro-thermal method prepares lithium manganese phosphate base composite positive pole |
| CN106997975A (en) * | 2017-06-06 | 2017-08-01 | 安徽安凯汽车股份有限公司 | A kind of method of waste lithium iron phosphate battery and lithium manganate battery regeneration |
| CN107955879A (en) * | 2017-12-05 | 2018-04-24 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
| TWI625882B (en) * | 2016-11-02 | 2018-06-01 | Dayeh University | Method for recovering positive electrode material resources in waste lithium iron battery |
| CN108110357A (en) * | 2017-12-14 | 2018-06-01 | 眉山顺应动力电池材料有限公司 | A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate |
| CN108376768A (en) * | 2018-01-29 | 2018-08-07 | 国网河南省电力公司电力科学研究院 | A kind of additive Mn regeneration lithium iron phosphate positive material and preparation method thereof |
| CN108923090A (en) * | 2018-05-29 | 2018-11-30 | 深圳市德方纳米科技股份有限公司 | A method of carbon-coated lithium iron manganese phosphate anode material is prepared from waste lithium iron phosphate battery recycling |
| CN109082525A (en) * | 2018-08-29 | 2018-12-25 | 北京理工大学 | A method of raising relates to weight dangerous waste bioleaching-regeneration enrichment efficiency |
| CN109193059A (en) * | 2018-09-26 | 2019-01-11 | 王书珍 | A kind of regeneration treating method of LiFePO4 waste material |
| CN110649342A (en) * | 2018-06-26 | 2020-01-03 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN110759644A (en) * | 2019-10-16 | 2020-02-07 | 许昌学院 | Method for synthesizing iron phosphate and iron oxide film by using waste lithium iron phosphate battery |
| CN111333048A (en) * | 2020-03-10 | 2020-06-26 | 桑顿新能源科技(长沙)有限公司 | Method for preparing lithium manganese iron phosphate by using waste lithium iron phosphate and lithium manganate materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130316233A1 (en) * | 2011-02-02 | 2013-11-28 | Furukawa Electric Co., Ltd. | Particulate mixture, cathode active material, cathode, secondary battery, and production method thereof |
| CN103474719A (en) * | 2013-08-30 | 2013-12-25 | 国家电网公司 | Method for recycling positive electrode of LiFePO4 battery |
| CN103825064A (en) * | 2014-02-27 | 2014-05-28 | 北京工业大学 | Demonstration process for recovering waste and old dynamic lithium iron phosphate cell in environmental protection mode |
-
2015
- 2015-01-30 CN CN201510049888.2A patent/CN104609385B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130316233A1 (en) * | 2011-02-02 | 2013-11-28 | Furukawa Electric Co., Ltd. | Particulate mixture, cathode active material, cathode, secondary battery, and production method thereof |
| CN103474719A (en) * | 2013-08-30 | 2013-12-25 | 国家电网公司 | Method for recycling positive electrode of LiFePO4 battery |
| CN103825064A (en) * | 2014-02-27 | 2014-05-28 | 北京工业大学 | Demonstration process for recovering waste and old dynamic lithium iron phosphate cell in environmental protection mode |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11876194B2 (en) | 2015-06-19 | 2024-01-16 | 24M Technologies, Inc. | Methods for electrochemical cell remediation |
| WO2016205780A1 (en) * | 2015-06-19 | 2016-12-22 | 24M Technologies, Inc. | Methods for electrochemical cell remediation |
| US10411310B2 (en) | 2015-06-19 | 2019-09-10 | 24M Technologies, Inc. | Methods for electrochemical cell remediation |
| US11094976B2 (en) | 2015-06-19 | 2021-08-17 | 24M Technologies, Inc. | Methods for electrochemical cell remediation |
| TWI625882B (en) * | 2016-11-02 | 2018-06-01 | Dayeh University | Method for recovering positive electrode material resources in waste lithium iron battery |
| CN106848221A (en) * | 2017-01-18 | 2017-06-13 | 昆明理工大学 | A kind of method that hydro-thermal method prepares lithium manganese phosphate base composite positive pole |
| CN106997975A (en) * | 2017-06-06 | 2017-08-01 | 安徽安凯汽车股份有限公司 | A kind of method of waste lithium iron phosphate battery and lithium manganate battery regeneration |
| CN107955879A (en) * | 2017-12-05 | 2018-04-24 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
| CN107955879B (en) * | 2017-12-05 | 2019-08-30 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
| CN108110357A (en) * | 2017-12-14 | 2018-06-01 | 眉山顺应动力电池材料有限公司 | A kind of method that valuable metal is recycled from positive material of waste lithium iron phosphate |
| CN108110357B (en) * | 2017-12-14 | 2020-07-17 | 眉山顺应动力电池材料有限公司 | Method for recovering valuable metals from waste lithium iron phosphate battery positive electrode materials |
| CN108376768A (en) * | 2018-01-29 | 2018-08-07 | 国网河南省电力公司电力科学研究院 | A kind of additive Mn regeneration lithium iron phosphate positive material and preparation method thereof |
| CN108923090A (en) * | 2018-05-29 | 2018-11-30 | 深圳市德方纳米科技股份有限公司 | A method of carbon-coated lithium iron manganese phosphate anode material is prepared from waste lithium iron phosphate battery recycling |
| CN110649342A (en) * | 2018-06-26 | 2020-01-03 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN110649342B (en) * | 2018-06-26 | 2022-08-12 | 中天储能科技有限公司 | Method for recycling positive active material of waste lithium iron phosphate battery |
| CN109082525A (en) * | 2018-08-29 | 2018-12-25 | 北京理工大学 | A method of raising relates to weight dangerous waste bioleaching-regeneration enrichment efficiency |
| CN109193059A (en) * | 2018-09-26 | 2019-01-11 | 王书珍 | A kind of regeneration treating method of LiFePO4 waste material |
| CN110759644A (en) * | 2019-10-16 | 2020-02-07 | 许昌学院 | Method for synthesizing iron phosphate and iron oxide film by using waste lithium iron phosphate battery |
| CN111333048A (en) * | 2020-03-10 | 2020-06-26 | 桑顿新能源科技(长沙)有限公司 | Method for preparing lithium manganese iron phosphate by using waste lithium iron phosphate and lithium manganate materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104609385B (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104609385A (en) | Method for recycling and preparing lithium iron manganese phosphate from positive electrode materials of waste lithium iron phosphate batteries | |
| Kwade et al. | Recycling of lithium-ion batteries | |
| CN102751548B (en) | Method for recovering and preparing lithium iron phosphate from waste lithium iron phosphate battery | |
| Wu et al. | Direct recovery: A sustainable recycling technology for spent lithium-ion battery | |
| CN106997975B (en) | method for recycling waste lithium iron phosphate battery and lithium manganate battery | |
| CN103915661B (en) | A kind of direct recovery the method repairing anode material for lithium-ion batteries | |
| CN104810566B (en) | A kind of waste lithium iron phosphate electrokinetic cell green reclaim processing method | |
| CN108923090A (en) | A method of carbon-coated lithium iron manganese phosphate anode material is prepared from waste lithium iron phosphate battery recycling | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN111224187B (en) | Method for directly repairing and regenerating waste lithium iron phosphate battery positive electrode material | |
| CN102208707A (en) | Method for repair and regeneration of waste lithium iron phosphate battery cathode material | |
| CN106910889A (en) | A kind of method that positive active material is regenerated from waste lithium iron phosphate battery | |
| CN103449395A (en) | Method for recycling positive material from water-system waste lithium iron phosphate battery | |
| CN106976852A (en) | The green reparative regeneration technology of LiFePO 4 material in a kind of old and useless battery | |
| CN101847763A (en) | Comprehensive recovering method of waste lithium iron phosphate battery | |
| CN104362408B (en) | A kind of recycling method of ferric phosphate lithium cell manufacture link LiFePO4 waste material | |
| CN102738539A (en) | Method and apparatus for recovering lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries | |
| CN106505273A (en) | The method that a kind of recovery of ferric phosphate lithium cell production link positive pole waste and scrap is repaired and recycled | |
| WO2024021233A1 (en) | Method for preparing lithium iron phosphate by means of comprehensive recovery of lithium-containing wastewater and use thereof | |
| KR20210145454A (en) | Reuse method of active material of positive electrode scrap | |
| WO2023155544A1 (en) | Preparation method for polyanionic positive electrode material | |
| CN102583297A (en) | Method for recycling lithium ion battery cathode material lithium iron phosphate | |
| KR20220050541A (en) | Reuse method of active material of positive electrode scrap | |
| KR20220042659A (en) | Reuse method of active material of positive electrode scrap | |
| CN113381089B (en) | Method for preparing nano lithium iron phosphate material by recycling ferrous phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161214 Address after: 100125 Beijing city Chaoyang District Liangmaqiao Road No. 39 in the first Shanghai C202 Center Patentee after: BEIJING SAIDEMEI RESOURCES RECYCLING RESEARCH INSTITUTE CO.,LTD. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan road 932 Patentee before: HUNAN ZHENGYUAN INSTITUTE FOR ENERGY STORAGE MATERIALS AND DEVICES |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for preparation of lithium iron manganese phosphate from waste lithium iron phosphate battery cathode material Effective date of registration: 20210209 Granted publication date: 20160831 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING SAIDEMEI RESOURCES RECYCLING RESEARCH INSTITUTE Co.,Ltd. Registration number: Y2021990000173 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20211223 Granted publication date: 20160831 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING SAIDEMEI RESOURCES RECYCLING RESEARCH INSTITUTE CO.,LTD. Registration number: Y2021990000173 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for preparing lithium iron manganese phosphate by recovering cathode material of waste lithium iron phosphate battery Effective date of registration: 20211223 Granted publication date: 20160831 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING SAIDEMEI RESOURCES RECYCLING RESEARCH INSTITUTE CO.,LTD. Registration number: Y2021110000113 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20160831 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING SAIDEMEI RESOURCES RECYCLING RESEARCH INSTITUTE CO.,LTD. Registration number: Y2021110000113 |