CN107579304A - A kind of method that phosphoric acid vanadium iron lithium is prepared in the anode pole piece from waste lithium iron phosphate - Google Patents
A kind of method that phosphoric acid vanadium iron lithium is prepared in the anode pole piece from waste lithium iron phosphate Download PDFInfo
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of method that phosphoric acid vanadium iron lithium is prepared in anode pole piece from waste lithium iron phosphate.Bao includes Bu Zhou ﹕ under Yi（1）Waste lithium iron phosphate anode pole piece is crushed, sieves, respectively obtains aluminium powder A and positive pole reclaimed materials B；（2）The elementary composition in lithium source, vanadium source, source of iron and phosphorus source regulation positive pole reclaimed materials B is added, mixes, dry, obtain compound C；（3）Compound C is calcined, phosphoric acid vanadium iron lithium is made.Phosphoric acid vanadium iron lithium prepared by the inventive method can use directly as battery material.The present invention reclaims by easy technological process, has recycled waste lithium iron phosphate anode pole piece, green non-pollution.
Description
Technical field
The invention belongs to the recycling of waste lithium ion cell anode pole piece and technical field of regeneration, and in particular to one
The method that kind prepares phosphoric acid vanadium iron lithium from waste lithium iron phosphate anode pole piece.
Background technology
According to incompletely statistics, ended for the end of the year 2016, lithium-ion-power cell sale amount reaches 56.5GWh, is applied to each row
Each industry.Lithium ion battery after the use of 3 ~ 5 years, is having different degrees of scrap.According to incompletely statistics, 2015 it is waste and old
Ferric phosphate lithium cell is up to more than 20,000 tons, it is contemplated that the year two thousand twenty waste lithium iron phosphate battery will be up to more than 150,000 tons.Equally, in phosphoric acid
, can factor causes scrapping for anode pole piece because technology is immature, technique is unstable etc. in lithium iron battery manufacturing process.Such one
Come, substantial amounts of waste lithium iron phosphate battery can be produced, if handling not in time, necessarily cause the wasting of resources and environmental pollution.
Publication No. CN101847763A, CN102956936A, CN103280610A, CN106191466A Chinese invention
The method of patent application publication is handled waste lithium iron phosphate anode pole piece, is soaked, recycled by roasting, acidleach, alkali
Valuable metal.Above method uses acid, aqueous slkali dissolving phosphoric acid iron lithium anode material, and complex process, long flow path, cost are high, and
Certain pollution is produced to environment.
Publication No. CN102208706A, CN102751548A, CN104362408A reclaim to waste lithium iron phosphate positive pole
Material is heated at high temperature, and except carbon elimination, bonding agent etc., then adds lithium source, carbon source, is mixed, calcining prepares iron phosphate lithium positive pole material
Material.Above-mentioned technique has not only broken up the original structure of LiFePO4 in positive pole reclaimed materials, and complicated, long flow path, high energy consumption,
Carbonaceous gas is produced during except carbon elimination and bonding agent, adds greenhouse effects to a certain extent.
After Publication No. CN103050698A is by the way that lithium source, source of iron, vanadium source, phosphorus source are matched by certain mol ratio, add
Enter carbon source and dispersant, ball mill mixing, calcine, prepare the phosphoric acid vanadium iron lithium of rich lithium.
In view of the shortcomings of the prior art, the present invention uses waste lithium iron phosphate anode pole piece as raw material, first passes through crushing, sieve
Point, positive pole reclaimed materials is obtained, it is suitable by adding on the basis of LiFePO 4 material original structure in not destroying positive pole reclaimed materials
Lithium source, vanadium source, source of iron, the phosphorus source of amount adjust the composition of element in positive pole reclaimed materials, while to be glued present in positive pole reclaimed materials
It is reducing agent to connect agent, high-temperature roasting, prepares phosphoric acid vanadium iron lithium, can be directly used for positive electrode.Whole technological process does not destroy phosphorus
The carbon coating layer of sour iron lithium material, technique is simple, flow is short, green economy.
The content of the invention
The present invention, by crushing, sieving, obtains cathode mixture, not using waste lithium iron phosphate anode pole piece as raw material
Destroy in positive pole reclaimed materials on the basis of LiFePO 4 material original structure, using the bonding agent contained in positive pole reclaimed materials as reduction
Agent prepares phosphoric acid vanadium iron lithium, and whole process does not introduce other impurities, technique is simple, flow is short, energy consumption without using acid, aqueous slkali
It is low, economic and environment-friendly.The advantages of phosphoric acid vanadium iron lithium prepared using the method has been provided simultaneously with LiFePO4 and phosphoric acid vanadium lithium, can be direct
It is applied to as positive electrode in lithium ion battery, realizes recycling for resource.
The Ji art Fang An ﹕ of use
1）Waste lithium iron phosphate anode pole piece is crushed, sieves, respectively obtains aluminium powder A and positive pole reclaimed materials B；
2）The elementary composition in lithium source, vanadium source, source of iron and phosphorus source regulation positive pole reclaimed materials B is added, mixes, dry, mixed
Expect C；
3）Compound C is calcined, phosphoric acid vanadium iron lithium is made.
Wherein, described waste lithium iron phosphate anode pole piece derives from ferric phosphate lithium cell, the retired ferric phosphate scrapped
At least one of LiFePO4 pole piece is scrapped caused by lithium battery, manufacturing process.
Wherein, described lithium source is at least one of lithium carbonate, lithium oxalate, lithium hydroxide, lithium fluoride, lithium chloride；Institute
The vanadium source stated is at least one of vanadic anhydride, vanadic acid ammonia, vanadium trioxide, vanadium oxide, sodium vanadate；The source of iron is phosphorus
At least one of sour iron, iron chloride；Described phosphorus source is at least one of DAP, ammonium di-hydrogen phosphate, ferric phosphate.
Wherein, lithium, iron, vanadium, the mol ratio of P elements are the ﹕ 1 of 1 ﹕, 0.7 ~ 0.99 ﹕ 0.01 ~ 0.3 in described compound C.
Wherein, described sintering temperature is 500 ~ 750 DEG C, and roasting time is 0.5 ~ 20h.
The present invention is directly crushed using waste lithium iron phosphate anode pole piece, screening prepares the method effect of phosphoric acid vanadium iron lithium
Shi ﹕ do not destroy the original structure of LiFePO 4 material in positive pole reclaimed materials, using the bonding agent in positive pole reclaimed materials as reducing agent system
Standby phosphoric acid vanadium iron lithium, without using acid, aqueous slkali in whole process, do not introduce other impurities, the product of acquisition can be directly as
Positive electrode is applied in lithium ion battery, realizes recycling for resource, and whole technological process is simple, pollution-free.
Brief description of the drawings
Fig. 1 is the process chart for the method that the present invention prepares phosphoric acid vanadium iron lithium from waste lithium iron phosphate anode pole piece.
Fig. 2 is the gram volume test result for the phosphoric acid vanadium iron lithium that the present invention is prepared in different embodiments.
Embodiment
Embodiment 1
1）The ferric phosphate lithium cell scrapped is disassembled, obtains waste lithium iron phosphate anode pole piece, is crushed, screening, respectively
To aluminium powder A and positive pole reclaimed materials B；
2）Lithium carbonate, vanadic anhydride, ferric phosphate, DAP are added, adjusts the constituent content in positive pole reclaimed materials B, is mixed
It is even, dry, obtain compound C.Lithium, iron, vanadium, the mol ratio of P elements are the ﹕ 1 of 1 ﹕, 0.7 ﹕ 0.3 in compound C；
3）Compound C is carried out 500 DEG C, 20h roasting, obtains phosphoric acid vanadium iron lithium.
4）Using the phosphoric acid vanadium iron lithium of above-mentioned acquisition as positive electrode, graphite is that negative material makes 18650 resultant batteries simultaneously
Electric performance test is carried out, gram volume test result is as shown in embodiment 1 in Fig. 2.
Embodiment 2
1）Retired ferric phosphate lithium cell is disassembled, obtains waste lithium iron phosphate anode pole piece, is crushed, screening, respectively
To aluminium powder A and positive pole reclaimed materials B；
2）Lithium oxalate, vanadic acid ammonia, iron chloride, ammonium di-hydrogen phosphate are added, adjusts the constituent content in positive pole reclaimed materials B, mixes, is dry
It is dry, obtain compound C.Lithium, iron, vanadium, the mol ratio of P elements are the ﹕ 1 of 1 ﹕, 0.99 ﹕ 0.01 in compound C；
3）Compound C is carried out 750 DEG C, 0.5h roasting, obtains phosphoric acid vanadium iron lithium.
4）Using the phosphoric acid vanadium iron lithium of above-mentioned acquisition as positive electrode, graphite is that negative material makes 18650 resultant batteries simultaneously
Electric performance test is carried out, gram volume test result is as shown in embodiment 2 in Fig. 2.
Embodiment 3
1）LiFePO4 pole piece is scrapped by caused in manufacturing process, crushes, screening, respectively obtains aluminium powder A and positive pole reclaimed materials
B；
2）Lithium hydroxide, vanadium trioxide, iron chloride, ferric phosphate are added, adjusts the constituent content in positive pole reclaimed materials B, mix,
Dry, obtain compound C.Lithium, iron, vanadium, the mol ratio of P elements are the ﹕ 1 of 1 ﹕, 0.8 ﹕ 0.2 in compound C；
3）Compound C is carried out 650 DEG C, 10h roasting, obtains phosphoric acid vanadium iron lithium.
4）Using the phosphoric acid vanadium iron lithium of above-mentioned acquisition as positive electrode, graphite is that negative material makes 18650 resultant batteries simultaneously
Electric performance test is carried out, gram volume test result is as shown in embodiment 3 in Fig. 2.
Embodiment 4
1）LiFePO4 pole piece is scrapped by caused in manufacturing process, crushes, screening, respectively obtains aluminium powder A and positive pole reclaimed materials
B；
2）Lithium fluoride, sodium vanadate, ferric phosphate are added, adjusts the constituent content in positive pole reclaimed materials B, mixes, dry, mixed
Expect C.Lithium, iron, vanadium, the mol ratio of P elements are the ﹕ 1 of 1 ﹕, 0.9 ﹕ 0.1 in compound C；
3）Compound C is carried out 550 DEG C, 15h roasting, obtains phosphoric acid vanadium iron lithium.
4）Using the phosphoric acid vanadium iron lithium of above-mentioned acquisition as positive electrode, graphite is that negative material makes 18650 resultant batteries simultaneously
Electric performance test is carried out, gram volume test result is as shown in embodiment 4 in Fig. 2.
Embodiment 5
1）LiFePO4 pole piece is scrapped by caused in manufacturing process, crushes, screening, respectively obtains aluminium powder A and positive pole reclaimed materials
B；
2）Lithium fluoride, sodium vanadate, ferric phosphate are added, adjusts the constituent content in positive pole reclaimed materials B, mixes, dry, mixed
Expect C.Lithium, iron, vanadium, the mol ratio of P elements are the ﹕ 1 of 1 ﹕, 0.9 ﹕ 0.1 in compound C；
3）Compound C is carried out 550 DEG C, 15h roasting, obtains phosphoric acid vanadium iron lithium.
4）Using the phosphoric acid vanadium iron lithium of above-mentioned acquisition as positive electrode, graphite is that negative material makes 18650 resultant batteries simultaneously
Electric performance test is carried out, gram volume test result is as shown in embodiment 4 in Fig. 2.
Claims (5)
1. preparing the method for phosphoric acid vanadium iron lithium in a kind of anode pole piece from waste lithium iron phosphate, this method step for example descends ﹕
1）Waste lithium iron phosphate anode pole piece is crushed, sieves, respectively obtains aluminium powder A and positive pole reclaimed materials B；
2）The elementary composition in lithium source, vanadium source, source of iron and phosphorus source regulation positive pole reclaimed materials B is added, mixes, dry, mixed
Expect C；
3）Compound C is calcined, phosphoric acid vanadium iron lithium is made.
2. prepare the method for phosphoric acid vanadium iron lithium its feature in the anode pole piece according to claim 1 from waste lithium iron phosphate to exist
Yu ﹕ steps 1）Described in waste lithium iron phosphate anode pole piece derive from ferric phosphate lithium cell, the retired LiFePO4 scrapped
At least one of LiFePO4 pole piece is scrapped caused by battery, manufacturing process.
3. prepare the method for phosphoric acid vanadium iron lithium its feature in the anode pole piece according to claim 1 from waste lithium iron phosphate to exist
Yu ﹕ steps 2）Described in lithium source be lithium carbonate, lithium oxalate, lithium hydroxide, lithium fluoride, at least one of lithium chloride；It is described
Vanadium source be vanadic anhydride, vanadic acid ammonia, vanadium trioxide, vanadium oxide, at least one of sodium vanadate；The source of iron is anhydrous
At least one of ferric phosphate, phosphate dihydrate iron, iron chloride；Described phosphorus source is DAP, ammonium di-hydrogen phosphate, ferric phosphate
At least one of.
4. prepare the method for phosphoric acid vanadium iron lithium its feature in the anode pole piece according to claim 1 from waste lithium iron phosphate to exist
Yu ﹕ steps 2）Described in compound C in lithium, iron, vanadium, the mol ratio of P elements be the ﹕ 1 of 1 ﹕, 0.7 ~ 0.99 ﹕ 0.01 ~ 0.3.
5. prepare the method for phosphoric acid vanadium iron lithium its feature in the anode pole piece according to claim 1 from waste lithium iron phosphate to exist
Yu ﹕ steps 3）Described in sintering temperature be 500 ~ 750 DEG C, roasting time is 0.5 ~ 20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108400399A (en) * | 2018-02-02 | 2018-08-14 | 昆明理工大学 | A kind of method that waste lithium manganese oxide battery prepares lithium manganese phosphate/carbon positive electrode |
| CN110828887A (en) * | 2019-11-15 | 2020-02-21 | 武汉瑞杰特材料有限责任公司 | Method for recycling waste lithium iron phosphate positive electrode material and obtained lithium iron phosphate positive electrode material |
| CN114024055A (en) * | 2021-11-05 | 2022-02-08 | 江西省科学院应用化学研究所 | Short-process recovery method for waste lithium iron phosphate battery material |
| CN115140722A (en) * | 2022-06-10 | 2022-10-04 | 广东邦普循环科技有限公司 | Method for preparing anode material by using waste vanadyl phosphate lithium battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447096A (en) * | 2010-10-08 | 2012-05-09 | 中国科学院理化技术研究所 | Lithium iron vanadium phosphate solid solution as lithium ion battery anode material and preparation method and application thereof |
| CN103050698A (en) * | 2013-01-15 | 2013-04-17 | 四川大学 | Vanadium lithium iron phosphate anode material and preparation method thereof |
| 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 |
| CN106976852A (en) * | 2017-04-26 | 2017-07-25 | 长沙理工大学 | The green reparative regeneration technology of LiFePO 4 material in a kind of old and useless battery |
-
2017
- 2017-09-06 CN CN201710796060.2A patent/CN107579304A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447096A (en) * | 2010-10-08 | 2012-05-09 | 中国科学院理化技术研究所 | Lithium iron vanadium phosphate solid solution as lithium ion battery anode material and preparation method and application thereof |
| CN103050698A (en) * | 2013-01-15 | 2013-04-17 | 四川大学 | Vanadium lithium iron phosphate anode material and preparation method thereof |
| 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 |
| CN106976852A (en) * | 2017-04-26 | 2017-07-25 | 长沙理工大学 | The green reparative regeneration technology of LiFePO 4 material in a kind of old and useless battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108400399A (en) * | 2018-02-02 | 2018-08-14 | 昆明理工大学 | A kind of method that waste lithium manganese oxide battery prepares lithium manganese phosphate/carbon positive electrode |
| CN108400399B (en) * | 2018-02-02 | 2020-07-07 | 昆明理工大学 | Method for preparing lithium manganese phosphate/carbon cathode material from waste lithium manganate battery |
| CN110828887A (en) * | 2019-11-15 | 2020-02-21 | 武汉瑞杰特材料有限责任公司 | Method for recycling waste lithium iron phosphate positive electrode material and obtained lithium iron phosphate positive electrode material |
| CN114024055A (en) * | 2021-11-05 | 2022-02-08 | 江西省科学院应用化学研究所 | Short-process recovery method for waste lithium iron phosphate battery material |
| CN115140722A (en) * | 2022-06-10 | 2022-10-04 | 广东邦普循环科技有限公司 | Method for preparing anode material by using waste vanadyl phosphate lithium battery |
| WO2023236595A1 (en) * | 2022-06-10 | 2023-12-14 | 广东邦普循环科技有限公司 | Method for preparing positive electrode material from waste livopo4 battery |
| CN115140722B (en) * | 2022-06-10 | 2024-02-09 | 广东邦普循环科技有限公司 | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery |
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Application publication date: 20180112 |