CN102694217B - A kind of method for recycling anode material of lithium ion battery - Google Patents
A kind of method for recycling anode material of lithium ion battery Download PDFInfo
- Publication number
- CN102694217B CN102694217B CN201110067952.1A CN201110067952A CN102694217B CN 102694217 B CN102694217 B CN 102694217B CN 201110067952 A CN201110067952 A CN 201110067952A CN 102694217 B CN102694217 B CN 102694217B
- Authority
- CN
- China
- Prior art keywords
- powder
- lithium ion
- ion battery
- anode material
- gas
- 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.)
- Active
Links
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
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to battery material field, more specifically a kind of method from battery material leftover pieces, slurry recovery positive active material is related to, it comprises the following steps: positive plate to be recycled or dry anode sizing agent are loaded pulverizer, be sieved into powder, powder put into fluid bed and remove conductive carbon and binding agent impurity; In fluid bed top gas through the powder of cyclone separator except deentrainment, then through fixed bed removing pernicious gas, eventually pass after heating and be passed into fluidized bed circulation utilization; After the powder cooling of bottom, sieve and obtain qualified positive pole powder.Present invention process flow process is short, and during heat treatment, powder is in fluidized state in fluid bed, and gas compares completely with the abundant haptoreaction of powder, thus it is high fundamentally to solve product impurity content in traditional handicraft, the problem that the rate of recovery is low.And reclaim while achieving cobalt and elemental lithium, and the active material rate of recovery is up to 94%, active material and chemical property thereof is not had side effects simultaneously.
Description
Technical field
The invention belongs to battery material field, more specifically relate to a kind of method from battery material leftover pieces, slurry recovery positive active material.
Background technology
Lithium ion battery is since commercialization, and because its energy density is high, operating voltage is high, memory-less effect, has extended cycle life and is widely used as the power supply of various mobile device.
The structure of lithium ion battery is made up of the major part such as positive pole and negative pole, positive pole is generally positive active material, acetylene black, binding agent Homogeneous phase mixing are coated in aluminum foil current collector, and common positive electrode active materials to mainly contain cobalt acid lithium, lithium nickel cobalt aluminium (NCA), lithium-nickel-manganese-cobalt (NCM), lithium manganese spinel (LMO) and iron lithium phosphate (LFP) etc. several.In lithium-ion battery system, the cost of positive electrode accounts for 30 ~ 40% of battery total cost.
In the prior art, when preparing the battery core of lithium ion battery, generally positive active material is first made slurry, then coat on positive pole and fluid and prepare positive plate, the slurry and pole piece scrapped all inevitably is produced in each operation prepared by battery battery core, although the positive electrode that different operation is scrapped is different according to its technological level, but learies roughly fluctuates between 2 ~ 15%, and, cobalt in Postive electrode material of li-ion accumulator is heavy metal element, to bad environmental, should be recycled.Therefore a kind of desirable method for recycling anode material of lithium ion battery of necessary exploitation.
At present, study the recovery of more mainly waste PAN yarn, the more traditional technological process taked, dissolve by cobalt acid lithium, purification, then extracts cobalt salt or metallic cobalt by extraction, chemical precipitation method, electrolysis etc. from solution.Traditional technique, long flow path, complexity, to equipment anticorrosion require high, severe operational environment, running cost is high.In addition, people's research floatations such as Jin Yongxun, matsuda are bright reclaim lithium and cobalt oxides from waste PAN yarn, but its lithium and cobalt oxides reclaimed is also containing impurity such as graphite, can not be used for making lithium-ions battery.
Disclose a kind of method that high-temperature process reclaims positive electrode in CN101707269, but the pole piece in recovery process after high-temperature process needs shedding process, and in processing procedure, gas-particle two-phase contact is abundant not, impurity treatment is incomplete.Do not deal carefully with the tail gas reclaiming generation under high temperature, heat utilization efficiency is not high, does not meet the needs of continuous prodution requirement yet.Therefore, a kind of operation of necessary exploitation is simple, production efficiency is high, capacity usage ratio is high, continuous prodution and removal process can not produce the positive electrode recovery process of other pollutants.
Summary of the invention
The present invention aims to provide a kind of method that technique is simple, environmental friendliness, economic benefits significantly reclaim positive electrode from lithium ion battery leftover pieces and slurry.
In order to reach above-mentioned requirements, the present invention adopts following technical scheme:
Step one, positive plate to be recycled or dry anode sizing agent are loaded pulverizer, in pulverizer, be ground into the powder that particle diameter is less than 5mm, then sieve powder with screening machine;
Step 2, puts into fluid bed by the powder sieved, and passes into the gas of 330 ~ 750 DEG C, and adjusting gas flow makes powder be in fluidisation state in the reactor, fully conductive carbon and binding agent impurity in reaction removing powder;
Step 3, fluid bed top gas through the powder of cyclone separator except deentrainment, then through fixed bed, eventually pass after heating and are passed into fluidized bed circulation utilization;
After the cooling of step 4, bottom powder, more namely obtain qualified positive pole powder after sieving with screening machine.
In patent of the present invention, positive plate to be recycled is uniformly coated on by positive electrode active materials on 10 ~ 20 μm of thick collectors, and main component sees the following form:
Table 1 positive electrode component list
| Component | Active material | Conductive carbon | Binding agent |
| Mass fraction (%) | 90～98 | 1～5 | 1～5 |
One as method for recycling anode material of lithium ion battery of the present invention is improved, the present invention adopts the positive pole leftover pieces and non-compliant positive plate that produce in lithium ion manufacturer battery manufacturing process, or the anode sizing agent not meeting production requirement produced in stirring painting process is raw material.
Operation principle of the present invention:
Described fluidized-bed reactor height 2000mm, internal diameter 100mm, has powder discharging opening in fluid bed bottom, bottom has gas feed, have powder inlet on the top of fluidized-bed reactor main body, top has gas vent, is provided with gas distribution grid at fluidized-bed bottom.
Gas is heated to 330 ~ 750 DEG C from fluidized-bed bottom gas feed through heater and is passed into fluid bed after gas distribution grid, the powder sieved adds from the upper feed inlet of fluidized-bed reactor main body, now adjustments of gas inlet flow rate, ensure that powder is in fluidized state in fluid bed on the one hand, on the other hand, ensure that the powder in reactor is not entrained with fluid bed by gas.Powder after process is discharged from fluid bed bottom, top gas is after cyclone separator is except the powder of deentrainment, after being passed into the fixed bed removing pernicious gas being mounted with alkaline powder, fluid bed is passed into again after heater heating, the waste heat of gas recovery, greatly increases energy utilization rate to greatest extent.
Compared with prior art, the present invention has following useful achievement:
Present invention process flow process is short, and powder is in fluidized state in bed body, and gas-particle two-phase fully contacts, thus it is high fundamentally to solve product magazine content in traditional handicraft, the problem that the rate of recovery is low.And reclaim while achieving cobalt and elemental lithium, and the active material rate of recovery is up to 94%, active material and chemical property thereof is not had side effects simultaneously.To the heat recycling in tail gas in the present invention, substantially increase energy utilization rate, the pernicious gas that simultaneous reactions produces is dealt carefully with, and fundamentally eliminates the destruction to environment.Present device life cycle is long, and heat utilization efficiency is high, and technics comparing easily amplifies.
After having carried out described step one, separating twice carried out to the positive mix of failing to sieve and has sieved, having reclaimed qualified positive mix further, having improved organic efficiency.
The sifted mesh number of described step one is 10 ~ 200 orders, and sieve number is less than 10 orders and easily brings aluminium bits impurity into, and the powder being greater than 200 order parts to be recycled can not sieve, and treatment effeciency is lower.
The grit number excessively of the screening machine in step 4 is 100 ~ 300 orders, can select suitable screen cloth according to the domain size distribution of active material.
Prove through test of many times, in step 2, the temperature of fluid bed controls to be 330 ~ 750 DEG C, and the time of staying of powder controls at 20min ~ 240min, can obtain pure active substances in cathode materials.Carry out full carbon analysis to sample, the phosphorus content in powder is 1% consistent with normal active material carbon content.
The gas passed in described step 2 is air or some other oxygen rich gas, and oxygen-enriched environment is conducive to the decomposition of bonding agent and the removal of conductive carbon.
In the fixed bed of described step 3, alkaline powder is housed, can in and the acidic materials such as hydrogen fluoride, eliminate the impact on environment.
Described alkaline powder is any one in calcium oxide, magnesium oxide or NaOH.
Accompanying drawing explanation
Fig. 1 is method for recycling anode material of lithium ion battery flow chart of the present invention
Fig. 2 is the Call Provision acid lithium of the embodiment of the present invention 1 acquisition and 1000 times of microscopic comparison of raw material cobalt acid lithium
Fig. 3 is the cycle graph that the positive electrode of the inventive method acquisition discharges with 0.7C charging and 0.5C at 23 DEG C.
Fig. 4 is the cycle graph that the positive electrode of the inventive method acquisition discharges with 0.7C charging and 0.5C at 45 DEG C.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, content of the present invention is further illustrated, but protection scope of the present invention is also not only confined to the content described by case study on implementation.
Embodiment 1
Get 30kg dry finish to be recycled and load pulverizer, drop into pulverizer in batches, pulverize after 10 ~ 60 minutes, be ground into the particle being less than 5mm.Use 10 orders to 200 order bolting powders again.Do not pulverized further by the material of 200 eye mesh screens and sieved discharging, the not filtrable chip of last small part can be cast out.Weigh 28.5kg, added by powder from charge door, and gas is heated to 600 DEG C through heater, passes into reactor from fluidized-bed bottom, and adjustments of gas inlet flow rate is 8.5m
3/ h ~ 40m
3/ h, powder mean residence time is 60min.Gas is separated after the powder carried secretly through cyclone separator, enters the fixed bed that CaO particle is housed, and then utilizes through heating Posterior circle through gas.4) after the cooling of bottom powder, then use 100 orders to 300 mesh sieve extension sets, after sieving, namely obtain qualified positive pole powder.Weigh 26.9kg.
Embodiment 2
Get 30kg positive plate to be recycled and load pulverizer, drop into batch mixer in batches, and add appropriate zirconium glass pearl, carry out shedding.Again by pole piece powder 10 orders handled well to 200 order bolting powders.Do not pulverized further by the material of 200 eye mesh screens and sieved discharging, the not filtrable chip of last small part can be cast out.Weigh 22.7kg, added by powder from charge door, added by powder from charge door, and gas is heated to 600 DEG C through heater, and adjustments of gas inlet flow rate is 8.5m
3/ h ~ 40m
3/ h, powder mean residence time is 60min.Gas, after cyclone separator separated powder, enters the fixed bed that CaO particle is housed, and then utilizes through heating Posterior circle through gas.4) after the cooling of bottom powder, then use 100 orders to 300 mesh sieve extension sets, namely obtain qualified positive pole powder after sieving, weigh 21.4kg.
Embodiment 3
Difference from Example 1 is: gas-heated temperature is 750 DEG C.Other is identical with embodiment 1, repeats no more here.
Embodiment 4
Difference from Example 1 is: gas-heated temperature is 330 DEG C.Other is identical with embodiment 1, repeats no more here.
Embodiment 5
Difference from Example 1 is: what load in fixed bed is NaOH.Other is identical with embodiment 1, repeats no more here.
In order to the performance of the organic efficiency and gained powder that detect method for recycling anode material of lithium ion battery of the present invention, the powder material weighing that obtains is reclaimed to embodiment 1 ~ 5 and button cell test obtains table 2, table 3, and sem test is carried out to recovery powder obtain Fig. 2.
The organic efficiency of table 2 embodiment
The button cell result of table 3 embodiment
As seen from Table 2, lithium ion battery organic efficiency of the present invention, more than 92%, can meet the requirement of production.It is close with material property that table 3 shows the cobalt acid lithium reclaimed.
Embodiment 1 and embodiment 2 reclaimed materials and raw material are designed respectively and helps battery and assess, the full battery of high spot reviews is at normal temperature, cycle performance at 45 DEG C, obtain the cycle performance figure of Fig. 3 and Fig. 4, visible salvage material performance compared with raw material is close, can come into operation together with raw material or separately.
It should be noted that, according to the above description the announcement of book and elaboration, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should in the protection range of claim of the present invention to equivalent modifications more of the present invention and change.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (6)
1. method for recycling anode material of lithium ion battery, is characterized in that: comprise the following steps:
Step one, loads pulverizer by positive plate to be recycled or dry anode sizing agent, is ground into the powder that particle diameter is less than 5mm, then sieves powder with screening machine in pulverizer;
Step 2, puts into fluid bed by the powder sieved, and passes into air or the oxygen rich gas of 330 ~ 750 DEG C, and regulates air or oxygen rich gas flow to make powder be in fluidisation state in the reactor, fully conductive carbon and binding agent impurity in reaction removing powder;
Step 3, fluid bed top gas through the powder of cyclone separator except deentrainment, then through the pernicious gas that the removing of overcuring bed reacts with the alkaline powder on solidification bed, eventually passes after heating and is passed into fluidized bed circulation utilization;
Namely step 4, after the cooling of bottom powder, then obtain qualified positive pole powder after sieving with screening machine.
2. method for recycling anode material of lithium ion battery according to claim 1, is characterized in that: the sieve number of the screening machine in described step one is 10 ~ 200 orders.
3. method for recycling anode material of lithium ion battery according to claim 1, is characterized in that: the sieve number of the screening machine in described step 4 is 100 ~ 300 orders.
4. method for recycling anode material of lithium ion battery according to claim 1, is characterized in that: in described step 2, the temperature of fluid bed is 330 ~ 750 DEG C, the time of staying 20min ~ 240min of powder.
5. method for recycling anode material of lithium ion battery according to claim 1, is characterized in that: described alkaline powder is calcium oxide, magnesium oxide or NaOH.
6. method for recycling anode material of lithium ion battery according to claim 1, is characterized in that: after having carried out described step one, carried out separating twice and sieve to the positive mix of failing to sieve, and reclaims qualified positive mix further.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110067952.1A CN102694217B (en) | 2011-03-22 | 2011-03-22 | A kind of method for recycling anode material of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110067952.1A CN102694217B (en) | 2011-03-22 | 2011-03-22 | A kind of method for recycling anode material of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102694217A CN102694217A (en) | 2012-09-26 |
| CN102694217B true CN102694217B (en) | 2016-01-20 |
Family
ID=46859544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110067952.1A Active CN102694217B (en) | 2011-03-22 | 2011-03-22 | A kind of method for recycling anode material of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102694217B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106207267B (en) * | 2016-08-12 | 2018-07-17 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion cell positive discards slurry recovery system and recovery method |
| CN106099236B (en) * | 2016-08-23 | 2019-09-24 | 中国科学院宁波材料技术与工程研究所 | A kind of recovery method of anode material for lithium-ion batteries |
| CN107069134A (en) * | 2017-03-24 | 2017-08-18 | 孙志廷 | A kind of method that waste lithium cell positive electrode is separated with collector |
| CN107069078B (en) * | 2017-03-24 | 2019-12-27 | 中航锂电（洛阳）有限公司 | Method for recovering lithium ion battery electrode plate material |
| CN108110356B (en) * | 2017-12-08 | 2024-02-06 | 天齐锂业股份有限公司 | Full-automatic waste lithium ion battery recycling process and system |
| KR20210117575A (en) * | 2020-03-19 | 2021-09-29 | 에스케이이노베이션 주식회사 | Classifier for cathode active material and method of regenerating lithium precursor used the same |
| CN114560513A (en) * | 2022-03-02 | 2022-05-31 | 湖北亿纬动力有限公司 | Method for recovering anode material by lithium supplement |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707269A (en) * | 2009-10-14 | 2010-05-12 | 东莞新能源科技有限公司 | Method for recycling anode material of lithium ion battery |
| CN101898196A (en) * | 2010-07-23 | 2010-12-01 | 中国科学院广州能源研究所 | Method and device for recycling electronic waste with complex components |
-
2011
- 2011-03-22 CN CN201110067952.1A patent/CN102694217B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707269A (en) * | 2009-10-14 | 2010-05-12 | 东莞新能源科技有限公司 | Method for recycling anode material of lithium ion battery |
| CN101898196A (en) * | 2010-07-23 | 2010-12-01 | 中国科学院广州能源研究所 | Method and device for recycling electronic waste with complex components |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102694217A (en) | 2012-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102694217B (en) | A kind of method for recycling anode material of lithium ion battery | |
| CN101383442B (en) | Method for recovering and preparing lithium cobaltate from waste lithium ionic cell | |
| CN102517448B (en) | Method for recycling metal ion from waste lithium-ion battery | |
| CN106169582B (en) | A kind of natural needle coke composite graphite negative electrode material production method | |
| CN102593434A (en) | Composite graphite particles for lithium secondary battery and preparation method thereof | |
| 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 | |
| CN110828887A (en) | Method for recycling waste lithium iron phosphate positive electrode material and obtained lithium iron phosphate positive electrode material | |
| CN105489893A (en) | Graphite anode material for lithium-ion battery and preparation method of graphite anode material | |
| CN102299330A (en) | Active carbon-nano silicon composite powder, synthetic method thereof and lithium ion battery prepared therefrom | |
| CN101707269A (en) | Method for recycling anode material of lithium ion battery | |
| CN103184340A (en) | Method for recovering lead plaster of negative pole of disused lead acid storage battery and application of recovered lead plaster | |
| CN109167028A (en) | A kind of regenerative preparation of lithium iron phosphate/carbon composite material | |
| CN102332623B (en) | Method for recovering anode material of lithium ion battery | |
| CN111252757A (en) | Method for preparing graphene by using waste lithium ion power battery | |
| CN111600091A (en) | Method for recycling graphite of negative electrode of lithium ion battery | |
| CN105244561A (en) | Method for preparing high-voltage multi-component material by taking waste multi-component power lithium battery as a raw material | |
| CN103184341A (en) | Method for recovering disused lead plaster to prepare superfine lead powder and application of superfine lead powder | |
| CN114006071A (en) | Method for stripping and recovering anode plate powder of waste lithium battery | |
| CN114243142A (en) | Method for fully recovering valuable components in waste lithium batteries | |
| CN110112459A (en) | A kind of preparation method of new sulfide compounds solid electrolyte and novel all solid state lithium-sulfur cell | |
| Zheng et al. | Upcycling of Cathode Materials from Spent Lithium-Ion Batteries: Progress, Challenges, and Outlook | |
| CN102556998B (en) | Preparation method of lithium iron phosphate material | |
| CN216311884U (en) | Broken recovery system of lithium cell positive plate of not annotating liquid | |
| CN110364722B (en) | Carbon-silicon double-shell hollow structure composite microsphere and preparation method and application thereof | |
| CN113086960A (en) | Preparation method of lithium titanium phosphate cathode material |
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 |