CN106169624B - A kind of lithium ion battery ternary material recovery method - Google Patents
A kind of lithium ion battery ternary material recovery method Download PDFInfo
- Publication number
- CN106169624B CN106169624B CN201610601695.8A CN201610601695A CN106169624B CN 106169624 B CN106169624 B CN 106169624B CN 201610601695 A CN201610601695 A CN 201610601695A CN 106169624 B CN106169624 B CN 106169624B
- Authority
- CN
- China
- Prior art keywords
- filtrate
- lithium ion
- ion battery
- ternary material
- filter residue
- 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.)
- Expired - Fee Related
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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium ion battery ternary material recovery methods, include the following steps：Lithium ion battery is disassembled to obtain anode pole piece；Ball milling and sieving are carried out, ternary material mixture is obtained；Acid liquid reaction is added in the mixture, obtains the first filtrate and the first filter residue；The pH value of the first filtrate is adjusted, is heated, oxidant is added, obtains the second filtrate and the second filter residue；Second filter residue is sintered after being mixed with carbon source, obtains MnOx/ C composite；Second filtrate is heated, pH value is adjusted to 4~8, ammonium oxalate is added, obtains third filtrate and third filter residue；Third filter residue is sintered, NiO/Co is obtained3O4Mixing material；Third filtrate is heated, pH value is adjusted to 9~12, Na is added2CO3Solution reaction obtains Li2CO3Material.The present invention has step simple, consumes energy in removal process few, obtained product is used directly in lithium ion battery；And the advantages of it is not necessary that other metallic compounds are added, reduce the wasting of resources.
Description
Technical field
The invention belongs to the recovery methods of waste lithium cell, more particularly, to a kind of lithium ion battery ternary material recycling side
Method.
Background technology
Serondary lithium battery is increasingly extensive because of the characteristic of its brilliance to be applied in 3C numbers, electric tool, electric bicycle
And the fields such as electric vehicle.Increasingly increase with the consumer group to such product consumption demand, the production of lithium ion battery
Amount and the quantity of waste and old lithium ion battery are also being continuously increased, it is contemplated that arrive the year two thousand twenty, the number of whole world waste and old lithium ion battery
Amount can be more than 25,000,000,000.In waste and old lithium ion battery, the proportional amount of various metals is very high, for example, Co content be 5~
30%, Li is 2~12%, Fe is 0~25%, Ni is 0~10%, Cu is 7~17% and Al is 3~10%.These metals
Content it is very high, it is many even to have been over its content in ore, therefore there is very high recovery value.
In anode material for lithium-ion batteries, ternary LiNixMnyCo1-x-yO2Material because its more excellent performance gradually at
For the active material of field of lithium ion battery, and it is used widely.In the recycling for ternary material, current approach master
Will there are two types of：(1) ternary material is leached, gradually recycling detaches metal later, such as 201510967179.2 He of patent
201110243034.X, such method recycling step is relatively complicated, and energy consumption is big, since finally obtained metallic compound can be again
For in battery production, therefore lead to energy waste；And Product recycling process is in great demand to other materials.(2) ternary
After material leaches, Ni, Mn, Co ion are additionally added in the solution to adjust the metal ratio in leachate, complexing is added later
Agent retrieves ternary precursor, then with Li2CO3Commercial ternary material is obtained after ball milling sintering, such as patent 201310104022.8
With 201610095291.6, such method still needs to increase other metal-containing compounds, and own material cannot be made full use of excellent
Gesture.
In consideration of it, the present invention proposes a kind of ternary cathode material of lithium ion battery recovery method, existing skill can be solved
The drawbacks of cardia method encounters.
Invention content
The purpose of the present invention is to provide a kind of lithium ion battery ternary material recovery methods, in capable of solving the above problems
It is at least one.
According to an aspect of the invention, there is provided a kind of lithium ion battery ternary material recovery method, including walk as follows
Suddenly：
A, lithium ion battery is disassembled to obtain anode pole piece；
B, ball milling and sieving are carried out to anode pole piece, obtains the mixture and aluminium of ternary material, bonding agent and conductive agent
Foil；
C, it is added in inorganic acid or organic acid and reacts in said mixture, obtain the first filtrate and the first filter residue；
D, then the pH value of the first filtrate obtained in regulating step c heats the first filtrate, and be added to 1~3
Oxidant is reacted, and the second filtrate and the second filter residue are obtained；
E, it is sintered after mixing the second filter residue obtained in step d with carbon source, obtains MnOx/ C composite；
F, the second filtrate obtained in step d is heated, and pH value is adjusted to 4~8, ammonium oxalate is then added and carries out
Reaction, obtains third filtrate and third filter residue；
G, third filter residue is sintered in an inert atmosphere, obtains NiO/Co3O4Mixing material；
H, third filtrate is heated, and pH value is adjusted to 9~12, and Na is added2CO3Solution reaction obtains Li2CO3Material.
The beneficial effects of the invention are as follows：By above-mentioned steps it is not necessary that other metallic compounds, entire removal process letter is added
Single, energy consumption is small, and reaction product is fully used, and saves resource.
In some embodiments, the anode pole piece obtained in step a is sintered at 150~300 DEG C, removal bonding
Agent.Thus, it is possible to which the bonding agent that anode pole piece is deleted is enable to fall off.
In some embodiments, the inorganic acid in step c or organic acid are wherein one in sulfuric acid, hydrochloric acid and nitric acid
Kind, organic acid is the one of which in malic acid and citric acid.
In some embodiments, the reaction temperature of mixture and acid is 50~90 DEG C in step c, and the time is 1~6 small
When.
In some embodiments, the heating temperature in step d is 60~90 DEG C, and oxidant is potassium permanganate or peroxidating
The reaction time of hydrogen, the first filtrate and oxidant is 1~6 hour.
In some embodiments, the carbon source in step e is glucose, ascorbic acid, gelatin or polyvinyl alcohol.
In some embodiments, in step e the second filter residue and carbon source at a temperature of inert atmosphere and 500~900 DEG C into
Row sintering, sintering time are 3~6 hours.
In some embodiments, the heating temperature in step f is 50~90 DEG C, and the second filtrate is with ammonium oxalate when reacting
Between be 1~6 hour.
In some embodiments, sintering temperature is 500~900 DEG C in step g, and sintering time is 3~6 hours.
In some embodiments, the heating temperature of third filtrate is 50~90 DEG C in step h, with Na2CO3Solution reaction
Time is 1~6 hour.
Specific implementation mode
The present invention is described in further detail below.
Embodiment 1
A kind of lithium ion battery ternary material recovery method, includes the following steps：
A, lithium ion battery is disassembled to obtain anode pole piece, anode pole piece is sintered at 200 DEG C, in high temperature action
Bonding agent on lower removal anode pole piece simplifies subsequent step to reduce bringing into for impurity on anode pole piece.
B, ball milling and sieving are carried out to anode pole piece, obtains the mixture and aluminium of ternary material, bonding agent and conductive agent
Foil；Obtained aluminium foil can be recycled, and reduce the wasting of resources.
C, it is added in inorganic acid or organic acid and reacts in said mixture, obtain the first filtrate and the first filter residue；Wherein,
Acid is the one of which in sulfuric acid, hydrochloric acid, nitric acid, malic acid and citric acid, you can inorganic acid sulfuric acid, hydrochloric acid or nitric acid are selected,
Also organic acid malic acid or citric acid can be selected.After acid is added in the mixture, reaction temperature is 60 DEG C, and the time is 5 hours；Instead
It should be filtered after the completion, obtain the first filtrate and the first filter residue, wherein the first filter residue is mainly bonding agent and conductive agent, is incited somebody to action
First filter residue removes, and leaves and takes the first filtrate.
D, then the pH value of the first filtrate obtained in regulating step c heats the first filtrate, heating temperature to 2
It is 60 DEG C, and oxidant is added and is reacted, obtains the second filtrate and the second filter residue；Wherein, oxidant is potassium permanganate or mistake
The reaction time of hydrogen oxide, the first filtrate and oxidant is 6 hours, is precipitated after the completion of reaction, and filter.The step obtains
The second filter residue be mainly MnO2, the second filtrate gives over to follow-up use.
E, it is sintered after mixing the second filter residue obtained in step d with carbon source, obtains MnOx/ C composite；Wherein, carbon
Source is glucose, ascorbic acid, gelatin or polyvinyl alcohol, and carbon source and the second filter residue are 1 by weight:1~3:1 is allocated
Reaction.Second filter residue is sintered with carbon source at a temperature of inert atmosphere nitrogen environment and 700 DEG C, and sintering time is 4 hours, is obtained
To MnOx/ C composite, the MnO that will be obtainedx/ C composite avoids material directly as the negative material of lithium ion battery
Waste, resource is fully used.
F, the second filtrate obtained in step d is heated, heating temperature is 80 DEG C, and the pH value of the second filtrate is led to
It crossing NaOH and is adjusted to 6, ammonium oxalate is then added and is reacted, the reaction time is 2 hours, obtains third filtrate and third filter residue, the
Three filter residues are the mixtures of nickel oxalate and cobalt oxalate；
G, third filter residue is sintered in inert atmosphere nitrogen, sintering temperature is 700 DEG C, and sintering time is 4 hours, is obtained
NiO/Co3O4Mixing material；Obtained NiO/Co3O4Mixing material is used as lithium ion battery negative material, and product is fully sharp
With saving resource.
H, third filtrate is heated, heating temperature is 90 DEG C, and pH value is adjusted to 11 by NaOH, and Na is added2CO3It is molten
Liquid reacts, and the reaction time is 1 hour, obtains Li2CO3Then material is collected, and filtration drying.
A kind of lithium ion battery ternary material recovery method step of the present invention is simple, and processing is convenient, in removal process
Energy consumption is few, and obtained product is used directly in lithium ion battery, saves resource；And it is not necessary that other metal compounds are added
Object reduces the wasting of resources.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, difference lies in：
The anode pole piece obtained in step a is sintered at 150 DEG C；The reaction temperature of mixture and acid is in step c
50 DEG C, the time is 6 hours；For the pH value of the first filtrate obtained in regulating step c in step d to 1, heating temperature is 80 DEG C, the
The reaction time of one filtrate and oxidant is 4 hours；The second filter residue and carbon source are at a temperature of inert atmosphere and 500 DEG C in step e
It is sintered, sintering time is 6 hours；Heating temperature in step f is 50 DEG C, and the reaction time of the second filtrate and ammonium oxalate is
6 hours, the pH value of the second filtrate was adjusted to 4 by NaOH；Sintering temperature is 500 DEG C in step g, and sintering time is 6 hours；Step
The heating temperature of third filtrate is 50 DEG C in h, with Na2CO3The solution reaction time is 6 hours, and third filtrate is by NaOH by pH value
It is adjusted to 9.Method in the embodiment can achieve the effect that same as Example 1.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, difference lies in：
The anode pole piece obtained in step a is sintered at 300 DEG C；The reaction temperature of mixture and acid is in step c
90 DEG C, the time is 1 hour；For the pH value of the first filtrate obtained in regulating step c in step d to 3, heating temperature is 90 DEG C, the
The reaction time of one filtrate and oxidant is 1 hour；The second filter residue and carbon source are at a temperature of inert atmosphere and 900 DEG C in step e
It is sintered, sintering time is 3 hours；Heating temperature in step f is 90 DEG C, and the reaction time of the second filtrate and ammonium oxalate is
1 hour, the pH value of the second filtrate was adjusted to 8 by NaOH；Sintering temperature is 900 DEG C in step g, and sintering time is 3 hours；Step
The heating temperature of third filtrate is 70 DEG C in h, with Na2CO3The solution reaction time is 4 hours, and third filtrate is by NaOH by pH value
It is adjusted to 12.Method in the embodiment can achieve the effect that same as Example 1.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection domain.
Claims (9)
1. a kind of lithium ion battery ternary material recovery method, which is characterized in that include the following steps：
A, lithium ion battery is disassembled to obtain anode pole piece；Obtained anode pole piece is sintered at 150~300 DEG C, is gone
Except bonding agent；
B, ball milling and sieving are carried out to anode pole piece, obtains the mixture and aluminium foil of ternary material, bonding agent and conductive agent；
C, it is added in inorganic acid or organic acid and reacts in said mixture, obtain the first filtrate and the first filter residue；
D, then the pH value of the first filtrate obtained in regulating step c heats the first filtrate to 1~3, and oxidation is added
Agent is reacted, and the second filtrate and the second filter residue are obtained；
E, it is sintered in an inert atmosphere after mixing the second filter residue obtained in step d with carbon source, obtains MnOx/ C composite；
F, the second filtrate obtained in step d is heated, and pH value is adjusted to 4~8, ammonium oxalate is then added and carries out instead
It answers, obtains third filtrate and third filter residue；
G, third filter residue is sintered in an inert atmosphere, obtains NiO/Co3O4Mixing material；
H, third filtrate is heated, and pH value is adjusted to 9~12, and Na is added2CO3Solution reaction obtains Li2CO3Material.
2. a kind of lithium ion battery ternary material recovery method according to claim 1, which is characterized in that the step c
In inorganic acid be sulfuric acid, hydrochloric acid and nitric acid in one of which, organic acid be malic acid and citric acid in one of which.
3. a kind of lithium ion battery ternary material recovery method according to claim 1 or 2, which is characterized in that the step
The reaction temperature of mixture and acid is 50~90 DEG C in rapid c, and the time is 1~6 hour.
4. a kind of lithium ion battery ternary material recovery method according to claim 1, which is characterized in that the step d
In heating temperature be 60~90 DEG C, oxidant be potassium permanganate or hydrogen peroxide, the reaction time of the first filtrate and oxidant
It is 1~6 hour.
5. a kind of lithium ion battery ternary material recovery method according to claim 1, which is characterized in that the step e
In carbon source be glucose, ascorbic acid, gelatin or polyvinyl alcohol.
6. a kind of lithium ion battery ternary material recovery method according to claim 5, which is characterized in that the step e
Middle sintering temperature is 500~900 DEG C, and sintering time is 3~6 hours.
7. a kind of lithium ion battery ternary material recovery method according to claim 1, which is characterized in that the step f
In heating temperature be 50~90 DEG C, the reaction time of the second filtrate and ammonium oxalate is 1~6 hour.
8. a kind of lithium ion battery ternary material recovery method according to claim 1, which is characterized in that the step g
Middle sintering temperature is 500~900 DEG C, and sintering time is 3~6 hours.
9. a kind of lithium ion battery ternary material recovery method according to claim 1, which is characterized in that the step h
The heating temperature of middle third filtrate is 50~90 DEG C, with Na2CO3The solution reaction time is 1~6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610601695.8A CN106169624B (en) | 2016-07-27 | 2016-07-27 | A kind of lithium ion battery ternary material recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610601695.8A CN106169624B (en) | 2016-07-27 | 2016-07-27 | A kind of lithium ion battery ternary material recovery method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106169624A CN106169624A (en) | 2016-11-30 |
| CN106169624B true CN106169624B (en) | 2018-09-18 |
Family
ID=58066030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610601695.8A Expired - Fee Related CN106169624B (en) | 2016-07-27 | 2016-07-27 | A kind of lithium ion battery ternary material recovery method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106169624B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109022793B (en) * | 2017-06-12 | 2021-04-13 | 长沙矿冶研究院有限责任公司 | Method for selectively leaching lithium from waste powder of cathode material containing at least one of cobalt, nickel and manganese |
| CN107739040A (en) * | 2017-11-15 | 2018-02-27 | 韶关中弘金属实业有限公司 | Waste material containing lithium produces the production technology of high-purity lithium carbonate |
| CN108134151B (en) * | 2017-12-28 | 2020-09-25 | 银隆新能源股份有限公司 | Method for recovering valuable metal from lithium ion battery |
| CN109439906A (en) * | 2018-11-20 | 2019-03-08 | 上海第二工业大学 | A method of selective recovery separating valuable metals and aluminium foil from abandoned car power ternary battery |
| CN114380309B (en) * | 2021-12-22 | 2024-06-11 | 威立雅新能源科技(江门)有限公司 | Method for extracting lithium from waste lithium ion battery and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538655A (en) * | 2009-04-28 | 2009-09-23 | 合肥工业大学 | MnO recovery from waste lithium manganate battery cathode material 2 And applications thereof |
| CN102956935A (en) * | 2011-08-16 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Waste and old power battery ternary-system anode material processing method |
| CN105591171A (en) * | 2015-12-18 | 2016-05-18 | 浙江天能能源科技有限公司 | Recycling method for valuable metals in waste nickel-cobalt-manganese ternary lithium ion batteries |
-
2016
- 2016-07-27 CN CN201610601695.8A patent/CN106169624B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538655A (en) * | 2009-04-28 | 2009-09-23 | 合肥工业大学 | MnO recovery from waste lithium manganate battery cathode material 2 And applications thereof |
| CN102956935A (en) * | 2011-08-16 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Waste and old power battery ternary-system anode material processing method |
| CN105591171A (en) * | 2015-12-18 | 2016-05-18 | 浙江天能能源科技有限公司 | Recycling method for valuable metals in waste nickel-cobalt-manganese ternary lithium ion batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106169624A (en) | 2016-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106169624B (en) | A kind of lithium ion battery ternary material recovery method | |
| Liang et al. | Hydrometallurgical recovery of spent lithium ion batteries: environmental strategies and sustainability evaluation | |
| Leal et al. | Recycling of spent lithium-ion batteries as a sustainable solution to obtain raw materials for different applications | |
| Do et al. | Green closed-loop cathode regeneration from spent NMC-based lithium-ion batteries through bioleaching | |
| Liu | Recycling waste batteries: recovery of valuable resources or reutilization as functional materials | |
| KR101497921B1 (en) | Recycling methdo of ncm type cathode active material from waste lithium ion battery and ncm type cathode active material recycled by the same | |
| CN109449523A (en) | A kind of comprehensive recovering process of waste and old lithium ion battery | |
| CN109881008A (en) | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery | |
| CN111082043A (en) | Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material | |
| CN112680598A (en) | Method for low-cost clean treatment of waste lithium ion battery anode material | |
| CN102030375A (en) | Method for preparing lithium cobaltate by directly using failed lithium ion battery | |
| CN110311186A (en) | A method of recycling valuable element from waste and old lithium ion battery | |
| CN109082522A (en) | Method for recovering anode powder of waste ternary lithium battery | |
| CN108023134A (en) | The recovery method of valuable element in a kind of waste lithium ion battery electrode material | |
| KR20170061206A (en) | Collection method of precursor material using disposed lithum-ion battery | |
| CN114335781A (en) | Method for extracting precious metal from waste lithium battery | |
| CN108808147A (en) | A kind of method that manganese is recycled in waste and old lithium ion battery | |
| JP2019169309A (en) | Cobalt, copper, and aluminum separation method | |
| CN113430390A (en) | Treatment method of laterite-nickel ore high-pressure acid leaching slag and positive electrode material | |
| KR20240096439A (en) | NiMnCoC2O4 recovery method from spent lithium-ion batteries and manufacturing method of energy storage device including recovered NiMnCoC2O4 | |
| WO2023029573A1 (en) | Method for extracting lithium from waste lithium battery | |
| CN102534247A (en) | Method for leaching valuable metal | |
| CN110791668B (en) | Method for recovering manganese from lithium ion battery anode waste containing manganese element | |
| CN110498434B (en) | Recovery method and application of lithium ion battery positive electrode active material | |
| Chen et al. | Hydrometallurgical processes for valuable metals recycling from spent lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180918 Termination date: 20190727 |