CN108321452A - A kind of method directly recycling lithium iron phosphate battery positive material - Google Patents
A kind of method directly recycling lithium iron phosphate battery positive material Download PDFInfo
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- CN108321452A CN108321452A CN201810103157.5A CN201810103157A CN108321452A CN 108321452 A CN108321452 A CN 108321452A CN 201810103157 A CN201810103157 A CN 201810103157A CN 108321452 A CN108321452 A CN 108321452A
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- power battery
- waste
- old power
- anode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
Abstract
The invention belongs to power lithium-ion battery MAT'L recycling technical field, it was demonstrated that the recuperability of lithium iron phosphate positive material, and disclose a kind of recovery method of simple and efficient with and its application.Include the following steps：Positive plate is split out from battery and Mechanical Crushing is in blocks, 2hrs is kept the temperature in 350 450 DEG C in the sintering furnace under protective atmosphere, then simply detaches aluminium foil and positive electrode, the positive electrode after positive electrode micronization processes as recycling.The method is simple and efficient, and obtained material has preferable stability, carries out cascade utilization to power battery material with being conducive to industrial inexpensive low stain.
Description
Technical field
The invention belongs to lithium ion battery utilization technology fields, and in particular to a kind of simple effective directly recycling is dynamic
The method of power lithium iron phosphate battery positive material and application.
Background technology
Lithium ion battery has high-energy density, high output voltage, long circulation life in being commercialized secondary cell,
The characteristics of self discharge is small and memory-less effect, because of the diversity of its electrode material selection, mobile phone, portable notebook,
It is used widely in the electronic equipments such as electric vehicle industry.
Currently, the positive electrode of business lithium ion battery is mainly LiFePO4, nickel-cobalt-manganese ternary material etc..Ferric phosphate
Lithium material is due to its higher energy density, reliable safety, the outstanding properties such as longer service life and excellent charging performance；
Moreover, with traditional lithium ion secondary battery anode material, the LiMn2O4 of spinel structure is compared with the cobalt acid lithium of layer structure,
The raw material source of LiFePO4 is more extensive, price is less expensive and non-environmental-pollution；Therefore LiFePO 4 material is by great
Concern, becomes the emphasis of early stage secondary cell industry research and development, and be widely used in the positive electrode of lithium ion battery.
With the development of lithium battery industry, lithium battery is widely used in power source, and produces a large amount of old and useless battery,
Wherein the positive electrode of most power batteries is LiFePO 4 material.In order to which reasonably Resource recovery and reduction are waste and old
Pollution effect of the battery to environment, while national policy call is responded, now to the recycling of lithium iron phosphate battery positive material
Problems demand solves.
LiFePO4 has higher stability and the ability of outstanding reversible embedding de- lithium as olivine structural material,
This is to extract LiFePO4 directly from battery to be recycled the condition of providing.In consideration of it, proving iron phosphate lithium positive pole material
The recuperability of material, and propose a kind of simple effective recycling method.Spy proposes the application.
Invention content
In order to solve the problems, such as the direct recycling of lithium iron phosphate positive material, it is an object of the present invention to prove to move
The recuperability of power battery lithium iron phosphate positive material.This method is by the positive plate of power battery using tube furnace in protective atmosphere
Under in certain temperature held for some time, obtained material by detach aluminium foil and then it is secondary be applied in lithium secondary battery, table
Reveal stable charge-discharge performance and good energy density.
Another object of the present invention is to provide a kind of direct recovery methods of the lithium iron phosphate positive material of high-efficient simple.
The invention is realized by the following technical scheme：
For the method for directly recycling and utilizing of waste lithium iron phosphate power battery anode, include the following steps：
(1) mechanical means is used to take out positive electrode from the complete power battery that discharges；
(2) it takes some materials to be put into crucible to be placed in tube furnace, N is passed through after vacuumizing2Protection, with 5 DEG C/min's
Heating rate rises to 400 DEG C, and keeps the temperature 2 hours, then furnace cooling；
(3) collector (aluminium flake) is removed, collects and be sealed by the sample obtained in step (2)；
(4) sample for obtaining step (3) carries out slurrying processing, and makes pole piece (φ=12mm), dresses up battery.
Slurrying processing step described in step (4) is：With 8:1:1 mass ratio mixed grinding sample, acetylene black and
Kynoar (PVDF) dissolves PVDF with N methyl pyrrolidones (NMP) solution；Sample is put into cylinder of steel and size each three is added
After steel ball is with six hours of rotating speed ball milling of 20r/min, the coating sizing-agent on aluminium foil；Subsequent vacuum drying, tabletting are simultaneously cut
It is about the pole piece that 40 μ m diameters are 12mm at thickness.
The operating method of the present invention has the following advantages that and advantageous effect：First, it was demonstrated that power battery LiFePO4 material
The recuperability of material, and unfailing performance is presented；Second, a kind of flow of simple and efficient is introduced to power battery iron phosphate lithium positive pole
Material is tentatively recycled, and the wasting of resources and environmental pollution in removal process are saved.It is further cleaned on this basis
The salvage material to match in excellence or beauty with commercial phosphoric acid iron lithium material can be obtained with optimization.
Description of the drawings
Fig. 1 is that embodiment 1 obtains the SEM scan images of material (right side) and commercial material (left side)；Fig. 2 is that embodiment 1 obtains
Material and commercial material XRD diffracting spectrum comparison diagrams；Fig. 3 is cyclical voltage-specific volume of the battery first circle of 1 gained of embodiment
Spirogram；Fig. 4 is the variation of the battery capacity conservation rate during 1 gained circulating battery of embodiment.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1：
By the shell breakage of commercial waste and old power battery, the iron phosphate lithium positive pole pole piece of battery is removed, pole piece is cut into 1
The sheet of × 5cm.By treated, collection fragment is heat-treated as in the tube furnace in nitrogen protection at a temperature of 400 DEG C
2hrs makes the binder in pole piece and organic conductive agent failure.After treatment, by very simple method by aluminium foil and anode
Material detaches, and positive electrode dusting is handled, and collects recycling respectively.The X-ray diffractogram (XRD diagram) of obtained positive electrode
With scanning electron microscope diagram (SEM figures) as shown in the figure 1 and 2, compared with XRD diagram and the SEM figure of commercial LiFePO 4 material
It is found that the diffraction maximum position of the two and intensity is roughly the same and sample is containing only a small amount of unconspicuous impurity peaks；In terms of SEM figures, sample
The microstructure of the product impurity and agglomerated particle very high, only a small amount of with commercial sample similarity degree are that some electrolyte decompose
Product and residue further study optimization in rear extended meeting.Thus the sample illustrated has recycling to be worth, and is applied to storage
Energy or energy device.
Under the action of not having binder, positive electrode is simply ground to powder, and is proportionally 8:1:1 ratio
Example modulates positive electrode, acetylene black and the slurry of PVDF, makes pole piece, fills half-cell processed and simultaneously carries out three with the multiplying power of 0.5C
Hundred charge and discharge cycles.Occurs stable chargin level in the first circle charge and discharge cycles of battery at the voltage of charging 3.45V
Platform is the capacity retention ratio of the first circle charge and discharge cycles figure of battery and 300 cycles as shown in Figures 3 and 4,300 cycles
Capacity retention ratio is 99% afterwards.Illustrate the lithium iron phosphate positive material recycled by this method still possess outstanding stability and
Energy storage potentiality.
Embodiment 2：
By the shell breakage of commercial waste and old power battery, the iron phosphate lithium positive pole pole piece of battery is removed, pole piece is cut into 1
The sheet of × 5cm.By treated, collection fragment is heat-treated as in the tube furnace in nitrogen protection at a temperature of 400 DEG C
2hrs makes the binder in pole piece and organic conductive agent failure.After treatment, by very simple mechanical means by aluminium foil and
Positive electrode detaches, and positive electrode dusting is handled, and collects recycling respectively.Obtained positive electrode XRD diagram and SEM figure with
XRD figures and the comparison of SEM figures of commercial LiFePO 4 material are it is found that the diffraction maximum position of the two and intensity is roughly the same and sample
Product are containing only a small amount of unconspicuous impurity peaks；In terms of SEM figures, the microstructure of sample and commercial sample similarity degree are very high, only
The particle of a small amount of impurity and reunion, is some electrolyte decomposition products and residue, is needed in follow-up further research optimization.
Thus the sample illustrated has recycling to be worth, and is applied to energy storage or energy device.
Under the action of not having binder, positive electrode is simply ground to powder, and is proportionally 8:1:1 ratio
Example modulates positive electrode, acetylene black and the slurry of PVDF, is fabricated to pole piece, fills half-cell processed and is simultaneously carried out with the multiplying power of 0.2C
300 charge and discharge cycles.Occurs stable chargin level in the first circle charge and discharge cycles of battery at the voltage of charging 3.45V
Platform, after 300 cycles capacity retention ratio be 99%. lithium iron phosphate positive materials that are recycled by this method of explanation remain unchanged possess it is outstanding
Stability and energy storage potentiality.
Application example 3：
By the shell breakage of commercial waste and old power battery, the iron phosphate lithium positive pole pole piece of battery is removed, pole piece is cut into 1
The sheet of × 5cm.By treated, collection fragment is heat-treated as in the tube furnace in nitrogen protection at a temperature of 450 DEG C
2hrs makes the binder in pole piece and organic conductive agent failure.After treatment, by very simple method by aluminium foil and anode
Material detaches, and positive electrode dusting is handled, and collects recycling respectively.The XRD diagram and SEM of obtained positive electrode are schemed, with quotient
XRD diagram and SEM the figure comparison of LiFePO 4 material it is found that the diffraction maximum position of the two and intensity is roughly the same and sample only
Containing a small amount of unconspicuous impurity peaks；In terms of SEM figures, the microstructure of sample and commercial sample similarity degree are very high, only on a small quantity
Impurity and agglomerated particle, be some electrolyte decomposition products and residue, need to further study optimization in rear extended meeting.Thus it says
Bright obtained sample has recycling to be worth, and is applied to energy storage or energy device.
Under the action of not having binder, positive electrode is simply ground to powder, and is proportionally 8:1:1 ratio
Example modulates positive electrode, acetylene black and the slurry of PVDF, makes pole piece, fills half-cell processed and simultaneously carries out 300 with the multiplying power of 0.2C
Secondary charge and discharge cycles.Occur stable charging platform in the first circle charge and discharge cycles of battery at the voltage of charging 3.45V,
Capacity retention ratio is 98% after 300 cycles, and it is outstanding to illustrate that the lithium iron phosphate positive material recycled by this method still possesses
Stability and energy storage potentiality.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (7)
1. a kind of recycling method of waste and old power battery anode material LiFePO4, which is characterized in that comprise the steps of：
1) positive plate is taken out from waste and old power battery, and broken in blocks；
2) fragment is placed in 350-450 DEG C under protective atmosphere of sintering furnace and keeps the temperature a period of time；
3) will treated iron phosphate lithium positive pole fragment, separation aluminium foil processing；
4) LiFePO 4 material of separation is subjected to micronization processes, the power battery lithium iron phosphate positive material being recycled.
2. the recycling method of waste and old power battery anode material LiFePO4 according to claim 1, it is characterised in that：Step
It is rapid 1) in also include step 1a)：With machinery method by the shell breakage of waste and old power battery, the positive plate of web-like is processed into
1 × 5cm fragments.
3. the recycling method of waste and old power battery anode material LiFePO4 according to claim 1, it is characterised in that：Step
It is rapid 2) in soaking time of the fragment in sintering furnace be 2hrs.
4. the recycling method of waste and old power battery anode material LiFePO4 according to claim 1, it is characterised in that：Step
It is rapid 2) used in sintering furnace should be tube furnace, Muffle furnace etc..
5. the recycling method of waste and old power battery anode material LiFePO4 according to claim 1, it is characterised in that：Step
Rapid 2) the middle protective atmosphere used should be nitrogen, argon gas etc..
6. the recycling method of waste and old power battery anode material LiFePO4 according to claim 1, it is characterised in that：Step
It is rapid 3) in further include step 3a)：The aluminium foil of separation and positive electrode are retained separately, aluminium foil can be used as aluminum metallic material recycling profit
With.
7. the recycling method of waste and old power battery anode material LiFePO4 according to claim 1, it is characterised in that：Step
It is rapid 4) in positive electrode micronization processes application grinding processing and high speed ball-milling treatment.
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| CN201810103157.5A CN108321452A (en) | 2018-02-01 | 2018-02-01 | A kind of method directly recycling lithium iron phosphate battery positive material |
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| CN201810103157.5A CN108321452A (en) | 2018-02-01 | 2018-02-01 | A kind of method directly recycling lithium iron phosphate battery positive material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109256595A (en) * | 2018-08-06 | 2019-01-22 | 株洲冶炼集团股份有限公司 | A kind of method that the useless powder pyrogenic method directly reparation of LiFePO4 prepares battery-grade iron phosphate lithium |
| CN117117369A (en) * | 2022-12-13 | 2023-11-24 | 山东华劲电池材料科技有限公司 | Recovery processing method of ternary positive electrode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383441A (en) * | 2007-09-06 | 2009-03-11 | 深圳市比克电池有限公司 | Synthetic recovering method for positive pole waste tablet from ferric phosphate lithium cell |
-
2018
- 2018-02-01 CN CN201810103157.5A patent/CN108321452A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383441A (en) * | 2007-09-06 | 2009-03-11 | 深圳市比克电池有限公司 | Synthetic recovering method for positive pole waste tablet from ferric phosphate lithium cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109256595A (en) * | 2018-08-06 | 2019-01-22 | 株洲冶炼集团股份有限公司 | A kind of method that the useless powder pyrogenic method directly reparation of LiFePO4 prepares battery-grade iron phosphate lithium |
| CN117117369A (en) * | 2022-12-13 | 2023-11-24 | 山东华劲电池材料科技有限公司 | Recovery processing method of ternary positive electrode material |
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Application publication date: 20180724 |
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