CN109950651A - A kind of integrated conduct method of waste lithium iron phosphate battery recycling carbon - Google Patents
A kind of integrated conduct method of waste lithium iron phosphate battery recycling carbon Download PDFInfo
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- CN109950651A CN109950651A CN201910264643.XA CN201910264643A CN109950651A CN 109950651 A CN109950651 A CN 109950651A CN 201910264643 A CN201910264643 A CN 201910264643A CN 109950651 A CN109950651 A CN 109950651A
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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 discloses a kind of integrated conduct methods of waste lithium iron phosphate battery recycling carbon, and the graphite content interlamellar spacing being utilized in recycling carbon is larger, defect increases and have impurity F e2O3、CuO、Al2O3The characteristics of, compound between graphite layers are prepared in the case where being not required to that intercalation reagent conditions additionally are added, then remove graphite for graphene nanometer sheet by low temperature calcination.The high added value recycling of graphite material in waste lithium iron phosphate battery recycling carbon can be achieved in the present invention, while can also recycle in a chloride-form metal impurities therein, has stronger application prospect and feasibility.Furthermore the technology can realize that hydrochloric acid, steam heat recycle, and have many advantages, such as low energy consumption, low cost, environmentally protective.
Description
Technical field
The invention belongs to old and useless battery recovery technology fields, and in particular to a kind of waste lithium iron phosphate battery recycling carbon it is comprehensive
Close processing method.
Background technique
Through LiFePO4 (LiFePO4) power battery due to low cost, security performance is high and cycle performance is good the advantages that,
It is widely used in the fields such as large-scale passenger car, hybrid-power electric vehicle.Due to limited battery life (3~5 years), and with new energy
The fast development of source industry, it will there are a large amount of ferric phosphate lithium cells to face the problem of scrapping processing, inside battery contains hexafluoro phosphorus
The chemical substances such as sour lithium, organic carbonate rouge, polyalkene diaphragm, if without recovery processing, it will big gas and water, soil are caused
Serious pollution.
The basic step of existing ferric phosphate lithium cell recycling include pretreatment (dismantling, pyrolysis etc.) and element recycling (or
Material regeneration) two parts.Pretreatment is to isolate positive/negative plate for after battery crushing, is made by the way of pyrogenic attack positive and negative
Pole active material is separated with collector.Element removal process is frequently with inorganic acid solution by the metallic element in active material later
Leach, then lithium, the metallic elements such as cobalt recycled by Wet-process metallurgy method, since carbon chemical property is stablized, by filter from
Recycling obtains carbon material used as anode in solution.
Compared with typical business cathode graphite, waste lithium iron phosphate battery, which recycles carbon, has following special physical chemistry
Property: 1) recycling the graphite content in carbon has the characteristics that graphite layers increase away from increase and gap.2) waste lithium iron phosphate electricity
Pond is easy to introduce Fe in recycling carbon in the treatment process such as dismantling, pyrogenic process pretreatment2O3、CuO、Al2O3Equal impurity components.Mesh
Before, also there is relevant report for the recycling of waste and old lithium ion battery carbon material used as anode, patent CN101710632B discloses one kind
The recycling of waste and old lithium ion battery cathode graphite and restorative procedure, after removal of impurities, using cellulose acetate as coating material, with
Acetone is that solvent is surface modified graphite, has obtained that a kind of purity is higher and surface is coated with the carbonaceous material of amorphous carbon
Material.Patent CN201610041766 discloses a kind of method of waste and old lithium ion battery graphite cathode recycling and reusing, by adding
Add ferrous salt or zinc salt to remove the extra organics in cathode, while surface is carried out to graphite particle and is modified, obtains one kind
Regenerated graphite cathode material.Above-mentioned patent recycles waste and old lithium ion battery carbon material used as anode by modified mode
It recycles, but can not mutually be equal to commercialized carbonaceous material since the fault of construction of recycling carbon material itself causes it to recycle product
Beauty, competitive advantage are unobvious；The valuable metal impurity (iron, copper, aluminium etc.) in carbon is recycled simultaneously after acid solution cleans as discarded
Object discharge, is not recycled, causes the waste of resource.
Summary of the invention
In order to solve the problems in the prior art, the purpose of the invention is to provide a kind of waste lithium iron phosphate batteries to return
The integrated conduct method of carbon is received, realizes the high added value recycling and the recycling of valuable metal element of graphite material in recycling carbon,
Recycling for hydrochloric acid and steam heat is realized in technical process simultaneously, reduces resource consumption, reduces operating cost.
It should be noted that heretofore described recycling carbon refers to that waste lithium iron phosphate power battery is disassembled, is crushed,
After recycling high-temperature heat treatment to separate positive and negative anodes active material with collector, work is recycled from solution using Wet-process metallurgy method
Valuable metal element in property substance, the carbon being finally recovered by filtration from solution.
In order to achieve the above technical purposes, the present invention adopts the following technical scheme:
A kind of integrated conduct method of waste lithium iron phosphate battery recycling carbon, comprising the following steps:
(1) consolidate 5~10:1 of mass ratio by liquid, carbon will be recycled and be added in the mix acid liquor A of hydrochloric acid and other acidic materials,
The concentration of hydrochloric acid is 3~10mol/L in mix acid liquor A, and the total concentration of other acidic materials is 0.5~1mol/L, is in temperature
30~60 DEG C of 6~12h of stirring, obtain solution B；
(2) by 10~30wt% of recycling carbonaceous amount, oxidant is added into solution B, is ultrasonically treated in 25~85 DEG C, function
Rate is 400~800W, and frequency is 20~300KHz, and ultrasonic time is 1~3h, and reducing agent is added later, obtains solution C；
(3) hydrochloric acid in solution C is volatilized and is collected, respectively obtain filter residue and filtrate through filtering, the heat in salt acid vapour
For the crystallization stoste of heating stepses (5), the hydrochloric acid of collection is spare as mix acid liquor D after mixing with filtrate, and filter residue is washed
Until the pH of eluate is 5~7, solid matter is obtained after dry；
(4) in the mixed atmosphere of oxygen and protection gas, solid matter is kept the temperature into 1~3h at 400~500 DEG C, is heated up
Rate is 5~10 DEG C/min；Or 0.5~2min of microwave treatment obtains solid mixture E under 500~1200W by solid matter；
(5) solid mixture E is placed in mix acid liquor D, in 30~60 DEG C of 6~12h of stirring, containing graphene is obtained by filtration
The carbonaceous material and crystallization stoste of nanometer sheet；
The volatilization of the hydrochloric acid in stoste will be crystallized to collect, in 100~120 DEG C of 1~2h of heat preservation, recycling is added first in crystallization stoste
The AlCl of 5~8wt% of carbonaceous amount3Crystal seed makes AlCl3Crystallization is precipitated, isolated AlCl3Crystal and first-time filtrate；
The CuCl of 5~8wt% of recycling carbonaceous amount is added in 80~100 DEG C of 1~2h of heat preservation in first-time filtrate2Crystal seed makes
CuCl2Crystallization is precipitated, isolated CuCl2Crystal and secondary filtrate；
The FeCl of 5~8wt% of recycling carbonaceous amount is added in 80~100 DEG C of 1~2h of heat preservation in secondary filtrate3Crystal seed makes
FeCl3Crystallization is precipitated, isolated FeCl3Crystal and three times filtrate；
Heat in salt acid vapour is used for the solution C of heating stepses (3), and the hydrochloric acid of collection returns after mixing with filtrate three times
Step (1) recycling.
Preferably, in step (1), agitating mode is selected from least one of mechanical stirring, airflow stirring and jet mixing.
Preferably, in step (1), other acidic materials are selected from H2SO4、HNO3、H3PO4、HPO3、HClO3、HClO、
H2FeO4, HCOOH and CH3At least one of COOH.
Preferably, in step (2), the oxidant is selected from NaClO, NaClO3、NaClO4、KClO、KClO3、KClO4、
NH4ClO3、NH4ClO4、Na2S2O8、K2S2O8、(NH4)2S2O8、K2FeO4And Na2FeO4At least one of.
Preferably, in step (2), the reducing agent is selected from H2O2、FeSO4, reduced iron powder, FeCl2、H2C2O4With
Na2SO3At least one of, the molar ratio of reducing agent and oxidant is 0.8~2:1.
Preferably, in step (3) and (5), the temperature that hydrochloric acid volatilization is collected is 80~120 DEG C.
Preferably, in step (4), mixed atmosphere flow be 30~200mL/min, wherein oxygen volume accounting be 21~
40%, protection gas is selected from least one of nitrogen, argon gas.
Compared with prior art, the invention has the following beneficial effects:
(1) method of traditional recycling ferric phosphate lithium cell is stacked carbon material used as anode as waste residue, and of the present invention
Method using recycling carbon in graphite content interlamellar spacing increase, defect increase and have impurity F e2O3、CuO、Al2O3The characteristics of,
Under conditions of not needing additional intercalation reagent, the method for taking chemical oxidation intercalation-ultrasonic treatment to combine is prepared for graphite
Intercalation compound, and then the carbonaceous material of containing graphene nanometer sheet has been obtained by removing, increase negative electrode of lithium ion battery carbon
The added value of material recovery；And the metal valuable metal ingredient (iron, copper, aluminium) in carbon can will be recycled in the form of metal chloride
Recycling, has saved resource.
(2) compared with the stripping means of existing compound between graphite layers (GIC), this method is made by chemical oxidation graft process
Graphite is converted into FeCl3-CuCl2-AlCl3- GIC intercalation compound, then allowing intercalation reagent that hydrolysis occurs makes interlayer chemical combination
Object is converted into Fe (OH)3-Cu(OH)2-Al(OH)3- GIC makes metal hydroxides that dehydration occur finally by high-temperature heating
Intercalation compound is set to be converted into Fe2O3-CuO-Al2O3- GIC keeps graphite linings peeling-off, most using the thrust that vapor generates
The carbonaceous material of containing graphene nanometer sheet is obtained eventually.In stripping process required heating temperature with FeCl3/CuCl2/AlCl3Gas
The removing mode of body volatilization expansion is compared to lower, and only 400~500 DEG C, energy consumption and cost reduce.
(3) hydrochloric acid used in this technique can be recycled by way of evaporative condenser, for other steps of the technique,
It realizes recycling for hydrochloric acid, greatly reduces the discharge amount of acid waste water.Heat needed for solution evaporation can also pass through steaming
Heat intercourses the energy consumption and cost that preparation process is reduced to be recycled between gas and liquid, environmentally protective.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Below with reference to concrete operations example, the present invention will be described in detail；The protection scope of the claims in the present invention is not
It is restricted by the embodiment.
Embodiment 1
(1) recycling carbon is added to HCl concentration is 10mol/L, H2SO4Concentration is in the mix acid liquor A of 1mol/L, and liquid is solid
Mass ratio 10:1 is 60 DEG C of mechanical stirring 12h in temperature, obtains solution B；
(2) NaClO of recycling carbonaceous amount 30% is added into solution B, is ultrasonically treated in 85 DEG C, ultrasonic power 800W, frequency
Rate is 300KHz, and H is added in ultrasonic time 3h later2O2To remove extra NaClO, the H of addition2O2With the molar ratio of NaClO
For 2:1, solution C is obtained；
(3) solution C is heated to 120 DEG C hydrochloric acid therein volatilizees, surplus solution after filtering respectively collect filter residue and
Filtrate, the crystallization stoste of heat heating stepses (5) in a manner of thermal convection in salt acid vapour, the hydrochloric acid that steam condenses with
It is spare as mix acid liquor D after the filtrate mixing of this collection step, filter residue surface is cleaned with deionized water, until the pH of eluate
It is 7, obtains solid matter；
(4) solid matter that step (3) obtains is placed in heating furnace, keeps being passed through oxygen with 200mL/min flow velocity
Volume fraction accounts for 40% and remaining gas ingredient is the gas of nitrogen, and temperature is increased to 500 DEG C from room temperature, and 10 DEG C of heating rate/
Min keeps the temperature 3h, obtains solid mixture E；
(5) solid mixture E is placed in mix acid liquor D, is 60 DEG C of mechanical stirring 12h in temperature, is obtained by filtration containing stone
The carbonaceous material and crystallization stoste of black alkene nanometer sheet.Crystallization stoste is first heated to 120 DEG C of heat preservation 2h, recycling carbonaceous amount is added
8% AlCl3Crystal seed makes AlCl3Crystallization is precipitated, and is recovered by filtration.Recycling carbonaceous amount is added in 100 DEG C of heat preservation 2h in solution again
8% CuCl2Crystal seed makes CuCl2Crystallization is precipitated, and is recovered by filtration.Recycling carbon finally is added in 100 DEG C of heat preservation 2h in surplus solution
The FeCl of quality 8%3Crystal seed makes FeCl3Crystallization is precipitated, and is recovered by filtration.Realize FeCl3、CuCl2And AlCl3With the classification of filtrate
Recycling.Solution C of the heat in a manner of thermal convection in heating stepses (3) in salt acid vapour, hydrochloric acid that steam condenses and
Mix acid liquor A after crystalline mother solution mixing as step (1).
The carbonaceous material for the graphene nanometer sheet for being 3 containing the piece number of plies has been prepared in the present embodiment, and recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 99.14%, 98.90%, 99.28%.
Embodiment 2
(1) recycling carbon is added to HCl concentration is 6mol/L, HNO3Concentration is in the mix acid liquor A of 0.8mol/L, and liquid is solid
Mass ratio 8:1 is 45 DEG C of airflow stirring 10h in temperature, obtains solution B.
(2) (the NH of recycling carbonaceous amount 20% is added into solution B4)2S2O8, it is ultrasonically treated in 55 DEG C, ultrasonic power
FeCl is added in 600W, frequency 150KHz, ultrasonic time 2h later2To remove extra (NH4)2S2O8, the FeCl of addition2With
(NH4)2S2O8Molar ratio be 1.4:1, obtain solution C；
(3) solution C is heated to 100 DEG C hydrochloric acid therein volatilizees, surplus solution after filtering respectively collect filter residue and
Filtrate.The crystallization stoste of heat heating stepses (5) in a manner of thermal convection in salt acid vapour, hydrochloric acid that steam condenses with
It is spare as mix acid liquor D after the filtrate mixing of this collection step.Filter residue surface is cleaned with deionized water, until the pH of eluate
It is 6, obtains solid matter；
(4) solid matter that step (3) obtains is placed in heating furnace, keeps being passed through oxygen with 120mL/min flow velocity
Volume fraction accounts for 30% and remaining gas ingredient is the gas of nitrogen, and temperature is increased to 450 DEG C from room temperature, and 7 DEG C of heating rate/
Min keeps the temperature 2h, obtains solid mixture E；
(5) solid mixture E is placed in mix acid liquor D, is 45 DEG C of airflow stirring 10h in temperature, is obtained by filtration containing stone
The carbonaceous material and crystallization stoste of black alkene nanometer sheet.Crystallization stoste is first heated to 110 DEG C of heat preservation 1.5h, recycling carbonaceous is added
The AlCl of amount 7%3Crystal seed makes AlCl3Crystallization is precipitated, and is recovered by filtration.Recycling carbonaceous is added in 90 DEG C of heat preservation 1.5h in solution again
The CuCl of amount 7%2Crystal seed makes CuCl2Crystallization is precipitated, and is recovered by filtration.Recycling finally is added in 90 DEG C of heat preservation 2h in surplus solution
The FeCl of carbonaceous amount 7%3Crystal seed makes FeCl3Crystallization is precipitated, and is recovered by filtration.Realize FeCl3、CuCl2And AlCl3With point of filtrate
Class recycling.Solution C of the heat in a manner of thermal convection in heating stepses (3) in salt acid vapour, the hydrochloric acid that steam condenses
With the mix acid liquor A after crystalline mother solution mixing as step (1)；
The carbonaceous material for the graphene nanometer sheet for being 5 containing the piece number of plies has been prepared in the present embodiment.Recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 98.79%, 98.60%, 98.90%.
Embodiment 3
(1) recycling carbon is added to HCl concentration is 3mol/L, H2SO4、H3PO4、CH3COOH three's total concentration is 0.5mol/
In the mix acid liquor A of L, liquid consolidates mass ratio 5:1, is 30 DEG C of jet mixing 6h in temperature, obtains solution B.
(2) Na of recycling carbonaceous amount 10% is added into solution B2FeO4, it is ultrasonically treated in 25 DEG C, ultrasonic power 400W, frequency
Rate is 20KHz, and Na is added in ultrasonic time 1h later2SO3To remove extra Na2FeO4, the Na of addition2SO3With Na2FeO4Rub
You obtain solution C than being 0.8:1.
(3) solution C is heated to 80 DEG C hydrochloric acid therein volatilizees, collects filter residue and filtrate after filtering respectively.Hydrochloric acid steams
The crystallization stoste of heat heating stepses (5) in a manner of thermal convection in gas, the hydrochloric acid and this collection step that steam condenses
Filtrate mixing after as mix acid liquor D it is spare.Filter residue surface is cleaned with deionized water, until the pH of eluate is 5, consolidate
Body substance.
(4) solid matter that step (3) obtains is placed in the microwave device of 500W power and handles 0.5min, keep with
30mL/min flow velocity is passed through that oxygen purity accounts for 21% and remaining gas ingredient is the gas of nitrogen, obtains solid mixture E.
(5) solid mixture E is placed in mix acid liquor D, is 30 DEG C of jet mixing 6h in temperature, graphitiferous is obtained by filtration
The carbonaceous material and crystallization stoste of alkene nanometer sheet.Crystallization stoste is first heated to 100 DEG C of heat preservation 1h, recycling carbonaceous amount is added
5% AlCl3Crystal seed makes AlCl3Crystallization is precipitated, and is recovered by filtration.Recycling carbonaceous amount 5% is added in 80 DEG C of heat preservation 1h in solution again
CuCl2Crystal seed makes CuCl2Crystallization is precipitated, and is recovered by filtration.Recycling carbonaceous amount finally is added in 80 DEG C of heat preservation 1h in surplus solution
5% FeCl3Crystal seed makes FeCl3Crystallization is precipitated, and is recovered by filtration.Realize FeCl3、CuCl2And AlCl3Classification with filtrate is recycled.
Solution of the heat in a manner of thermal convection in heating stepses (3) in salt acid vapour, the hydrochloric acid and crystallization that steam condenses are female
Mix acid liquor A after liquid mixing as step (1).
The carbonaceous material for the graphene nanometer sheet for being 8 containing the piece number of plies has been prepared in the present embodiment, and recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 98.40%, 98.33%, 97.96%.
Embodiment 4
The present embodiment is substantially the same manner as Example 3, the difference is that, the intercalated graphite that step (4) obtains step (3)
It is placed in the microwave device of 1200W power and handles 2min.The graphene that it is 5 containing the piece number of plies that the present embodiment, which has been prepared, is received
The carbonaceous material of rice piece, recycling obtain FeCl3、CuCl2And AlCl3Purity is respectively 98.29%, 97.96%, 98.34%.
Comparative example 1
This comparative example is substantially the same manner as Example 1, the difference is that, HCl concentration is 1mol/L in step (1).This is right
The carbonaceous material containing few layer of graphite flake has been prepared in ratio, and the graphite flake number of plies is more than 15 layers.Recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 95.29%, 94.96%, 93.34%.
Comparative example 2
This comparative example is substantially the same manner as Example 1, the difference is that, the amount that NaClO is added in step (2) is recycling carbon
Quality 3%.The carbonaceous material containing few layer of graphite flake has been prepared in this comparative example, and the graphite flake number of plies is more than 15
Layer.Recycling obtains FeCl3、CuCl2And AlCl3Purity is respectively 98.64%, 97.46%, 98.66%.
Comparative example 3
This comparative example is substantially the same manner as Example 1, the difference is that, the power of step (2) ultrasonic treatment is 200W.This
The carbonaceous material containing few layer of graphite flake has been prepared in comparative example, and the graphite flake number of plies is more than 12 layers.Recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 98.27%, 97.86%, 98.24%.
Comparative example 4
This comparative example is substantially the same manner as Example 1, the difference is that, the time of step (2) ultrasonic treatment is 0.5h.This
The carbonaceous material containing few layer of graphite flake has been prepared in comparative example, and the graphite flake number of plies is more than 20 layers.Recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 98.21%, 97.86%, 98.34%.
Comparative example 5
This comparative example is substantially the same manner as Example 1, the difference is that, it is 10KHz that step (2), which is ultrasonically treated frequency,.This
The carbonaceous material containing few layer of graphite flake has been prepared in comparative example, and the graphite flake number of plies is more than 18 layers.Recycling obtains
FeCl3、CuCl2And AlCl3Purity is respectively 98.39%, 97.85%, 98.77%.
Comparative example 6
This comparative example is substantially the same manner as Example 1, the difference is that, in step (4) when the heating and thermal insulation of solid matter
Between be 0.5h.The carbonaceous material containing few layer of graphite flake has been prepared in this comparative example, and the graphite flake number of plies is more than 15
Layer.Recycling obtains FeCl3、CuCl2And AlCl3Purity is respectively 98.49%, 97.66%, 98.22%.
Comparative example 7
This comparative example is substantially the same manner as Example 1, the difference is that, the heating temperature of solid matter is in step (4)
200℃.The carbonaceous material containing few layer of graphite flake has been prepared in this comparative example, and the graphite flake number of plies is more than 20 layers.
Recycling obtains FeCl3、CuCl2And AlCl3Purity is respectively 98.41%, 97.56%, 98.32%.
Comparative example 8
This comparative example is substantially the same manner as Example 3, the difference is that, solid matter is placed on 200W in step (4)
It is handled in the microwave device of power.The carbonaceous material containing few layer of graphite flake has been prepared in this comparative example, and graphite is thin
The piece number of plies is more than 18 layers.Recycling obtains FeCl3、CuCl2And AlCl3Purity is respectively 98.61%, 97.38%, 98.63%.
Comparative example 9
This comparative example is substantially the same manner as Example 3, the difference is that, solid matter is placed on microwave in step (4)
It is 10s that the time is handled in device.The carbonaceous material containing few layer of graphite flake, and graphite flake has been prepared in this comparative example
The number of plies is more than 20 layers.Recycling obtains FeCl3、CuCl2And AlCl3Purity is respectively 98.51%, 97.64%, 98.78%.
Comparative example 10
This comparative example is substantially the same manner as Example 1, the difference is that, in step (5), acid filtrate is in 80 always
FeCl is carried out under DEG C heating condition3、CuCl2And AlCl3The classification of three is recycled.The present embodiment, which has been prepared, contains the piece number of plies
For the carbonaceous material of 3 graphene nanometer sheet, recycling obtains FeCl3、CuCl2And AlCl3Purity is respectively 79.34%,
76.32%, 80.96%.
Comparative example 11
This comparative example is substantially the same manner as Example 1, the difference is that, in step (5), AlCl3Crystal seed, CuCl2Crystal seed and
FeCl3The additive amount of crystal seed is recycling carbonaceous amount 2%.The graphene that it is 3 containing the piece number of plies that the present embodiment, which has been prepared, is received
The carbonaceous material of rice piece, recycling obtain FeCl3、CuCl2And AlCl3Purity is respectively 75.36%, 71.38%, 76.55%.
Comparative example 12
This comparative example is substantially the same manner as Example 1, the difference is that, the agitating mode in step (1) is artificial stirring.
The carbonaceous material containing few layer of graphite flake has been prepared in this comparative example, and the graphite flake number of plies is more than 18 layers.It recycles
To FeCl3、CuCl2And AlCl3Purity is respectively 97.51%, 97.48%, 98.13%.
Claims (7)
1. a kind of integrated conduct method of waste lithium iron phosphate battery recycling carbon, which comprises the following steps:
(1) consolidate 5~10:1 of mass ratio by liquid, carbon will be recycled and be added in the mix acid liquor A of hydrochloric acid and other acidic materials, mixing
The concentration of hydrochloric acid is 3~10mol/L in acid solution A, the total concentrations of other acidic materials is 0.5~1mol/L, temperature be 30~
60 DEG C of 6~12h of stirring, obtain solution B；
(2) by 10~30wt% of recycling carbonaceous amount, oxidant is added into solution B, is ultrasonically treated in 25~85 DEG C, power is
400~800W, frequency are 20~300KHz, and ultrasonic time is 1~3h, and reducing agent is added later, obtains solution C；
(3) hydrochloric acid in solution C is volatilized and is collected, respectively obtain filter residue and filtrate through filtering, the heat in salt acid vapour is used for
The crystallization stoste of heating stepses (5), the hydrochloric acid of collection mixed with filtrate after as mix acid liquor D it is spare, filter residue it is washed until
The pH of eluate is 5~7, obtains solid matter after dry；
(4) in the mixed atmosphere of oxygen and protection gas, solid matter is kept the temperature into 1~3h, heating rate at 400~500 DEG C
For 5~10 DEG C/min；Or 0.5~2min of microwave treatment obtains solid mixture E under 500~1200W by solid matter；
(5) solid mixture E is placed in mix acid liquor D, in 30~60 DEG C of 6~12h of stirring, containing graphene nanometer is obtained by filtration
The carbonaceous material and crystallization stoste of piece；
The volatilization of the hydrochloric acid in stoste will be crystallized to collect, in 100~120 DEG C of 1~2h of heat preservation, recycling carbonaceous is added first in crystallization stoste
The AlCl of 5~8wt% of amount3Crystal seed makes AlCl3Crystallization is precipitated, isolated AlCl3Crystal and first-time filtrate；
The CuCl of 5~8wt% of recycling carbonaceous amount is added in 80~100 DEG C of 1~2h of heat preservation in first-time filtrate2Crystal seed makes CuCl2Knot
Partial crystallization goes out, isolated CuCl2Crystal and secondary filtrate；
The FeCl of 5~8wt% of recycling carbonaceous amount is added in 80~100 DEG C of 1~2h of heat preservation in secondary filtrate3Crystal seed makes FeCl3Knot
Partial crystallization goes out, isolated FeCl3Crystal and three times filtrate；
Heat in salt acid vapour is used for the solution C of heating stepses (3), return step after the hydrochloric acid of collection is mixed with filtrate three times
(1) it reuses.
2. the integrated conduct method of waste lithium iron phosphate battery recycling carbon according to claim 1, it is characterised in that: step
(1) in, agitating mode is selected from least one of mechanical stirring, airflow stirring and jet mixing.
3. the integrated conduct method of waste lithium iron phosphate battery recycling carbon according to claim 1, it is characterised in that: step
(1) in, other acidic materials are selected from H2SO4、HNO3、H3PO4、HPO3、HClO3、HClO、H2FeO4, HCOOH and CH3In COOH
It is at least one.
4. the integrated conduct method of waste lithium iron phosphate battery recycling carbon according to claim 1, it is characterised in that: step
(2) in, the oxidant is selected from NaClO, NaClO3、NaClO4、KClO、KClO3、KClO4、NH4ClO3、NH4ClO4、
Na2S2O8、K2S2O8、(NH4)2S2O8、K2FeO4And Na2FeO4At least one of.
5. the integrated conduct method of waste lithium iron phosphate battery recycling carbon according to claim 1, it is characterised in that: step
(2) in, the reducing agent is selected from H2O2、FeSO4, reduced iron powder, FeCl2、H2C2O4And Na2SO3At least one of, reduction
The molar ratio of agent and oxidant is 0.8~2:1.
6. the integrated conduct method of waste lithium iron phosphate battery recycling carbon according to claim 1, it is characterised in that: step
(3) and in (5), the temperature that hydrochloric acid volatilization is collected is 80~120 DEG C.
7. the integrated conduct method of waste lithium iron phosphate battery recycling carbon according to claim 1, it is characterised in that: step
(4) in, mixed atmosphere flow be 30~200mL/min, wherein oxygen volume accounting be 21~40%, protection gas be selected from nitrogen,
At least one of argon gas.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910264643.XA CN109950651B (en) | 2019-04-03 | 2019-04-03 | Comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries |
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| CN201910264643.XA CN109950651B (en) | 2019-04-03 | 2019-04-03 | Comprehensive treatment method for recycling carbon from waste lithium iron phosphate batteries |
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| CN110581323A (en) * | 2019-09-25 | 2019-12-17 | 深圳清华大学研究院 | In-situ regeneration method of waste lithium iron phosphate battery positive electrode material |
| CN111009660A (en) * | 2019-11-26 | 2020-04-14 | 宁夏百川新材料有限公司 | Method for preparing lithium iron phosphate positive electrode material from waste lithium iron phosphate battery |
| CN113023703A (en) * | 2021-03-24 | 2021-06-25 | 郑州中科新兴产业技术研究院 | Method for recycling waste lithium iron phosphate powder |
| CN113108291A (en) * | 2021-04-22 | 2021-07-13 | 红河州现代德远环境保护有限公司 | Device for pretreating dichloroethane by pyrogenic process |
| CN113594420A (en) * | 2021-09-30 | 2021-11-02 | 中南大学 | Regeneration method of lithium ion battery graphite cathode and regenerated graphite cathode thereof |
| CN114497796A (en) * | 2022-02-15 | 2022-05-13 | 湖南工程学院 | Full-component resource recycling method for lithium iron phosphate-carbon waste |
| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
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| CN113594420B (en) * | 2021-09-30 | 2022-02-01 | 中南大学 | Regeneration method of lithium ion battery graphite cathode and regenerated graphite cathode thereof |
| CN114497796A (en) * | 2022-02-15 | 2022-05-13 | 湖南工程学院 | Full-component resource recycling method for lithium iron phosphate-carbon waste |
| CN114497796B (en) * | 2022-02-15 | 2022-08-09 | 湖南工程学院 | Full-component resource recycling method for lithium iron phosphate-carbon waste |
| CN114853004A (en) * | 2022-04-25 | 2022-08-05 | 蜂巢能源科技股份有限公司 | Negative electrode material and preparation method and application thereof |
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