CN110233260A - Using the ternary cathode material of lithium ion battery and method of waste hand alloy material preparation - Google Patents
Using the ternary cathode material of lithium ion battery and method of waste hand alloy material preparation Download PDFInfo
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Abstract
A kind of ternary cathode material of lithium ion battery and method using waste hand alloy material preparation, belongs to the field of lithium ion battery and resource recycling.This method is using waste hand alloy material as raw material, acidleach is carried out to waste hand alloy material with acid and hydrogen peroxide, after leachate is aoxidized, pH value is adjusted with alkaline solution, contamination precipitation is removed, take supernatant, wherein cobalt is tested with atomic absorption spectrum, the content of nickel and third element, according to the tertiary cathode material ingredient of preparation, it is proportionally added into cobalt salt, nickel salt, manganese salt or aluminium salt, after stirring and dissolving, it is added drop-wise in alkaline solution and is co-precipitated, precipitating is washed, separation, it is dry, it is mixed into lithium salts, grinding is uniform, it is sintered obtained ternary cathode material of lithium ion battery again, realize the recycling of waste.This method effectively reduces production cost using discarded waste hand alloy material as raw material, easy to operate, the proportion of tertiary cathode material in adjustable lithium ion battery, product multiplicity.
Description
Technical field
The present invention relates to the fields of lithium ion battery and resource recycling, and in particular to is prepared using waste hand alloy material
Ternary cathode material of lithium ion battery and method.
Background technique
Lithium ion battery has many advantages, such as that energy density is big, long service life, memory-less effect, to become application at present most
Extensive secondary cell, and still there is wide development space.Currently, with the fast development in new-energy automobile field, to dynamic
Power lithium ion battery cost and safety are put forward higher requirements.The commercialized positive electrode that succeeded at present mainly has cobalt acid lithium
(LiCoO2), LiMn2O4 (LiMn2O4) and LiFePO 4 (LiFePO4).Cobalt acid lithium material price is expensive, and structural stability,
It thermal stability and overcharges safety-type poor, is not suitable as large-sized power and energy storage lithium ion battery positive electrode；LiMn2O4 ratio
Capacity is lower (about 120mAh/g), and high temperature circulation stability is poor, and capacity attenuation is too fast at higher voltages；LiFePO 4
Though have many advantages, such as to have extended cycle life and have a safety feature, the low (< 10 of its electronic conductivity-9S/cm), specific capacity is also limited
In 170mAh/g hereinafter, big multiplying power current charge-discharge electrical property is poor, and compacted density is low, and volume energy density is low.And nickel cobalt
LiMn2O4 (NCM) and nickel cobalt lithium aluminate (NCA) due to its specific discharge capacity is big, energy density is high and LiFePO4 together as
Three kinds of mainstream positive electrodes of power lithium-ion battery.For save the cost and the course continuation mileage of raising electric car, have
The ternary cathode material of lithium ion battery of high-energy density just becomes first choice therein.
Waste hand alloy material main methods are to recycle at a low price at present, at the method for then carrying out founding again
Reason, but that there are density is low, firmness change is big, bending strength is low, alloy structure mixes for hard alloy obtained again for this method
And solution generates the problems such as dirtyization, and high-temperature process is needed in reflow process, energy consumption is larger.
Summary of the invention
The object of the present invention is to provide it is a kind of using waste hand alloy material preparation ternary cathode material of lithium ion battery and
Method, the preparation method carry out acidleach to waste hand alloy material using waste hand alloy material as raw material, with acid and hydrogen peroxide, leach
Liquid with alkaline solution slowly adjusts pH value after being aoxidized, and contamination precipitation is removed, supernatant is taken, is tested with atomic absorption spectrum
The wherein content of cobalt, nickel and third element, according in the tertiary cathode material of preparation, the content of each ingredient is proportionally added into
A certain amount of cobalt salt, nickel salt, manganese salt or aluminium salt after stirring and dissolving, are added drop-wise in alkaline solution are co-precipitated dropwise.It has precipitated
Quan Hou washs precipitating, is separated.By the precipitating drying after separation, it is mixed into appropriate lithium salts, grinding uniformly, then is sintered
Ternary cathode material of lithium ion battery is made, realizes the recycling of waste.This method is made with discarded waste hand alloy material
For raw material, the production cost of ternary cathode material of lithium ion battery can be effectively reduced, easy to operate, adjustable lithium ion
The proportion of tertiary cathode material in battery, product multiplicity.
A kind of method that ternary cathode material of lithium ion battery is prepared using waste hand alloy material of the invention, including it is following
Step:
Step 1: the acidleach of waste hand alloy material
According to the amount of waste hand alloy material to be processed, the amount of acid solution and hydrogenperoxide steam generator is determined；Wherein, acid solution
In hydrionic molar concentration be 4~10mol/L, by solid-to-liquid ratio, waste hand alloy material: acid solution=1g:(6~12) mL；
The mass concentration of hydrogen peroxide is 25~35% in hydrogenperoxide steam generator, by solid-to-liquid ratio, waste hand alloy material: hydrogenperoxide steam generator
=1g:(3~5) mL；
Acid solution and hydrogenperoxide steam generator are mixed, stirring is heated to 60~90 DEG C, obtains mixed liquor；
Waste hand alloy material is added in mixed liquor, stirring carries out acidleach >=5h, is separated by solid-liquid separation, obtains leachate；
Step 2: leachate removal of impurities
Into leachate, oxidant is added or is passed through air, while with stirring, being heated to 60~90 DEG C, it is molten with alkalinity
Drop, which adds, adjusts pH value to 4~5, preferably 4.2~4.5, is separated by solid-liquid separation, obtains supernatant；
Tested using atomic absorption spectrum, measure nickel in supernatant, cobalt, third element content；Wherein, third element is
Manganese or aluminium；
Step 3: the preparation of ternary cathode material of lithium ion battery
(1) nickel salt, cobalt salt, manganese are added into supernatant according to the content of nickel in the supernatant of measurement, cobalt, third element
One or more of salt or aluminium salt are adjusted in supernatant, and the molar ratio of each element is nickel: cobalt: third element=(1~
8): (1~2): (0.5~4)；Supernatant after obtaining modifying ingredients；
(2) by the supernatant after modifying ingredients, be added drop-wise in reactor respectively with alkaline solution, adjust pH value be 10.5~
11.5, stirring is heated to 40~60 DEG C, carries out ageing reaction >=6h, is separated by solid-liquid separation, the sediment that will be obtained, washing, drying,
Obtain ternary material precursor；
(3) ternary material precursor and lithium salts are mixed, grinding uniformly, under air or oxygen atmosphere, is sintered, obtains
To ternary cathode material of lithium ion battery；Wherein, in molar ratio, the Li in lithium salts: total metal content Me in ternary material precursor
=1.05:1.
In the step 1, in the waste hand alloy material, the mass percent of the element and each element that contain
Are as follows: it be 48.4%~60.1%, Co be 12.0%~15.0%, Mo is 3.5%~5.0% that Cr, which is 18.0%~21.0%, Ni,
Al is that 1.2%~1.6%, Ti is 2.75%~3.25%, Fe≤2%, and surplus is impurity.
In the step 1, the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid.
In the step 1, the stirring, mixing speed is 100~500r/min.
In the step 2, the oxidant is one or more of sodium hypochlorite, hydrogen peroxide, by solid-to-liquid ratio, oxygen
Agent: leachate=(1~4) g:1L；
In the step 2, the flow for being passed through air is 4~8L/min.
In the step 2, the stirring, mixing speed is 300~800r/min.
In the step 2, the alkaline solution is that aqueous sodium carbonate, sodium hydrate aqueous solution, potassium carbonate are water-soluble
One or more of liquid, potassium hydroxide aqueous solution, the molar concentration of alkaline solution are 0.01~3mol/L, are adjusting pH value
In, it is adjusted using the stage.
In the step 2, the rate of change of pH value is 0.2/min.
In the step 2, the separation of solid and liquid is preferably centrifugated.
In the step 3 (1), nickel salt is soluble nickel salt, preferably nickel chloride and/or nickel sulfate；Cobalt salt is solvable
Property cobalt salt, preferably cobalt chloride and/or cobaltous sulfate；Manganese salt is soluble manganese salt, preferably manganese chloride and/or manganese sulfate；Aluminium salt
For aluminum soluble salt, preferably aluminium chloride and/or sodium metaaluminate.
In the step 3 (1), preferably, being in molar ratio nickel: cobalt: third element=1:1:1,6:2:2,5:2:
3, one of 4:2:4,8:1:1,8:1.5:0.5.
In the step 3 (2), drop rate 10mL/min.
In the step 3 (2), the stirring, mixing speed is 500~1000r/min.
In the step 3 (2), the drying is vacuum drying, and drying temperature is 70~100 DEG C.
In the step 3 (2), alkaline solution is the mixed solution of sodium hydroxide and ammonium hydroxide, wherein presses molar concentration
Than sodium hydroxide: ammonium hydroxide: total metal=(2~3) in the supernatant after modifying ingredients: 1:1.
In the step 3 (3), the lithium salts is one or two kinds of in lithium carbonate or lithium hydroxide.
In the step 3 (3), the sintering, using crucible, preferably alumina crucible.
In the step 3 (3), the sintering, technique are as follows: first 5~8h of sintering at 300~500 DEG C, then
8~20h is sintered at 700~950 DEG C.
In the step 3 (3), the sintering, heating rate and rate of temperature fall are 3~5 DEG C/min.
The ternary cathode material of lithium ion battery, after preparation, after grinding >=1h, encapsulation.
A kind of ternary cathode material of lithium ion battery prepared using waste hand alloy material, using above-mentioned preparation method system
?.
A kind of electrode slice, using the above-mentioned ternary cathode material of lithium ion battery prepared using waste hand alloy material.
A kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, wherein the anode uses above-mentioned electrode
Piece.
A kind of preparation method of electrode slice, comprising the following steps:
Step I: ternary cathode material of lithium ion battery, conductive agent, binder are mixed, and after grinding uniformly, NMP tune is added
Viscosity is saved, stirs evenly, obtains slurry；Wherein, in mass ratio, ternary cathode material of lithium ion battery, conductive agent, binder=
8:1:1；By solid-to-liquid ratio, (ternary cathode material of lithium ion battery+conductive agent+binder): NMP=0.5g:(6~10) mL.
Step II: slurry is coated uniformly on aluminium foil, and vacuum drying obtains electrode slice.
Using above-mentioned electrode slice as the anode of lithium ion battery, it is assembled in lithium ion button shape cell, tests its cycle performance
Are as follows: first circle specific discharge capacity reaches 150~210mAh/g, and after circulation 100 is enclosed, capacity retention ratio is 75%~90%.
In the step I, the conductive agent is one of acetylene carbon black, carbon nanotube, Super-P Li, graphite
Or it is several.
In the step I, the binder is one or more of PVDF, CMC.
In the step I, the grinding, milling time 1h.
A kind of ternary cathode material of lithium ion battery and method using waste hand alloy material preparation of the invention, principle
It is: prepares ternary cathode material of lithium ion battery to recycle the waste hand alloy material of the nickel containing cobalt.Pass through the catalysis oxygen of hydrogen peroxide
Change effect carries out acidleach to waste hand alloy material.According to the different solubility of different metal ions hydroxide in aqueous solution,
Remove the impurity element in leachate in addition to cobalt, nickel.By the way that a certain amount of nickel salt, cobalt salt, manganese salt (aluminium salt) is added, to solution
In nickel, cobalt, manganese (aluminium) ratio be adjusted.Chemical precipitation is carried out to the solution after adjusting ratio with alkaline solution, filters, wash
It washs, dry, add lithium salts, be sintered under air or oxidizing atmosphere, pass through metal hydroxides and carbonate product
Decomposition reaction obtain ternary cathode material of lithium ion battery.
A kind of ternary cathode material of lithium ion battery and method using waste hand alloy material preparation of the invention is beneficial
Effect is:
1, nickeliferous, cobalt alloyed scrap can effectively be recycled using method of the invention, solves hard
The processing problem of alloyed scrap.
2, using alloyed scrap as raw material, the cost of ternary cathode material of lithium ion battery is effectively reduced, and ratio can
It adjusts, the ternary material product of available any different proportion.
Detailed description of the invention
Fig. 1 is a kind of method of ternary cathode material of lithium ion battery using waste hand alloy material preparation of the invention
Process flow diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
In the embodiment of the present invention, unless specifically indicated, the raw material and equipment of use be it is commercially available, purity be analyze it is pure and with
On；The concentrated hydrochloric acid that specially uses, sulfuric acid, nitric acid, hydrogen peroxide is commercial products.The alumina crucible used is commercially available production
Product.Manganese salt, aluminium salt, carbonate, lithium salts, sodium hydroxide and the sodium hypochlorite of use, purity are that analysis is pure.
In following embodiment, using the technique of the method for the ternary cathode material of lithium ion battery of waste hand alloy material preparation
Flow diagram is shown in Fig. 1.
In following embodiment, in the waste hand alloy material of use, the mass percent of the element and each element that contain is such as
Shown in following table:
The element and its percentage composition contained in 1 hard alloy cutting waste material of table
Embodiment 1
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material, is sequentially included the following steps:
Step 1: the acidleach of waste hand alloy material
20g waste hand alloy material is weighed, 180mL 6mol/L hydrochloric acid is mixed with 30% hydrogen peroxide of 60mL, 90 DEG C of water
Bath heating obtains mixed liquor, then waste hand alloy material is put into mixed liquor, and mechanical stirring carries out acidleach, and leaching time 5h is obtained
To leachate.
Step 2: leachate removal of impurities
Into leachate, drum air, air mass flow 6L/min are stirred under the stirring rate of 400r/min, 80 DEG C of water-baths
Heating, first slowly adjusts pH value to 3 with 3mol/L sodium hydroxide, then slowly adjusts pH value to 4.5 with 0.1mol/L sodium hydroxide,
Wherein, this pH is 0.2/min to rate of change, and centrifuge separation obtains supernatant.Supernatant is measured with atomic absorption spectrum
The content of middle nickel, cobalt, manganese.
Step 3: the preparation of ternary cathode material of lithium ion battery
(1) 200mL supernatant is taken, is added a certain amount of nickel salt, cobalt salt or manganese salt, nickel in supernatant, cobalt, manganese is adjusted and rubs
You are than being Ni:Co:Mn=1:1:1, the supernatant after obtaining modifying ingredients.
(2) supernatant after taking modifying ingredients drips it with the mixed solution of 200mL sodium hydroxide and ammonium hydroxide dropwise respectively
It is added in reactor, adjusts pH most 11, wherein drop rate 10mL/min, naoh concentration are metal in supernatant
2 times of concentration of element, ammonia concn is identical as metallic element concentration in supernatant, and 50 DEG C of heating water baths are with mixing speed
900r/min stirring, reacts 12h, obtains sediment, sediment is washed, and 80 DEG C of vacuum drying 12h are to get to before ternary material
Drive body.
(3) obtained ternary material precursor is mixed with a certain amount of lithium carbonate, makes elemental lithium and transition metal element
Molar ratio be Li:Me=1.05:1, grinding uniformly, be put into alumina crucible, under air atmosphere, heating rate be 3~5
DEG C/min, and 6h being first sintered at 450 DEG C, then 12h is sintered at 900 DEG C, rate of temperature fall is 3~5 DEG C/min, it is taken out after cooling,
Ternary cathode material of lithium ion battery is obtained, is ground, encapsulation.
Step 4: performance test
(1) ternary cathode material of lithium ion battery, acetylene carbon black and PVDF being mixed, three's gross mass is 0.5g,
1h is ground, the NMP that 8mL is added adjusts viscosity, stirs 1h or more, obtains slurry；In mass ratio, lithium ion battery tertiary cathode
Material, acetylene carbon black, PVDF=8:1:1.
(2) slurry stirred evenly is uniformly coated on aluminium foil with spreader, is dried in vacuo, obtains electrode slice.
(3) electrode slice after drying is assembled into lithium ion button shape cell as the anode of lithium ion battery, tests it
Cycle performance.After the circle of loop test 100 under the conditions of 2.8~4.3V, 0.5C, specific capacity is decayed to from 160.8mAh/g
137.2mAh/g, capacity retention ratio 85.3%.
Embodiment 2
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 6h, then in 850 DEG C of sintering 12h；
(2) lithium ion button shape cell prepared, specific capacity decay to 120.4mAh/g from 151.2mAh/g, and capacity is kept
Rate is 79.6%.
Other modes are identical.
Embodiment 3
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 6h, then in 800 DEG C of sintering 16h；
(2) lithium ion button shape cell prepared, specific capacity decay to 113.5mAh/g from 145.3mAh/g, and capacity is kept
Rate is 78.1%.
Other modes are identical.
Embodiment 4
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 6h, then in 750 DEG C of sintering 16h；
(2) lithium ion button shape cell prepared, specific capacity decay to 100.5mAh/g from 132.8mAh/g, and capacity is kept
Rate is 75.7%.
Other modes are identical.
Embodiment 5
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) during (1) of step 3 adjusts nickel, cobalt, manganese ratio, molar ratio Ni:Co:Mn=6:2:2；
(2) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 900 DEG C of sintering 15h；
(3) lithium ion button shape cell prepared, specific capacity decay to 116.3mAh/g from 143.6mAh/g, and capacity is kept
Rate is 81.0%.
Other modes are identical.
Embodiment 6
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 5, difference
It is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 850 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 135.3mAh/g from 161.8mAh/g, and capacity is kept
Rate is 83.6%.
Other modes are identical.
Embodiment 7
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 5, difference
It is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 800 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 118.3mAh/g from 145.7mAh/g, and capacity is kept
Rate is 81.2%.
Other modes are identical.
Embodiment 8
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 5, difference
It is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 750 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 95.7mAh/g from 120.4mAh/g, and capacity is kept
Rate is 79.5%.
Other modes are identical.
Embodiment 9
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) during (1) of step 3 adjusts nickel, cobalt, manganese ratio, molar ratio Ni:Co:Mn=5:2:3；
(2) in (3) sintering process of step 3, first in 750 DEG C of sintering 4h, then in 900 DEG C of sintering 16h；
(3) lithium ion button shape cell prepared, specific capacity decay to 124.6mAh/g from 151.2mAh/g, and capacity is kept
Rate is 82.4%.
Other modes are identical.
Embodiment 10
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 9, difference
It is:
(1) in (3) sintering process of step 3, first in 750 DEG C of sintering 5h, then in 850 DEG C of sintering 16h；
(2) lithium ion button shape cell prepared, specific capacity decay to 146.2mAh/g from 165.3mAh/g, and capacity is kept
Rate is 88.4%.
Other modes are identical.
Embodiment 11
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 9, difference
It is:
(1) in (3) sintering process of step 3, first in 750 DEG C of sintering 5h, then in 800 DEG C of sintering 16h；
(2) lithium ion button shape cell prepared, specific capacity decay to 116.3mAh/g from 143.6mAh/g, and capacity is kept
Rate is 81.0%.
Other modes are identical.
Embodiment 12
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) during (1) of step 3 adjusts nickel, cobalt, manganese ratio, molar ratio Ni:Co:Mn=4:2:4；
(2) in (3) sintering process of step 3, first in 450 DEG C of sintering 10h, then in 900 DEG C of sintering 20h；
(3) lithium ion button shape cell prepared, specific capacity decay to 94.2mAh/g from 124.6mAh/g, and capacity is kept
Rate is 75.6%.
Other modes are identical.
Embodiment 13
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 12
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 10h, then in 850 DEG C of sintering 20h；
(2) lithium ion button shape cell prepared, specific capacity decay to 116.3mAh/g from 143.6mAh/g, and capacity is kept
Rate is 81.0%.
Other modes are identical.
Embodiment 14
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 12
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 10h, then in 800 DEG C of sintering 20h；
(2) lithium ion button shape cell prepared, specific capacity decay to 142.1mAh/g from 168.4mAh/g, and capacity is kept
Rate is 84.4%.
Other modes are identical.
Embodiment 15
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 12
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 10h, then in 750 DEG C of sintering 20h；
(2) lithium ion button shape cell prepared, specific capacity decay to 125.7mAh/g from 152.6mAh/g, and capacity is kept
Rate is 82.4%.
Other modes are identical.
Embodiment 16
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.With embodiment 1, difference
It is:
(1) during (1) of step 3 adjusts nickel, cobalt, manganese ratio, molar ratio Ni:Co:Mn=8:1:1；
(2) it in (3) sintering process of step 3, is carried out under oxygen atmosphere, first in 450 DEG C of sintering 5h, then in 850 DEG C of burnings
Tie 15h；
(3) lithium ion button shape cell prepared, specific capacity decay to 122.5mAh/g from 156.2mAh/g, and capacity is kept
Rate is 78.4%.
Other modes are identical.
Embodiment 17
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 16
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 800 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 131.9mAh/g from 162.8mAh/g, and capacity is kept
Rate is 81.0%.
Other modes are identical.
Embodiment 18
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 16
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 750 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 155.7mAh/g from 184.7mAh/g, and capacity is kept
Rate is 84.3%.
Other modes are identical.
Embodiment 19
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 16
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 5h, then in 700 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 137.2mAh/g from 166.7mAh/g, and capacity is kept
Rate is 82.3%.
Other modes are identical.
Embodiment 20
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material, is sequentially included the following steps:
Step 1: the acidleach of waste hand alloy material
20g waste hand alloy material is weighed, 180mL 6mol/L hydrochloric acid is mixed with 30% hydrogen peroxide of 60mL, 90 DEG C of water
Bath heating, obtains mixed liquor；Waste hand alloy material is put into mixed liquor again, mechanical stirring carries out acidleach, and leaching time 5h is obtained
To leachate.
Step 2: leachate removal of impurities
The drum air into leachate, the flow for being passed through air is 7L/min, is stirred under the stirring rate of 500r/min, 80
DEG C heating water bath, first slowly adjusts pH value with 3mol/L sodium hydroxide and slowly adjusts pH value to 3, then with 0.1mol/L sodium hydroxide
To 4.5, wherein this time pH to rate of change is 0.2/min, and centrifuge separation obtains supernatant.It is measured with atomic absorption spectrum
The content of nickel, cobalt, aluminium in supernatant.
Step 3: the preparation of ternary cathode material of lithium ion battery
(1) 200mL supernatant is taken, is added a certain amount of nickel salt, cobalt salt or aluminium salt, nickel in supernatant, cobalt, aluminium is adjusted and rubs
You are than being Ni:Co:Mn=0.8:0.15:0.05, the supernatant after obtaining modifying ingredients.
(2) supernatant after modifying ingredients is taken, it is added dropwise dropwise respectively with the mixed solution of 200mL sodium hydroxide and ammonium hydroxide
Into reactor, pH most 11 is adjusted, wherein drop rate 10mL/min, naoh concentration are metal member in supernatant
2 times of plain concentration, ammonia concn is identical as metallic element concentration in supernatant, and 50 DEG C of heating water baths, are 800r/ with mixing speed
Min stirring, reacts 12h, obtains sediment, sediment is washed, and 80 DEG C of vacuum drying 12h are to get to ternary material precursor.
(3) obtained ternary material precursor is mixed with a certain amount of lithium hydroxide, makes elemental lithium and transition metal element
Molar ratio be Li:Me=1.05:1, grinding uniformly, be put into alumina crucible, under oxygen atmosphere, heating rate be 3~5
DEG C/min, and 4h being first sintered at 500 DEG C, then 12h is sintered at 900 DEG C, rate of temperature fall is 3~5 DEG C/min, it is taken out after cooling,
Ternary cathode material of lithium ion battery is obtained, is ground, encapsulation.
Step 4: performance test
(1) in mass ratio by ternary cathode material of lithium ion battery, acetylene carbon black and PVDF are as follows: lithium ion battery ternary is just
Pole material: acetylene carbon black: the ratio of PVDF=8:1:1 is mixed, and three's gross mass is 0.5g, is ground 1h, is added 10mL's
NMP adjusts viscosity, stirs 1h or more, obtains slurry.
(2) slurry stirred evenly is uniformly coated on aluminium foil with spreader, is dried in vacuo, obtains electrode slice.
(3) electrode slice after drying is assembled into lithium ion button shape cell as anode, tests its cycle performance.?
After loop test 100 encloses under the conditions of 2.8~4.3V, 0.5C, specific capacity decays to 137.2mAh/g from 160.8mAh/g, and capacity is protected
Holdup is 85.3%.
Embodiment 21
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 20
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 4h, then in 850 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 154.1mAh/g from 176.5mAh/g, and capacity is kept
Rate is 87.3%.
Other modes are identical.
Embodiment 22
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 20
Point is:
(1) in (3) sintering process of step 3, first in 450 DEG C of sintering 4h, then in 800 DEG C of sintering 15h；
(2) lithium ion button shape cell prepared, specific capacity decay to 167.8mAh/g from 189.4mAh/g, and capacity is kept
Rate is 88.6%.
Other modes are identical.
Embodiment 23
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 20
Point is:
(1) in step 2, into leachate, hydrogen peroxide is added as oxidant, by solid-to-liquid ratio, oxidant: leachate=
4g:1L.
(2) in (3) sintering process of step 3, first in 450 DEG C of sintering 4h, then in 750 DEG C of sintering 15h；
(3) lithium ion button shape cell prepared, specific capacity decay to 183.5mAh/g from 204.6mAh/g, and capacity is kept
Rate is 89.7%.
Other modes are identical.
Embodiment 24
A method of ternary cathode material of lithium ion battery is prepared using waste hand alloy material.It is different with embodiment 20
Point is:
(1) in step 2, into leachate, sodium hypochlorite is added as oxidant, by solid-to-liquid ratio, oxidant: leachate=
3g:1L.
(2) in (2) of step 3, naoh concentration is 3 times of metallic element concentration in supernatant.
(3) lithium ion button shape cell prepared, specific capacity decay to 180.3mAh/g from 200.4mAh/g, and capacity is kept
Rate is 89.9%.
Other modes are identical.
Claims (12)
1. a kind of method for preparing ternary cathode material of lithium ion battery using waste hand alloy material, which is characterized in that including with
Lower step:
Step 1: the acidleach of waste hand alloy material
According to the amount of waste hand alloy material to be processed, the amount of acid solution and hydrogenperoxide steam generator is determined；Wherein, in acid solution
Hydrionic molar concentration is 4~10mol/L, by solid-to-liquid ratio, waste hand alloy material: acid solution=1g:(6~12) mL；Peroxide
The mass concentration for changing hydrogen peroxide in hydrogen solution is 25~35%, by solid-to-liquid ratio, waste hand alloy material: hydrogenperoxide steam generator=
1g:(3~5) mL；
Acid solution and hydrogenperoxide steam generator are mixed, stirring is heated to 60~90 DEG C, obtains mixed liquor；
Waste hand alloy material is added in mixed liquor, stirring carries out acidleach >=5h, is separated by solid-liquid separation, obtains leachate；
Step 2: leachate removal of impurities
Into leachate, oxidant is added or is passed through air, while with stirring, being heated to 60~90 DEG C, being dripped with alkaline solution
Add and adjust pH value to 4~5, is separated by solid-liquid separation, obtains supernatant；
Tested using atomic absorption spectrum, measure nickel in supernatant, cobalt, third element content；Wherein, third element be manganese or
Aluminium；
Step 3: the preparation of ternary cathode material of lithium ion battery
(1) according to nickel in the supernatant of measurement, cobalt, third element content, into supernatant, be added nickel salt, cobalt salt, manganese salt or
One or more of aluminium salt is adjusted in supernatant, and the molar ratio of each element is nickel: cobalt: third element=(1~8): (1
~2): (0.5~4)；Supernatant after obtaining modifying ingredients；
(2) by the supernatant after modifying ingredients, be added drop-wise in reactor respectively with alkaline solution, adjust pH value be 10.5~
11.5, stirring is heated to 40~60 DEG C, carries out ageing reaction >=6h, is separated by solid-liquid separation, the sediment that will be obtained, washing, drying,
Obtain ternary material precursor；
(3) ternary material precursor and lithium salts are mixed, grinding uniformly, under air or oxygen atmosphere, is sintered, obtains lithium
Ion battery tertiary cathode material；Wherein, in molar ratio, the Li in lithium salts: total metal content Me=in ternary material precursor
1.05:1.
2. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It is characterized in that, in the step 1, in the waste hand alloy material, the mass percent of the element and each element that contain
Are as follows: it be 48.4%~60.1%, Co be 12.0%~15.0%, Mo is 3.5%~5.0% that Cr, which is 18.0%~21.0%, Ni,
Al is that 1.2%~1.6%, Ti is 2.75%~3.25%, Fe≤2%, and surplus is impurity.
3. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It is characterized in that, in the step 1, the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid.
4. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It being characterized in that, in the step 2, the oxidant is one or more of sodium hypochlorite, hydrogen peroxide, by solid-to-liquid ratio,
Oxidant: leachate=(1~4) g:1L；The flow for being passed through air is 4~8L/min.
5. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It is characterized in that, in the step 2, the alkaline solution is that aqueous sodium carbonate, sodium hydrate aqueous solution, potassium carbonate are water-soluble
One or more of liquid, potassium hydroxide aqueous solution, the molar concentration of alkaline solution are 0.01~3mol/L, are adjusting pH value
In, it is adjusted using the stage.
6. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It being characterized in that, in the step 3 (1), nickel salt is soluble nickel salt, and cobalt salt is soluble cobalt, and manganese salt is soluble manganese salt,
Aluminium salt is aluminum soluble salt.
7. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It is characterized in that, in the step 3 (2), alkaline solution is the mixed solution of sodium hydroxide and ammonium hydroxide, wherein presses molar concentration
Than sodium hydroxide: ammonium hydroxide: total metal=(2~3) in the supernatant after modifying ingredients: 1:1.
8. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It is characterized in that, in the step 3 (3), the lithium salts is one or two kinds of in lithium carbonate or lithium hydroxide.
9. the method according to claim 1 that ternary cathode material of lithium ion battery is prepared using waste hand alloy material,
It is characterized in that, in the step 3 (3), the sintering, technique are as follows: first 5~8h of sintering at 300~500 DEG C, then
8~20h is sintered at 700~950 DEG C；The heating rate and rate of temperature fall of sintering are 3~5 DEG C/min.
10. a kind of ternary cathode material of lithium ion battery prepared using waste hand alloy material, which is characterized in that wanted using right
Method described in 1~9 any one is asked to be made.
11. a kind of electrode slice, which is characterized in that using the lithium ion described in any one of claim 10 prepared using waste hand alloy material
Battery tertiary cathode material.
12. a kind of lithium ion battery, including anode, cathode, diaphragm and electrolyte, which is characterized in that the anode is using power
Benefit require 11 described in electrode slice.
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