CN108649291A - It is a kind of using waste and old lithium ion battery as the technique of raw materials recovery nickel-cobalt lithium manganate cathode material - Google Patents
It is a kind of using waste and old lithium ion battery as the technique of raw materials recovery nickel-cobalt lithium manganate cathode material Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
It is a kind of using waste and old lithium ion battery as the technique of raw materials recovery nickel-cobalt lithium manganate cathode material, belong to waste lithium cell recycling field.Lithium ion battery positive plate is crushed, is pyrolyzed under the conditions of temperature is 400 450 DEG C, is sieved, make positive powder and other materials physical separation.Then positive electrode and hydrosulphate are roasted, product of roasting is dissolved in deionized water, and specifically discloses specific dissolving step and the setting to each parameter in course of dissolution.Then it after cleaning to leachate, then is co-precipitated as precipitating reagent using sodium carbonate and sodium bicarbonate mixed liquor and carbonate precursor is made, mixed then and with lithium carbonate and nickle cobalt lithium manganate tertiary cathode material then is made by calcining.The present invention is by waste lithium ion cell anode closed matereial cycle, and by reverse reclamation technique, nickle cobalt lithium manganate tertiary cathode material is made again, realizes recycling.
Description
Technical field
The invention belongs to waste and old lithium ion battery recycling fields, are related to one kind using waste and old lithium ion battery as raw materials recovery system
The technique for making nickel-cobalt lithium manganate cathode material.
Background technology
Lithium ion battery is widely used in mobile phone, number as a kind of secondary cell of high-energy high power and high life
The numerous civilian and military fields such as code camera, laptop, electronic instrument.With the yield of China's lithium ion battery in recent years
With increasing rapidly for consumption figure, the increasingly sharp increase of waste and old lithium ion battery learies is brought.It is counted according to China Battery Industry, in advance
The year two thousand twenty is counted, China's lithium ion consumption figure will have reached 25,000,000,000, if these lithium ion batteries for being scrapped after
It is not subject to appropriate reuse, does not only result in a large amount of valuable resource wastes, and the elements such as the cobalt being wherein mingled with and fluorine have environment
Certain toxicity.Lithium ion battery is other than with battery quality that cobalt acid lithium is anode, also nickel cobalt manganese, nickel cobalt manganese aluminium and phosphorus
The materials such as sour iron lithium are the lithium ion battery of anode.In existing lithium ion battery, nickel-cobalt-manganternary ternary anode material is higher with it
Specific capacity and longer cycle life, had been widely used in power battery field.Usually, lithium ion battery contains
Some cobalt contents are 5~20wt%, and lithium content is 1~3wt%, and nickel content is 5~10wt%, these elements belong to rare gold
Belong to, is significantly higher than corresponding tenor in nature ore.Therefore the recycling for carrying out waste and old lithium ion battery, not only realizes
Valuable scarce resource efficiently uses, and reduces its damage to environment, is to realize lithium ion battery industry sustainable development
Key technology.
In existing lithium ion battery recovery technology, such as the Chinese patent literature of publication number CN107326181A discloses
The recovery method that a step is completed is leached in a kind of waste and old lithium ion battery stripping, and it is original to disclose it with waste and old lithium ion battery
Material immerses after electric discharge, being manually or mechanically crushed in pure water or certain density sulfuric acid solution, then adjusts the acidity of solution
And the solution for being leached after reducing agent is removed and relevant metal ions being obtained by filtration is added, the sulfuric acid of removal process can set production
Have stronger corrosiveness.In addition, valuable metal nickel, cobalt in battery, manganese, lithium enter in filtrate, copper foil, aluminium foil, graphite
Into being recycled in filter residue.
The Chinese patent literature of publication number CN106834703A discloses a kind of waste lithium ion cell anode active material
Leaching method, waste and old lithium ion battery through short circuit dischange, dismantling, binder stripping, crushing and screening obtain electrode material powder；It will
The electrode material powder roasts to obtain calcining under sulfur dioxide carrier gas atmosphere, wherein sulfur dioxide carrier gas flux be 30~
50L/h, calcination temperature are 300~450 DEG C；The calcining is dispersed in water agitation and filtration and obtains the water-soluble of positive electrode active materials
Liquid.
In the Chinese patent literature of publication number CN101570750, a kind of cobalt in waste lithium ion batteries and lithium are disclosed
High-efficiency strain breeding method for biologically leaching, it is characterized in that selection step is：(1) place of lithium ion battery electrode material
Reason；(2) acquisition, enrichment, the purifying of high-performance strain；(3) Fe is added2+, the energy substances such as sulphur and thiosulfate and institute is added
The lithium battery powder culture bacterium that need to be leached, is tamed, is cultivated；(4) mutagenesis is carried out to bacterium with ultraviolet light, is mutated
Hybrid bacterial strain；Regrettably, it recycles yield and the rate of recovery is limited by bacterium itself.
From the point of view of the analysis to paper both domestic and external and patent document, valuable gold in existing recycling waste and old lithium ion battery
The step of category is：Old and useless battery is split first, then passes through isolated each component part；Last waste and old lithium ion battery ternary
Positive electrode, which is re-dissolved, could further be made high value added product, realize the recycling of valuable metal in addition to carrying above
For the three kinds of typical methods arrived, there is also sulfuric acid-hydrogen peroxide to leach, citric acid-hydrogen peroxide leaches, HNO3And HNO3-H2O2Body
The methods of system leaches active material.In order to ensure the higher leaching rate of these active materials, the excessive nothing of generally use
Machine acid and reducing agent carry out reproducibility acidleach in tertiary cathode material, and acid leaching solution excessive so not only causes sternly equipment
Weight corrosiveness, and subsequent step also need go to neutralize with a large amount of alkali, increase industrial cost and environmental pressure.
Although newest research further includes some organic acid+hydrogen peroxide to dissolve anode material for lithium-ion batteries, organic acid and
Commercial recovery cost has been significantly greatly increased in hydrogen peroxide higher price.
In view of this, this patent proposes waste lithium ion cell anode material and faintly acid sulfate carries out reproducibility roasting
It burns, then obtains leachate by leaching agent of distilled water.Since the pH value of leachate is weakly acidic pH, excessive acid is significantly reduced
To the corrosion of equipment and the cost of follow-up alkali neutralization.In addition, just due to the use of neutral leachate, weakly acidic pH that the present invention obtains
Leachate further uses weakly alkaline sodium carbonate and sodium bicarbonate pH mixing buffer solution to be made as precipitating reagent co-precipitation
Manufacture the presoma of lithium ion anode material.
Invention content
The present invention provides one kind using waste and old lithium ion battery as raw materials recovery nickel cobalt in order to overcome the deficiencies of the prior art
The technique of manganate cathode material for lithium, the present invention is intended to provide a kind of by recycling waste lithium cell nickel-cobalt lithium manganate cathode material
Method achievees the purpose that resource circulation utilization.
It is a kind of using waste and old lithium ion battery as the technique of raw materials recovery nickel-cobalt lithium manganate cathode material, including following step
Suddenly：
(1) lithium ion battery positive plate is subjected to pretreatment and obtains the positive electrode powder containing cobalt, nickel, manganese；
(2) positive powder of step (1) and hydrosulphate are subjected to atmosphere roasting, are solubility by nickel cobalt manganese cycling of elements
Sulfate；
(3) deionized water will be added in obtained product of roasting in step (2), and is leached under water bath condition,
The leachate of nickeliferous, cobalt and manganese is obtained after filtering and impurity removing, detects nickel cobalt manganese ion concentration；
(4) nickel source, cobalt source or manganese source is added toward step (3) leachate China and foreign countries, adjusts the mole dense of nickel cobalt manganese in leachate
Degree is than being 1:1:1；
(5) using sodium carbonate and sodium bicarbonate mixed liquor as precipitating reagent, nickel cobalt manganese metal ion is made to be co-precipitated, after filtration washing
Carbonate precursor is obtained, the carbonate precursor is after ageing and then nickle cobalt lithium manganate is made by calcining in lithium carbonate mixing
Tertiary cathode material.
Pretreatment described in step (1) is to crush battery anode slice, in the case where temperature is 400-450 DEG C of air conditions
It is pyrolyzed, is sieved under vibration using 20-80 the polished standard screens, obtain positive powder.
Above-mentioned pyrolysis carries out in air or/and nitrogen or/and argon gas or/and ammonia atmosphere.
Step (2) is roasted in air or/and nitrogen or/and argon gas or/and ammonia atmosphere, preferably roast in ammonia or
It is carried out under the conditions of person's ammonia and nitrogen atmosphere, in addition to directly using additional ammonia condition, or/and the anode that is obtained in step (1)
Powder is added ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, the ammonium dihydrogen phosphate of weight ratio 5-130%, in diammonium hydrogen phosphate, urea
A kind of, two kinds or two or more mixtures.Waste and old lithium ion battery tertiary cathode material described in step (2) and acid
The molar ratio of property sulfate is preferably 1:1-1:5；Calcination temperature is 300 DEG C -600 DEG C, and preferable temperature is 350 DEG C -550 DEG C, most
Preferable temperature is 350 DEG C -490 DEG C；Roasting time is 0.5-2h.
Removal of impurities described in step (3) is to remove iron with yellow sodium ferrum vanadium process, i.e., first by the pH of leachate be adjusted to 0.3-2.7 it
Between, it is heated to 60-102 DEG C, is then slowly added into NaOH solution, the pH for adjusting solution is 1.7-1.9, after reacting 2h, control
The pH of terminal between 3 and 6, after so that iron ion is formed ferric hydroxide precipitate, is filtered to remove；Aluminium is removed with Hydrolyze method again, i.e., by filtrate
It is heated to 75-100 DEG C, adjusting pH value of solution is 3-6, reacts 0.2-3h, aluminium ion is made to hydrolyze to form Al (OH)3Precipitation, through filtering
Obtain the leachate containing nickel cobalt manganese ion.The extraction temperature of product of roasting described in step (3) is 10-90 DEG C, preferably warm
Degree is 20 DEG C -90 DEG C, and preferably temperature is 25 DEG C -80 DEG C；Extraction time is 10-120min.
Step (5) precipitating reagent sodium carbonate and sodium bicarbonate total mole number and the total mole number of ions ratio of nickel cobalt manganese Metal are (1-
3):1；The molar ratio of sodium carbonate and sodium bicarbonate mixed liquor precipitating reagent is 1:(0.5-3)；Step (5) is according to nickel cobalt manganese total moles
Number is 1 with lithium total mole number:(1.05-1.2) mixes carbonate precursor and lithium carbonate.Co-precipitation described in step (5)
The condition of reaction carbonate precursor obtained is that pH is controlled between 7-12, and reaction temperature is 40-80 DEG C, and the reaction time is
0.2-3 hours, digestion time 4-24h.
In the technique of recycling nickel-cobalt lithium manganate cathode material, which is characterized in that the hydrosulphate described in step (2) is
It is one or more in ammonium sulfate, ammonium hydrogen sulfate, niter cake, potassium acid sulfate；Nickel source described in step (4) be nickel nitrate,
One kind in nickel sulfate；Cobalt source is one kind in cobalt nitrate, cobaltous sulfate；Manganese source is one kind in manganese sulfate or manganese nitrate.
In order to ensure to obtain the good nickel-cobalt-manganese ternary material of chemical property, by a large number of experiments, step (5) calcining
Temperature is 700-1200 DEG C, and preferable temperature is 800-1000 DEG C；Calcination time is 6-20h, and the preferably time is 8-18h.
The present invention is had the following advantages relative to present technology and effect：
(1) present invention recycles waste lithium ion cell anode material, then recombines new nickle cobalt lithium manganate just
Pole material realizes that the Efficient Cycle of resource utilizes.
(2) prior art uses inorganic Ore Leaching, in order to enable positive electrode to dissolve to greatest extent, so acid should mistake
Amount, causes leachate acidity too strong.It also needs to adjust acid-base value with a large amount of alkali to make subsequent step be normally carried out, it can also be to equipment
There is corrosiveness.And the present invention uses the method that is leached again with weakly acidic pH sulfating roasting, leachate acid-base property close to neutrality,
Highly basic is omitted and adjusts acid-base value step, has many advantages, such as that operating procedure is simple and environmentally-friendly, simple for process and can commercial introduction.
(3) present invention is on the basis of neutral leachate, using carbonate-bicarbonate composite buffering solution coprecipitation method
Precursor of nickel-cobalt-lithium-manganese-oxide is synthesized, compared with existing coprecipitation method, composite buffering solution ph is stablized, easily controllable, easily
In obtaining crystallization and the good nickel cobalt manganese carbonate deposition of pattern by subsequent ageing process, to be to prepare nickle cobalt lithium manganate
Material provides quality raw materials.
Description of the drawings
Fig. 1 is waste and old lithium ion battery tertiary cathode material extract technology flow chart；
Fig. 2 is the XRD diagram and EDS figures of 1 nickle cobalt lithium manganate of embodiment；
(a) XRD diagram of nickle cobalt lithium manganate and (b) EDS scheme.
Fig. 3 is the electrical property of 1 gained nickle cobalt lithium manganate of embodiment；(a) it is the charging and discharging curve figure of gained nickle cobalt lithium manganate,
(b) it is the cycle life figure recycled after 50 circles.
Specific implementation mode
Below will by specific implementation mode, the present invention will be described in detail, but the present invention is not limited to following implementations
Example.
The pH of leachate is first adjusted to 1.0 or so, is heated to 95 DEG C, then delays by removal of impurities to remove iron with yellow sodium ferrum vanadium process
Slow that NaOH solution is added, the pH for adjusting solution is that 1.7-1.9 controls the pH of terminal 3.2, gradually form hydrogen after reacting 2h
Iron oxide precipitates, and iron ion is removed by filtration；Aluminium is removed by Hydrolyze method again, i.e., filtrate is heated to 95 DEG C, adjusting pH value of solution is
3.5-4.3 reacts 2h, aluminium ion therein is made to hydrolyze to form Al (OH)3Precipitation, is finally obtained by filtration containing purer nickel cobalt manganese
Leachate.
Embodiment 1：
A kind of technique preparing nickel-cobalt lithium manganate cathode material using waste and old lithium ion battery as raw materials recovery, including it is following several
A step：
(1) battery cell positive plate is crushed, is pyrolyzed at 400 DEG C in air, under vibration using 200 the polished standard screens
It is sieved, obtains positive powder 10g.
(2) will in positive powder be added 28g ammonium sulfate be sufficiently mixed uniformly, then under the conditions of blowing air in Muffle furnace into
Row roasting, calcination temperature are 470 DEG C, roasting time 2h.Then 100mL deionized waters are added in product of roasting, at 60 DEG C
Under leached, leachate is obtained by filtration.
(3) leachate yellow sodium ferrum vanadium process is removed into impurity iron, while after Hydrolyze method removing impurity aluminum, survey is analyzed to obtain and be leached
Nickel ion concentration is 0.95mol L in liquid-1, concentration of cobalt ions is 0.97mol L-1, manganese ion concentration is 0.92mol L-1。
(4) according to analysis result, nickel sulfate and cobaltous sulfate are added into the mixed liquor of step (3), make nickel ion and cobalt from
Sub- concentration is increased to 0.97mol L-1。
(5) it is 45 DEG C of sodium carbonate and sodium bicarbonate mixed solution that temperature is added into step (4) solution, controls pH value in reaction
It is 9.7, wherein the molar ratio of sodium carbonate and sodium bicarbonate is 1:2mol increasingly generates the carbonate deposition of nickel cobalt manganese at this time.It waits for
Reaction 1 hour after precipitation is complete, continues ageing 4 hours, so that the particle by nickel cobalt manganese carbonate deposition is grown into, then pass through
Isolated carbonate precursor.The presoma is spare after 150 DEG C of dry 4h.
(6) it is that the molar ratio of elemental lithium in the lithium carbonate being added meets 1 according to nickel cobalt manganese total mole number:1.1.Through mixing
After uniformly, then the first preroast 5h at 550 DEG C of the mixture calcines 10h at 900 DEG C again, after naturally cooling to room temperature,
300 mesh are ground to be sieved to obtain LiNi1/3Co1/3Mn1/3O2。
1 gained nickle cobalt lithium manganate of embodiment is detected by XRD, and collection of illustrative plates such as Fig. 2 (a) is described, and atomic ratio is detected by EDS,
As shown in collection of illustrative plates 2 (b).It can be seen that from figure, tri- kinds of elements of Ni, Co, Mn in material substantially conform to 1:1:1 atomic ratio.Analysis
As a result it is shown as LiNi1/3Co1/3Mn1/3O2。
Using metal lithium sheet as cathode, with the LiNi of above-mentioned steps (6) acquisition1/3Co1/3Mn1/3O2For anode, it is assembled into button
Battery carries out discharge test with 0.2C multiplying powers, and experimental result is as shown in Figure 3.Experiment shows the ratio of electric discharge for the first time of the battery material
Capacity is 224.1mAh g-1, coulombic efficiency is 97.6% for the first time.Shown in specific capacity situation such as Fig. 3 (b) after its 50 circle of cycle,
Specific discharge capacity is 189.4mAh g-1, capacity retention ratio 84.5% illustrates that the chemical property of material has preferable electrification
Learn stability.
Embodiment 2：
A kind of technique preparing nickel-cobalt lithium manganate cathode material using waste and old lithium ion battery as raw materials recovery, including it is following several
A step：
(1) battery cell positive plate is crushed, is pyrolyzed at 400 DEG C in air, under vibration using 200 the polished standard screens
It is sieved, obtains positive powder 9.8g.
(2) 29g ammonium sulfate+3g urea will be added in positive powder to be sufficiently mixed uniformly, then leads under ammonia atmosphere in Muffle
It is roasted in stove, calcination temperature is 450 DEG C, roasting time 1.5h.Then 100mL deionizations are added in product of roasting
Water is leached at 60 DEG C, leachate is obtained by filtration.
(3) leachate yellow sodium ferrum vanadium process is removed into impurity iron, after Hydrolyze method removes impurity aluminum, measure in leachate nickel from
A concentration of 0.94mol L of son-1, concentration of cobalt ions is 0.95mol L-1, manganese ion concentration is 0.95mol L-1。
(4) nickel nitrate and cobalt nitrate are added into the mixed liquor of step (3), makes the nickel ion and concentration of cobalt ions be
0.95mol L-1。
(5) sodium carbonate and sodium bicarbonate are added into step (4) solution, it is 1 to make the molar ratio of sodium carbonate and sodium bicarbonate:
2.5mol, control pH be 8.2, it is to be precipitated completely after, continue be aged 8h, precipitation is then detached into obtain presoma.The presoma passes through
It crosses spare after 120 DEG C of dry 8h.
(6) according to forerunner's weight is obtained, lithium carbonate quality is calculated, makes mole of the nickel cobalt manganese to feed intake and elemental lithium
Than meeting 1:1.05.Then it is agitated after mixing, the first first pre-burning 5h at 550 DEG C, then calcine 12h at 900 DEG C is natural
After being cooled to room temperature, it is ground to 300 mesh and is sieved to obtain LiNi1/3Co1/3Mn1/3O2.Through Electrochemical Detection, the recycle ratio under 0.1C
Capacity is 219.5mAh g-1。
Embodiment 3：
A kind of technique preparing nickel-cobalt lithium manganate cathode material using waste and old lithium ion battery as raw materials recovery, including it is following several
A step：
(1) battery cell is disassembled, takes out positive plate；Positive plate is crushed, in ammonia+nitrogen (1:1) 400 DEG C in atmosphere
Lower pyrolysis, is sieved under vibration using 200 the polished standard screens, obtains positive powder 11g.
(2) 31g ammonium sulfate+5g ammonium hydrogen carbonate will be added in positive powder to be sufficiently mixed uniformly, then under logical ammonia atmosphere
It is roasted in Muffle furnace, calcination temperature is 470 DEG C, roasting time 1.5h.Then 100mL is added in product of roasting to go
Ionized water is leached at 60 DEG C, leachate is obtained by filtration.
(3) after leachate yellow sodium ferrum vanadium process being removed impurity iron and Hydrolyze method removing impurity aluminum, nickel in leachate is measured
Ion concentration is 0.98mol L-1, concentration of cobalt ions is 1.0mol L-1, manganese ion concentration is 1.0mol L-1。
(4) nickel sulfate and manganese nitrate are added into the mixed liquor of step (3), makes the nickel ion and concentration of cobalt ions be
1.0mol L-1。
(5) it is 60 DEG C of sodium carbonate and sodium bicarbonate solution temperature to be added into step (4) solution, makes sodium carbonate and bicarbonate
The molar ratio of sodium is 2:1, pH=9.2 is adjusted, waits for after reaction, continuing to be aged 6h, finally through presoma is obtained by filtration to obtain.It should
Presoma is spare after 140 DEG C of dry 3h.
(6) according to forerunner's weight is obtained, control is added lithium carbonate, makes nickel cobalt manganese summation：The molar ratio of elemental lithium meets
1:1.12, it is uniformly mixed, then the first pre-burning 5h at 550 DEG C, then 12h is calcined at 950 DEG C, after naturally cooling to room temperature, grinds
300 mesh are milled to be sieved to obtain LiNi1/3Co1/3Mn1/3O2.Through Electrochemical Detection, the cycle specific capacity under 0.1C is 220.3mAh
g-1
Embodiment 4：
A kind of technique preparing nickel-cobalt lithium manganate cathode material using waste and old lithium ion battery as raw materials recovery, including it is following several
A step：
(1) battery cell is disassembled, takes out positive plate；It is pyrolyzed, uses at 420 DEG C in argon atmospher after positive plate is crushed
200 the polished standard screens are sieved under vibration, obtain positive powder 10.5g.
(2) 28g ammonium hydrogen sulfate+3g ammonium dihydrogen phosphates will be added in positive powder to be sufficiently mixed uniformly, then in logical argon atmospher
Under roasted in Muffle furnace, calcination temperature be 480 DEG C, roasting time 0.8h.Then 120mL is added in product of roasting
Deionized water is leached at 70 DEG C, leachate is obtained by filtration.
(3) after leachate yellow sodium ferrum vanadium process being removed impurity iron and Hydrolyze method removing impurity aluminum, nickel in leachate is measured
Ion concentration is 0.95mol L-1, concentration of cobalt ions is 0.99mol L-1, manganese ion concentration is 0.97mol L-1。
(4) nickel sulfate and manganese nitrate are added into the mixed liquor of step (3), makes the nickel ion and concentration of cobalt ions be
0.99mol L-1。
(5) sodium carbonate and sodium bicarbonate are added into step (4) solution, makes the molar ratio of sodium carbonate and sodium bicarbonate be
1.5:1, pH=9.0 is adjusted, obtains the compound carbonate precipitation of nickel cobalt manganese at this time.It is 55 DEG C to continue thereafter with and keep temperature, makes to sink
Shallow lake is continued after being aged 7h, and presoma is centrifugally separating to obtain.The presoma is spare after 120 DEG C of dry 6h.
(6) presoma for taking step (5) to obtain is added the lithium carbonate of calculation amount, makes nickel according to its nickel cobalt manganese moles total number
The molar ratio of cobalt manganese and elemental lithium meets 1:1.1.It is ground uniformly after, the first first pre-burning 5h at 500 DEG C, then forged at 900 DEG C
10h is burnt, after naturally cooling to room temperature, 300 mesh is ground to and is sieved to obtain LiNi1/3Co1/3Mn1/3O2.Through Electrochemical Detection, 0.2C
Under cycle specific capacity be 215.2mAh g-1
Embodiment 5：
The implementation process that waste and old lithium ion battery prepares nickel-cobalt lithium manganate cathode material for raw materials recovery is as follows：
(1) positive plate of battery cell dismantling is pyrolyzed in argon atmospher at 450 DEG C by crushing obtained powder
Then 30min is sieved under vibration using 200 the polished standard screens, obtain positive powder 12g.
(2) it will be added after 32g ammonium sulfate+4g urea and be sufficiently mixed uniformly, then in logical argon gas+ammonia atmosphere in positive powder
(volume ratio=1:4) it is roasted in Muffle furnace under, calcination temperature is 480 DEG C, and roasting time is 0.8 h.Then it is roasting
200mL deionized waters are added in product, is leached at 70 DEG C, leachate is obtained by filtration.
(3) after the method for leachate embodiment 1 being removed impurity, it is 0.59mol to measure nickel ion concentration in leachate
L-1, concentration of cobalt ions is 0.59mol L-1, manganese ion concentration is 0.57mol L-1。
(4) manganese sulfate is added into the mixed liquor of step (2), manganese ion is made to reach 0.59mol L-1。
(5) sodium carbonate is added into step (3) solution and sodium bicarbonate, the molar ratio of wherein sodium carbonate and sodium bicarbonate is
1.2:1, pH=8.8 is adjusted, obtains the compound carbonate precipitation of nickel cobalt manganese at this time.It is 65 DEG C to continue thereafter with and keep temperature, makes to sink
Shallow lake is continued after being aged 7h, and presoma is centrifugally separating to obtain.The presoma is spare after 120 DEG C of dry 6h.
(6) presoma for taking step (4) to obtain is added the lithium carbonate of calculation amount, makes nickel according to its nickel cobalt manganese moles total number
The molar ratio of cobalt manganese and elemental lithium meets 1:1.1.It is ground after mixing, the first first pre-burning 5h at 500 DEG C, then at 880 DEG C
Lower calcining 11h after naturally cooling to room temperature, is ground to 300 mesh and is sieved to obtain LiNi1/3Co1/3Mn1/3O2。
Through Electrochemical Detection, the cycle specific capacity under 0.2C is 214.3mAh g-1。
Claims (10)
1. it is a kind of using waste and old lithium ion battery as the technique of raw materials recovery nickel-cobalt lithium manganate cathode material, including following step
Suddenly：
(1) lithium ion battery positive plate is subjected to pretreatment and obtains the positive electrode powder containing cobalt, nickel, manganese；
(2) positive powder of step (1) and hydrosulphate are subjected to atmosphere roasting, are soluble sulfuric acid by nickel cobalt manganese cycling of elements
Salt；
(3) deionized water will be added in obtained product of roasting in step (2), and is leached under water bath condition, filtered
The leachate of nickeliferous, cobalt and manganese is obtained after removal of impurities, detects nickel cobalt manganese ion concentration；
(4) nickel source, cobalt source or manganese source is added toward step (3) leachate China and foreign countries, adjusts the molar concentration rate of nickel cobalt manganese in leachate
It is 1:1:1；
(5) using sodium carbonate and sodium bicarbonate mixed liquor as precipitating reagent, nickel cobalt manganese metal ion is made to be co-precipitated, carbon is obtained after filtration washing
Hydrochlorate presoma, the carbonate precursor is after ageing and then nickle cobalt lithium manganate ternary is made by calcining in lithium carbonate mixing
Positive electrode.
2. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that the pretreatment described in step (1) is to crush battery anode slice, is 400-450 DEG C of air in temperature
Under the conditions of be pyrolyzed, sieved under vibration using 20-80 the polished standard screens, obtain positive powder；
Above-mentioned pyrolysis carries out in air or/and nitrogen or/and argon gas or/and ammonia atmosphere.
3. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that step (2) is roasted in air or/and nitrogen or/and argon gas or/and ammonia atmosphere.Calcination temperature is
300 DEG C -600 DEG C, preferable temperature is 350 DEG C -550 DEG C, and preferably temperature is 350 DEG C -490 DEG C；Roasting time is 0.5-2h.
4. described in accordance with the claim 3 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that roasting carries out under the conditions of ammonia or ammonia and nitrogen atmosphere, except directly using additional ammonia condition
Outside, or/and in step (1) ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, the phosphoric acid of weight ratio 5-130% is added in the positive pole powder obtained
Ammonium dihydrogen, one kind, two kinds or two or more mixtures in diammonium hydrogen phosphate, urea.
5. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that the molar ratio of waste and old lithium ion battery tertiary cathode material and hydrosulphate described in step (2) is
1:1-1:5。
6. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that the removal of impurities described in step (3) is to remove iron with yellow sodium ferrum vanadium process, i.e., the pH of leachate is first adjusted to 0.3-
Between 2.7, it is heated to 60-102 DEG C, is then slowly added into NaOH solution, the pH for adjusting solution is 1.7-1.9, after reacting 2h,
The pH for controlling terminal between 3 and 6, after so that iron ion is formed ferric hydroxide precipitate, is filtered to remove；Aluminium is removed with Hydrolyze method again, i.e., will
Filtrate is heated to 75-100 DEG C, and adjusting pH value of solution is 3-6, reacts 0.2-3h, aluminium ion is made to hydrolyze to form Al (OH)3Precipitation, warp
The leachate containing nickel cobalt manganese ion is obtained by filtration.
7. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that the extraction temperature of the product of roasting described in step (3) is 10-90 DEG C, and preferable temperature is 20 DEG C -90 DEG C,
Preferably temperature is 25 DEG C -80 DEG C；Extraction time is 10-120min.
8. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that step (5) precipitating reagent sodium carbonate and sodium bicarbonate total mole number and the total mole number of ions ratio of nickel cobalt manganese Metal
For (1-3):1；The molar ratio of sodium carbonate and sodium bicarbonate mixed liquor precipitating reagent is 1:(0.5-3)；Step (5) is total according to nickel cobalt manganese
Molal quantity is 1 with lithium total mole number:(1.05-1.2) mixes carbonate precursor and lithium carbonate；Being total to described in step (5)
The condition of carbonate precursor made from precipitation reaction is that pH is controlled between 7-12, and reaction temperature is 40-80 DEG C, the reaction time
It is 0.2-3 hours, digestion time 4-24h.
9. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as the work of raw materials recovery nickel-cobalt lithium manganate cathode material
Skill, which is characterized in that the hydrosulphate described in step (2) is in ammonium sulfate, ammonium hydrogen sulfate, niter cake, potassium acid sulfate
It is one or more；Nickel source described in step (4) is one kind in nickel nitrate, nickel sulfate；Cobalt source is in cobalt nitrate, cobaltous sulfate
One kind；Manganese source is one kind in manganese sulfate or manganese nitrate.
10. described in accordance with the claim 1 a kind of using waste and old lithium ion battery as raw materials recovery nickel-cobalt lithium manganate cathode material
Technique, which is characterized in that step (5) calcination temperature is 700-1200 DEG C, and preferable temperature is 800-1000 DEG C；Calcination time is 6-
20h, preferably time are 8-18h.
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