CN106785177A - A kind of method for being reclaimed from waste and old nickel-cobalt-manganese ternary lithium ion battery, preparing nickel cobalt manganese aluminium quaternary positive electrode - Google Patents
A kind of method for being reclaimed from waste and old nickel-cobalt-manganese ternary lithium ion battery, preparing nickel cobalt manganese aluminium quaternary positive electrode Download PDFInfo
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Abstract
The invention discloses a kind of method for being reclaimed from waste and old nickel-cobalt-manganese ternary lithium ion battery, preparing quaternary positive electrode, comprise the steps of：Step 1：By waste and old ternary lithium ion battery by manually disassembling, magnetic separation, broken, organic solvent immersion, screening, sulfuric acid leaching, the Cu that is contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate；Leachate is through removal of impurities (Cu2+) process to obtain removal of impurities liquid；Step 2：The mol ratio of Al, Ni, Co, Mn in regulation removal of impurities liquid；Alkali metal hydroxide and adjustment and control system pH >=10 are then added, one-level precipitation is carried out, the dirty solution of NCM hydroxide must be precipitated；Step 3：Two-stage precipitation is carried out to carbonate is added in the dirty solution of step 2, quaternary material presoma is obtained through separation of solid and liquid after；Step 4：Described quaternary material presoma is calcined in atmosphere and obtains Al doping NCM quaternary positive electrodes.The method process is simple, raw material sources are wide, and degree of repeatability is high, and the quaternary positive electrode cycle performance of preparation is excellent, can be mass-produced.
Description
Technical field
The present invention relates to waste and old lithium ion battery recycling field, one kind is related specifically to waste and old nickel-cobalt-manganese ternary lithium ion
Battery is the method for the quaternary positive electrode that the step of raw material one prepares aluminium doping nickel cobalt manganese.
Background technology
The serious change of shortage and the ball ecological environment increasingly of the energy, is just progressively turning into and is hindering the two of Development of Human Civilization
Big obstacle, opens up the new energy and new, the free of contamination energy-saving material of research and development and energy storage and transition material
The task of top priority is turned into.With continuing to develop for the increase of energy demand, electronic market and electric motor car market, lithium ion battery by
The favor of people is received in the superior performance such as its safe and environment-friendly, high-energy-density and good chemical property.
Lithium battery service life is general about 3 years according to statistics, and cycle period is about 500 times.It is extensive with lithium ion battery
Using its usage amount increases year by year, and the environmental problem caused by waste and old lithium ion battery has caused the extensive concern of countries in the world.
Existing original component in waste and old lithium ion battery, the novel substance for having side reaction generation in charge and discharge process again, old and useless battery
It is dropped in the environment, the material in making battery because of a variety of causes rupture is entered into environment, causes environmental pollution.Lithium ion
On the one hand battery allows energy resource supply more convenience and high-efficiency, another aspect disabled lithium ion cell to also bring along environmental problem.With
The shipment amount and learies of lithium ion battery rapidly increase, and thing followed environmental problem has also caused the extensive concern in the whole world.
Be different from conventional batteries, waste and old ion battery into complexity is grouped into, with significant resource and contaminative, it is necessary to the work of synthesis
Skill could realize the innoxious and resource of disabled lithium ion cell.Currently for the recovery scheme of waste and old ternary lithium ion battery
Middle major part is to be separately recovered for nickel, cobalt, manganese, and recovery process is long, complex process, and separation method is easily produced comprising extraction etc.
The high pollution method of raw organic waste.Ideal flow both can again should may be used with efficient process waste and old lithium ion battery
Realize that the comprehensive of various valuable metals recycles with shorter flow.
The Chinese patent literature of Publication No. CN 101871048A discloses one kind Call Provision, nickel from waste lithium cell
With the method for manganese：Waste lithium ion cell anode material is immersed in low-concentration alkali liquor, nonreactive positive pole black powder is reclaimed,
To the black powder for reclaiming, low acid dissolving is first carried out, then using Na2SO5Or Na2SO3Or Fe powder enriching sulfuric acid carry out reduction it is molten
Solution, last peracid dissolving；The material for obtaining removes alkaline earth metal impurity after carrying out separation of solid and liquid using agent precipitate depth.Separating
During respective metal is extracted using P204 and P507 extractants, improve reclaim metal purity.But whole
In flow, the use of extractant can produce a large amount of organic liquid wastes, and larger harm is caused to environment.
The Chinese patent literature of Publication No. CN 105633500A discloses a kind of utilization and reclaims lithium ion battery material system
The method of standby ternary anode material precursor：Anode material for lithium-ion batteries is reclaimed with sulfuric acid and dioxygen water dissolves, is leached
Liquid, adds filter aid and the removal of impurity is gone in filtering, then adds nickel sulfate, cobalt sulfate and mn sulphate and adjusts nickel, cobalt, manganese
Mol ratio be 0.4~0.6: 0.1~0.3: 0.2~0.4, obtain corresponding solution, in the solution add complex precipitant simultaneously
The pH for adjusting solution obtains nickel-cobalt-manganese ternary material precursor precipitation, is washed and be dried to obtain tertiary cathode material forerunner
Body.This patent utilization precipitation method are prepared for corresponding ternary anode material precursor, but are not carried for remaining liquid containing lithium
Go out effective solution, the addition of lithium salts is stilled need in follow-up positive electrode preparation process；Meanwhile, the method is for adopting
With precipitation filtration method removal of impurities, and utilization not yet in effect metallic element therein.
In sum, a set of disabled lithium ion cell and can be with waste and old lithium of can effectively processing of exploitation is badly in need of in this area
Ion battery is the flow that the step of raw material one prepares high-performance aluminum doping nickel cobalt manganese quaternary positive electrode.
The content of the invention
Waste and old ion battery into complexity is grouped into, with significant resource and contaminative, it is necessary to the technique ability of synthesis
Realize the innoxious and resource of disabled lithium ion cell.The invention provides one kind from waste and old nickel-cobalt-manganese ternary lithium ion battery
The method for reclaiming, preparing nickel cobalt manganese aluminium quaternary positive electrode, it is intended to the quaternary positive pole of electric property high is prepared using waste material
Material.
Valuable metal in waste and old ternary lithium ion battery can be comprehensively utilized it is a further object to provide one kind
Method, realize under short route high-performance quaternary positive electrode regeneration prepare.
In order to realize above-mentioned technical purpose, reclaimed from waste and old nickel-cobalt-manganese ternary lithium ion battery the invention provides one kind,
The method for preparing quaternary positive electrode, comprises the following steps：
Step 1：By waste and old ternary lithium ion battery by manually disassembling, magnetic separation, broken, organic solvent immersion, sieve, sulphur
Ore Leaching, the Cu for being contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, leachate processes to obtain removal of impurities liquid through removal of impurities；
Step 2：The mol ratio of Al, Ni, Co, Mn in regulation removal of impurities liquid；Then add alkali metal hydroxide and regulate and control body
It is pH >=10, carries out one-level precipitation, the dirty solution of NCMA hydroxide must be precipitated；
Step 3：Two-stage precipitation is carried out to carbonate is added in the dirty solution of step 2, Li quaternarys are obtained through separation of solid and liquid after
Material precursor.
Step 4：Described Li quaternary materials presoma is calcined the quaternary positive pole material for obtaining Al doping NCM in atmosphere
Material.
In the present invention, the mol ratio of Al, Ni, Co, Mn is adjusted according to the actual requirements, then carried out under the conditions of described pH
One-level is precipitated, and Al, Ni, Co, the Mn in system is co-precipitated in the form of hydroxide；Then again through follow-up two-stage precipitation,
Make the Li of the system sediments that in-stiu coating is precipitated in one-level in the form of carbonate (NCMA hydroxide) surface.By this hair
Two-step precipitation described in bright method is prepared for Li quaternarys presoma (Li2CO3-NCMA), it is to avoid the not separation of same metal,
Technological process is shortened, it is simple to operate, reduce production difficulty.Additionally, Li quaternary presomas are with the hydroxide of nickel cobalt manganese
It is core, lithium carbonate is surface, described core shell structure can avoid the generation of gas in calcination process, hence it is evident that improve the quaternary for reclaiming
The chemical property of positive electrode.The inventive method also has efficient, and cleaning, flow is simple, low cost, and repeatability is high, can be with
The features such as industrialized production.
In preferred method, ensure not containing iron-clad, box hat in the sample by manually disassembling, after magnetic separation.
In preferred method, the organic solvent is 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), tetrahydrochysene
One or more in furans (THF).Binding agent in lithium electricity positive pole is by macromolecular compound, such as Kynoar
(PVDF), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) etc. are dissolved in composition in water or organic solvent (such as NMP).From
The organic solvents such as NMP, DMF, THF dissolve the binding agent solvent of lithium ion battery, can reach separating active substances with collector
Purpose, subsequently realizes the recycling of organic solvent by modes such as distillations again.
Broken material is immersed in described organic solvent, preferred soak time is 1~5h.
Through screening process after immersion treatment, active component is obtained, active component is immersed in acid solution, carry out leaching process, with
Cu is obtained by separation of solid and liquid2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, carry out removal of impurities treatment to leachate, removing is leached
Cu in liquid system2+。
In dedoping step, water-soluble sulphurizing salt (vulcanization source), the Cu in precipitation, removing leachate are added2+。
Described water-soluble sulphurizing salt is that can in aqueous dissociate S2-Sulphur source.
Preferably, described water-soluble sulphurizing salt is vulcanized sodium, potassium sulfide, sodium thiosulfate, potassium thiosulfate, over cure
At least one in sour sodium, potassium peroxydisulfate, thiocarbamide.
Further preferably, described water-soluble sulphurizing salt is sodium thiosulfate, potassium thiosulfate, sodium peroxydisulfate, persulfuric acid
At least one in potassium, thiocarbamide.Further preferred sulphurizing salt has reproducibility, and Ni, Co, Mn in solution can be effectively ensured
Exist in the form of lower valency, meet the requirement of ternary material preparation.
After removal of impurities treatment, obtain including Al3+, Li+, Ni2+, Co2+, Mn2+Removal of impurities liquid, then can by Al, Ni, Co,
The Al that Mn at least one water soluble salt comes in adjustment and control system3+、Ni2+、Co2+、Mn2+Ratio；Make quaternary positive pole obtained in recovery
Material meets different demands.
In the present invention, at least one of water soluble nickel salt, water soluble nickel salt, water soluble cobaltous salt, water-soluble manganese salt can be added
To regulate and control Al, Ni, Co, Mn mol ratio in removal of impurities liquid.
Preferably, described water-soluble aluminum salt is Al3+Sulfate, chlorate, nitrate at least one；Enter one
Step is preferably the sulfate of aluminium.
Preferably, described water soluble nickel salt is Ni2+Sulfate, chlorate, nitrate at least one；Enter one
Step is preferably the sulfate of nickel.
Preferably, described water soluble cobaltous salt is Co2+Sulfate, chlorate, nitrate at least one；Enter one
Step is preferably the sulfate of cobalt.
Preferably, described water-soluble manganese salt is Mn2+Sulfate, chlorate, nitrate at least one；Enter one
Step is preferably the sulfate of manganese.
In the present invention, in step 2, the ratio for adjusting Ni, Co, Mn is 1~8: 1~2: 1~2.
Further preferably, the ratio of regulation Ni, Co, Mn is the one kind in 6: 2: 2,8: 1: 1.
Under the ratio of described Ni, Co, Mn, preferably, Al accounts for the 1~5% of (Al+Ni+Co+Mn) integral molar quantity.
The ratio of nickel is higher in lithium ion anode material, and under certain discharge current, its capacity is higher.The content control of Al
System can effectively ensure against Al between 1-5% and add excessive and cause the overall capacity of electrode material to decline, appropriate
Al is added and can be strengthened ionic conductivity, rock-steady structure.
Preferably, in step 2, described alkali metal hydroxide is at least one in NaOH, KOH, LiOH.
In step 2, alkali metal hydroxide can be added by the form of solid or the aqueous solution.
Preferably, in step 2, described pH is regulated and controled by the aqueous solution (alkali lye) of alkali metal hydroxide, it is described
The concentration of alkali lye is 1-6mol/L.
Preferably, in step 2, in one-level precipitation process, the pH of control system is 10~11.
In step 2, by the regulation and control of alkali metal hydroxide, make the Al in system3+、Ni2+、Co2+、Mn2+PH be 10~
One pot in the form of hydroxide, co-precipitation under conditions of 11.
The dirty solution that the precipitation that step 2 is obtained has NCMA hydroxide need not carry out separation of solid and liquid, directly be mixed to described
Carbonate is added in turbid liquid, the Li in suspended liquid system original position, deposition in the form of lithium carbonate is coated on NCMA hydroxide
Surface.
In step 3, described carbonate is the water soluble salt that can go out carbonate in dissociation in water.
Preferably, described carbonate is sodium carbonate and/or potassium carbonate.
In step 3, described carbonate can be added directly in solid form, it is also possible to which the form of the aqueous solution is added.
Preferably, during the carbonate for adding makes Li quaternary material presomas, Li: (Al+Ni+Co+Mn) mol ratio is 1~
1.1∶1。
Preferably, in step 4, calcining heat is 900~1000.
In step 4, the heating rate of calcination process is 5-10 DEG C/min.
In step 4, calcination time is 12-24h.
It is a kind of preferred from the recovery of waste and old nickel-cobalt-manganese ternary lithium ion battery, preparation quaternary positive electrode in the present invention
Method, specifically comprise the following steps：
Step (1)：By waste and old ternary lithium ion battery by manually disassembling, magnetic separation, broken, organic solvent immersion, sieve,
Sulfuric acid leaching, the Cu for being contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, leachate adds thiocarbamide removal of impurities (Cu2+) place
Manage to obtain removal of impurities liquid；The organic solvent is at least one in 1-METHYLPYRROLIDONE, dimethylformamide, tetrahydrofuran,
The time soaked in described organic solvent is 1-5h；
Step (2)：Water-soluble aluminum salt, water soluble nickel salt, water soluble cobaltous salt, water-soluble is added in removal of impurities liquid to step (1)
Property manganese salt at least one, regulation and control removal of impurities liquid in Al, Ni, Co, Mn mol ratio；Make the ratio of Ni, Co, Mn for 1~8: 1~
2: 1~2；Al accounts for the 1~5% of (Al+Ni+Co+Mn) integral molar quantity；
Alkali metal hydroxide and adjustment and control system pH >=10 are then added, one-level precipitation is carried out, obtaining precipitation there are NCMA hydrogen-oxygens
The dirty solution of compound；Described alkali metal hydroxide is at least one in NaOH, KOH, LiOH；
Step (3)：Two-stage precipitation is carried out to carbonate is added in the dirty solution of step 2, Li tetra- is obtained through separation of solid and liquid after
First material precursor；
Described carbonate is sodium carbonate and/or potassium carbonate；
The carbonate for adding makes in Li quaternary material presomas, Li: (Al+Ni+Co+Mn)=1~1.1: 1.
Step (4)：Described quaternary material presoma is calcined into 12-24h in atmosphere, at 900~1000 DEG C；It is calcined
The heating rate of journey is in 5-10 DEG C/min；Al doping NCM quaternary positive electrodes are obtained final product after calcining.
Compared with the prior art, the beneficial effect that technical solution of the present invention is brought：
(1) it is effectively utilized Al present in system3+, the presence of trivalent Al improves the ionic conductivity of positive electrode,
The presence of Al simultaneously enhances stability of the NCM materials in discharge process.
(2) it is prepared for Li using two-step precipitation2CO3- NCMA quaternary presomas, it is to avoid the not separation of same metal, contracting
Short technological process, it is simple to operate, reduce production difficulty.
(3)Li2CO3With the hydroxide of nickel cobalt manganese aluminium as core in-NCMA quaternary presomas, with lithium carbonate as surface (shell),
Described nucleocapsid structure avoids the generation of gas in calcination process, hence it is evident that improve the electrification of the product quaternary material of recovery
Learn performance.
(4) the method process is simple, raw material sources are wide, and degree of repeatability is high, and organic efficiency is high, can be mass-produced.
(5) valuable metal in system is fully utilized, the efficient utilization of resource is realized.
Brief description of the drawings
Fig. 1 is the flow chart of embodiment 1；
Fig. 2 is the constant current charge-discharge performance map of the lithium ion battery of the NCMA quaternarys positive electrode assembling that embodiment 1 is obtained；
Specific embodiment
Following examples are intended to be described in further details present invention, are protected rather than to the claims in the present invention
The limitation of scope.
Embodiment 1：
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 3h is soaked in NMP, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 8: 1: 1, and it is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 2mol/L, adjust pH=10.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.05, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are carried out at being warmed up to 900 DEG C with the speed of 5 DEG C/min
High-temperature roasting 24h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, its flow and chemical property
As shown in the figure：
Fig. 1 is the flow chart of the technique.
Fig. 2 shows to prepare the electrode that NCMA materials are made using the method, when at room temperature with 0.5C constant-current discharges, circulation
200 circle specific capacities may remain in 175mAh/g；Show good cycle performance.
Embodiment 2
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 3h is soaked in NMP, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding sodium thiosulfate to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 8: 1: 1, and it is 5% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 6mol/L, adjust pH=11.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.1, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are carried out at being warmed up to 900 DEG C with the speed of 5 DEG C/min
High-temperature roasting 18h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 169mAh/g；Show good cycle performance.
Embodiment 3
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 2h is soaked in THF, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 6: 2: 2, and it is 5% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 4mol/L, adjust pH=11.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.07, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are carried out at being warmed up to 900 DEG C with the speed of 5 DEG C/min
High-temperature roasting 24h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 165mAh/g；Show good cycle performance.
Embodiment 4
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 5h is soaked in DMF, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 6: 2: 2, and it is 4% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 6mol/L, adjust pH=10.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.07, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are warmed up at 1000 DEG C with the speed of 10 DEG C/min
Row high-temperature roasting 12h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 166mAh/g；Show good cycle performance.
Embodiment 5
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 3h is soaked in DMF, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 8: 1: 1, and it is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 6mol/L, adjust pH=10.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.03, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are warmed up at 1000 DEG C with the speed of 5 DEG C/min
Row high-temperature roasting 24h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 170mAh/g；Show good cycle performance.
Comparative example 1
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 1h is soaked in THF, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 8: 1: 1, and it is 10% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.In then
The NaOH solution of 6mol/L is added, pH=11 is adjusted.After question response is complete, potassium carbonate is added thereto to, control addition is caused
Li: (Ni+Co+Mn+Al)=1.03, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the forerunner of quaternary material containing Li is prepared
Body.The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are warmed up at 900 DEG C with the speed of 5 DEG C/min
Carry out high-temperature roasting 24h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 143mAh/g, and cycle performance has declined.
Comparative example 2
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 2h is soaked in NMP, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 1: 1: 1, and it is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 6mol/L, adjust pH=11.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.03, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are warmed up at 1000 DEG C with the speed of 5 DEG C/min
Row high-temperature roasting 30h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 153mAh/g, and cycle performance has declined.
Comparative example 3
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 4h is soaked in NMP, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 5: 2: 3, and it is 1% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 6mol/L, adjust pH=11.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.1, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are warmed up at 1100 DEG C with the speed of 5 DEG C/min
Row high-temperature roasting 12h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 151mAh/g, and cycle performance has declined.
Comparative example 4
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 3h is soaked in DMF, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 6: 2: 2, and it is 3% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.Add in then
Enter the NaOH solution of 6mol/L, adjust pH=11.After question response is complete, potassium carbonate is added thereto to, control addition causes Li:
(Ni+Co+Mn+Al)=1.2, Li is made2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, are warmed up at 1000 DEG C with the speed of 5 DEG C/min
Row high-temperature roasting 20h, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 152mAh/g, and cycle performance has declined.
Comparative example 5
By waste and old ternary lithium ion battery by being disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
First it is placed in afterwards and 3h is soaked in DMF, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.React
Black insoluble matter is filtered out after complete, to adding thiocarbamide to be produced to there is no precipitation in filtrate, insoluble matter is filtered.
Al, Ni, Co, Mn ratio of the filtrate after removal of impurities are determined, and corresponding sulfate is added thereto to according to ratio, adjusted
Section Ni, Co, Mn are matched to 6: 2: 2, and it is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn) to control Al content.It is then direct
Sodium carbonate is added, control addition causes Li: (Ni+Co+Mn)=1.08, makes Li2CO3Homogeneously precipitate in NCMA hydroxide tables
Face, prepares the presoma of quaternary material containing Li.The Li that will be filtrated to get2CO3- NCMA persursor materials are placed in tube furnace, with 5 DEG C/
The speed of min carries out high-temperature roasting 16h at being warmed up to 1000 DEG C, you can obtain NCMA quaternary positive electrodes.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, it is at room temperature, permanent with 0.5C
When banishing electricity, circulation 200 is enclosed specific capacity and may remain in 141mAh/g, and cycle performance has declined.
Claims (10)
1. it is a kind of from the recovery of waste and old nickel-cobalt-manganese ternary lithium ion battery, the method for preparing quaternary positive electrode, it is characterised in that bag
Containing following steps：
Step 1：By waste and old ternary lithium ion battery by manually disassembling, magnetic separation, broken, organic solvent immersion, screening, sulfuric acid soaks
The Cu for go out, being contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, leachate processes to obtain removal of impurities liquid through removal of impurities；
Step 2：The mol ratio of Al, Ni, Co, Mn in regulation removal of impurities liquid；Then add alkali metal hydroxide and adjustment and control system pH
>=10, one-level precipitation is carried out, the dirty solution of NCMA hydroxide must be precipitated；
Step 3：Two-stage precipitation is carried out to carbonate is added in the dirty solution of step 2, Li quaternary materials are obtained through separation of solid and liquid after
Presoma；
Step 4：Described Li quaternary materials presoma is calcined the quaternary positive electrode for obtaining Al doping NCM in atmosphere.
2. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 1
Method, it is characterised in that：The ratio for adjusting Ni, Co, Mn is 1~8: 1~2: 1~2.
3. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 2
Method, it is characterised in that：It is the one kind in 6: 2: 2,8: 1: 1 to adjust the ratio of Ni, Co, Mn.
4. according to any one of claims 1 to 3 from waste and old nickel-cobalt-manganese ternary lithium ion battery reclaim, prepare quaternary positive pole
The method of material, it is characterised in that：Al accounts for the 1~5% of (Al+Ni+Co+Mn) integral molar quantity.
5. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 1
Method, it is characterised in that：Described carbonate is sodium carbonate and/or potassium carbonate.
6. reclaimed from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 1 or 5, prepare quaternary positive electrode
Method, it is characterised in that：The carbonate for adding makes in Li quaternary material presomas, Li: (Al+Ni+Co+Mn) mol ratio be 1~
1.1∶1。
7. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 1
Method, it is characterised in that：Calcining heat is 900~1000 DEG C.
8. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 7
Method, it is characterised in that：Calcination time is 12-24h, and the heating rate of calcination process is 5-10 DEG C/min.
9. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 1
Method, it is characterised in that：In step 1, the organic solvent is in 1-METHYLPYRROLIDONE, dimethylformamide, tetrahydrofuran
At least one, the time soaked in described organic solvent is 1-5h；
In dedoping step, water-soluble sulphurizing salt, the Cu in precipitation, removing leachate are added2+。
10. the side that quaternary positive electrode is reclaimed, prepared from waste and old nickel-cobalt-manganese ternary lithium ion battery according to claim 1
Method, it is characterised in that：In step 2, by adding water-soluble aluminum salt, water soluble nickel salt, water soluble cobaltous salt, water-soluble manganese salt extremely
A kind of few mol ratio to regulate and control Al, Ni, Co, Mn in removal of impurities liquid.
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