CN106785177B - A method of from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, preparation nickel cobalt manganese aluminium quaternary positive electrode - Google Patents
A method of from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, preparation nickel cobalt manganese aluminium quaternary positive electrode Download PDFInfo
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Abstract
The invention discloses a kind of from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the method for preparation quaternary positive electrode comprising the steps of: step 1: by waste and old ternary lithium ion battery by artificial dismantling, magnetic separation, broken, organic solvent immersion, screening, sulfuric acid leaching, the Cu contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate；Leachate is through (the Cu that cleans2+) handle to obtain removal of impurities liquid；Step 2: adjusting the molar ratio of Al, Ni, Co, Mn in removal of impurities liquid；Alkali metal hydroxide and adjustment and control system pH >=10 are then added, level-one precipitating is carried out, the dirty solution of NCM hydroxide must be precipitated；Step 3: adding carbonate into the dirty solution of step 2 and carry out two-stage precipitation, quaternary material presoma is separated by solid-liquid separation to obtain after；Step 4: the quaternary material presoma being calcined in air and obtains Al doping NCM quaternary positive electrode.This method simple process, 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 fields, are related specifically to one kind with waste and old nickel-cobalt-manganese ternary lithium ion
Battery is the method that one step of raw material prepares that aluminium adulterates the quaternary positive electrode of nickel cobalt manganese.
Background technique
The serious variation of shortage and the ball ecological environment increasingly of the energy, just gradually becomes and hinders the two of development of human civilization
Big obstacle opens up the new energy and novel, the free of contamination energy-saving material of research and development and energy storage and transition material
It has become a top priority.With the increase of energy demand, the continuous development of electronic market and electric vehicle market, lithium ion battery by
The superior performance such as, high-energy-density safe and environment-friendly in its and good chemical property receives the favor of people.
Lithium battery service life generally about 3 years according to statistics, cycle period is about 500 times.It is extensive with lithium ion battery
Using usage amount increases year by year, and the environmental problem as 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, and have the novel substance that side reaction generates in charge and discharge process, old and useless battery
It is dropped in the environment, enters the substance in battery in environment because of a variety of causes rupture, cause environmental pollution.Lithium ion
On the one hand battery allows energy resource supply more convenient efficiently, another aspect disabled lithium ion cell also brings along environmental problem.With
The shipment amount and learies of lithium ion battery rapidly increase, and the following environmental problem has also caused the extensive concern in the whole world.
Conventional batteries are different from, waste and old ion battery ingredient complicated composition have significant resource and pollution, need comprehensive work
Skill is just able to achieve the innoxious and recycling of disabled lithium ion cell.It is directed to the recovery scheme of waste and old ternary lithium ion battery at present
Middle major part is to be separately recovered for nickel, cobalt, manganese, and recovery process is long, complex process, and separation method includes that extraction etc. easily produces
The high pollution method of raw organic waste.Ideal process should not only can be with efficient process waste and old lithium ion battery, but also can
To realize that the comprehensive of a variety of valuable metals recycles in shorter process.
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 black powder is recycled,
To the black powder of recycling, low acid dissolution is first carried out, then use Na2SO5Or Na2SO3Or Fe powder enriching sulfuric acid restore it is molten
Solution, last high acid dissolution；Obtained substance uses agent precipitate depth except alkaline earth metal impurity after being separated by solid-liquid separation.It is separating
Respective metal is extracted using P204 and P507 extractant in the process, improves the purity of recycling metal.But entire
In process, the use of extractant can generate a large amount of organic liquid wastes, cause biggish harm to environment.
The Chinese patent literature of Publication No. CN 105633500A discloses a kind of utilization recycling lithium ion battery material system
The method of standby ternary anode material precursor: it with sulfuric acid and hydrogen peroxide dissolution recycling anode material for lithium-ion batteries, is leached
Liquid, is added filter aid and filters removal impurity, and nickel sulfate, cobalt sulfate and mn sulphate is then added and adjusts nickel, cobalt, manganese
Molar ratio be 0.4~0.6: 0.1~0.3: 0.2~0.4, obtain corresponding solution, into the solution be added complex precipitant simultaneously
The pH for adjusting solution obtains nickel-cobalt-manganese ternary material precursor precipitating, is washed and is dried to obtain tertiary cathode material forerunner
Body.This patent is utilized the precipitation method and is prepared for corresponding ternary anode material precursor, but remaining liquid containing lithium is not mentioned
Effective solution measure out, there is still a need for the additions of lithium salts in subsequent positive electrode preparation process；Meanwhile this method is for adopting
With precipitating filtration method removal of impurities, metallic element therein is not efficiently used.
In conclusion this field is badly in need of, exploitation is a set of can be effectively treated disabled lithium ion cell and can be with waste and old lithium
Ion battery is the process that one step of raw material prepares that high-performance aluminum adulterates nickel cobalt manganese quaternary positive electrode.
Summary of the invention
Waste and old ion battery ingredient complicated composition have significant resource and pollution, need comprehensive technique ability
Realize the innoxious and recycling of disabled lithium ion cell.The present invention provides one kind from waste and old nickel-cobalt-manganese ternary lithium ion battery
Recycling, the method for preparing nickel cobalt manganese aluminium quaternary positive electrode, it is intended to the quaternary anode of high electric property is prepared using waste material
Material.
It is a further object to provide one kind can comprehensively utilize valuable metal in waste and old ternary lithium ion battery
Method, realize short route under high-performance quaternary positive electrode regenerate preparation.
In order to achieve the above technical purposes, the present invention provides one kind recycles from waste and old nickel-cobalt-manganese ternary lithium ion battery,
The method for preparing quaternary positive electrode, comprises the following steps:
Step 1: waste and old ternary lithium ion battery being impregnated by artificial dismantling, magnetic separation, broken, organic solvent, screening, sulphur
Ore Leaching, the Cu contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, leachate through removal of impurities handle to obtain removal of impurities liquid；
Step 2: adjusting the molar ratio of Al, Ni, Co, Mn in removal of impurities liquid；Then adds alkali metal hydroxide and regulate and control body
It is pH >=10, carries out level-one precipitating, the dirty solution of NCMA hydroxide must be precipitated；
Step 3: adding carbonate into the dirty solution of step 2 and carry out two-stage precipitation, Li quaternary is separated by solid-liquid separation to obtain after
Material precursor.
Step 4: the Li quaternary material presoma is calcined to the quaternary anode material for obtaining Al doping NCM in air
Material.
In the present invention, the molar ratio of Al, Ni, Co, Mn are adjusted according to actual needs, is then carried out under the conditions of the pH
Level-one precipitating, is co-precipitated Al, Ni, Co, Mn in system in the form of hydroxide；Then again through subsequent two-stage precipitation,
Make the Li of the system sediment that in-stiu coating is precipitated in level-one in the form of carbonate (NCMA hydroxide) surface.By this hair
Two-step precipitation described in bright method is prepared for Li quaternary presoma (Li2CO3-NCMA), avoids the separation of not same metal,
Process flow is shortened, it is easy to operate, reduce production difficulty.In addition, Li quaternary presoma is the hydroxide with nickel cobalt manganese
For core, lithium carbonate is surface, and the core-shell structure can avoid the generation of gas in calcination process, hence it is evident that improve the quaternary of recycling
The chemical property of positive electrode.The method of the present invention also has efficiently, and cleaning, process is simple, at low cost, and repeatability is high, can be with
The features such as industrialized production.
In preferred method, by manually disassembling, guarantee not containing iron-clad, steel shell in the sample after magnetic separation.
In preferred method, the organic solvent is N-Methyl pyrrolidone (NMP), dimethylformamide (DMF), tetrahydro
One or more of furans (THF).Binder in lithium electricity anode is by high-molecular compound, such as Kynoar
(PVDF), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) etc. are dissolved in composition in water or organic solvent (such as NMP).It selects
The organic solvents such as NMP, DMF, THF dissolve the binder solvent of lithium ion battery, can reach separating active substances and collector
Purpose, the subsequent recycling for realizing organic solvent by modes such as distillations again.
Broken material is immersed in the organic solvent, preferred soaking time is 1~5h.
Through screening process after immersion treatment, active constituent is obtained, active constituent is immersed in acid solution, leaching process is carried out, with
By being separated by solid-liquid separation to obtain Cu2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, removal of impurities processing carried out to leachate, removing is leached
Cu in liquid system2+。
It in dedoping step, adds in water-soluble sulphurizing salt (vulcanization source), the Cu in precipitating, removing leachate2+。
The water-soluble sulphurizing salt is that can dissociate S in aqueous solution2-Sulphur source.
Preferably, the water-soluble sulphurizing salt is vulcanized sodium, potassium sulfide, sodium thiosulfate, potassium thiosulfate, over cure
At least one of sour sodium, potassium peroxydisulfate, thiocarbamide.
Further preferably, the water-soluble sulphurizing salt is sodium thiosulfate, potassium thiosulfate, sodium peroxydisulfate, persulfuric acid
At least one of 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, meets the requirement of ternary material preparation.
After removal of impurities processing, obtain including Al3+, Li+, Ni2+, Co2+, Mn2+Removal of impurities liquid, then can by Al, Ni, Co,
Mn at least one water soluble salt carrys out the Al in adjustment and control system3+、Ni2+、Co2+、Mn2+Ratio；Make to recycle quaternary anode obtained
Material meets different demands.
In the present invention, water soluble nickel salt, water soluble nickel salt, at least one of water soluble cobaltous salt, water-soluble manganese salt can be added
To regulate and control Al, Ni, Co, Mn molar ratio in removal of impurities liquid.
Preferably, the water-soluble aluminum salt is Al3+Sulfate, chlorate, at least one of nitrate；Into one
Step is preferably the sulfate of aluminium.
Preferably, the water soluble nickel salt is Ni2+Sulfate, chlorate, at least one of nitrate；Into one
Step is preferably the sulfate of nickel.
Preferably, the water soluble cobaltous salt is Co2+Sulfate, chlorate, at least one of nitrate；Into one
Step is preferably the sulfate of cobalt.
Preferably, the water-soluble manganese salt is Mn2+Sulfate, chlorate, at least one of nitrate；Into 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 for adjusting Ni, Co, Mn is one of 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, capacity is higher.The content control of Al
System can effectively ensure against Al between 1-5% and be added excessive and the capacity of electrode material entirety be caused to decline, appropriate
Al is added and ionic conductivity, rock-steady structure can be enhanced.
Preferably, the alkali metal hydroxide is at least one of NaOH, KOH, LiOH in step 2.
In step 2, alkali metal hydroxide can be added by way of solid or aqueous solution.
Preferably, in step 2, it is described by aqueous solution (lye) regulation of the alkali metal hydroxide pH
The concentration of lye is 1-6mol/L.
Preferably, in level-one precipitation process, the pH of control system is 10~11 in step 2.
In step 2, by the regulation of alkali metal hydroxide, make the Al in system3+、Ni2+、Co2+、Mn2+PH be 10~
Under conditions of 11 in the form of hydroxide one pot, co-precipitation.
The precipitating that step 2 obtains has the dirty solution of NCMA hydroxide without being separated by solid-liquid separation, and directly mixes to described
Carbonate is added in turbid, and the Li in suspended liquid system original position, deposition in the form of lithium carbonate is made to be coated on NCMA hydroxide
Surface.
In step 3, the carbonate is the water soluble salt that can dissociate carbonate in water.
Preferably, the carbonate is sodium carbonate and/or potassium carbonate.
In step 3, the carbonate can be added directly in solid form, can also be added in form of an aqueous solutions.
Preferably, the carbonate added makes in Li quaternary material presoma, Li: (Al+Ni+Co+Mn) molar ratio is 1~
1.1∶1。
Preferably, calcination temperature is 900~1000 in step 4.
In step 4, the heating rate of calcination process is 5-10 DEG C/min.
In step 4, calcination time 12-24h.
It is a kind of more preferably from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, preparation quaternary positive electrode in the present invention
Method, specifically include the following steps:
Step (1): waste and old ternary lithium ion battery is impregnated by artificial dismantling, magnetic separation, broken, organic solvent, is sieved,
Sulfuric acid leaching, the Cu contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Thiocarbamide removal of impurities (Cu is added in leachate, leachate2+) at
Manage to obtain removal of impurities liquid；The organic solvent be at least one of N-Methyl pyrrolidone, dimethylformamide, tetrahydrofuran,
The time impregnated in the organic solvent is 1-5h；
Step (2): water-soluble aluminum salt, water soluble nickel salt, water soluble cobaltous salt, water-soluble is added into the removal of impurities liquid of step (1)
Property manganese salt at least one, regulation removal of impurities liquid in Al, Ni, Co, Mn molar ratio；Make the ratio 1~8: 1 of Ni, Co, Mn~
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, carry out level-one precipitating, obtaining precipitating has NCMA hydrogen-oxygen
The dirty solution of compound；The alkali metal hydroxide is at least one of NaOH, KOH, LiOH；
Step (3): carbonate is added into the dirty solution of step 2 and carries out two-stage precipitation, Li tetra- is separated by solid-liquid separation to obtain after
First material precursor；
The carbonate is sodium carbonate and/or potassium carbonate；
The carbonate added makes in Li quaternary material presoma, Li: (Al+Ni+Co+Mn)=1~1.1: 1.
Step (4): the quaternary material presoma is calcined into 12-24h in air, at 900~1000 DEG C；It is calcined
The heating rate of journey is in 5-10 DEG C/min；NCM quaternary positive electrode is adulterated after calcining up to Al.
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
(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 enhances the stability of NCM material during discharge simultaneously.
(2) Li is prepared for using two-step precipitation2CO3- NCMA quaternary presoma avoids the separation of not same metal, contracting
Short process flow, it is easy to operate, reduce production difficulty.
(3)Li2CO3Using the hydroxide of nickel cobalt manganese aluminium as core in-NCMA quaternary presoma, using lithium carbonate as surface (shell),
The nucleocapsid structure avoids the generation of gas in calcination process, hence it is evident that improves the electrification of the product quaternary material of recycling
Learn performance.
(4) this method simple process, raw material sources are wide, and degree of repeatability is high, and recovery efficiency is high, can be mass-produced.
(5) valuable metal in system is fully utilized, the efficient utilization of resource is realized.
Detailed description of the invention
Fig. 1 is the flow chart of embodiment 1；
Fig. 2 is the constant current charge-discharge performance map of the lithium ion battery for the NCMA quaternary positive electrode assembling that embodiment 1 obtains；
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention, rather than protects to the claims in the present invention
The limitation of range.
Embodiment 1:
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in NMP afterwards and impregnates 3h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 8: 1: 1, and control Al content is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 2mol/L, adjusts pH=10.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.05, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, is warming up at 900 DEG C and is carried out with the rate of 5 DEG C/min
For 24 hours, NCMA quaternary positive electrode can be obtained in high-temperature roasting.
Button cell, process and chemical property are assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece
It is as shown in the figure:
Fig. 1 is the flow chart of the technique.
Fig. 2 show using this method preparation NCMA material made of electrode, at room temperature with 0.5C constant-current discharge when, circulation
200 circle specific capacities may remain in 175mAh/g；Show good cycle performance.
Embodiment 2
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in NMP afterwards and impregnates 3h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, sodium thiosulfate is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 8: 1: 1, and control Al content is 5% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 6mol/L, adjusts pH=11.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.1, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, is warming up at 900 DEG C and is carried out with the rate of 5 DEG C/min
NCMA quaternary positive electrode can be obtained in high-temperature roasting 18h.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 169mAh/g；Show good cycle performance.
Embodiment 3
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in THF afterwards and impregnates 2h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 6: 2: 2, and control Al content is 5% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 4mol/L, adjusts pH=11.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.07, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, is warming up at 900 DEG C and is carried out with the rate of 5 DEG C/min
For 24 hours, NCMA quaternary positive electrode can be obtained in high-temperature roasting.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 165mAh/g；Show good cycle performance.
Embodiment 4
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in DMF afterwards and impregnates 5h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 6: 2: 2, and control Al content is 4% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 6mol/L, adjusts pH=10.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.07, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, with the rate of 10 DEG C/min be warming up at 1000 DEG C into
NCMA quaternary positive electrode can be obtained in row high-temperature roasting 12h.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 166mAh/g；Show good cycle performance.
Embodiment 5
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in DMF afterwards and impregnates 3h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 8: 1: 1, and control Al content is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 6mol/L, adjusts pH=10.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.03, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, with the rate of 5 DEG C/min be warming up at 1000 DEG C into
For 24 hours, NCMA quaternary positive electrode can be obtained in row high-temperature roasting.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 170mAh/g；Show good cycle performance.
Comparative example 1
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in THF afterwards and impregnates 1h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 8: 1: 1, and control Al content is 10% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).In then
The NaOH solution of 6mol/L is added, adjusts pH=11.After complete reaction, potassium carbonate is added thereto, control additional amount makes
Li: (Ni+Co+Mn+Al)=1.03 makes Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the forerunner of quaternary material containing Li is prepared
Body.The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, is warming up at 900 DEG C with the rate of 5 DEG C/min
It carries out high-temperature roasting for 24 hours, NCMA quaternary positive electrode can be obtained.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 143mAh/g, and cycle performance is declined.
Comparative example 2
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in NMP afterwards and impregnates 2h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 1: 1: 1, and control Al content is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 6mol/L, adjusts pH=11.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.03, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, with the rate of 5 DEG C/min be warming up at 1000 DEG C into
NCMA quaternary positive electrode can be obtained in row high-temperature roasting 30h.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 153mAh/g, and cycle performance is declined.
Comparative example 3
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in NMP afterwards and impregnates 4h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 5: 2: 3, and control Al content is 1% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 6mol/L, adjusts pH=11.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.1, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, with the rate of 5 DEG C/min be warming up at 1100 DEG C into
NCMA quaternary positive electrode can be obtained in row high-temperature roasting 12h.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 151mAh/g, and cycle performance is declined.
Comparative example 4
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in DMF afterwards and impregnates 3h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 6: 2: 2, and control Al content is 3% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Add in then
Enter the NaOH solution of 6mol/L, adjusts pH=11.After complete reaction, potassium carbonate is added thereto, control additional amount makes Li:
(Ni+Co+Mn+Al)=1.2, make Li2CO3NCMA hydroxide surfaces are homogeneously precipitated in, the presoma of quaternary material containing Li is prepared.
The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, with the rate of 5 DEG C/min be warming up at 1000 DEG C into
NCMA quaternary positive electrode can be obtained in row high-temperature roasting 20h.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 152mAh/g, and cycle performance is declined.
Comparative example 5
Waste and old ternary lithium ion battery is disassembled after safe-discharge, core is obtained after iron removal by magnetic separation, core is crushed
It is first placed in DMF afterwards and impregnates 3h, sieve active material and pole piece, powder (active material) is placed in sulfuric acid and is leached.It has reacted
Black insoluble matter is filtered out after complete, thiocarbamide is added into filtrate to there is no precipitatings to generate, filters insoluble matter.
Al, Ni, Co, Mn ratio of filtrate after measurement removal of impurities, and corresponding sulfate is added thereto according to ratio, it adjusts
Section Ni, Co, Mn are matched to 6: 2: 2, and control Al content is 2% (on the basis of the integral molar quantity of Al, Ni, Co, Mn).Then directly
Sodium carbonate is added, control additional amount makes Li: (Ni+Co+Mn)=1.08 makes Li2CO3Homogeneously precipitate in NCMA hydroxide table
Face prepares the presoma of quaternary material containing Li.The Li that will be obtained by filtration2CO3- NCMA persursor material is placed in tube furnace, with 5 DEG C/
The rate of min is warming up to progress high-temperature roasting 16h at 1000 DEG C, and NCMA quaternary positive electrode can be obtained.
Button cell is assembled into using quaternary positive electrode manufactured in the present embodiment and lithium piece, at room temperature, with 0.5C perseverance
When banishing electricity, 200 circle specific capacity of circulation may remain in 141mAh/g, and cycle performance is declined.
Claims (7)
1. a kind of from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the method for preparation quaternary positive electrode, which is characterized in that packet
Containing following steps:
Step 1: waste and old ternary lithium ion battery being impregnated by artificial dismantling, magnetic separation, broken, organic solvent, is sieved, sulfuric acid soaks
Out, the Cu contained2+, Al3+, Li+, Ni2+, Co2+, Mn2+Leachate, leachate through removal of impurities handle to obtain removal of impurities liquid；
Step 2: adjust removal of impurities liquid in Al, Ni, Co, Mn molar ratio wherein, Al account for (Al+Ni+Co+Mn) integral molar quantity 1~
5%；Alkali metal hydroxide and adjustment and control system pH≤10 are then added, carry out level-one precipitating, obtaining precipitating has NCMA hydroxide
Dirty solution；
Step 3: adding carbonate into the dirty solution of step 2 and carry out two-stage precipitation, Li quaternary material is separated by solid-liquid separation to obtain after
Presoma；The carbonate added makes in Li quaternary material presoma, Li:(Al+Ni+Co+Mn) molar ratio be 1~1.1:1；
Step 4: calcining at the Li quaternary material presoma in air 900~1000 DEG C is obtained Al doping NCM's
Quaternary positive electrode.
2. according to claim 1 from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the side of preparation quaternary positive electrode
Method, it is characterised in that: the ratio for adjusting Ni, Co, Mn is 1~8:1~2:1~2.
3. according to claim 2 from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the side of preparation quaternary positive electrode
Method, it is characterised in that: the ratio for adjusting Ni, Co, Mn is one of 6:2:2,8:1:1.
4. according to claim 1 from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the side of preparation quaternary positive electrode
Method, it is characterised in that: the carbonate is sodium carbonate and/or potassium carbonate.
5. according to claim 1 from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the side of preparation quaternary positive electrode
Method, it is characterised in that: calcination time 12-24h, the heating rate of calcination process are 5-10 DEG C/min.
6. according to claim 1 from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the side of preparation quaternary positive electrode
Method, it is characterised in that: in step 1, the organic solvent is N-Methyl pyrrolidone, in dimethylformamide, tetrahydrofuran
At least one, the time impregnated in the organic solvent are 1-5h；
In dedoping step, water-soluble sulphurizing salt, the Cu in precipitating, removing leachate are added2+。
7. according to claim 1 from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, the side of preparation quaternary positive electrode
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 molar ratio to regulate and control Al, Ni, Co, Mn in removal of impurities liquid.
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