CN108110362A - The method that the ternary material precursor of zinc doping is synthesized by waste lithium cell recycling - Google Patents
The method that the ternary material precursor of zinc doping is synthesized by waste lithium cell recycling Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
Containing Zn elements in waste lithium cell, and after ternary precursor doping Zn, the structural stability under the interface stability and high voltage of electrode/electrolyte can be improved, inhibits the increase of the charge transfer resistance in cyclic process, is conducive to Li+Diffusion.Therefore, the invention discloses a kind of method for the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling, the method comprising the steps of：Doped chemical, the content of adjusting Ni, Co, Mn, Co deposited synthesis dopant material precipitation, washing and the drying in waste lithium cell battery core crushed material pickle liquor beyond Zn are removed, finally obtains the ternary material precursor of single zinc doping.The method of the present invention obtains the ternary material precursor of single zinc doping while waste lithium cell recycles synthesis of ternary presoma, has technological process simple, and doping effect is good, cost-effective, the advantages that can significantly improving presoma chemical property.
Description
Technical field
The invention belongs to battery material fields, and in particular to a kind of ternary material that zinc doping is synthesized by waste lithium cell recycling
The method of material precursor.
Background technology
Nickel-cobalt-manganese ternary presoma, that is, nickel cobalt manganese hydroxide (NixCoyMnz(OH)2), nickel cobalt manganese carbonate, oxalates etc.
Compound is mainly used for tertiary cathode material nickle cobalt lithium manganate (LiNixCoyMnzO2) synthesis.Ternary precursor is main at present
Pass through Co deposited synthesis.Tertiary cathode material is synthesized by ternary precursor and lithium hydroxide or lithium carbonate high temperature sintering, tool
There is the features such as specific capacity is big, energy density is high, good cycle, synthetic method simple possible, be mainly used in power neck at present
Domain.
Tertiary cathode material is doped modified thermal stability and improves, and cycle performance improves, and structure is more stablized.Ternary
The doped chemical of positive electrode can be divided into anion and cationic two major classes, wherein anion doped element mainly has F, C,
Cl, S, Zr, Ba, Y, Ca, B, Sn, Sb, Na and Zn etc., cation doping element mainly have Al, Mg, Ti, Cr, V, Fe and Ga etc..
Doping method mainly has sol-gel method and atomic layer deposition method (ALD) etc..Doping at present is mainly to the ternary forerunner of synthesis
Body or positive electrode are doped.
As patent EP2421077A1 discloses the anode material in a kind of serondary lithium battery with high security and high-energy
Material.It is using the sulfate of associated metal, nitrate, carbonate or chloride as raw material, using NaOH as precipitating reagent, ammonium hydroxide conduct
Complexing agent synthesizes the hydroxide precursor containing doped chemical, then adulterates presoma with lithium carbonate at 980 DEG C with synthesis
The tertiary cathode material that 10h obtains doping is calcined in oxygen atmosphere.And propose that doped chemical includes anion doped element F, C,
Cl, S, Zr, Ba, Y, Ca, B, Sn, Sb, Na and Zn, cation doping element al, Mg, Ti, Cr, V, Fe and Ga.And it elaborates to mix
The influence of the grain size, chemical property of the miscellaneous presoma and positive electrode to synthesis.
Patent US 9590244B2 disclose a kind of method for preparing nickel cobalt manganese oxalates and doping,
NiqMnxCoyMzC2O4.nH2O, q+x+y+z=1,0<q<1,0<x<1,0≤y<1,0≤z<0.15,0≤n≤5, doped chemical M
Including Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe and V.It is by 2.9gCo (NO3)2.6H2O,
11.8g NiSO4.6H2O, 7.6g MnSO4.H2O is dissolved in 1L water, adds in 12.6g oxalic acid, 6.4g NaOH and 6.8mL
(28%) ammonium hydroxide stirs 30s at 50 DEG C with 600rpm, places 3h to obtain the co-precipitation of nickel cobalt manganese oxalates.By acquisition
Up to positive electrode after co-precipitation and lithium carbonate calcining.The presoma of doped chemical is dissolved in alcoholic solution or distilled water, it will
Fluorine-containing solution adds in above-mentioned solution, obtains metal fluoride powder, then positive electrode is added in mixed solution to get doping
Positive electrode.
Patent US 2004/023485A1 disclose a kind of positive electrode of doping and preparation method thereof.The anode material of doping
Expect for Li1+xNiαMnβAγO2, A Mg, Zn, Al, Co, Ga, B, Zr or Ti, 0<x<0.2,0.1≤α≤0.5,0.4≤β≤0.6,
0≤γ≤0.1.Positive electrode is prepared by solid phase reaction, solution reaction or sol-gel method, and is used in liquid nitrogen or liquid helium
The method of middle rapid cooling.
Yu Xiaoyuan etc. is with NH4HCO3And Na2CO3For precipitating reagent, by metering than weigh a certain amount of soluble nickel salt, cobalt salt,
The soluble-salt of manganese salt and foreign cation is made into the mixed solution of debita spissitudo, by the precipitation of mixed solution and debita spissitudo
Agent is added to by flowmeter in reaction kettle, controls mixing speed, the pH value of reaction system in 8.0 or so, temperature at 55 DEG C,
After a certain period of time, ageing, filtering, gained precipitation are washed repeatedly with deionized water, and Ni is obtained after dry for reaction1/3Co1/3Mn1/3- xMxCO3(M=Cr, Al, Mg；X=0.02,0.05) presoma (China YouSe Acta Metallurgica Sinica, 2010,20 (6):1170-
1176.)。
Rui Guo etc. utilize sol-gel method, to positive electrode LiNi0.5Co0.25Mn0.25O2Carry out coating-doping.By second
Sour zinc is dissolved in by magnetic agitation in 50 DEG C of ethyl alcohol, and ethanolamine is added in as complexing agent in above-mentioned solution and adjusts ethanolamine
With the molar ratio of metal ion to 1.By positive electrode LiNi0.5Co0.25Mn0.25O2It adds in colloidal sol and is evaporated up in 80 DEG C of stirrings
Black gel occurs.Gel is calcined into 3h to obtain the LiNi0.5Co0.25Mn0.25O2 of doping Zn at 700 DEG C
(Electrochimica Acta,2009,54(24):5796-5803.)。
Ji-Zhou Kong etc. are by the method for atomic layer deposition (ALD) to positive electrode Li1.2Ni0.54Co0.13Mn0.13O2
And LiNi0.5Co0.2Mn0.3O2Cladding ZnO be doped (Journal of Alloys and Compounds, 2017,694:
848-856.Journal of Power Sources,2014,266:433-439.)。
In order to reduce cost, the recycling value of waste lithium cell is improved, this field has been developed in useless old lithium
The method that the ternary material precursor of doped metallic elements is prepared in the recycling of pond.
It, will if patent CN104868190A discloses metal leaching and recovery method in a kind of lithium ion cell anode waste
Lithium ion cell anode waste is with 2~4mol/L organic acid solns containing 2~6% reducing agents with the solid-liquid of 50~100g/L
Than at 30~70 DEG C, 10~30min being reacted under conditions of 100~500rpm, wherein the organic acid is formic acid, acetic acid, third
Any one of acid, butyric acid or valeric acid or at least two combination, reducing agent is sulfurous acid, sodium sulfite, sodium thiosulfate or
In hydrogen peroxide it is any or at least two combination.Separation of solid and liquid is carried out after reaction, obtains leachate and filter residue, realize lithium from
The leaching of metal in sub- cell anode waste.In leachate with raw material composition and content, adjust leachate in Ni, Co,
The content of one kind or at least two elements in Mn or M, makes the molar ratio of Ni, Co, Mn and M meet molecular formula
LiNixCoyMn1-x-yMzO2The molar ratio of middle Ni, Co, Mn and M, wherein, M is from separation lithium ion cell anode waste process
In mixed foreign metal, positive electrode due to mixed foreign metal, introduced metal during doping or coating modification
For any one of Cu, Al, Fe, Mg, Cr, Ti, Ce or Y or at least two, 0<x<1,0<y<1,0≤z<0.1, and 0<x+y+z<
1, obtain precursor solution.But all M elements in waste material can only be doped by this method, it is impossible to which the acquisition of orientation is single
Metallic element adulterates, particularly the ternary material of single zinc doping.
Patent CN104953199A discloses a kind of metal-doped nickle cobalt lithium manganate of lithium ion cell anode waste synthesis
And its preparation method and application.The binding agent and conductive agent in lithium ion cell anode waste are removed, obtains positive electrode powder；
Measure the element composition of positive active material；Adjust one kind in positive electrode powder in Ni, Co, Mn or M or at least two
Content makes its molar ratio meet molecular formula LiNixCoyMn1-x-yMzO2The molar ratio of middle Ni, Co, Mn and M obtain anode presoma
Powder；Lithium source is added, metal-doped nickle cobalt lithium manganate is obtained using high temperature solid state reaction.Wherein, M Cu, Al, Fe, Mg,
Any one of Cr, Ti, Ce or Y or at least two, 0<x<1,0<y<1,0<z<0.1, and 0<x+y+z<1.The M sources derive from
It separates during mixed foreign metal or positive electrode are due to doping or coating modification during lithium ion cell anode waste
Mixed foreign metal.Adjust oxide, chloride, the sulfuric acid that Ni, Co, Mn or M source used in molar ratio are Ni, Co, Mn or M
Salt, nitrate, acetate or oxalates.This method recycles positive electrode using high-temperature roasting method, it is impossible to remove foreign metal, together
Sample is non-orientable to obtain single metallic element doping, the particularly ternary material of single zinc doping.
The content of the invention
The method that metal-doped presoma or positive electrode are synthesized currently with waste and old lithium ion battery, is to utilize back
Mixed one or more foreign metals in receipts or modifying process, it is impossible to accomplish orientation, solely doped metallic elements.For existing
The problem of with the presence of technology, it is an object of the invention to provide a kind of ternary materials that zinc doping is synthesized by waste lithium cell recycling
The method of presoma.This method utilizes the Zn elements contained in waste lithium cell, passes through letter in waste lithium cell removal process
Single effective method removes the other impurities element beyond Zn, and single being entrained in of Zn is recycled synthesize three by waste lithium cell
In first material precursor, the chemical property of positive electrode is effectively improved.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of method for the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling, including step：
1) ingredient of waste lithium cell battery core crushed material pickle liquor is detected, and pH is adjusted with 5%~20% alkaline solution
To 4~6, the iron powder of 2~5 times of Cu contents is added in, after being stirred to react 0.5~2h with 100~200rpm, then is added in by the amount of iron powder
1.2~1.5 times of hydrogen peroxide is stirred to react other doping members that can be removed after 0.5~1h beyond Zn with 100~200rpm
Element；
2) analysis removes after other doped chemicals Ni, the content of Co, Mn, according to the content demand tune of each component in pickle liquor
A kind of or at least two elements content in section Ni, Co, Mn；
3) pickle liquor of step 2) is subjected to reaction synthesis dopant material；
4) dried after the dopant material of acquisition is washed to get the ternary material precursor of single doping Zn.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, the Zn members of doping
Element can also be added additionally according to actual needs entirely from waste lithium cell battery core crushed material pickle liquor.Root
According to some specific embodiments of the present invention, the Zn elements contained in pickle liquor, which can meet, improves positive electrode chemical property
It is required that without remaking addition, it is both cost-effective in turn simplify technique, therefore be preferred method.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, step 1) are described
Alkaline solution be NaOH, KOH or LiOH solution.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, the step 2)
The middle Ni for adjusting content, Co, Mn sources are selected from oxide, chloride, sulfate, nitrate, acetate or the grass of Ni, Co, Mn
At least one of hydrochlorate.
As additionally addition Zn, Zn sources are in zinc oxide, zinc chloride, zinc sulfate, zinc nitrate, zinc acetate or zinc oxalate
It is at least one.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, the step 3)
Reaction add in complexing agent include but not limited to ammonium hydroxide, acetylacetone,2,4-pentanedione, ethylenediamine, sodium ethylene diamine tetracetate, citric acid, winestone
Any one in acid；Precipitating reagent includes but not limited to any one in NaOH, oxalic acid, carbonate.
Some specific embodiments according to the present invention, it is above-mentioned the ternary material of zinc doping is synthesized by waste lithium cell recycling before
The method for driving body, the concentration of the complexing agent of addition is 0.3~0.8mol/L, and the concentration of precipitating reagent is 3~6mol/L.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, the step 3)
Synthesizing the method for dopant material includes the precipitation method and sol-gel method.
Some specific embodiments according to the present invention, step 3) uses coprecipitation, i.e., under stiring, to the acid of step 2)
Complexing agent and precipitating reagent are added in immersion liquid, is reacted under nitrogen atmosphere with certain pH；
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, step 3) use
Coprecipitation is 10~12 times reactions in pH, and reaction temperature is 40~60 DEG C.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, step 3) use
Coprecipitation, mixing speed are to be reacted under 400~600rpm.
The method of the above-mentioned ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, the step 4)
It is dry at 80 DEG C~100 DEG C.
The method of the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling of the present invention, with prior art phase
Than having the advantages that：By the control doped chemical that cleans to waste lithium cell pickle liquor, can accomplish Zn elements only
It is entrained on ternary precursor；The present invention obtains presoma by the way that Zn and Ni, Co, Mn are co-precipitated, therefore can be by waste and old
Lithium battery pickle liquor obtains the ternary material precursor of doping Zn while recycling synthesis of ternary material precursor, reduce follow-up work
Skill flow improves recycling value-added content of product.
Specific embodiment
The method that the present invention is synthesized the ternary material precursor of zinc doping by waste lithium cell recycling, including following 4 steps
Suddenly：
1) ingredient of waste lithium cell battery core crushed material pickle liquor is detected, and pH to 4 is adjusted with 5~20% alkaline solution
~6, the iron powder of 2~5 times of Cu contents is added in, after being stirred to react 0.5~2h with 100~200rpm, then the amount addition 1.2 by iron powder
~1.5 times of hydrogen peroxide is stirred to react other doped chemicals that can be removed after 0.5~1h beyond Zn with 100~200rpm；
2) analysis removes after other doped chemicals Ni, the content of Co, Mn, according to the content demand tune of each component in pickle liquor
A kind of or at least two elements content in section Ni, Co, Mn；
3) pickle liquor of step 2) is subjected to reaction synthesis dopant material；
4) dried after washing of precipitate being obtained to get the ternary material precursor of single doping Zn.
Step 1) is the weight that the present invention removes other doped chemicals beyond Zn from waste lithium cell positive electrode pickle liquor
Step is wanted, the data of some specific embodiments are shown according to the present invention, and the step operation is simple, good impurity removing effect, are mixed to be single
Miscellaneous Zn has established important foundation.
The alkaline solution that step 1) adjusts pH is selected from NaOH, KOH or LiOH solution.
Step 2) adjust content Ni, Co, Mn or Zn source be selected from the oxide of Ni, Co, Mn or Zn, chloride, sulfate,
At least one of nitrate, acetate or oxalates.Oxide of the present invention, chloride, sulfate, nitrate, second
Hydrochlorate or oxalates include its hydrate, such as NiSO4.6H2O、MnSO4.H2O etc..
In some embodiments, step 3) uses coprecipitation, i.e., under stiring, the pickle liquor into step 2) adds in network
Mixture and precipitating reagent, are reacted under nitrogen atmosphere with certain pH.Complexing agent be concentration be 0.3~0.8mol/L ammonium hydroxide,
Any one in acetylacetone,2,4-pentanedione, ethylenediamine, sodium ethylene diamine tetracetate, citric acid, tartaric acid；Precipitating reagent is that concentration is 3~6mol/
Any one in the NaOH of L, oxalic acid, carbonate.The preferred reaction condition of step 3 is：40~60 DEG C of temperature, mixing speed 400
~600rpm, pH 10~12.
It is illustrated below by way of specific embodiment is further to the content of the invention of the present invention, but should not be construed as the present invention
Scope be only limitted to following example, invention thinking according to the present invention and entire contents, can will be each in following instance
Technical characteristic makes appropriate combination/replacement/adjustment/modification etc., this is will be obvious to those skilled in the art that still
Belong to the scope that the present invention protects.
Embodiment 1
A kind of method for the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling, comprises the following steps：
1. the ingredient of waste lithium cell positive electrode pickle liquor is shown in Table 1, pH to 4 is adjusted with 5% NaOH solution, adds in Cu
The iron powder that 3 times of content is stirred to react 0.5h with 150rpm, then 1.2 times of hydrogen peroxide is added in by the amount of iron powder, is stirred with phase same rate
Other doped chemicals can be removed after mixing 0.5~1h of reaction.
1 (unit of table：g/L)
| Mn | Ni | Co | SO4 2- | Na+ | Li+ | Al | Fe | Cu | Zn | Pb | Si |
| 12.92 | 14.36 | 23.08 | 366.4 | 0.038 | 5.33 | 2.11 | 0.44 | 0.060 | 0.094 | 0 | 0.038 |
2. removing the pickle liquor ingredient after other doped chemicals is shown in Table 2.The pickle liquor after 200mL removal of impurities is taken, is added
8.15gNiSO4.6H2O and 5.58g MnSO4.H2O is configured to Ni, Co, Mn molar ratio as 1:1:1 solution.
2 (unit of table：g/L)
| Mn | Ni | Co | SO4 2- | Na+ | Li+ | Al | Fe | Cu | Zn | Pb | Si |
| 10.31 | 11.76 | 20.83 | 359.8 | 0.016 | 4.93 | 0.00047 | 0.000012 | 0.003 | 0.085 | 0 | 0.025 |
3. step 2 is adjusted into the pickle liquor of Ni, Co, Mn molar ratio under conditions of 40 DEG C, stir speed (S.S.) 400rpm, with dense
The complexing agent of 0.5mol/L is spent, the precipitating reagent of 3mol/L is reacted under nitrogen atmosphere with pH 10.9.
In 100 DEG C of dry ternary precursors to get doping Zn after 4. washing of precipitate will be obtained.
The ternary material precursor that the ternary material precursor not being doped and the present embodiment are carried out to Zn doping is distinguished
With Li2CO3It sinters positive electrode into, tests chemical property, related data is shown in Table 3.
Table 3
Embodiment 2
A kind of method for the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling, comprises the following steps：
1. the ingredient of waste lithium cell positive electrode pickle liquor is shown in Table 4, pH to 4 is adjusted with 5% NaOH solution, adds in Cu
The iron powder that 3 times of content is stirred to react 0.5h with 150rpm, then 1.2 times of hydrogen peroxide is added in by the amount of iron powder, is stirred with phase same rate
Other doped chemicals can be removed after mixing reaction 0.5h.
4 (unit of table：g/L)
| Mn | Ni | Co | SO4 2- | Na+ | Li+ | Al | Fe | Cu | Zn | Pb | Si |
| 12.92 | 14.36 | 23.08 | 366.4 | 0.038 | 5.33 | 2.11 | 0.44 | 0.060 | 0.094 | 0 | 0.038 |
2. removing the pickle liquor ingredient after other doped chemicals is shown in Table 5.The pickle liquor after 200mL removal of impurities is taken, is added
36.14gNiSO4.6H2O and 11.58g MnSO4.H2O is configured to Ni, Co, Mn molar ratio as 5:2:3 solution.
5 (unit of table：g/L)
| Mn | Ni | Co | SO4 2- | Na+ | Li+ | Al | Fe | Cu | Zn | Pb | Si |
| 10.31 | 11.76 | 20.83 | 359.8 | 0.016 | 4.93 | 0.00047 | 0.000012 | 0.003 | 0.081 | 0 | 0.025 |
3. step 2 is adjusted into the pickle liquor of Ni, Co, Mn molar ratio under conditions of 50 DEG C, stir speed (S.S.) 500rpm, with dense
The complexing agent of 0.6mol/L is spent, the precipitating reagent of 4mol/L is reacted under nitrogen atmosphere with pH 11.0.
In 100 DEG C of dry ternary precursors to get doping Zn after 4. washing of precipitate will be obtained.
The ternary material precursor that the ternary material precursor not being doped and the present embodiment are carried out to Zn doping is distinguished
With Li2CO3It sinters positive electrode into, tests chemical property, related data is shown in Table 6.
Table 6
Embodiment 3
A kind of method for the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling, comprises the following steps：
1. the ingredient of waste lithium cell positive electrode pickle liquor is shown in Table 7, pH to 5 is adjusted with 5% NaOH solution, adds in Cu
The iron powder that 4 times of content is stirred to react 0.5h with 150rpm, then 1.4 times of hydrogen peroxide is added in by the amount of iron powder, is stirred with phase same rate
Other doped chemicals can be removed by mixing reaction.
7 (unit of table：g/L)
| Mn | Ni | Co | SO4 2- | Na+ | Li+ | Al | Fe | Cu | Zn | Pb | Si |
| 12.92 | 14.36 | 23.08 | 366.4 | 0.038 | 5.33 | 2.11 | 0.44 | 0.060 | 0.094 | 0 | 0.038 |
2. removing the pickle liquor ingredient after other doped chemicals is shown in Table 8.The pickle liquor after 200mL removal of impurities is taken, is added
8.41gNiSO4.6H2O、6.08g MnSO4.H2O and 0.1gZnSO4, Ni, Co, Mn molar ratio are configured to as 1:1:1 solution.
8 (unit of table：g/L)
3. step 2 is adjusted into the pickle liquor of Ni, Co, Mn molar ratio under conditions of 60 DEG C, stir speed (S.S.) 400rpm, with dense
The complexing agent of 0.6mol/L is spent, the precipitating reagent of 4mol/L is reacted under nitrogen atmosphere with pH 11.1.
In 100 DEG C of dry ternary precursors to get doping Zn after 4. washing of precipitate will be obtained.
The ternary material precursor that the ternary material precursor not being doped and the present embodiment are carried out to Zn doping is distinguished
With Li2CO3It sinters positive electrode into, tests chemical property, related data is shown in Table 9.
Table 9
According to the result of the test of above example as it can be seen that the method for the present invention is being recycled waste lithium cell
Other doped chemicals are effectively removed in the process, obtain the ternary material precursor of single doping Zn, and the presoma sinters into
Positive electrode significantly improves chemical property, improves recycling value-added content of product, and recycling and modified production are integrated,
Subsequent process flow is reduced, has saved cost.
Claims (10)
- A kind of 1. method for the ternary material precursor that zinc doping is synthesized by waste lithium cell recycling, which is characterized in that including step Suddenly：1) detect waste lithium cell battery core crushed material pickle liquor ingredient, and with 5%~20% alkaline solution adjusting pH to 4~ 6, the iron powder of 2~5 times of Cu contents is added in, 0.5~2h is stirred to react with 100~200rpm, then 1.2 are added in by the amount of iron powder~ 1.5 times of hydrogen peroxide is stirred to react other doped chemicals that can be removed after 0.5~1h beyond Zn with 100~200rpm；2) Ni, the content of Co, Mn are adjusted according to the content demand of each component in pickle liquor after other doped chemicals of analysis removing A kind of or at least two elements content in Ni, Co, Mn；3) pickle liquor of step 2) is subjected to reaction synthesis dopant material；4) dried after the dopant material of acquisition is washed to get the ternary material precursor of single doping Zn.
- 2. the method for the ternary material precursor according to claim 1 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, the alkaline solution described in step 1) is NaOH, KOH or LiOH solution.
- 3. the method for the ternary material precursor according to claim 1 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, the Ni of content, Co are adjusted in step 2), and Mn sources are selected from oxide, chloride, sulfate, the nitre of Ni, Co, Mn At least one of hydrochlorate, acetate or oxalates.
- 4. the method for the ternary material precursor according to claim 1 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, the complexing agent that the reaction of step 3) adds in is ammonium hydroxide, acetylacetone,2,4-pentanedione, ethylenediamine, sodium ethylene diamine tetracetate, lemon Any one in acid, tartaric acid；Precipitating reagent is NaOH, any one in oxalic acid, carbonate.
- 5. the method for the ternary material precursor according to claim 4 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, the concentration for the complexing agent that step 3) adds in is 0.3~0.8mol/L, and the concentration of precipitating reagent is 3~6mol/L.
- 6. the method for the ternary material precursor according to claim 1 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, the method for the reaction synthesis dopant material of step 3) is coprecipitation or sol-gel method.
- 7. the method for the ternary material precursor according to claim 6 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, step 3) uses Co deposited synthesis dopant material, i.e., under stiring, complexing is added in into the pickle liquor of step 2) Agent and precipitating reagent, are reacted under nitrogen atmosphere with certain pH.
- 8. the method for the ternary material precursor according to claim 7 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, step 3) is 10~12 times reactions in pH, and reaction temperature is 40~60 DEG C.
- 9. the method for the ternary material precursor according to claim 7 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, the mixing speed of step 3) is 400~600rpm.
- 10. the method for the ternary material precursor according to claim 1 that zinc doping is synthesized by waste lithium cell recycling, It is characterized in that, step 4) is dry at 80~100 DEG C.
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Cited By (3)
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|---|---|---|---|---|
| CN109449434A (en) * | 2018-09-20 | 2019-03-08 | 广东佳纳能源科技有限公司 | A method of ternary anode material of lithium battery presoma is prepared using waste and old lithium ion battery |
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| CN113582246B (en) * | 2021-06-30 | 2023-02-21 | 南通金通储能动力新材料有限公司 | Preparation method of high-nickel polycrystalline quaternary precursor |
| CN113772693A (en) * | 2021-10-27 | 2021-12-10 | 江西金辉锂业有限公司 | Method for selectively leaching and extracting lithium from lithium iron phosphate waste |
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