CN106654205A - Method for preparing ternary cathode material precursor by using waste lithium battery material - Google Patents
Method for preparing ternary cathode material precursor by using waste lithium battery material Download PDFInfo
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- CN106654205A CN106654205A CN201611177778.5A CN201611177778A CN106654205A CN 106654205 A CN106654205 A CN 106654205A CN 201611177778 A CN201611177778 A CN 201611177778A CN 106654205 A CN106654205 A CN 106654205A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method for preparing a ternary cathode material precursor by using a waste lithium battery material. The method comprises the steps of adding an acid for leaching a cathode material to obtain a solution; adding an ascorbic acid to further reduce Co<3+>, Ni<3+> and Mn<4+> in the solution into a bivalent ion state, adjusting pH by using an alkali liquid and removing impurities of aluminum, iron and the like; adding a proper amount of nickel-cobalt-manganese nitrate to adjust the molar ratio of nickel, cobalt, manganese and lithium in the solution; and adding a complexing agent, finally adjusting the pH value, adding a precipitator for precipitation to prepare the ternary cathode material precursor. The method for preparing the ternary cathode material precursor which is narrow in particle size distribution and is evenly mixed by using the waste lithium battery material is provided for the problems that trace amounts of high-valence nickel-cobalt-manganese ions and ternary material precursor particles can be reunited in precursor precipitation and the particle size and the shape and form of the ternary material cannot be effectively regulated and controlled.
Description
Technical field
The invention belongs to electrode material of lithium battery technical field, and in particular to one kind prepares three using waste lithium cell material
The method of first positive electrode material precursor.
Background technology
Lithium ion battery has more advantages than other chargeable batteries (such as Ni-Cd batteries and Ni-H batteries), including
Specific energy is big, energy density is high, output voltage is high, have extended cycle life, self-discharge rate is low, can high current charge-discharge, memoryless effect
Should be wider with operating temperature range, therefore, it is widely used in the modern times such as mobile phone, panel computer and digital camera digital electronic goods
In, and it is increasingly becoming the first-selected electrical source of power in the fields such as energy storage device and electric motor car.
According to the statistics of China Battery Industry Association, whole year in 2015, national lithium ion battery industry accumulation is completed
Yield 5,600,000,000 (naturally only), increases by 3% on a year-on-year basis, and China becomes the maximum production and consumption state of whole world lithium ion battery.
Additionally, in energy storage device and the potential application of electric automobiles, also causing the consumption of lithium ion battery to enter in the near future
One step expands length.Because the average life of lithium battery was in 1～3 year, predict according to China Automotive Technology ＆ Research Center, to the year two thousand twenty
Electric Cars in China electrokinetic cell accumulation learies are up to 12 ten thousand to 17 ten thousand tons.And according to the statistical number of United States Geological Survey
26.99%, 1.07%, 4.01% and the 7.02% of global reserves are only accounted for according to the mineral resources of the lithium of, China, cobalt, nickel and manganese, it is raw
Produce the metal imbalance between supply and demand needed for lithium ion battery increasingly to project in China.Meanwhile, lithium, cobalt in waste and old lithium ion battery
5～7%, 5～20% and 5～10% are respectively with the content of the valuable metal such as nickel, wherein the content of valuable metal is sometimes even
More than natural crystal.Therefore, the valuable metal in high efficiente callback waste and old lithium ion battery can be provided to produce lithium ion battery
The metal of replacement, mitigates the deficient pressure of ore resource.Additionally, the recovery of waste and old lithium ion battery can also mitigate it to environment and
The threat of human health, promotes sustainable development and the industrial upgrading of lithium ion battery industry.
The production of ternary anode material precursor mainly adopts nickel cobalt mn sulphate for raw material, and production cost is high, and passes through
The positive electrode that process waste and old lithium ion battery is obtained can be used to synthesis of ternary positive electrode material precursor, and related art is
Jing is present.Existing recovery method is leached using sulfuric acid and hydrogen peroxide and reclaims anode material for lithium-ion batteries, is adjusted pH and is added
The mol ratio of nickel, cobalt and manganese is adjusted after filter aid removal of impurities with nickel cobalt mn sulphate, complex precipitant reaction is added and is obtained
Nickel-cobalt-manganese ternary material precursor is precipitated, and existing in presoma precipitation may have micro high price nickel cobalt manganese ion and ternary material
The problems such as material precursor particle agglomeration, and can not effectively regulate and control the particle diameter and pattern of ternary material, affect final tertiary cathode
The chemical property of material.
Therefore, it is necessary to provide low a kind of process is simple, energy consumption, applied range, environmental protection, the abundant simultaneously energy of raw material sources
The utilization waste and old lithium ion battery material of effectively solving particle agglomeration problem prepares narrow diameter distribution and is well mixed tertiary cathode
The method of material precursor.
The content of the invention
The technical problem of solution：Present invention aim to address may have micro high price nickel in prior art presoma precipitation
Cobalt and manganese, ternary material precursor particle agglomeration and the problems such as can not effectively regulate and control the particle diameter and pattern of ternary material, carry
For a kind of process is simple, low energy consumption, applied range, environmental protection, the abundant simultaneously energy effectively solving particle agglomeration problem of raw material sources
Utilization waste and old lithium ion battery material prepare narrow diameter distribution and the method for being well mixed ternary anode material precursor.
Technical scheme：The method for preparing ternary anode material precursor using waste lithium cell material, comprises the following steps：
Step 1, with salpeter solution anode material for lithium-ion batteries is reclaimed, and obtains suspension 1；
Step 2, by the filtering and impurity removing of suspension 1, obtains filtrate 1；
Step 3, adds ascorbic acid to be reacted in filtrate 1, and regulation reacting liquid pH value is 4-5, obtains suspension 2；
Step 4, by the filtering and impurity removing of suspension 2, obtains filtrate 2；
Step 5, adds nickel nitrate, cobalt nitrate, manganese nitrate, lithium salts and complexing agent to be reacted in filtrate 2, to
Precipitating reagent is added in reactant liquor, is stirred, obtain suspension 3；
Step 6, suspension 3 is filtered, and nickel-cobalt-manganese ternary material precursor precipitation is obtained after filter residue is scrubbed.
Further, it is to adopt leaching process to reclaim in step 1, and salpeter solution concentration is 1～8mol/L, and treatment temperature is
50～65 DEG C, process time is 30～60min.
Further, it is to add carry out filtering and impurity removing again after filter aid in suspension in step 2.
Further, the addition of ascorbic acid is 10～15wt.% in step 3, and reaction temperature is 30～60 DEG C, time
For 1～2h.
Further, it is to add carry out filtering and impurity removing again after filter aid in suspension in step 4.
Further, step 5 complexing agent is acetylacetone,2,4-pentanedione, and its addition is 30～50v/v%.
Further, precipitating reagent is sodium carbonate in step 5, and concentration is 1～2mol/L.
Further, in step 5 stirring condition be 35～60 DEG C, 1～4h, 1000～1200rpm, pH value is 7-9.
Further, lithium salts is lithium carbonate, lithium hydroxide or lithium nitrate in step 5.
Beneficial effect：Technical scheme can effectively remove Fe3+And Al3+ impurity；Add the side of ascorbic acid one
Face can be by Co3+、Ni3+And Mn4+The ionic state of divalence is reduced to, the organic efficiency for making nickel, cobalt, manganese is improved, by the waste and old electricity of recovery
Ternary material precursor purity prepared by pond is higher；Another aspect ascorbic acid can adjust and limit the growth of particle so that
The ternary material precursor particle diameter distribution that prepared by recovery old and useless battery is narrower and is well mixed；Using acetylacetone,2,4-pentanedione as complexing
Agent, this complex ion contributes to the slow release of metal ion in course of reaction and generates precipitation, is conducive to the rule of product morphology
In order, the good and tap density of sphericity is high, and is prevented from particle agglomeration.
Specific embodiment
The present invention is described in further detail below by specific embodiment.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Unreceipted concrete skill in embodiment
Art or condition person, are carried out according to the technology or condition described by document in the art or according to product description.Examination used
Agent or the unreceipted production firm person of instrument, be can pass through city available from conventional products.
The invention provides a kind of method that utilization waste lithium cell material prepares ternary anode material precursor, adopts and adds
Ore Leaching positive electrode obtains solution, adds ascorbic acid further by the Co in solution3+、Ni3+And Mn4+It is reduced to divalence
Ionic state, then adjusted with alkali lye and pH and remove impurity aluminum, iron etc., add appropriate nickel cobalt manganese nitrate adjust nickel in solution,
The mol ratio of cobalt, manganese and lithium, adds complexing agent, finally adjusts pH value and adds precipitating reagent precipitation that tertiary cathode material forerunner is obtained
Body.
Exemplary embodiment of the invention, the utilization waste and old lithium ion battery material is prepared before tertiary cathode material
Driving the method for body includes following multiple steps.
Step 1, with salpeter solution anode material for lithium-ion batteries is reclaimed, and obtains suspension 1.
The old and useless battery material that the present invention is utilized is to be decomposed to obtain or Battery Plant's positive electrode side by waste and old lithium ion battery
Corner material, including cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate and other contain cobalt, nickel, the waste lithium ion cell anode material of manganese.And
And, the lithium ion battery material processed in this step can be the anode material for lithium-ion batteries through smashing, after purified treatment.
This step specifically carries out leaching process using acid solution to waste lithium ion cell anode material, makes applying waste lithium ionic
Metal in cell positive material becomes metal ion and is dissolved in acid solution.In this step, the concentration of nitric acid be 1～
8mol/L, and control process temperature is 50～65 DEG C, and process time is 30～60min.
Step 2, filter aid is added in suspension 1 and the removal of impurity is gone in filtration, obtains filtrate 1；
The processing intent of this step is removed in waste and old positive electrode not by sour dissolved impurity.Specific operation is to add
Filter aid diatomite, so that the rate of filtration is greatly improved, while the lithium rate of recovery is also significantly enhanced.
Step 3, adds ascorbic acid to be reacted in filtrate 1, and the pH value for adjusting reactant liquor is 4-5, obtains suspension
2。
This step is by the Co in solution3+、Ni3+And Mn4+The ionic state of divalence is reduced to, while ascorbic acid construction unit
In contain a certain amount of hydroxyl, and with certain chemism, can be bonded with chemistry with many metal ions, can point
Supermolecule is formed by hydrogen bond between son, can be used as template to guide the growth of crystal, the growth of particle is controlled, so that it is guaranteed that finally
The degree of purity and particle diameter distribution of obtained presoma.In this step, the addition of ascorbic acid is 10～15wt.%, so as to
Ensure the Fe in solution3+Will not be reduced, and treatment temperature is 30～60 DEG C, and process time is 1～2h.
The pH for adjusting reactant liquor is further to carry out removal of impurities to solution, precipitates aluminium, iron in solution etc., so that it is guaranteed that most
The degree of purity of presoma obtained in eventually.The concrete operations of this step be pH value is adjusted to 4 first with alkali lye such as NaOH～
5, make the precipitation such as aluminium, iron in solution, and nickelous cobalt and manganese etc. under the conditions of this pH substantially will not Precipitation, this mistake
The sedimentation time is controlled in journey for 30～50min.
Step 4, filter aid is added in suspension 2 and the removal of impurity is gone in filtration, obtains filtrate 2；
The processing intent of this step is further to remove the iron aluminium impurity in solution.The concrete operations of this step are to add to help
Filtering agent diatomite, so that the rate of filtration is greatly improved, while the lithium rate of recovery is also significantly enhanced.
Step 5, nickel nitrate, cobalt nitrate, manganese nitrate and lithium salts are added in filtrate 2 and total nickel cobalt manganese and lithium is adjusted
Mol ratio be 1：1, and complexing agent is added, reacted, precipitating reagent is added in reactant liquor and pH value is adjusted for 7-9, control
Certain mixing speed, reaction obtains suspension 3,
The mol ratio of nickel, cobalt, manganese and lithium is adjusted in this step by adding nitrate, it is ensured that obtained ternary material
Atom ratio in material precursor, more accurately obtains target product.In this step, the nickel nitrate is nickel nitrate, described
Cobalt nitrate is cobalt nitrate, the manganese nitrate is manganese nitrate, and the lithium salts is lithium carbonate, lithium hydroxide or lithium nitrate etc..
Complexing agent described in this step is acetylacetone,2,4-pentanedione, and its addition is 30～50vol.%, using acetylacetone,2,4-pentanedione as complexing agent,
Because it can occur the complex ion that complex reaction forms metal-acetylacetone,2,4-pentanedione with nickel, cobalt and manganese ion, this complex ion is helped
The slow release of metal ion in course of reaction generates precipitation, is conducive to the regular of product morphology, sphericity it is good
And tap density is high, and it is prevented from particle agglomeration.
Nickel-cobalt-manganese ternary material precursor precipitation is obtained by adding precipitating reagent, nickel-cobalt-manganese ternary material forerunner is obtained then
Body.Precipitating reagent used in this process is sodium carbonate, and the concentration of sodium carbonate is 1～2mol/L, and reaction temperature is 35～60 DEG C,
Solution ph is maintained at 7～9, and the reaction time is 1～4h, 1000～1200rpm of mixing speed.During sheet, using complexing
The precipitation method, because complexing agent can occur complex reaction with nickel, cobalt and manganese Metal ion metel complex ion is formed, and this complex ion has
Help metal ion in course of reaction and slowly discharge generation precipitation so that the pH value of slurry easily keeps steady in course of reaction
Fixed, this is conducive to generating, and pattern is regular, and sphericity is good, and tap density is high, and particle size distribution is narrow and is well mixed
Presoma is precipitated.
Step 6, by suspension 3 filter residue is filtrated to get, and nickel-cobalt-manganese ternary material precursor will be obtained after its carrying out washing treatment and is sunk
Form sediment.
Washing operation includes that deionized water is washed 3～5 times and ethanol and washed 3～5 times, then by the nickel-cobalt-manganese ternary material
Presoma washing of precipitate is simultaneously dried to obtain ternary anode material precursor.
Embodiment 1
Take the nickle cobalt lithium manganate positive pole band 50g of waste and old lithium ion battery, adopt concentration for 8mol/L nitric acid at 55 DEG C
To positive pole band leaching 30min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add diatomite,
It is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Add in the solution
15wt.% ascorbic acid, 30 DEG C of controlling reaction temperature reacts 2h；After reaction using sodium hydroxide solution adjust solution ph to
5, aluminum hydroxide precipitation is generated, keep that diatomite is added after 30min and removal aluminum hydroxide precipitation is filtered, obtain containing only divalence
Nickel, cobalt, manganese and lithium nitrate mixed solution；Nickel nitrate, cobalt nitrate and manganese nitrate mol ratio is added to be 1 in the solution：1：1, plus
Enter lithium salts to cause the mol ratio of total nickel cobalt manganese and lithium is 1：1, it is subsequently adding 30vol.% complexing agents, normal temperature mixing 10min；Again plus
Enter sodium carbonate as precipitating reagent and adjust pH value to 7, to react 4h at 35 DEG C, mixing speed is 1000rpm to controlling reaction temperature
Reaction generates nickel-cobalt-manganese ternary material precursor precipitation, and Jing is filtered, washed and be dried to obtain spherical nickel cobalt manganese ternary material forerunner
Body.
The chemical composition of gained presoma and performance test are as follows：
Embodiment 2
Take waste and old lithium ion battery cobalt acid lithium and nickle cobalt lithium manganate positive pole band 50g, adopt concentration for 6mol/L nitric acid
At 60 DEG C to positive pole band leaching 40min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add
Diatomite, is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Molten
15wt.% ascorbic acid, 40 DEG C of controlling reaction temperature is added to react 1.5h in liquid；Adjusted using sodium hydroxide solution after reaction
Solution ph generates aluminum hydroxide precipitation to 4.5, keeps that diatomite is added after 40min and removal aluminum hydroxide precipitation is filtered, and obtains
To containing only nickelous, cobalt, manganese and lithium nitrate mixed solution；Nickel nitrate, cobalt nitrate and manganese nitrate mol ratio are added in the solution
For 0.5：0.2：0.3, it is 1 to add lithium salts to cause the mol ratio of total nickel cobalt manganese and lithium：1,40vol.% complexing agents are subsequently adding, often
Temperature mixing 10min；Sodium carbonate is added as precipitating reagent and pH value is adjusted to 8, controlling reaction temperature is stirred to react 3h at 40 DEG C
Mix speed and generate nickel-cobalt-manganese ternary material precursor precipitation for 1100rpm reactions, Jing is filtered, washed and be dried to obtain spherical nickel-cobalt
Manganese ternary material precursor.
The chemical composition of gained presoma and performance test are as follows：
Embodiment 3
Take the nickle cobalt lithium manganate positive pole band 50g of waste and old lithium ion battery, adopt concentration for 4mol/L nitric acid at 60 DEG C
To positive pole band leaching 50min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add diatomite,
It is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Add in the solution
10wt.% ascorbic acid, 50 DEG C of controlling reaction temperature reacts 1.5h；Solution ph is adjusted after reaction using sodium hydroxide solution
To 4, aluminum hydroxide precipitation is generated, keep that diatomite is added after 40min and removal aluminum hydroxide precipitation is filtered, obtained containing only divalence
Nickel, cobalt, manganese and lithium nitrate mixed solution；Nickel nitrate, cobalt nitrate and manganese nitrate mol ratio is added to be 0.3 in the solution：0.2：
0.5, it is 1 to add lithium salts to cause the mol ratio of total nickel cobalt manganese and lithium：1, it is subsequently adding 45vol.% complexing agents, normal temperature mixing
10min；Sodium carbonate is added as precipitating reagent and pH value is adjusted to 8, controlling reaction temperature is to react 2h, mixing speed at 50 DEG C
Nickel-cobalt-manganese ternary material precursor precipitation is generated for 1150rpm reactions, Jing is filtered, washed and be dried to obtain spherical nickel cobalt manganese ternary
Material precursor.
The chemical composition of gained presoma and performance test are as follows：
Embodiment 4
Take waste and old lithium ion battery cobalt acid lithium and nickle cobalt lithium manganate positive pole band 50g, adopt concentration for 1mol/L nitric acid
At 65 DEG C to positive pole band leaching 60min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add
Diatomite, is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Molten
10wt.% ascorbic acid, 60 DEG C of controlling reaction temperature is added to react 1h in liquid；Adjust molten using sodium hydroxide solution after reaction
Liquid pH value generates aluminum hydroxide precipitation to 4, keeps that diatomite is added after 50min and removal aluminum hydroxide precipitation is filtered, and obtains only
Containing nickelous, cobalt, manganese and lithium nitrate mixed solution；In the solution addition nickel nitrate, cobalt nitrate and manganese nitrate mol ratio are
0.4：0.2：0.4, it is 1 to add lithium salts to cause the mol ratio of total nickel cobalt manganese and lithium：1, it is subsequently adding 50vol.% complexing agents, normal temperature
Mixing 10min；Sodium carbonate is added as precipitating reagent and pH value is adjusted to 9, controlling reaction temperature is 60 DEG C and reacts 1h, is stirred
Speed is that 1200rpm reactions generate nickel-cobalt-manganese ternary material precursor precipitation, and Jing is filtered, washed and be dried to obtain spherical nickel cobalt manganese
Ternary material precursor.
The chemical composition of gained presoma and performance test are as follows：
Comparative example 1
The present embodiment is to be added without ascorbic acid with the difference of embodiment 1.
Take the nickle cobalt lithium manganate positive pole band 50g of waste and old lithium ion battery, adopt concentration for 8mol/L nitric acid at 55 DEG C
To positive pole band leaching 30min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add diatomite,
It is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Add in the solution
0wt.% ascorbic acid, 30 DEG C of controlling reaction temperature reacts 2h；After reaction solution ph is adjusted to 5 using sodium hydroxide solution,
Generate aluminum hydroxide precipitation, keep being added after 30min and diatomite and filter removal aluminum hydroxide precipitation, obtain containing only nickelous,
Cobalt, manganese and lithium nitrate mixed solution；Nickel nitrate, cobalt nitrate and manganese nitrate mol ratio is added to be 1 in the solution：1：1, add lithium
It is 1 that salt causes the mol ratio of total nickel cobalt manganese and lithium：1, it is subsequently adding 30vol.% complexing agents, normal temperature mixing 10min；Add carbon
Sour sodium is as precipitating reagent and adjusts pH value to 7, and to react 4h at 35 DEG C, mixing speed is 1000rpm reactions to controlling reaction temperature
Nickel-cobalt-manganese ternary material precursor precipitation is generated, Jing is filtered, washed and be dried to obtain spherical nickel cobalt manganese ternary material precursor.
The chemical composition of gained presoma and performance test are as follows：
Comparative example 2
The present embodiment is with the difference of embodiment 1：The addition of ascorbic acid is 20wt.%.
Take the nickle cobalt lithium manganate positive pole band 50g of waste and old lithium ion battery, adopt concentration for 8mol/L nitric acid at 55 DEG C
To positive pole band leaching 30min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add diatomite,
It is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Add in the solution
20wt.% ascorbic acid, 30 DEG C of controlling reaction temperature reacts 2h；After reaction using sodium hydroxide solution adjust solution ph to
5, aluminum hydroxide precipitation is generated, keep that diatomite is added after 30min and removal aluminum hydroxide precipitation is filtered, obtain containing only divalence
Nickel, cobalt, manganese and lithium nitrate mixed solution；Nickel nitrate, cobalt nitrate and manganese nitrate mol ratio is added to be 1 in the solution：1：1, plus
Enter lithium salts to cause the mol ratio of total nickel cobalt manganese and lithium is 1：1, it is subsequently adding 30vol.% complexing agents, normal temperature mixing 10min；Again plus
Enter sodium carbonate as precipitating reagent and adjust pH value to 7, to react 4h at 35 DEG C, mixing speed is 1000rpm to controlling reaction temperature
Reaction generates nickel-cobalt-manganese ternary material precursor precipitation, and Jing is filtered, washed and be dried to obtain spherical nickel cobalt manganese ternary material forerunner
Body.
The chemical composition of gained presoma and performance test are as follows：
Comparative example 3
The present embodiment is with the difference of embodiment 1：Add and solution ph is adjusted after ascorbic acid reaction to 3.
Take the nickle cobalt lithium manganate positive pole band 50g of waste and old lithium ion battery, adopt concentration for 8mol/L nitric acid at 55 DEG C
To positive pole band leaching 30min, nickel, cobalt, manganese, lithium, aluminium nitrate mixed solution are filtrated to get after leaching；Add diatomite,
It is filtered to remove in positive electrode not by sour dissolved impurity, obtains nickel, cobalt, manganese, lithium nitrate mixed solution；Add in the solution
15wt.% ascorbic acid, 30 DEG C of controlling reaction temperature reacts 2h；After reaction using sodium hydroxide solution adjust solution ph to
3, aluminum hydroxide precipitation is generated, keep that diatomite is added after 30min and removal aluminum hydroxide precipitation is filtered, obtain containing only divalence
Nickel, cobalt, manganese and lithium nitrate mixed solution；Nickel nitrate, cobalt nitrate and manganese nitrate mol ratio is added to be 1 in the solution：1：1, plus
Enter lithium salts to cause the mol ratio of total nickel cobalt manganese and lithium is 1：1, it is subsequently adding 30vol.% complexing agents, normal temperature mixing 10min；Again plus
Enter sodium carbonate as precipitating reagent and adjust pH value to 7, to react 4h at 35 DEG C, mixing speed is 1000rpm to controlling reaction temperature
Reaction generates nickel-cobalt-manganese ternary material precursor precipitation, and Jing is filtered, washed and be dried to obtain spherical nickel cobalt manganese ternary material forerunner
Body.
The chemical composition of gained presoma and performance test are as follows：
Technical scheme can effectively remove Fe3+And Al3+ impurity；On the one hand add the ascorbic acid can be by
Co3+、Ni3+And Mn4+The ionic state of divalence is reduced to, the organic efficiency for making nickel, cobalt, manganese is improved, and is prepared by recovery old and useless battery
Ternary material precursor purity is higher；Another aspect ascorbic acid can adjust and limit the growth of particle so that useless by reclaiming
Ternary material precursor particle diameter distribution prepared by used batteries is narrower and be well mixed；It is this using acetylacetone,2,4-pentanedione as complexing agent
Complex ion contributes to the slow release of metal ion in course of reaction and generates precipitation, is conducive to the regular of product morphology, ball
The good and tap density of shape degree is high, and is prevented from particle agglomeration.
Claims (9)
1. the method for preparing ternary anode material precursor using waste lithium cell material, it is characterised in that：Comprise the following steps：
Step 1, with salpeter solution anode material for lithium-ion batteries is reclaimed, and obtains suspension 1；
Step 2, by the filtering and impurity removing of suspension 1, obtains filtrate 1；
Step 3, adds ascorbic acid to be reacted in filtrate 1, and regulation reacting liquid pH value is 4-5, obtains suspension 2；
Step 4, by the filtering and impurity removing of suspension 2, obtains filtrate 2；
Step 5, adds nickel nitrate, cobalt nitrate, manganese nitrate, lithium salts and complexing agent to be reacted, to reaction in filtrate 2
Precipitating reagent is added in liquid, is stirred, obtain suspension 3；
Step 6, suspension 3 is filtered, and nickel-cobalt-manganternary ternary anode material presoma is obtained after filter residue is scrubbed.
2. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：It is to adopt leaching process to reclaim in step 1, and salpeter solution concentration is 1～8 mol/L, and treatment temperature is 50～65 DEG C,
Process time is 30～60min.
3. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：It is to add carry out filtering and impurity removing again after filter aid in suspension in step 2.
4. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：The addition of ascorbic acid is 10～15wt.% in step 3, and reaction temperature is 30～60 DEG C, the time is 1～2h.
5. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：It is to add carry out filtering and impurity removing again after filter aid in suspension in step 4.
6. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：Step 5 complexing agent is acetylacetone,2,4-pentanedione, and its addition is 30～50v/v%.
7. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：Precipitating reagent is sodium carbonate in step 5, and concentration is 1～2 mol/L.
8. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：In step 5 stirring condition be 35～60 DEG C, 1～4h, 1000～1200rpm, pH value be 7-9.
9. the method that utilization waste lithium cell material according to claim 1 prepares ternary anode material precursor, it is special
Levy and be：Lithium salts is lithium carbonate, lithium hydroxide or lithium nitrate in step 5.
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| CN111082178B (en) * | 2019-12-16 | 2021-12-31 | 中南大学 | Method for regenerating lithium-rich manganese-based positive electrode material by using waste lithium batteries |
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| CN113991205A (en) * | 2021-10-26 | 2022-01-28 | 中南大学 | Method for reducing alkali consumption in aluminum removal of battery anode waste |
| CN113991205B (en) * | 2021-10-26 | 2023-10-20 | 中南大学 | Method for reducing alkali consumption in aluminum removal of battery anode waste |
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