CN109449434A - A method of ternary anode material of lithium battery presoma is prepared using waste and old lithium ion battery - Google Patents
A method of ternary anode material of lithium battery presoma is prepared using waste and old lithium ion battery Download PDFInfo
- Publication number
- CN109449434A CN109449434A CN201811101102.7A CN201811101102A CN109449434A CN 109449434 A CN109449434 A CN 109449434A CN 201811101102 A CN201811101102 A CN 201811101102A CN 109449434 A CN109449434 A CN 109449434A
- Authority
- CN
- China
- Prior art keywords
- waste
- anode material
- lithium ion
- presoma
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
A kind of method of waste and old lithium ion battery preparation ternary lithium battery material presoma, major ingredient includes positive material waste powder and metal sulfide, using product among ternary lithium battery anode waste material and nickel sulfide as raw material, product waste among nickel sulfide is added into lithium ion battery anode material waste material, moderate amount of sulfuric acid is added and reacts leaching under high pressure, a small amount of hydrogen peroxide is added after release to continue to leach nickel cobalt manganese valuable element as reducing agent, and it cleans to leachate, proportion, again with the metal ion mixed liquor after proportion, ammonium hydroxide and sodium hydroxide are that raw material prepares precursor of lithium ionic cell positive material.Waste material leaching rate of the present invention is high, process is short, simple process, low in cost, it not only can be with large scale processing anode material of lithium battery waste material, product among scrap vulcanized nickel can also be handled, the recycling of product among lithium ion battery anode material waste material and scrap vulcanized nickel is promoted.
Description
Technical field
The present invention relates to a kind of method for preparing ternary lithium battery material presoma, in particular to it is a kind of using waste and old lithium from
The method of sub- battery preparation ternary anode material of lithium battery presoma.
Background technique
Lithium ion battery because have many advantages, such as energy density height, good cycle, be easy to carry about with one, efficiency for charge-discharge it is high and wide
It is general apply each class of electronic devices, electric car, in terms of, especially with the development of electric car, power type lithium from
Sub- battery is even more to have welcome to develop on an unprecedented scale.But waste and old lithium ion battery MAT'L recycling problem is also following, especially
It is used as first generation lithium battery in China's to scrap peak within 2018, recycling and reusing market value is even more inestimable.
Because containing the metallic elements such as a large amount of nickel, cobalt, manganese and lithium in lithium ion cell anode waste, therefore how efficiently again
It makes profits and has become the hot spot of domestic and international researcher with these waste and old lithium ion batteries.Using and hydrometallurgical process because have place
Reason effect it is good, process is short, simple process and be concerned.And its different technique based on recycling product are also different.
CN107475538A, which is disclosed, a kind of to be soaked valuable metal in waste and old cobalt acid lithium using citric acid and sodium thiosulfate
Method out, it is expensive that citric acid compares common inorganic acid, and carries out heavy cobalt with ammonium oxalate and be easy to cause pollution.
CN106848474A disclose one kind from lithium ion battery anode material waste material recycle positive electrode material precursor and
The method of lithium carbonate, but the acid that the method uses has containing volatility, be easy to cause sour loss, and stronger to equipment corrosion.
CN106848470A disclose it is a kind of nickel cobalt manganese will obtain leachate after leaching in anode waste, then cleaned, passed through
Adjusting solution concentration and etc., ternary precursor is obtained through the secondary co-precipitation of hydroxide and carbonate, but presoma is deposited at this time
It is the mixture of two distinct types of presoma in miscellaneous phase.
CN106450548A discloses a kind of method that waste lithium manganese oxide positive electrode prepares tertiary cathode material, the invention
The raw material of patent is waste lithium manganese oxide, and what is finally prepared is ternary anode material for lithium-ion batteries, prepares ternary lithium-ion electric
The raw material of pond positive electrode are excessively single, cannot mix a variety of waste and old positive electrodes.
CN104659438B discloses a kind of method using refuse battery preparation ternary anode material precursor, and the invention is special
Benefit needs to split old and useless battery, roasts, and the process is more complicated, increases production cost.
That there are disadvantages is as follows for the above-mentioned prior art: leaching process introduces new impurity and enters in leachate, increases and removes
Miscellaneous cost.It is also relatively high to equipment corrosion requirement simultaneously, contain impurity phase in obtained final products.Use sodium thiosulfate for
Reducing agent, leaching process can not only introduce sodium ion, can also generate a large amount of sulfur dioxide, larger to working environment harm, together
When precipitating reagent ammonia pollution has also been introduced.Sour waste is not only caused using volatile acid, and volatile acid has corrosivity to equipment,
Production is increased to the requirement of equipment corrosion resistance, and lithium source burning is added compared to presoma in the positive electrode that chemical coprecipitation obtains
It ties obtained positive electrode performance and wants poor；And the ternary precursor of secondary precipitation leads to product that there are miscellaneous phases.
Summary of the invention
Invention is designed to provide a kind of utilization waste and old lithium ion battery preparation ternary anode material of lithium battery presoma
Method, waste material leaching rate of the present invention is high, process is short, simple process, low in cost, not only can be with large scale processing lithium battery just
Pole material waste can also handle product among scrap vulcanized nickel, promote lithium ion battery anode material waste material and scrap vulcanized
The recycling of product among nickel, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme:
A method of ternary anode material of lithium battery presoma being prepared using waste and old lithium ion battery, major ingredient includes anode
Material waste powder and metal sulfide, wherein the weight of positive material waste powder is 30~45g, the weight of metal sulfide
Amount is 5~20g, and preparation step is as follows:
S1: the anode material of lithium battery wasted powder after prebake is uniformly mixed with metal sulfide；
S2: gained mixture in S1 is added in autoclave, using inorganic acid as leaching agent, 80 are heated to feed liquid
DEG C, and it is passed through high pressure gas, starting is stirred to react；
S3: when S2 after the reaction was completed, release be added reducing agent continue pressure leaching residue waste material, formed segmentation leach, to
Reaction stops release and stands；
S4: leachate and leached mud is obtained by filtration after step S3 stands a period of time, cleans to leachate, and survey
Nickel cobalt manganese concentration of metal ions after removal of impurities adds corresponding metal salt according to concentration difference and is made into mixing salt solution；
S5: the final gained nickel cobalt manganese salt solution of S4 and complexing agent and precipitating reagent are added to simultaneously add mode containing bottom liquid
In presoma reaction kettle, reaction process maintains the temperature at 55 DEG C, and stirring rate 260rpm stands 2h mistake after the completion of reacted
Filter, obtain nickel cobalt manganese hydroxide precipitating, then it is aged, with 70 DEG C of hot water to filtrate wash, finally obtain after drying lithium from
Sub- cell positive material presoma.
Further, in step S1 anode material of lithium battery waste material be NCM111, NCM424, NCM523, NCM622,
Two or more mixed-powder in NCM811, LiNiO2, LiCoO2, LiMnO2.
Further, in step S1 metal sulfide be one or both of nickel sulfide, cobalt sulfide or cobalt sulfide nickel with
On, and the mixed proportion of anode material of lithium battery waste material and metal sulfate is 1:1~10:1.
Further, it is 1-4mol/ that inorganic acid, which is one of which and concentration in sulfuric acid, hydrochloric acid or nitric acid, in step S2
L。
Further, step S2 mesohigh gas is one of nitrogen, air, oxygen, and the reaction time is 1~5h.
Further, in step S3 reducing agent be one of hydrogen peroxide, starch, sodium thiosulfate or more than one,
Reducing agent additive amount is 10-40ml, and the second-stage reaction time is 1~3h.
Further, corresponding metal salt is one of chlorate, sulfate or nitrate in step S4, and final golden
Category concentration of salt solution is 1.0-2.5mol/L.
Further, complexing agent is one of ammonium hydroxide, EDTA, citric acid, ammonium hydrogen carbonate in step S5, and precipitating reagent is hydrogen
One of sodium oxide molybdena, sodium carbonate or sodium oxalate.
Further, in step S5 presoma be one of NCM424, NCM523, NCM622, NCM811 or a kind of with
On.
Compared with prior art, the beneficial effects of the present invention are:
1, the method proposed by the present invention using waste and old lithium ion battery preparation ternary anode material of lithium battery presoma, leads to
It crosses the product among scrap vulcanized nickel that add to leach under high pressure as leading portion reducing agent, a small amount of hydrogen peroxide is added after release
Continue high pressure as reducing agent to leach, valuable metal has obtained effective leaching in waste lithium ion material and nickel sulfide, can
With large scale processing anode material of lithium battery waste material, product among lithium ion battery anode material waste material and scrap vulcanized nickel are promoted
Recycling.
2, compared with conventional valuable metal recovery utilizes, the present invention by leachate by cleaning, match, then adds complexing
Agent and precipitating reagent prepare precursor of lithium ionic cell positive material, compared with conventional valuable metal recovery, the present invention do not need into
The separating-purifying of row valuable metal directly is precipitated the mixed liquor after removal of impurities proportion to obtain presoma, and process is short, technique is simple
It is single, save production cost.
Detailed description of the invention
Fig. 1 is the electron microscope of the corresponding presoma of the embodiment of the present invention 1；
Fig. 2 is the electron microscope of the corresponding presoma of the embodiment of the present invention 2；
Fig. 3 is the electron microscope of the corresponding presoma of the embodiment of the present invention 3；
Fig. 4 is the electron microscope of the corresponding presoma of the embodiment of the present invention 4.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In the embodiment of the present invention: a kind of side using waste and old lithium ion battery preparation ternary anode material of lithium battery presoma
Method, major ingredient include positive material waste powder and metal sulfide, wherein and the weight of positive material waste powder is 30~45g,
The weight of metal sulfide is 5~20g.
Embodiment 1
A method of ternary anode material of lithium battery presoma being prepared using waste and old lithium ion battery, including is walked as follows
It is rapid:
Step 1: product are uniformly mixed among the 45g anode material of lithium battery wasted powder and 5g nickel sulfide after taking prebake；
Step 2: sulfuric acid will be added in S/L=1:10 ratio in the solid mixed-powder in step 1, feed liquid is heated to
80 DEG C, under the conditions of high pressure gas under react 2h；
Step 3: unloading after step 2 reaction 2h to normal pressure, adds 20ml hydrogen peroxide and is passed through gas again and is formed to be segmented and soaks
Out, stop release standing wait react；
Step 4: leachate and leached mud is obtained by filtration after step 3 stands a period of time, to the nickel cobalt in leached mud
Manganese measures, and cleans to leachate, measures to nickel cobalt manganese ion concentration in solution after removal of impurities, is carried out according to concentration difference
Match into the mixing salt solution that concentration of metal ions is 1.5mol/L；
Step 5: ammonium hydroxide will be added in the final gained nickel cobalt manganese salt solution of step 4 and sodium hydroxide is reacted to certain
Stop reaction after partial size, reaction process maintains the temperature at 55 DEG C, stirring rate 260rpm；
Step 6: standing 2h filtering to step 5 after the reaction was completed, obtains nickel cobalt manganese hydroxide and precipitates, then aged,
Filtrate is washed with 70 DEG C of hot water, finally obtains precursor of lithium ionic cell positive material after drying.
Fig. 1 is the electron microscope of presoma.
The ingredient of the anode material of lithium battery wasted powder of the present embodiment is as follows:
1 waste material of table, 1 ingredient
| Ingredient | Ni | Co | Mn | Li | It is other |
| Content/% | 34.79 | 13.82 | 18.63 | 0.273 | |
| Leaching rate/% | ≥98 | ≥99 | ≥99 | ≥99.2 |
As can be seen from Table 1, when the content of the ingredient Ni of anode material of lithium battery wasted powder is 34.79%, valuable gold
Leaching rate >=98% of category, when the content of the ingredient Co of anode material of lithium battery wasted powder is 13.82%, the leaching of valuable metal
Extracting rate >=99%, when the content of the ingredient Mn of anode material of lithium battery wasted powder is 18.63%, the leaching rate of valuable metal >=
When the content of 98%, the ingredient Li of anode material of lithium battery wasted powder are 0.273%, the leaching rate of valuable metal >=
99.2%, it is 98.8% by average leaching rate is calculated.
Embodiment 2
A method of ternary anode material of lithium battery presoma being prepared using waste and old lithium ion battery, including is walked as follows
It is rapid:
Step 1: product mixing is equal among the 40g anode material of lithium battery wasted powder and 10g nickel sulfide after taking prebake
It is even；
Step 2: sulfuric acid will be added in S/L=1:10 ratio in the solid mixed-powder in step 1, feed liquid is heated to
80 DEG C, under the conditions of high pressure gas under react 2h；
Step 3: unloading after step 2 reaction 2h to normal pressure, adds 15ml hydrogen peroxide and is passed through gas again and is formed to be segmented and soaks
Out, stop release standing wait react；
Step 4: leachate and leached mud is obtained by filtration after step 3 stands a period of time, to the nickel cobalt in leached mud
Manganese measures, and cleans to leachate, measures to nickel cobalt manganese ion concentration in solution after removal of impurities, is carried out according to concentration difference
Match into the mixing salt solution that concentration of metal ions is 1.5mol/L；
Step 5: ammonium hydroxide will be added in the final gained nickel cobalt manganese salt solution of step 4 and sodium hydroxide is reacted to certain
Stop reaction after partial size, reaction process maintains the temperature at 55 DEG C, stirring rate 260rpm；
Step 6: standing 2h filtering to step 5 after the reaction was completed, obtains nickel cobalt manganese hydroxide and precipitates, then aged,
Filtrate is washed with 70 DEG C of hot water, finally obtains precursor of lithium ionic cell positive material after drying.
Fig. 2 is the electron microscope of presoma.
The ingredient of the anode material of lithium battery wasted powder of the present embodiment is as follows:
2 waste material of table, 2 ingredient
| Ingredient | Ni | Co | Mn | Li | It is other |
| Content/% | 30.70 | 12.14 | 24.8 | 0.174 | |
| Leaching rate/% | ≥97.2 | ≥98 | ≥98.5 | ≥98.7 |
As can be seen from Table 2, when the content of the ingredient Ni of anode material of lithium battery wasted powder is 30.70%, valuable gold
Leaching rate >=97.2% of category, when the content of the ingredient Co of anode material of lithium battery wasted powder is 12.14%, valuable metal
Leaching rate >=98%, when the content of the ingredient Mn of anode material of lithium battery wasted powder is 24.8%, the leaching rate of valuable metal
When the content of >=98.5%, the ingredient Li of anode material of lithium battery wasted powder are 0.174%, the leaching rate of valuable metal >=
98.7%, it is 98.1% by average leaching rate is calculated.
Embodiment 3
A method of ternary anode material of lithium battery presoma being prepared using waste and old lithium ion battery, including is walked as follows
It is rapid:
Step 1: product mixing is equal among the 35g anode material of lithium battery wasted powder and 15g nickel sulfide after taking prebake
It is even；
Step 2: sulfuric acid will be added in S/L=1:10 ratio in the solid mixed-powder in step 1, feed liquid is heated to
80 DEG C, under the conditions of high pressure gas under react 2h；
Step 3: unloading after step 2 reaction 2h to normal pressure, adds 25ml hydrogen peroxide and is passed through gas again and is formed to be segmented and soaks
Out, stop release standing wait react；
Step 4: leachate and leached mud is obtained by filtration after step 3 stands a period of time, to the nickel cobalt in leached mud
Manganese measures, and cleans to leachate, measures to nickel cobalt manganese ion concentration in solution after removal of impurities, is carried out according to concentration difference
Match into the mixing salt solution that concentration of metal ions is 1.5mol/L；
Step 5: ammonium hydroxide will be added in the final gained nickel cobalt manganese salt solution of step 4 and sodium hydroxide is reacted to certain
Stop reaction after partial size, reaction process maintains the temperature at 55 DEG C, stirring rate 260rpm；
Step 6: standing 2h filtering to step 5 after the reaction was completed, obtains nickel cobalt manganese hydroxide and precipitates, then aged,
Filtrate is washed with 70 DEG C of hot water, finally obtains precursor of lithium ionic cell positive material after drying.
Fig. 3 is the electron microscope of presoma.
The ingredient of the anode material of lithium battery wasted powder of the present embodiment is as follows:
3 waste material of table, 3 ingredient
| Ingredient | Ni | Co | Mn | Li | It is other |
| Content/% | 37.93 | 11.22 | 14.93 | 0.199 | |
| Leaching rate/% | ≥96 | ≥97.1 | ≥98.1 | ≥99 |
As can be seen from Table 3, when the content of the ingredient Ni of anode material of lithium battery wasted powder is 37.93%, valuable gold
Leaching rate >=96% of category, when the content of the ingredient Co of anode material of lithium battery wasted powder is 11.22%, the leaching of valuable metal
Extracting rate >=97.1%, when the content of the ingredient Mn of anode material of lithium battery wasted powder is 14.93%, the leaching rate of valuable metal
When the content of >=98.1%, the ingredient Li of anode material of lithium battery wasted powder are 0.199%, the leaching rate of valuable metal >=
99%, it is 97.55% by average leaching rate is calculated.
Embodiment 4
A method of ternary anode material of lithium battery presoma being prepared using waste and old lithium ion battery, including is walked as follows
It is rapid:
Step 1: product mixing is equal among the 30g anode material of lithium battery wasted powder and 20g nickel sulfide after taking prebake
It is even；
Step 2: sulfuric acid will be added in S/L=1:10 ratio in the solid mixed-powder in step 1, feed liquid is heated to
80 DEG C, under the conditions of high pressure gas under react 2h；
Step 3: unloading after step 2 reaction 2h to normal pressure, adds 30ml hydrogen peroxide and is passed through gas again and is formed to be segmented and soaks
Out, stop release standing wait react；
Step 4: leachate and leached mud is obtained by filtration after step 3 stands a period of time, to the nickel cobalt in leached mud
Manganese measures, and cleans to leachate, measures to nickel cobalt manganese ion concentration in solution after removal of impurities, is carried out according to concentration difference
Match into the mixing salt solution that concentration of metal ions is 1.5mol/L；
Step 5: ammonium hydroxide will be added in the final gained nickel cobalt manganese salt solution of step 4 and sodium hydroxide is reacted to certain
Stop reaction after partial size, reaction process maintains the temperature at 55 DEG C, stirring rate 260rpm；
Step 6: standing 2h filtering to step 5 after the reaction was completed, obtains nickel cobalt manganese hydroxide and precipitates, then aged,
Filtrate is washed with 70 DEG C of hot water, finally obtains precursor of lithium ionic cell positive material after drying.
Fig. 4 is the electron microscope of presoma.
The ingredient of the anode material of lithium battery wasted powder of the present embodiment is as follows:
4 waste material of table, 4 ingredient
| Ingredient | Ni | Co | Mn | Li | It is other |
| Content/% | 34.06 | 9.45 | 18.52 | 0.194 | |
| Leaching rate/% | ≥95 | ≥96.4 | ≥98 | ≥99.1 |
As can be seen from Table 4, when the content of the ingredient Ni of anode material of lithium battery wasted powder is 34.06%, valuable gold
Leaching rate >=95% of category, when the content of the ingredient Co of anode material of lithium battery wasted powder is 9.45%, the leaching of valuable metal
Extracting rate >=96.4%, when the content of the ingredient Mn of anode material of lithium battery wasted powder is 18.52%, the leaching rate of valuable metal
When the content of >=98%, the ingredient Li of anode material of lithium battery wasted powder are 0.194%, the leaching rate of valuable metal >=
99.1%, it is 97.125% by average leaching rate is calculated.
By comparing four above-mentioned embodiments, the average leaching rate of embodiment 1 is 98.8%, the average leaching of embodiment 2
Extracting rate is 98.1%, and the average leaching rate of embodiment 3 is 97.55%, and the average leaching rate of embodiment 4 is 97.125%, lithium electricity
When the weight of pond positive material waste powder is 45g, the average leaching rate highest of valuable metal, the average leaching rate of valuable metal
It is reduced with the reduction of anode material of lithium battery wasted powder content.
Difference with the prior art of the present invention is: raw material of the invention is a variety of waste and old anodes of waste and old lithium ion battery
The mixture of material, has been subjected to pretreatment, and the waste and old raw material in part has been subjected to and proposes lithium processing, the present invention use waste vulcanized nickel for
Reducing agent, Ore Leaching valuable metal under high pressure, then through proportion, precipitating, drying and etc. obtain tertiary cathode material before
Body is driven, since waste vulcanized nickel is a kind of fine and close slightly solubility substance, in order to efficiently leach valuable metal, using addition
Hydrogen peroxide carries out two sections of reducing leachings.
The principle of the present invention: product are raw material among ternary lithium battery anode waste material and nickel sulfide, to lithium ion cell positive
Product waste among nickel sulfide is added in material waste, and moderate amount of sulfuric acid is added and reacts leaching under high pressure, is added after release
A small amount of hydrogen peroxide continues to leach nickel cobalt manganese valuable element as reducing agent, and is cleaned, matched to leachate, then with proportion
Metal ion mixed liquor, ammonium hydroxide and sodium hydroxide afterwards is that raw material prepares precursor of lithium ionic cell positive material, phase of the present invention
It is high for prior art waste material leaching rate, process is short, simple process, low in cost, not only can be with large scale processing lithium battery just
Pole material waste can also handle product among scrap vulcanized nickel and prepare lithium ion battery presoma.
In conclusion the method for waste and old lithium ion battery preparation ternary lithium battery material presoma proposed by the present invention, this
Invention is leached by adding product among scrap vulcanized nickel as leading portion reducing agent under high pressure, and mistake on a small quantity is added after release
Hydrogen oxide continues high pressure as reducing agent and leaches, and valuable metal has obtained effective leaching in waste lithium ion material and nickel sulfide
Out, lithium ion battery anode material waste material and scrap vulcanized nickel can be promoted with large scale processing anode material of lithium battery waste material
The recycling of intermediate product.Compared with conventional valuable metal recovery utilizes, the present invention by leachate by cleaning, match, then adds
Complexing agent and precipitating reagent prepare precursor of lithium ionic cell positive material, and compared with conventional valuable metal recovery, the present invention is not required to
It carries out the separating-purifying of valuable metal, the mixed liquor after removal of impurities proportion directly is precipitated to obtain presoma, process is short, work
Skill is simple, has saved production cost.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of method using waste and old lithium ion battery preparation ternary anode material of lithium battery presoma, which is characterized in that main
Material includes positive material waste powder and metal sulfide, and the weight of positive material waste powder is 30~45g, metal sulfide
Weight be 5~20g, preparation step is as follows:
S1: the anode material of lithium battery wasted powder after prebake is uniformly mixed with metal sulfide；
S2: gained mixture in S1 being added in autoclave, using inorganic acid as leaching agent, is heated to 80 DEG C to feed liquid,
And it is passed through high pressure gas, starting is stirred to react；
S3: when S2 after the reaction was completed, release be added reducing agent continue pressure leaching residue waste material, formed segmentation leach, wait react
Stop release standing；
S4: leachate and leached mud is obtained by filtration after step S3 stands a period of time, cleans to leachate, and survey removal of impurities
Nickel cobalt manganese concentration of metal ions afterwards adds corresponding metal salt according to concentration difference and is made into mixing salt solution；
S5: the final gained nickel cobalt manganese salt solution of S4 and complexing agent and precipitating reagent are added to the forerunner containing bottom liquid with simultaneously add mode
In precursor reactant kettle, reaction process maintains the temperature at 55 DEG C, and stirring rate 260rpm stands 2h filtering, obtains after the completion of reacted
To nickel cobalt manganese hydroxide precipitate, then it is aged, with 70 DEG C of hot water to filtrate wash, finally obtain lithium ion battery after drying
Positive electrode material precursor.
2. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, in step S1 anode material of lithium battery waste material be NCM111, NCM424, NCM523, NCM622, NCM811,
Two or more mixed-powder in LiNiO2, LiCoO2, LiMnO2.
3. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, metal sulfide is one or more of nickel sulfide, cobalt sulfide or cobalt sulfide nickel in step S1, and lithium
The mixed proportion of battery anode material waste material and metal sulfate is 1:1~10:1.
4. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, it is 1-4mol/L that inorganic acid, which is one of which and concentration in sulfuric acid, hydrochloric acid or nitric acid, in step S2.
5. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, step S2 mesohigh gas is one of nitrogen, air, oxygen, the reaction time is 1~5h.
6. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, in step S3 reducing agent be one of hydrogen peroxide, starch, sodium thiosulfate or more than one, reducing agent
Additive amount is 10-40ml, and the second-stage reaction time is 1~3h.
7. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, corresponding metal salt is one of chlorate, sulfate or nitrate in step S4, and final metal salt is molten
Liquid concentration is 1.0-2.5mol/L.
8. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, complexing agent is one of ammonium hydroxide, EDTA, citric acid, ammonium hydrogen carbonate in step S5, precipitating reagent is hydroxide
One of sodium, sodium carbonate or sodium oxalate.
9. the method for preparing ternary anode material of lithium battery presoma using waste and old lithium ion battery according to claim 1,
It is characterized in that, in step S5 presoma be one of NCM424, NCM523, NCM622, NCM811 or more than one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811101102.7A CN109449434B (en) | 2018-09-20 | 2018-09-20 | Method for preparing ternary lithium battery positive electrode material precursor by using waste lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811101102.7A CN109449434B (en) | 2018-09-20 | 2018-09-20 | Method for preparing ternary lithium battery positive electrode material precursor by using waste lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109449434A true CN109449434A (en) | 2019-03-08 |
| CN109449434B CN109449434B (en) | 2021-08-20 |
Family
ID=65533020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811101102.7A Active CN109449434B (en) | 2018-09-20 | 2018-09-20 | Method for preparing ternary lithium battery positive electrode material precursor by using waste lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109449434B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129571A (en) * | 2019-06-11 | 2019-08-16 | 中国科学院过程工程研究所 | A method of extracting valuable metal from waste and old lithium ion battery material |
| CN111994966A (en) * | 2020-07-20 | 2020-11-27 | 中南大学 | Method for recycling waste ternary positive electrode under high-temperature condition of hydrogen sulfide atmosphere |
| CN112029997A (en) * | 2020-07-20 | 2020-12-04 | 中南大学 | Recovery process for large-scale treatment of waste lithium ion battery anode material |
| CN112250120A (en) * | 2020-12-21 | 2021-01-22 | 矿冶科技集团有限公司 | Method for preparing ternary precursor and lithium carbonate by using waste lithium ion battery black powder and nickel cobalt sulfide ore in synergy mode and application |
| CN112259820A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for preparing core-shell type ternary positive electrode material by using waste lithium battery |
| CN112646976A (en) * | 2020-12-17 | 2021-04-13 | 矿冶科技集团有限公司 | Method for synergistically leaching nickel, cobalt and manganese by utilizing waste lithium ion battery black powder and nickel cobalt sulfide ore and application |
| CN112831662A (en) * | 2020-12-31 | 2021-05-25 | 九江天赐高新材料有限公司 | Recycling method of nickel cobalt lithium manganate ternary positive electrode powder |
| CN113444880A (en) * | 2021-06-10 | 2021-09-28 | 贵州理工学院 | Method for preparing ternary precursor by pressure acid leaching |
| CN113846224A (en) * | 2021-10-25 | 2021-12-28 | 贵州中伟资源循环产业发展有限公司 | Method for recovering valuable metal from positive electrode material containing binder and valuable metal |
| CN114480850A (en) * | 2022-01-19 | 2022-05-13 | 长沙有色冶金设计研究院有限公司 | Method and system for recovering valuable metals in anode materials of waste lithium ion batteries through pressure reduction |
| CN115449636A (en) * | 2022-09-05 | 2022-12-09 | 中南大学 | Recovery and regeneration process and equipment for lithium ion battery anode material |
| CN116837216A (en) * | 2023-09-01 | 2023-10-03 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538655A (en) * | 2009-04-28 | 2009-09-23 | 合肥工业大学 | MnO recovery from waste lithium manganate battery cathode material 2 And applications thereof |
| US20120068107A1 (en) * | 2010-09-20 | 2012-03-22 | Korea Institute Of Science And Technology | Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery |
| CN102751549A (en) * | 2012-07-04 | 2012-10-24 | 中国科学院过程工程研究所 | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries |
| CN103199320A (en) * | 2013-03-28 | 2013-07-10 | 四川天齐锂业股份有限公司 | Method for recycling nickel-cobalt-manganese ternary anode material |
| CN105633500A (en) * | 2016-02-22 | 2016-06-01 | 四川天齐锂业股份有限公司 | Method for preparing ternary cathode material precursor by recycling lithium-ion battery material |
| CN106834675A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | A kind of combined leaching process of cobalt hydroxide nickel and cobalt sulfide nickel |
| CN107706477A (en) * | 2017-08-31 | 2018-02-16 | 长沙佳纳锂业科技有限公司 | A kind of waste and old ternary anode material for lithium-ion batteries solid phase regeneration method |
| CN107946687A (en) * | 2017-12-08 | 2018-04-20 | 天齐锂业股份有限公司 | A kind of system and technique for continuously recycling waste and old ternary lithium ion battery |
| CN108110362A (en) * | 2017-12-21 | 2018-06-01 | 天齐锂业股份有限公司 | The method that the ternary material precursor of zinc doping is synthesized by waste lithium cell recycling |
-
2018
- 2018-09-20 CN CN201811101102.7A patent/CN109449434B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538655A (en) * | 2009-04-28 | 2009-09-23 | 合肥工业大学 | MnO recovery from waste lithium manganate battery cathode material 2 And applications thereof |
| US20120068107A1 (en) * | 2010-09-20 | 2012-03-22 | Korea Institute Of Science And Technology | Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery |
| CN102751549A (en) * | 2012-07-04 | 2012-10-24 | 中国科学院过程工程研究所 | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries |
| CN103199320A (en) * | 2013-03-28 | 2013-07-10 | 四川天齐锂业股份有限公司 | Method for recycling nickel-cobalt-manganese ternary anode material |
| CN105633500A (en) * | 2016-02-22 | 2016-06-01 | 四川天齐锂业股份有限公司 | Method for preparing ternary cathode material precursor by recycling lithium-ion battery material |
| CN106834675A (en) * | 2017-01-24 | 2017-06-13 | 烟台金钪稀贵金属材料有限公司 | A kind of combined leaching process of cobalt hydroxide nickel and cobalt sulfide nickel |
| CN107706477A (en) * | 2017-08-31 | 2018-02-16 | 长沙佳纳锂业科技有限公司 | A kind of waste and old ternary anode material for lithium-ion batteries solid phase regeneration method |
| CN107946687A (en) * | 2017-12-08 | 2018-04-20 | 天齐锂业股份有限公司 | A kind of system and technique for continuously recycling waste and old ternary lithium ion battery |
| CN108110362A (en) * | 2017-12-21 | 2018-06-01 | 天齐锂业股份有限公司 | The method that the ternary material precursor of zinc doping is synthesized by waste lithium cell recycling |
Non-Patent Citations (1)
| Title |
|---|
| 冯雅丽 等: "大洋多金属结核与低品位硫化镍矿耦合浸出特性", 《中南大学学报(自然科学版)》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129571A (en) * | 2019-06-11 | 2019-08-16 | 中国科学院过程工程研究所 | A method of extracting valuable metal from waste and old lithium ion battery material |
| CN111994966A (en) * | 2020-07-20 | 2020-11-27 | 中南大学 | Method for recycling waste ternary positive electrode under high-temperature condition of hydrogen sulfide atmosphere |
| CN112029997A (en) * | 2020-07-20 | 2020-12-04 | 中南大学 | Recovery process for large-scale treatment of waste lithium ion battery anode material |
| CN112029997B (en) * | 2020-07-20 | 2021-12-07 | 中南大学 | Recovery process for large-scale treatment of waste lithium ion battery anode material |
| CN112259820A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for preparing core-shell type ternary positive electrode material by using waste lithium battery |
| CN112259820B (en) * | 2020-10-22 | 2022-02-08 | 中钢集团南京新材料研究院有限公司 | Method for preparing core-shell type ternary positive electrode material by using waste lithium battery |
| CN112646976A (en) * | 2020-12-17 | 2021-04-13 | 矿冶科技集团有限公司 | Method for synergistically leaching nickel, cobalt and manganese by utilizing waste lithium ion battery black powder and nickel cobalt sulfide ore and application |
| CN112250120A (en) * | 2020-12-21 | 2021-01-22 | 矿冶科技集团有限公司 | Method for preparing ternary precursor and lithium carbonate by using waste lithium ion battery black powder and nickel cobalt sulfide ore in synergy mode and application |
| CN112831662A (en) * | 2020-12-31 | 2021-05-25 | 九江天赐高新材料有限公司 | Recycling method of nickel cobalt lithium manganate ternary positive electrode powder |
| CN113444880A (en) * | 2021-06-10 | 2021-09-28 | 贵州理工学院 | Method for preparing ternary precursor by pressure acid leaching |
| CN113846224A (en) * | 2021-10-25 | 2021-12-28 | 贵州中伟资源循环产业发展有限公司 | Method for recovering valuable metal from positive electrode material containing binder and valuable metal |
| CN114480850A (en) * | 2022-01-19 | 2022-05-13 | 长沙有色冶金设计研究院有限公司 | Method and system for recovering valuable metals in anode materials of waste lithium ion batteries through pressure reduction |
| CN114480850B (en) * | 2022-01-19 | 2024-04-09 | 长沙有色冶金设计研究院有限公司 | Method and system for recycling valuable metals in waste lithium ion battery anode materials through pressurized reduction |
| CN115449636A (en) * | 2022-09-05 | 2022-12-09 | 中南大学 | Recovery and regeneration process and equipment for lithium ion battery anode material |
| CN115449636B (en) * | 2022-09-05 | 2023-11-21 | 中南大学 | Recycling and regenerating process of lithium ion battery anode material |
| CN116837216A (en) * | 2023-09-01 | 2023-10-03 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
| CN116837216B (en) * | 2023-09-01 | 2023-11-21 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109449434B (en) | 2021-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109449434A (en) | A method of ternary anode material of lithium battery presoma is prepared using waste and old lithium ion battery | |
| Yang et al. | Stepwise recycling of valuable metals from Ni-rich cathode material of spent lithium-ion batteries | |
| CN104868190B (en) | The leaching of metal and recovery method in a kind of lithium ion cell anode waste | |
| CN109935922A (en) | A method of recycling valuable metal from waste and old lithium ion battery material | |
| CN106848474A (en) | A kind of method of high efficiente callback positive electrode material precursor and lithium carbonate from lithium ion cell anode waste | |
| CN106916952B (en) | A kind of round-robin method of sulfur acid scrap lead sulfur removal technology and its desulphurization mother solution | |
| CN109881008A (en) | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery | |
| CN109088115A (en) | Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method | |
| CN102390863B (en) | Method for regenerating lithium titanate serving as anode material of waste lithium ion battery | |
| CN106848469A (en) | A kind of method that valuable metal is reclaimed in the material from waste lithium ion cell anode | |
| CN107326181A (en) | Waste and old lithium ion battery, which is peeled off, leaches the recovery method that a step is completed | |
| CN108486376A (en) | A method of leaching metal in waste lithium ion cell anode material | |
| CN109439904A (en) | A method of the leaching valuable metal from waste lithium cell positive electrode | |
| CN105374988B (en) | The method of waste lead accumulator comprehensive utilization of resources | |
| CN106916955A (en) | A kind of method of valuable metal in selective recovery lithium ion cell anode waste | |
| CN104538696A (en) | Method for recycling metal from waste lithium ion battery with Ni-Co lithium manganite positive electrode materials | |
| CN110240207A (en) | A kind of method that waste lithium cell recycling prepares tertiary cathode material | |
| CN108963371A (en) | A method of recycling valuable metal from waste and old lithium ion battery | |
| CN104466292A (en) | Method for recovering cobalt lithium metal from waste lithium ion battery of lithium cobalt oxide positive material | |
| CN109097581A (en) | The recovery method of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN103384002A (en) | Method for preparing electronic ternary material precursor from Ni-Co residues | |
| CN109216817A (en) | A kind of element recovery method of waste and old nickle cobalt lithium manganate cell positive material | |
| CN112267023B (en) | Two-stage defluorination method for fluorine-containing material | |
| CN114421045A (en) | Method for closed-loop recovery of retired power battery by using low-viscosity green solvent | |
| CN108808147A (en) | A kind of method that manganese is recycled in waste and old lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |