CN109088115A - Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method - Google Patents

Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method Download PDF

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CN109088115A
CN109088115A CN201810816435.1A CN201810816435A CN109088115A CN 109088115 A CN109088115 A CN 109088115A CN 201810816435 A CN201810816435 A CN 201810816435A CN 109088115 A CN109088115 A CN 109088115A
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lithium
liquid
acid
presoma
nickel
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CN109088115B (en
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王成彦
荆乾坤
张家靓
马保中
陈永强
邢鹏
张文娟
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GUANGDONG GUANGHUA SCI-TECH CO LTD
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University of Science and Technology Beijing USTB
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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
    • 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
    • H01M10/05—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
    • 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
    • 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
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method, belongs to the recycling field of non-ferrous metal secondary resource.The present invention prepares presoma after first mentioning lithium-, eliminates Li when preparing presoma with waste material leachate+Influence to pattern and crystal form: waste and old positive electrode is after alkali leaching, reduction roasting, mentioning lithium, using inorganic Ore Leaching, configures nickel cobalt manganese salt solution by product requirements after leachate removal of impurities, subsequent co-precipitation prepares presoma.Positive electrode is preliminarily formed under the conditions of low lithium dosage, low liquid-solid ratio using hydro-thermal method, hydrothermal product is washed without filtering and convection drying, is ground, then can be obtained through an one-step baking that embedding lithium is abundant, crystal form is good, the tertiary cathode material of soilless sticking, electrochemical performance.The present invention organically combines the recycling of old and useless battery material with the preparation of positive electrode, is suitable for the processing various cell anode wastes of mesh, and raw material sources are extensive, and short flow, equipment is simple, preparation nickel-cobalt-manganternary ternary anode material function admirable.

Description

Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method
Technical field
The present invention relates to non-ferrous metal secondary resource recycle more particularly to waste and old lithium ion battery in positive electrode Recycling and circulation prepare tertiary cathode material.
Background technique
In recent years, lithium ion battery is widely used in electric car, unmanned plane and mobile phone, plate as secondary energy sources The removable intelligent terminal such as computer, laptop.The development advanced by leaps and bounds in the world with application market, lithium ion The also sharp increase of the yield of battery, while also resulting in large quantities of waste and old lithium ion battery flow directions society, it would be highly desirable to it recycles therein Resource and avoid potential environmental pollution.
Anode material for lithium-ion batteries mainly has cobalt acid lithium, LiMn2O4, LiFePO4, nickel cobalt previous and current mainstream Lithium aluminate and ternary nickle cobalt lithium manganate etc., the valuable metals such as lithium rich in, nickel, cobalt, manganese, aluminium.Develop circulation warp advocating Ji, secondary resource green high-efficient utilize under the new situation, and high-valued recycle becomes current processing waste and old lithium ion battery New trend, therefore need to develop new process and organically tie the resource reclaim of waste and old lithium ion battery and new material synthesis Altogether.
Recycling aspect, waste and old lithium ion battery is when recycling, it is difficult to classified to different types of positive electrode, The waste and old anode obtained after dismantling sorting usually contains a variety of positive electrodes, and it is valuable to remove Li, Ni, Co, Mn etc. in subsequent leachate It further include the impurity such as Cu, Fe, Al, Ca, Mg outside metal.Currently, there are mainly two types of the roadmaps of the leachate after removal of impurities: first is that Nickel cobalt manganese classification recycling, but face complicated extraction and separation process；Second is that adjustment ratio co-precipitation prepares presoma, but soak Li in liquid out+It is difficult to remove before co-precipitation, leads to Li+Seriously affect the crystal form and pattern of presoma, thus influence it is subsequent just The performance of pole material.
Synthesis aspect, nickel-cobalt-manganternary ternary anode material is because the features such as its is at low cost, capacity is high, is widely used, and nickel The main component of the waste and old positive electrode of cobalt manganese systems is consistent with tertiary cathode material, is ideal recovery product.Co-precipitation-roasting is The Commercial processes of mainstream, the presoma Ni for the nickel and cobalt containing manganese being co-precipitatedxCoyMn1-x-y(OH)2Or NixCoyMn1-x- yCO3With Li2CO3Or LiOHH2The lithium sources such as O are obtained by two-stage roasting.Although co-precipitation-calcination process is commercially obtained into Function, but roasting technique usually need be after 450~550 DEG C of pre-burning 5h or more in 750~950 DEG C of roasting 10h or more, for a long time Roasting brings obvious disadvantage: energy consumption is high, and lithium volatilization loss is serious, and gained positive electrode poor crystal form is reunited seriously, influences finished product Rate and its chemical property.
Hydro-thermal method is mainly used for precursor preparation, positive electrode preparation and positive electrode in positive electrode preparation field and is modified Etc.；Hydro-thermal method prepares material and carries out usually in closed container, and raw material and aqueous solution are heated to 100 DEG C or more, is pressing certainly Or the material that could be synthesized under high temperature is realized into the preparation under low temperature under impressed pressure.
Patent CN101355161A discloses a kind of method for preparing anode material lithium nickle cobalt manganic acid of lithium ion battery, skill Art scheme is using manganese compound, nickel compound and cobalt acid lithium and lithium hydroxide as raw material, and filtration washing is dry after hydro-thermal To precursor, lithium hydroxide mixing is added in precursor by one section of roasting and obtains tertiary cathode material.Although this method is utilized Hydrothermal synthesis and roasting process is simplified, but the consumption of lithium is larger in the process；
Patent CN105428639A discloses a kind of using nickel cobalt manganese hydroxide as the hydrothermal synthesis method of raw material, nickel cobalt manganese It is passed through ozone oxidation after hydroxide and lithium source mixing, follow-up hydrothermal reaction product obtains tertiary cathode material after being fired.It should Although method is avoiding the non-uniform situation of nickel cobalt manganese mixing on raw material, do not avoid lithium hydroxide dosage is big to ask yet Topic.
To sum up, waste lithium ion cell anode material prepares positive electrode drawback in recycling and essentially consists at present: not It is complicated and lithium is caused to lose to exclude influence and subsequent roasting technique process of the lithium in co-precipitation, and product is easy to reunite；Water The technology drawback of thermal synthesis tertiary cathode material essentially consists in lithium dosage is big, process is complicated etc., especially on lithium cost of material Rise instantly, undoubtedly improves production cost.
Summary of the invention
The technical issues of in order to solve in the presence of the above-mentioned prior art, it is waste and old with nickel cobalt manganese systems that the present invention provides one kind Lithium ion battery is that raw material prepares presoma, prepares tertiary cathode material subsequently through hydrothermal synthesis under low lithium dosage.It adopts first With reduction roasting-carbonating water extraction lithium, eliminate Li when subsequent co-precipitation prepares presoma+It will lead to the unfavorable shadow of crystal grain refinement It rings；The presoma of preparation is mixed when carrying out hydrothermal synthesis with lithium source using low lithium dosage, low liquid-solid ratio, obtains the three of preliminary embedding lithium First material, hydrothermal product need not be separated by solid-liquid separation and convection drying, avoid filtering cleaning process and its bring Li loss, dry It can be obtained that soilless sticking, crystal form be good, product of electrochemical performance by grinding, simple roasting.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method, includes the following steps:
Step 1: alkali leaching aluminium: alkaline leaching aluminium is added in anode waste, and alkali phase analysis and alkali immersion liquid, alkali phase analysis is obtained by filtration Dry, aluminium is separately recycled in alkali immersion liquid；
Step 2: roast/mentioning lithium: alkali phase analysis and reducing agent are baking mixed, lead to carbon dioxide simultaneously using water logging after roasting Lithium is mentioned, rich lithium solution and filter residue is obtained by filtration, rich lithium solution obtains product containing lithium by evaporative crystallization；
Step 3: acidleach: the filter residue acid adding of step 2 is leached, filter leachate and acid leaching residue, acid leaching residue separately return Receive carbon；
Step 4: removal of impurities: into pickle liquor plus vulcanizing agent is except Fe, Cu, addition villiaumite are except Ca, Mg, is finally removed using hydrolysis Liquid after aluminium must clean；
Step 5: proportion liquid: nickel cobalt manganese concentration in liquid after detection removal of impurities, according to nickel cobalt manganese component ratio in target product, Soluble nickel salt, cobalt salt or manganese salt is added；And water is added to make the total 0.5~2.5mol/L of concentration of metal ions of nickel cobalt manganese；
Step 6: co-precipitation: solution, sodium hydroxide solution, the weak aqua ammonia that step 5 is obtained are slow under protective atmosphere It is added in stirred reactor and is co-precipitated, presoma Ni is obtained by filtrationxCoyMn1-x-y(OH)2；
Step 7: hydrothermal synthesis: presoma, lithium source, additive and water being added in autoclave；Additive is dioxygen Water, oxygen, ozone one or more mixtures；Lithium dosage is molar ratio Li/ (Ni+Co+Mn)=1.0~1.07；Additive Dosage be molar ratio O/ (Ni+Co+Mn)=0.1~10, preferably 0.4~4；Liquid-solid ratio L/S=1:1~4:1, preferably 1:1 ~2:1；
Step 8: drying/mixing: hydrothermal product is without separation of solid and liquid convection drying, desciccate ball mill mixing；
Step 9: roasting: roasting 2~10h after mixing under the conditions of 750~900 DEG C and obtain positive electrode, maturing temperature is excellent 800~850 DEG C are selected as, calcining time is preferably 4~5h.
Further, handled anode waste is cobalt acid lithium, LiMn2O4, lithium nickelate, nickel ion doped, nickel cobalt manganese in step 1 One of sour lithium, nickel cobalt lithium aluminate and rich lithium manganese base solid solution or a variety of mixtures.
Further, reducing agent used is solid state reduction agent lignite, bituminous coal, anthracite or gaseous reducing agent in step 2 CO、H2One of or mixture, C and H quality sum are the 4%~20% of anode waste quality in reducing agent, maturing temperature It is 400~700 DEG C, calcining time is 0.5~4h；Liquid-solid ratio is 1:1~10:1 when water logging, is passed through CO2Mole is in solid 0.55~10 times of lithium mole, 0.5~3h of extraction time.
Further, in step 3, acid used is one of sulfuric acid, nitric acid or hydrochloric acid, liquid-solid ratio 2:1~20:1, dense Degree is 1~2.5mol/L, and acidleach temperature is 20~90 DEG C.
Further, the concentration of the sodium hydroxide used in step 6 is 0.5~2.5mol/L, and weak aqua ammonia concentration is 0.2 ~1.0mol/L, protection gas are one of nitrogen or argon gas or gaseous mixture；40~70 DEG C of reaction temperature, the reaction time 5~ 20h。
Further, in step 7, presoma used is fresh dry material or wet stock；Hydrothermal temperature be 140~ 250 DEG C, 1~6h of soaking time.
Further, hydrothermal product convection drying in step 8, drying temperature are 80~120 DEG C, 2~10h of drying time.
As seen from the above technical solution provided by the invention, what the present invention was implemented, which be mainly characterized by, prepares presoma First to mention lithium-to be co-precipitated afterwards, when hydrothermal synthesis lithium dosage it is low, without separation of solid and liquid, most lithium is embedded in presoma by process, Preliminarily form ternary material, it is subsequent to can be obtained that soilless sticking, crystal form be good, product of electrochemical performance through one section of roasting.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing.
Fig. 1 is principle flow chart of the invention；
Fig. 2 is the charge-discharge performance figure at 1C of tertiary cathode material prepared by embodiment 1；
Fig. 3 is the electron microscope of tertiary cathode material prepared by embodiment 2.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this The embodiment of invention, those of ordinary skill in the art's every other implementation obtained under that premise of not paying creative labor Example, belongs to protection scope of the present invention.
Embodiment 1
Alkali after 200g nickel cobalt manganese series lithium ion battery anode waste crushing grinding is soaked, it is mixed with lignite after alkali phase analysis is dry It closes, the carbonaceous amount in lignite is the 10% of alkali phase analysis quality, is placed in Muffle kiln roasting, and temperature is 600 DEG C, time 3h.Roasting Product, which is placed in water, to be stirred and is passed through CO2, liquid-solid ratio 3:1 when water logging is passed through CO2Mole is 2 times of lithium mole in solid, Time 1.5h filters to obtain rich lithium solution.It is in 2mol/L sulfuric acid solution that filter residue, which is added to 3L concentration, and 60 DEG C of constant temperature are stirred 3 hours, Be obtained by filtration containing cobalt, nickel, manganese sulfate liquor.The rate of recovery of each valuable element are as follows: lithium 92.3%, cobalt 99.0%, nickel 98.0%, manganese 99.2%.Add Na into pickle liquor2S removes Ca, Mg except Fe, Cu, addition NaF, finally using hydrolysis except aluminium must clean Liquid afterwards, ingredient are as shown in table 1:
Ni Co Mn Cu Fe Al Ca Mg
10.5g/L 18.8g/L 9.8g/L <0.1ppm <2.0ppm <1.0ppm <2.0ppm <1.0ppm
Nickel cobalt manganese sulfate liquor ingredient after table 1 purifies
Solution is configured according to nickel cobalt manganese equimolar amounts, Cobalt monosulfate heptahydrate is added into purified sulfate liquor respectively It is dense that 105.4g, six hydration nickel sulfate 209.0g, manganese sulfate monohydrate 136.7g, dissolution and constant volume obtain the total metal ion of 4L nickel cobalt manganese Degree is the sulfate liquor of 1mol/L.Ascorbic acid 50g is added into the sulfate liquor, with 0.4mol/L ammonium hydroxide, 1mol/L Sodium hydroxide solution slowly, is parallel added dropwise in the stirred reactor of nitrogen protection, controls pH 11.2, and temperature is 65 DEG C, charging After the reaction was continued 16h, presoma Ni is obtained by filtration1/3Co1/3Mn1/3(OH)2。
Presoma after taking 321g dry adds in autoclave, and hydrogen peroxide is added, and dioxygen water consumption is molar ratio O/ (Ni+ Co+Mn)=1.0, water is added by liquid-solid ratio L/S=3:1, monohydrate lithium hydroxide 151.2g is added and makes molar ratio Li/ (Ni+Co+ Mn)=1.03；Autoclave sealing is heated to 220 DEG C and stirs, soaking time 5h；The direct 100 DEG C of dryings of slurry are poured out after cooling 4h is ground, and obtains tertiary cathode material finished product after 800 DEG C of roasting 5h in box Muffle furnace.
Embodiment 2
Alkali after 100g nickel cobalt manganese series lithium ion battery anode waste crushing grinding is soaked, filtration drying is placed in Muffle furnace Roasting, temperature are 500 DEG C, time 2 h, are during which slowly introducing CO, and carbonaceous amount is the 4% of alkali phase analysis quality in CO.Roasting produces Object by be placed in water stir and be passed through CO2, liquid-solid ratio 5:1 when water logging is passed through CO2Mole is 4 times of lithium mole in solid, Time 1.0h filters to obtain rich lithium solution.Filter residue is added in the hydrochloric acid solution that 1L concentration is 2.5mol/L, 40 DEG C of constant temperature stirrings 3 Hour, be obtained by filtration containing cobalt, nickel, manganese chloride solution.The rate of recovery of each valuable element are as follows: lithium 91.2%, cobalt 99.2%, nickel 98.5%, manganese 99.0%.Add Na into pickle liquor2S removes Ca, Mg except Fe, Cu, addition NaF, finally using hydrolysis except aluminium must clean Liquid afterwards, ingredient are as shown in table 2:
Ni Co Mn Cu Fe Al Ca Mg
18.2g/L 15.3g/L 12.2g/L <0.1ppm <2.0ppm <2.0ppm <2.0ppm <1.0ppm
Nickel cobalt manganese sulfate liquor ingredient after table 2 purifies
Solution is configured according to nickel cobalt manganese equimolar amounts, cobalt chloride hexahydrate is added into purified sulfate liquor respectively 45.0g, Nickel dichloride hexahydrate 194.0g, four chloride hydrate manganese 89.6g, dissolve and constant volume obtains the total metal ion of 1.5L nickel cobalt manganese Concentration is the chloride solution of 1.5mol/L.Ascorbic acid 20g is added into the chloride solution, with 0.6mol/L ammonium hydroxide, 1.5mol/ L sodium hydroxide solution is added dropwise to parallel in the stirred reactor of nitrogen protection, controls pH 11.0, and temperature is 55 DEG C, and charging finishes The reaction was continued afterwards 20h, is obtained by filtration presoma Ni0.5Co0.2Mn0.3(OH)2。
Presoma after taking 160g dry adds in autoclave, and water, monohydrate lithium hydroxide is added by liquid-solid ratio L/S=2:1 76g makes molar ratio Li/ (Ni+Co+Mn)=1.04；Autoclave sealing is heated to 200 DEG C and stirs, and is passed through oxygen to pressure For 3MPa, soaking time 6h；Direct 120 DEG C of slurry dry 2h are poured out after cooling, are ground, 850 DEG C in box Muffle furnace Tertiary cathode material finished product is obtained after roasting 4h.
The scope of protection of the invention shall be subject to the scope of protection specified in the patent claim.

Claims (8)

1. a kind of waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method, which is characterized in that including Following steps:
Step 1: alkali leaching aluminium: alkaline leaching aluminium is added in anode waste, and alkali phase analysis and alkali immersion liquid is obtained by filtration, and alkali phase analysis is dry, Aluminium is separately recycled in alkali immersion liquid；
Step 2: roast/mentioning lithium: alkali phase analysis and reducing agent are baking mixed, and using water logging, logical carbon dioxide mentions lithium simultaneously after roasting, Rich lithium solution and filter residue is obtained by filtration, product containing lithium is obtained by evaporative crystallization；
Step 3: acidleach: the filter residue acid adding of step 2 is leached, filter leachate and acid leaching residue, acid leaching residue separately recycle carbon；
Step 4: removal of impurities: into pickle liquor plus vulcanizing agent is except Fe, Cu, addition villiaumite are except Ca, Mg, finally using hydrolysis except aluminium obtains Liquid after removal of impurities；
Step 5: proportion liquid: nickel cobalt manganese concentration is added according to nickel cobalt manganese component ratio in target product in liquid after detection removal of impurities Soluble nickel salt, cobalt salt or manganese salt；And water is added to make the total 0.5~2.5mol/L of concentration of metal ions of nickel cobalt manganese；
Step 6: co-precipitation: solution, sodium hydroxide solution, weak aqua ammonia that step 5 obtains are slowly added under protective atmosphere It is co-precipitated in stirred reactor, presoma Ni is obtained by filtrationxCoyMn1-x-y(OH)2；
Step 7: hydrothermal synthesis: presoma, lithium source, additive and water being added in autoclave；Additive is hydrogen peroxide, oxygen One or more mixtures of gas, ozone；Lithium dosage is molar ratio Li/ (Ni+Co+Mn)=1.0~1.07；Additive amount is Molar ratio O/ (Ni+Co+Mn)=0.1~10, liquid-solid ratio L/S=1:1~4:1；
Step 8: drying/mixing: hydrothermal product is without separation of solid and liquid convection drying, desciccate ball mill mixing；
Step 9: roasting: roasting 2~10h after mixing under the conditions of 750~900 DEG C and obtain positive electrode.
2. the method according to claim 1, wherein anode waste used is cobalt acid lithium, mangaic acid in step 1 One of lithium, lithium nickelate, nickel ion doped, nickle cobalt lithium manganate, nickel cobalt lithium aluminate and rich lithium manganese base solid solution or a variety of mixtures.
3. the method according to claim 1, wherein reducing agent is solid state reduction agent lignite, cigarette in step 2 Coal, anthracite or gaseous reducing agent CO, H2One of or mixture, C and H quality sum are anode waste quality in reducing agent 4%~20%, maturing temperature be 400~700 DEG C, calcining time be 0.5~4h；Liquid-solid ratio is 1:1~10:1 when water logging, is led to Enter CO2Mole is 0.55~10 times of lithium mole in solid, 0.5~3h of extraction time.
4. the method according to claim 1, wherein acid used is in sulfuric acid, nitric acid or hydrochloric acid in step 3 One kind, liquid-solid ratio 2:1~20:1, concentration be 1~2.5mol/L, acidleach temperature be 20~90 DEG C.
5. the method according to claim 1, wherein the concentration of the sodium hydroxide used in step 6 is 0.5 ~2.5mol/L, weak aqua ammonia concentration are 0.2~1.0mol/L, and protection gas is one of nitrogen or argon gas or gaseous mixture；Instead 40~70 DEG C of temperature are answered, 5~20h of reaction time.
6. the method according to claim 1, wherein presoma used is fresh dry material in step 7 Or wet stock；Hydrothermal temperature is 140~250 DEG C, 1~6h of soaking time；Additive amount is molar ratio O/ (Ni+Co+Mn) =0.4~4；Liquid-solid ratio L/S=1:1~2:1.
7. the method according to claim 1, wherein the hydrothermal product convection drying in step 8, drying temperature It is 80~120 DEG C, 2~10h of drying time.
8. being roasted the method according to claim 1, wherein maturing temperature is 800~850 DEG C in step 9 Time is 4~5h.
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CN114207162A (en) * 2019-07-26 2022-03-18 巴斯夫欧洲公司 Method for recovering lithium and other metals from spent lithium ion batteries
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CN114291829A (en) * 2021-12-01 2022-04-08 殷衡 Method for recycling ternary battery positive electrode material by combining plasma with ozone
CN114583309A (en) * 2022-03-08 2022-06-03 骆驼集团资源循环襄阳有限公司 Method for preparing precursor by recycling waste ternary lithium ion battery
CN115354161A (en) * 2022-08-29 2022-11-18 通化建新科技有限公司 Method for recycling lithium from waste power batteries by rotary hearth furnace
EP4177988A1 (en) * 2021-11-05 2023-05-10 Battery Resources LLC Charge material synthesized from recycled lithium-ion batteries
WO2023184656A1 (en) * 2022-03-28 2023-10-05 贵州大龙汇成新材料有限公司 Trimanganese tetraoxide lithium pre-embedded intermediate, preparation method therefor and use thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450815A (en) * 2008-10-07 2009-06-10 佛山市邦普镍钴技术有限公司 Method for preparing nickel and cobalt doped lithium manganate by using waste and old lithium ionic cell as raw material
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
CN103606651A (en) * 2013-12-02 2014-02-26 河南师范大学 Method for preparing lithium nickelate cobaltate manganate cathode material by taking waste lithium ion batteries as raw material
CN104538696A (en) * 2015-01-08 2015-04-22 兰州理工大学 Method for recycling metal from waste lithium ion battery with Ni-Co lithium manganite positive electrode materials
CN105428639A (en) * 2015-11-12 2016-03-23 广东邦普循环科技有限公司 Nickel cobalt lithium manganate positive electrode material and preparation method therefor
CN106129511A (en) * 2016-06-27 2016-11-16 北京科技大学 A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material
KR101682217B1 (en) * 2016-09-02 2016-12-05 주식회사 재영텍 A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery
CN106328927A (en) * 2016-11-03 2017-01-11 王坚 Resource recycling method of waste battery cathode materials

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101450815A (en) * 2008-10-07 2009-06-10 佛山市邦普镍钴技术有限公司 Method for preparing nickel and cobalt doped lithium manganate by using waste and old lithium ionic cell as raw material
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
CN103606651A (en) * 2013-12-02 2014-02-26 河南师范大学 Method for preparing lithium nickelate cobaltate manganate cathode material by taking waste lithium ion batteries as raw material
CN104538696A (en) * 2015-01-08 2015-04-22 兰州理工大学 Method for recycling metal from waste lithium ion battery with Ni-Co lithium manganite positive electrode materials
CN105428639A (en) * 2015-11-12 2016-03-23 广东邦普循环科技有限公司 Nickel cobalt lithium manganate positive electrode material and preparation method therefor
CN106129511A (en) * 2016-06-27 2016-11-16 北京科技大学 A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material
KR101682217B1 (en) * 2016-09-02 2016-12-05 주식회사 재영텍 A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery
CN106328927A (en) * 2016-11-03 2017-01-11 王坚 Resource recycling method of waste battery cathode materials

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN112680598A (en) * 2020-12-15 2021-04-20 中南大学 Method for low-cost clean treatment of waste lithium ion battery anode material
CN112830526A (en) * 2021-01-04 2021-05-25 赣州有色冶金研究所 Method for regenerating ternary precursor by utilizing nickel-cobalt-manganese slag
CN112830526B (en) * 2021-01-04 2023-10-13 赣州有色冶金研究所有限公司 Method for regenerating ternary precursor by using nickel-cobalt-manganese slag
CN113200574A (en) * 2021-03-29 2021-08-03 中南大学 Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery
CN113117637A (en) * 2021-04-19 2021-07-16 重庆大学 Method for preparing carbon dioxide adsorbing material by using waste lithium cobaltate battery as raw material
CN113897488A (en) * 2021-09-01 2022-01-07 格林美股份有限公司 Method for recovering valuable metals from waste lithium ion batteries
US20240063455A1 (en) * 2021-09-01 2024-02-22 Gem Co., Ltd. Method for recovering valuable metals from spent lithium ion batteries
CN113945477A (en) * 2021-10-18 2022-01-18 安徽安瓦新能源科技有限公司 Method for detecting carbon content in battery electrode material
EP4177988A1 (en) * 2021-11-05 2023-05-10 Battery Resources LLC Charge material synthesized from recycled lithium-ion batteries
CN114085995A (en) * 2021-11-09 2022-02-25 湖北亿纬动力有限公司 Method for preparing metal simple substance and compound thereof by recycling waste lithium ion battery and application thereof
CN114291828A (en) * 2021-12-01 2022-04-08 殷衡 Method for recycling ternary battery positive electrode material by combining plasma with hydrogen peroxide
CN114291829A (en) * 2021-12-01 2022-04-08 殷衡 Method for recycling ternary battery positive electrode material by combining plasma with ozone
CN114197046A (en) * 2021-12-10 2022-03-18 合肥国轩高科动力能源有限公司 Single crystal lithium-containing metal composite oxide material and preparation method and application thereof
CN114197046B (en) * 2021-12-10 2023-11-03 合肥国轩高科动力能源有限公司 Single crystal lithium-containing metal composite oxide material and preparation method and application thereof
CN114162840A (en) * 2021-12-30 2022-03-11 江西赣锋循环科技有限公司 Method for preferentially extracting lithium from retired ternary lithium battery material
CN114162840B (en) * 2021-12-30 2023-04-14 江西赣锋循环科技有限公司 Method for preferentially extracting lithium from retired ternary lithium battery material
CN114583309A (en) * 2022-03-08 2022-06-03 骆驼集团资源循环襄阳有限公司 Method for preparing precursor by recycling waste ternary lithium ion battery
WO2023184656A1 (en) * 2022-03-28 2023-10-05 贵州大龙汇成新材料有限公司 Trimanganese tetraoxide lithium pre-embedded intermediate, preparation method therefor and use thereof
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CN115354161B (en) * 2022-08-29 2024-02-02 通化建新科技有限公司 Method for recycling lithium in waste power battery by rotary hearth furnace

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