CN106591584A - Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery - Google Patents

Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery Download PDF

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Publication number
CN106591584A
CN106591584A CN201611213800.7A CN201611213800A CN106591584A CN 106591584 A CN106591584 A CN 106591584A CN 201611213800 A CN201611213800 A CN 201611213800A CN 106591584 A CN106591584 A CN 106591584A
Authority
CN
China
Prior art keywords
cobalt
lithium
lithium battery
cobalt acid
acid 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.)
Pending
Application number
CN201611213800.7A
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Chinese (zh)
Inventor
郭永兴
祝宏帅
王迎春
曾小毛
欧阳红勇
刘金练
樊磊
刘志成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi He Zongli Industry Science And Technology Ltd
Original Assignee
Jiangxi He Zongli Industry Science And Technology Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangxi He Zongli Industry Science And Technology Ltd filed Critical Jiangxi He Zongli Industry Science And Technology Ltd
Priority to CN201611213800.7A priority Critical patent/CN106591584A/en
Publication of CN106591584A publication Critical patent/CN106591584A/en
Priority to PCT/CN2017/113056 priority patent/WO2018113477A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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

The invention belongs to the field of waste recycling, and relates to a method of recovering cobalt and lithium from an anode material of a spent cobalt acid lithium battery, in order to overcome the technical deficiencies in the prior art that the recovering cost is high and the treatment step is complicated in a process of recovering cobalt and lithium from the anode material of the spent cobalt acid lithium battery. The method of recovering cobalt and lithium from the anode material of the spent cobalt acid lithium battery is characterized in that sodium hydrogen sulfate is mixed with the anode material of the spent cobalt acid lithium battery, a mixture is subjected to high temperature roasting, then water is added and leaching is carried out, and a sulphate solution comprising cobalt and lithium is obtained after filtration. The method is simple in preparation technology and high in process controllability, and is very suitable for recycling of cobalt and lithium from the cobalt acid lithium battery.

Description

A kind of method of Call Provision and lithium in cobalt acid lithium battery positive electrode from failure
Technical field
The present invention relates to it is a kind of failure cobalt acid lithium battery positive electrode in Call Provision and lithium method, belong to scrap concrete Using field.
Background technology
As population is continuously increased, resource is constantly exhausted, and people put forward higher requirement to chemical energy source, i.e., high-quality Amount, long-life, low stain, and the lithium rechargeable battery of high-tech, high added value is a wherein spotlight, is caused many big Company is competitively added in the research and development ranks of the product.There is certain longevity as the lithium rechargeable battery of " green energy resource " Life, generally 3 years or so.It is expected that lithium rechargeable battery will become part very important in following solid waste.Such as What deals carefully with them, will be the big problem that people face.
With regard to the method from Call Provision, lithium in failure cobalt acid lithium battery positive electrode, prior art mostly is in acid system Middle addition reducing agent is (such as hydrogen peroxide, Na2SO3) leaching cobalt, lithium.Abroad, the company such as SONY is had been presented for from applying waste lithium ionic two The scheme of cobalt compound is reclaimed in primary cell.Additionally, some researcheres have been also carried out the research of correlation：The employing extraction such as Zhang, The method of precipitation has reclaimed lithium carbonate and cobalt oxalate；And Lee etc. proposes recovery LiCoO2Scheme.Wherein, Contestabile etc. goes back the afflux such as stainless steel casing and aluminum, copper of synthetical recovery spent lithium-ion secondary batteries pole.In state Inside not yet there is company to propose the spent lithium-ion secondary batteries recovery scheme of oneself, the purpose of these recovery schemes is mainly reclaimed Cobalt compound or cobalt metal simple-substance.
《The recovery of waste lithium ion cell anode material lithium cobaltate》It is middle using different recovery schemes to applying waste lithium ionic Secondary cell has carried out reclaiming research：Electrolyte is reclaimed using Allyl carbonate (PC)；Existed using N-Methyl pyrrolidone (NMP) 70 DEG C of stripping active substances；Carbon dust is removed by heat treatment method；Using dissolving with hydrochloric acid cobalt, with Co (OH)2Form is reclaimed, then is weighed New synthesis cobalt acid lithium.The response rate of cobalt is more than 99% in the method, but the handling process process is complicated, and cost recovery is higher.
The content of the invention
From cost recovery during Call Provision in failure cobalt acid lithium battery positive electrode and lithium in order to overcome prior art It is higher, and the technical deficiency of complicated process steps, Call Provision in a kind of cobalt acid lithium battery positive electrode from failure of present invention offer With the method for lithium, sodium bisulfate is mixed with failure cobalt acid lithium battery positive electrode in the method, after compound high-temperature roasting Add water leaching, is filtrated to get the sulfate liquor comprising cobalt element and elemental lithium.The method preparation process is simple, process control By force, it is especially suitable for the recycling of cobalt acid lithium battery cobalt and elemental lithium.
The present invention is achieved through the following technical solutions above-mentioned technical purpose：
A kind of method of Call Provision and lithium in cobalt acid lithium battery positive electrode from failure, it is sour with failure cobalt by sodium bisulfate Anode material of lithium battery mixes, and by the leaching that adds water after compound high-temperature roasting, is filtrated to get the sulfur comprising cobalt element and elemental lithium Acid salt solution.
The method of Call Provision and lithium in the cobalt acid lithium battery positive electrode from failure described above, it specifically includes following steps Suddenly：
(1) sodium bisulfate is mixed homogeneously and obtains compound with failure cobalt acid lithium battery positive electrode, control cobalt element with The mol ratio of element sulphur is 1：3；
(2) roasting 5min～40min obtains baked material under the conditions of compound being placed in into 200 DEG C～600 DEG C；
(3) take out and add water after baked material leaching, extraction temperature is 20 DEG C～90 DEG C, and extraction time is 4-6h；
(4) solid-liquor separation, sulfate liquor of the filtrate as comprising cobalt element and elemental lithium are filtered.
It is above-mentioned from failure cobalt acid lithium battery positive electrode in Call Provision and lithium method in, described step 3) in water with roasting The mass ratio of material is 40-80:1.
The principle of the method is：
4LiCoO2+12NaHSO4==2Li2SO4+6Na2SO4+4CoSO4+6H2O+O2
The present invention has following technical advantage relative to prior art：
The method of Call Provision and lithium uses NaHSO in the cobalt acid lithium battery positive electrode from failure of the present invention4With mistake After effect cobalt acid lithium battery positive electrode is baking mixed, add water leaching；It can obtain the cobalt of higher concentration, lithium leachate, cobalt Leaching rate is more than 95%, the leaching rate of lithium is more than 93%.
Specific embodiment
The technology contents of the present invention are further illustrated below by way of specific embodiment, but the technical staff in the field should be able to Know, the embodiment and the never in any form protection domain of restriction patent of the present invention.Those skilled in the art's here basis On the modification made or equivalent substitute, all should be included within this patent protection domain.
The method of Call Provision and lithium in a kind of cobalt acid lithium battery positive electrode from failure of embodiment 1
By sodium bisulfate with failure cobalt acid lithium battery positive electrode with cobalt sulfur ratio as 1：After 3 mixing, in 200 DEG C of roastings 40min, takes out and add water after baked material leaching, and extraction temperature is 90 DEG C.Solid-liquor separation is filtered, filtrate is as comprising cobalt element and lithium unit The sulfate liquor of element.After testing the leaching rate of cobalt be 97.50%, lithium leaching rate be 96.82%.
The method of Call Provision and lithium in a kind of cobalt acid lithium battery positive electrode from failure of embodiment 2
By sodium bisulfate with failure cobalt acid lithium battery positive electrode with cobalt sulfur ratio as 1：After 3 mixing, in 600 DEG C of roastings 20min, takes out and add water after baked material leaching, and extraction temperature is 20 DEG C.Solid-liquor separation is filtered, filtrate is as comprising cobalt element and lithium unit The sulfate liquor of element.After testing the leaching rate of cobalt be 98.35%, lithium leaching rate be 97.76%.
The method of Call Provision and lithium in a kind of cobalt acid lithium battery positive electrode from failure of embodiment 3
By sodium bisulfate with failure cobalt acid lithium battery positive electrode with cobalt sulfur ratio as 1：After 3 mixing, in 400 DEG C of roastings 30min, takes out and add water after baked material leaching, and extraction temperature is 60 DEG C.Solid-liquor separation is filtered, filtrate is as comprising cobalt element and lithium unit The sulfate liquor of element.After testing the leaching rate of cobalt be 98.12%, lithium leaching rate be 97.98%.

Claims (3)

1. it is a kind of from failure cobalt acid lithium battery positive electrode in Call Provision and lithium method, its by sodium bisulfate with failure cobalt acid lithium Cell positive material mixes, and by the leaching that adds water after compound high-temperature roasting, is filtrated to get the sulphuric acid comprising cobalt element and elemental lithium Saline solution.
2. in the cobalt acid lithium battery positive electrode from failure according to claim 1 Call Provision and lithium method, its feature exists In it specifically includes following step：
(1) sodium bisulfate is mixed homogeneously with failure cobalt acid lithium battery positive electrode and obtains compound, control cobalt element is first with sulfur The mol ratio of element is 1：3；
(2) roasting 5min～40min obtains baked material under the conditions of compound being placed in into 200 DEG C～600 DEG C；
(3) take out and add water after baked material leaching, extraction temperature is 20 DEG C～90 DEG C, and extraction time is 4-6h；
(4) solid-liquor separation, sulfate liquor of the filtrate as comprising cobalt element and elemental lithium are filtered.
3. in the cobalt acid lithium battery positive electrode from failure according to claim 1 Call Provision and lithium method, its feature exists In described step 3) in the mass ratio of water and baked material be 40-80:1.
CN201611213800.7A 2016-12-23 2016-12-23 Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery Pending CN106591584A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201611213800.7A CN106591584A (en) 2016-12-23 2016-12-23 Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery
PCT/CN2017/113056 WO2018113477A1 (en) 2016-12-23 2017-11-27 Method for recovering cobalt and lithium from positive electrode material of spent lithium cobalt oxide battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611213800.7A CN106591584A (en) 2016-12-23 2016-12-23 Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery

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Cited By (2)

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WO2018113477A1 (en) * 2016-12-23 2018-06-28 江西合纵锂业科技有限公司 Method for recovering cobalt and lithium from positive electrode material of spent lithium cobalt oxide battery
CN109182732A (en) * 2018-09-18 2019-01-11 惠州亿纬锂能股份有限公司 Waste and old ternary lithium battery stagewise recovery method

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CN109935922B (en) * 2019-03-14 2020-11-27 北京矿冶科技集团有限公司 Method for recovering valuable metals from waste lithium ion battery materials
CN111533108A (en) * 2020-05-11 2020-08-14 蒋达金 Method for preparing lithium cobalt phosphate by using waste lithium cobalt oxide
CN111621643A (en) * 2020-05-29 2020-09-04 江苏大学 Method for selectively extracting lithium from waste lithium battery powder
CN113300019A (en) * 2021-05-21 2021-08-24 湖南杉杉能源科技股份有限公司 Recovered product and recovery method of waste lithium cobalt oxide battery
CN115074540B (en) * 2022-08-16 2022-11-25 矿冶科技集团有限公司 Comprehensive recovery method for valuable components of waste power battery
CN115367732B (en) * 2022-09-20 2023-08-22 中南大学 Industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery collaborative recycling method
CN115893511A (en) * 2022-12-28 2023-04-04 武汉大学 Method for recovering waste cobalt acid lithium battery cathode material by reduction of biomass pyrolysis gas

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Publication number Priority date Publication date Assignee Title
WO2018113477A1 (en) * 2016-12-23 2018-06-28 江西合纵锂业科技有限公司 Method for recovering cobalt and lithium from positive electrode material of spent lithium cobalt oxide battery
CN109182732A (en) * 2018-09-18 2019-01-11 惠州亿纬锂能股份有限公司 Waste and old ternary lithium battery stagewise recovery method

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Application publication date: 20170426