CN103606719B - A kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material - Google Patents

A kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material Download PDF

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Publication number
CN103606719B
CN103606719B CN201310630619.6A CN201310630619A CN103606719B CN 103606719 B CN103606719 B CN 103606719B CN 201310630619 A CN201310630619 A CN 201310630619A CN 103606719 B CN103606719 B CN 103606719B
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lithium
cathode material
manganate cathode
ion battery
waste
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CN103606719A (en
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姚路
席国喜
姚海森
许会道
刘玉民
牛全海
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Henan Normal University
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Henan Normal University
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material.Drip irrigation device of the present invention is: a kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material, main is leaching agent and gel with citric acid solution, adopt the method for sol-gel to prepare manganate cathode material for lithium, and disclose concrete preparation process.Present invention, avoiding conventional method adopts inorganic acid to be the pollution of leaching agent S, N of producing and the gas such as chlorine, and the generation of accessory substance in separation of metal ions process and waste water, environmental protection, cost is low, and the manganate cathode material for lithium of preparation directly can return factory to be continued to use.

Description

A kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material
Technical field
The present invention relates to waste and old lithium ion battery reutilization field, being specifically related to a kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material.
Background technology
It is high that lithium ion battery has energy density, the excellent chemical property such as have extended cycle life, be widely used in various portable electricity consumption facility now, as mobile phone, notebook computer, video camera etc., simultaneously, in new-energy automobile field, lithium ion battery is also playing vital effect.Along with the development of various electricity consumption facility and new-energy automobile industry, the market demand of lithium ion battery increases year by year.Containing a large amount of precious metals and some flammable poisonous electrolyte in waste and old lithium ion battery, if waste and old lithium ion battery is not processed, not only can cause the waste of resource, also can cause certain environmental pollution.
But now the recycling to cobalt acid lithium is mainly concentrated on to the recovery research of waste and old lithium ion battery, cobalt is very rare metal material, solid content in waste and old lithium ion battery is even higher than the content of native deposits, and the precious metals such as Call Provision nickel have good economic benefit and the value of environmental protection.But because cobalt resource is limited, cause cobalt acid lithium cost more and more higher, occupation rate of market declines, in addition cobalt acid lithium security performance particularly high-temperature behavior still allow people worry, in recent years, people have mainly been placed on research energy on LiMn2O4, nickle cobalt lithium manganate and LiFePO 4, it is desirable to prepare high performance chemical power source on the basis reduced costs.LiMn2O4 is as important anode material for lithium-ion batteries, there is cost low, environmental friendliness, the advantages such as security performance is good, at lamp power, electrical source of power field has a wide range of applications, therefore, be that the waste and old lithium ion battery of positive electrode also gets more and more with LiMn2O4, however less for the recovery research of this type of lithium ion battery.
Publication number is patent discloses of the CN102347521A recovery method of manganese and lithium " in a kind of dynamic lithium manganate battery used for electric vehicle ", wherein main take inorganic acid as leachate, adopt electrochemical deposition and carbonate precipitation method to reclaim respectively and obtain manganese dioxide solid and lithium carbonate, although inorganic acid leaching in early stage metal ion leaching rate is high, cost is low, but the exhaust environment produced is seriously polluted, metal ion reclaim the intractability causing complexity in operation and waste water byproduct respectively.Publication number is patent discloses " a kind of method reclaiming valuable metal in waste lithium manganese oxide battery " of CN101831548A, proposes to adopt NaOH precipitate and separate final high temperature calcining preparation MnO 2, carbonate deposition reclaims lithium with the form of lithium carbonate, is still difficult to avoid the negative effect that in conventional recovery method, separation of metal ions produces.
Summary of the invention
The present invention overcomes the deficiencies in the prior art to provide a kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material, the method had both avoided the environmental pollution that in conventional recovery method, inorganic acid causes, also save the use of gel in material preparation process simultaneously, environmental friendliness, pollution-free, and prepared the manganate cathode material for lithium of high added value.
Technical scheme of the present invention is: a kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material, it is characterized in that main is leaching agent and gel with citric acid solution, the method of sol-gel is adopted to prepare manganate cathode material for lithium, specifically comprise the following steps: (1) is after the waste and old lithium ion battery electric discharge of positive electrode with LiMn2O4, disassemble battery, isolate positive plate; (2) positive plate that step (1) obtains is put into high-temperature process in vacuum furnace, decomposes binding agent; (3) process the positive plate after high-temperature vacuum pyrolysis, obtain anode sizing agent; (4) be dissolved in citric acid solution by the anode sizing agent after high temperature pyrolysis, wherein the quality of anode sizing agent is 45-75g/L with the ratio of the volume of citric acid solution, and the molar concentration of citric acid solution is 0.5-2mol/L; (5) hydrogenperoxide steam generator is added, dissolution filter; (6) measure the content of metal ion in solution, regulate Li in solution with soluble lithium salt and manganese salt +and Mn 2+mol ratio be 1:2; (7) regulate the pH of solution to be 5-9 with ammoniacal liquor, be stirred to gel; (8) ageing is dry obtains xerogel, obtains manganate cathode material for lithium after 250-350 DEG C of pre-burning 0.5-5h in 450-900 DEG C of calcining.
In step of the present invention (4), the quality of anode sizing agent is 60g/L with the ratio of the volume of citric acid solution; The molar concentration of described citric acid solution is 1.0mol/L; In described step (6), soluble lithium salt is lithium nitrate, and lithium acetate or lithium sulfate, soluble manganese salt is manganese nitrate, manganese acetate or manganese sulfate.
Present invention, avoiding conventional method adopts inorganic acid to be the pollution of leaching agent S, N of producing and the gas such as chlorine, and the generation of accessory substance in separation of metal ions process and waste water, environmental protection, cost is low, and the manganate cathode material for lithium of preparation directly can return factory to be continued to use.
Accompanying drawing explanation
Fig. 1 is the present invention take waste and old lithium ion battery as the process chart that manganate cathode material for lithium prepared by raw material, and Fig. 2 is the XRD collection of illustrative plates of the manganate cathode material for lithium that the embodiment of the present invention 1 obtains.
Embodiment
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
(1) with LiMn2O4 be positive electrode waste and old lithium ion battery electric discharge after, disassemble battery, isolate positive plate; (2) positive plate that step (1) obtains is put into high-temperature process in vacuum furnace, decomposes binding agent; (3) process the positive plate after high-temperature vacuum pyrolysis, obtain anode sizing agent; (4) be dissolved in citric acid solution by the anode sizing agent after high temperature pyrolysis, wherein the quality of anode sizing agent and the volume ratio of citric acid solution are 60g/L, and the molar concentration of citric acid solution is 1.0mol/L; (5) hydrogenperoxide steam generator is added, dissolution filter; (6) measure the content of the metal ion in solution, regulate Li in solution with lithium nitrate and manganese nitrate +and Mn 2+mol ratio be 1:2; (7) regulate the pH=8 of solution with ammoniacal liquor, be stirred to gel; (8) ageing is dry obtains xerogel, and in 350 DEG C of pre-burning 2h, 750 DEG C of calcining 12h obtain manganate cathode material for lithium.Fig. 2 is the XRD collection of illustrative plates of the manganate cathode material for lithium of preparation, and consistent with the diffraction maximum of LiMn2O4 standard diagram by the product of the known preparation of collection of illustrative plates, the product therefore prepared is manganate cathode material for lithium.
Embodiment 2
(1) with LiMn2O4 be positive electrode waste and old lithium ion battery electric discharge after, disassemble battery, isolate positive plate; (2) positive plate that step (1) obtains is put into high-temperature process in vacuum furnace, decomposes binding agent; (3) process the positive plate after high-temperature vacuum pyrolysis, obtain anode sizing agent; (4) be dissolved in citric acid solution by the anode sizing agent after high temperature pyrolysis, wherein the quality of anode sizing agent and the volume ratio of citric acid solution are 45g/L, and the molar concentration of citric acid solution is 0.5mol/L; (5) hydrogenperoxide steam generator is added, dissolution filter; (6) measure the content of the metal ion in solution, regulate Li in solution with lithium acetate and manganese acetate +and Mn 2+mol ratio be 1:2; (7) regulate the pH=5 of solution with ammoniacal liquor, be stirred to gel; (8) ageing is dry obtains xerogel, and in 350 DEG C of pre-burning 0.5h, 900 DEG C of calcinings obtain manganate cathode material for lithium.
Embodiment 3
(1) with LiMn2O4 be positive electrode waste and old lithium ion battery electric discharge after, disassemble battery, isolate positive plate; (2) positive plate that step (1) obtains is put into high-temperature process in vacuum furnace, decomposes binding agent; (3) process the positive plate after high-temperature vacuum pyrolysis, obtain anode sizing agent; (4) be dissolved in citric acid solution by the anode sizing agent after high temperature pyrolysis, wherein the quality of anode sizing agent and the volume ratio of citric acid solution are 75g/L, and the molar concentration of citric acid solution is 2mol/L; (5) hydrogenperoxide steam generator is added, dissolution filter; (6) measure the content of the metal ion in solution, regulate Li in solution with lithium sulfate and manganese sulfate +and Mn 2+mol ratio be 1:2; (7) regulate the pH=9 of solution with ammoniacal liquor, be stirred to gel; (8) ageing is dry obtains xerogel, and 250 DEG C of pre-burning 5h, 450 DEG C of calcinings obtain manganate cathode material for lithium.
Embodiment above describes general principle of the present invention, principal character and advantage.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.

Claims (1)

1. be the method that manganate cathode material for lithium prepared by raw material with waste and old lithium ion battery, it is characterized in that, comprise the following steps: (1) is after the waste and old lithium ion battery electric discharge of positive electrode with LiMn2O4, disassembles battery, isolates positive plate; (2) positive plate that step (1) obtains is put into high-temperature process in vacuum furnace, decomposes binding agent; (3) process the positive plate after high-temperature vacuum pyrolysis, obtain anode sizing agent; (4) be dissolved in citric acid solution by the anode sizing agent after high temperature pyrolysis, wherein the quality of anode sizing agent and the volume ratio of citric acid solution are 60g/L, and the molar concentration of citric acid solution is 1.0mol/L; (5) hydrogenperoxide steam generator is added, dissolution filter; (6) measure the content of the metal ion in solution, regulate Li in solution with soluble lithium salt and manganese salt +and Mn 2+mol ratio be 1:2; (7) regulate the pH=8 of solution with ammoniacal liquor, be stirred to gel; (8) ageing is dry obtains xerogel, and in 350 DEG C of pre-burning 2h, 750 DEG C of calcining 12h obtain manganate cathode material for lithium; Wherein, in described step (6), soluble lithium salt is lithium acetate or lithium sulfate, and soluble manganese salt is manganese acetate or manganese sulfate.
CN201310630619.6A 2013-12-02 2013-12-02 A kind of take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material Expired - Fee Related CN103606719B (en)

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CN105865876A (en) * 2016-05-29 2016-08-17 合肥国轩高科动力能源有限公司 Pretreatment method for detecting metal ions in lithium ion battery anode material
CN109022793B (en) * 2017-06-12 2021-04-13 长沙矿冶研究院有限责任公司 Method for selectively leaching lithium from waste powder of cathode material containing at least one of cobalt, nickel and manganese
CN107699692A (en) * 2017-09-18 2018-02-16 北京理工大学 A kind of recovery and the method for regenerating waste used anode material for lithium-ion batteries
CN109207725B (en) * 2018-09-19 2020-06-30 中国科学院青海盐湖研究所 Method and system for recovering lithium and manganese from waste lithium manganate battery
CN109742364A (en) * 2019-01-09 2019-05-10 东北师范大学 A kind of recovery method of waste and old lithium cobaltate cathode
CN109734068B (en) * 2019-01-09 2021-03-19 东北师范大学 Method for recycling waste lithium manganate positive electrode
CN111041230B (en) * 2019-08-16 2021-06-04 中国科学院过程工程研究所 Method for recovering metal from waste lithium ion battery
CN110564978A (en) * 2019-10-15 2019-12-13 俞杰 operation process for recovering nickel and cobalt in ternary battery material by wet method
CN111530470B (en) * 2020-05-06 2022-03-18 合肥工业大学 Preparation method of manganese dioxide and composite material thereof and degradation method of sulfadiazine
CN114906863B (en) * 2022-05-31 2023-12-15 宁波容百新能源科技股份有限公司 Comprehensive recovery method of waste lithium manganate anode material

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