CN102593450B - Method for preparing multielement-doped lithium iron phosphate by using waste phosphate slag as main raw material - Google Patents

Method for preparing multielement-doped lithium iron phosphate by using waste phosphate slag as main raw material Download PDF

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CN102593450B
CN102593450B CN201210054761.6A CN201210054761A CN102593450B CN 102593450 B CN102593450 B CN 102593450B CN 201210054761 A CN201210054761 A CN 201210054761A CN 102593450 B CN102593450 B CN 102593450B
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waste residue
phosphatization waste
phosphatization
phosphate
lithium iron
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CN102593450A (en
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李辽沙
岳海峰
李敏红
吴照金
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Anhui University of Technology AHUT
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Abstract

The invention discloses a method for preparing multielement-doped lithium iron phosphate by using waste phosphate slag as a main raw material, belonging to the technical field of preparation of an anode material of a lithium battery. According to the method, a mixture which mainly contains iron phosphate and also contains a defined amount of phosphates of Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti and the like is prepared from waste phosphate slag through oxidation and an acid-washing method. The mixture is used as a main raw material, and Li is added into the mixture according to a chemical ratio, and the mixture with Li is sintered under the protection of inert gas such as N2 or Ar to synthesize multielement-doped lithium iron phosphate. Fe, P and all doped elements used in the method for preparing the multielement-doped lithium iron phosphate are from the phosphate slag, so that the difficult technical problem in the traditional process that raw materials used for preparing the multi-doped lithium iron phosphate only depend on a great amount of various battery-grade raw materials is solved. The method is a new method for harmless and high-additional-value utilization of the dangerous solid waste phosphate slag while the preparation cost of the lithium iron phosphate is obviously reduced.

Description

Prepare the method for multi-component doped lithium ferrous phosphate take phosphatization waste residue as primary raw material
Technical field
The invention belongs to anode material for lithium-ion batteries preparing technical field, be specifically related to a kind of prepare take phosphatization waste residue as primary raw material multi-element doping type LiFePO4 method.
Background technology
There is the LiFePO of olivine-type structure 4can reversibly embed and removal lithium embedded ion, consider that it is nontoxic, environmentally friendly, raw material source is abundant, specific capacity is high, good cycle, being considered to become the desirable positive electrode of lithium ion battery.But its poorly conductive, is not suitable for high current charge-discharge, cannot directly apply as electrode material.At present conventional method of modifying has carbon coated and transition metal element doped, or two kinds of methods adopt simultaneously.Simple carbon is coated is only to have strengthened particle surface electric conductivity, and its improvement effect and persistence are all undesirable.Amount of literature data demonstration, the LiFePO4 of suitability for industrialized production is all to prepare take expensive chemical reagent as raw material both at home and abroad at present, the technology of preparing multi-element doping type LiFePO4 take phosphatization waste residue as primary raw material there is not yet report.
Steel product Surface Finishing preprocessing process extensively adopts phosphorization treatment process both at home and abroad at present.Based on the mechanism of parkerizing process, the film formed process of phosphatization can be with FePO 4the side reaction that generates and precipitate, this is the main component of composition phosphatization waste residue, in phosphatization operating process, have the calcium phosphate precipitation slagging of a certain amount of Zn, Ca simultaneously, according to different phosphating process and handling object, in phosphatization waste residue, also can contain the metallic elements such as micro-Cr, Mn, Al, Ni, Mg, Ti in addition.The main disposal options of phosphatization slag is after body refuse is filtered dry, to transfer to environmental administration to concentrate landfill or stacking at present, and fraction phosphatization waste residue is used for configuring composite phosphorized liquid, has achievement in research to obtain zinc ingot metal and ingot iron by pyrocarbon thermal reduction abroad.By looking through a great amount of information and document, do not find to solve preferably the method for phosphatization waste reside comprehensive utilization problem.
FePO in phosphatization waste residue 4content is about 60 ~ 80%, if as preparation LiFePO 4raw material, phosphatization waste residue can be realized higher utilance.Phosphatization waste residue also contains the LiFePO such as Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti 4useful doped chemical, these elements exist with phosphatic form, can carry out Composition Control to it by the method for pickling.In the phosphatization waste residue mud of some treatment process, can contain a small amount of Fe in addition 2+, need to carry out simple oxidation to body refuse, then drip phosphoric acid, make it with FePO 4form precipitates.
Phosphatization waste residue main component is the FePO of value 4, contain the LiFePO of multiple beneficial simultaneously 4doped chemical.Excessive Zn, Ca can affect LiFePO 4chemical property, can reach by the adjusting to technological parameter in acid cleaning process the object of control composition.So phosphatization waste residue possesses through pickling processes and in order to prepare the theoretical foundation of multi-element doping type LiFePO4.
Summary of the invention
The object of this invention is to provide a kind of method of preparing multi-element doping type LiFePO4 take phosphatization waste residue as primary raw material, the method is to provide FePO with phosphatization waste residue 4with multiple doped chemical, to prepare multi-element doping type LiFePO4.
The concrete steps of the inventive method are as follows:
(1) in described phosphatization waste residue, drip a small amount of oxidant or phosphatization waste residue is carried out to Air Exposure, oxidation processes to light green in phosphatization waste residue thoroughly disappears and transfers faint yellow or yellow-white to, then in described phosphatization waste residue, drips a small amount of phosphoric acid,diluted;
(2) phosphatization waste residue pretreated step (1) is first cleaned by proper inorganic acid, the backward filtrate of suction filtration drips excessive sodium hydrate solution until there is obvious red precipitate, then filter residue is cleaned suction filtration after 3 ~ 5 times, dries the primary raw material that obtains preparing multi-element doping type ferric lithium phosphate precursor with running water;
(3) with Li source material LiOHH 2o or Li 2c 2o 4it is modified that the phosphatization raw slag material that described step (2) is obtained is joined Li, make mol ratio=(1 ~ 1.05) of Li:P: 1 or make Li:(Fe+M) mol ratio=(1 ~ 1.05): 1, obtain preparing the presoma of multi-element doping type LiFePO4, wherein M refers to multiple beneficial doped chemical, comprises Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti;
(4) by above-mentioned presoma with 300 ~ 500r/min ball milling after 4 ~ 8 hours; mix Li:C=1:0.2 ~ 1.5 in molar ratio with carbon source; described carbon source is olefin polymer or glucose or graphite; under N2 or Ar inert gas shielding; in 600 ℃ ~ 800 ℃ roastings 5 ~ 10 hours, obtain target product: multi-element doping type LiFePO4.
Described phosphatization waste residue comprises and of infusion process phosphating process, steel products is made the phosphatization waste residue producing in Phosphating Treatment Process.
Described step (1) is specific as follows:
Mud shape phosphatization waste residue is done to blast aeration and process or drip a small amount of oxidant, described oxidant can select natrium nitrosum or hydrogen peroxide etc. not to contain the oxidising agent of heavy metal ion, the mud shape phosphatization waste residue of 1.2 ~ 1.4kg moisture content 85% ~ 95% drips phosphoric acid,diluted 5 ~ 8ml of 0.01mol/L, between 2 ~ 4, make oxidation of divalent iron ion in mud shape phosphatization waste residue be ferric ion and precipitate with ferric phosphate form by ammoniacal liquor adjusting supernatant pH value.
Described step (2) is specific as follows:
Per kilogram mud shape phosphatization waste residue uses 200ml inorganic acid to stir 5 ~ 20min at 50 ~ 80 ℃ at every turn, regulate the pH value of supernatant between 2 ~ 4 with ammoniacal liquor, suction filtration or press filtration, repeating above step has obvious red precipitate until suction filtration drop adds excessive sodium hydrate solution, main component after filter residue is dried is the ferric phosphate with some crystallizations water, contains in addition several or whole phosphatic mixture in trace Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti; Described inorganic acid is watery hydrochloric acid or dilute sulfuric acid or phosphoric acid,diluted.
Oxidation processes is containing Fe for phosphatization waste residue mud 2+more, the aobvious pre-treatment step adopting when green of slag slurry, if aobvious green this step can skip.
The object of carrying out pickling processes with inorganic acid is at FePO 4lose under less prerequisite, can effectively remove Zn excessive in body refuse, Ca, simultaneously the LiFePO such as Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti 4useful doped chemical can obtain appropriate the retaining of mol ratio.
Described useful doped chemical refers to by appropriate doping LiFePO 4chemical property improves useful, comprises Zn appropriate in phosphatization waste residue, Ca, Cr, Mn, Al, Ni, Mg, Ti element.
Described harmful element refers to has dysgenic element to prepared electrochemical performances of lithium iron phosphate, mainly comprises Zn excessive in phosphatization waste residue, Ca.
The present invention is the method for preparing multi-element doping type LiFePO4 take phosphatization waste residue after treatment as primary raw material, its key problem in technology is by adopting proper inorganic acid (watery hydrochloric acid or dilute sulfuric acid or phosphoric acid,diluted) to do pickling processes to phosphatization waste residue mud under certain physics, electrochemical conditions, and then regulation and control composition, remove excessive Zn, Ca, making gained filter residue main component is ferric phosphate, and simultaneously multiple beneficial doped chemical (comprise in Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti several or whole) retains with appropriate mol ratio.
Be with the remarkable difference that chemical reagent is prepared doped lithium ferric phosphate method with traditional, new method of the present invention is prepared doped lithium ferric phosphate ferric phosphate used and each doped chemical (comprise in Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti several or whole) all from phosphatization waste residue, it is the comprehensive utilization of, high efficiency innoxious to harmful phosphatization waste residue, high added value, also overcome the limitation that the raw material of preparing doped lithium ferric phosphate relies on merely number of chemical reagent simultaneously, reduced preparation cost.
Accompanying drawing explanation
Figure is that multi-element doping type LiFePO4 prepared by the present invention adds appropriate additive and binding agent to make the first charge-discharge curve chart of electrode.
Embodiment
Embodiment 1: weigh the partially green phosphatization waste residue of color of 250g moisture content 90%, drip 1ml H 2o 2, the phosphoric acid,diluted of 1ml 0.01mol/L, simple agitation to color is uniform white or yellow-white.Add 50ml 0.005mol/L watery hydrochloric acid, 3 ~ 4, in 60 ℃ of water-baths, add thermal agitation 15min by ammoniacal liquor adjusting pH value, after filtering, get 5ml filtrate, drip excessive NaOH solution, if repeat above-mentioned acid pickling step without obvious red precipitate.Gained filter residue is 180 ℃, 2h oven dry in baking oven.XRF surveys its composition, and wherein Fe, P and the relative molar percentage of each doped chemical are respectively: 48.57%, 50.12%, 1.31%.Do thermogravimetic analysis (TGA), after 180 ℃ of oven dry, in every 10g filter residue, contain crystallization water 0.62g.Weigh 10g filter residue, join 2.61g LiOH.H 2o, 1.5g polypropylene powder, ball milling (380rpm, 6h).After ball milling, sample is placed in enamel crucible, and 700 ℃, N 2the lower roasting of protection 6 hours, cools to room temperature with the furnace, obtains multi-element doping type LiFePO 4product, pack label is for subsequent use.
Embodiment 2: the white or the yellow-white phosphatization waste residue that weigh 250g moisture content 90%, add 50ml 0.001mol/L phosphoric acid,diluted, regulate pH value 3 ~ 4 with ammoniacal liquor, in 80 ℃ of water-baths, add thermal agitation 10min, after filtering, get 5ml filtrate, drip excessive NaOH solution, if repeat above-mentioned acid pickling step without obvious red precipitate.Gained filter residue is 100 ℃, 4h oven dry in baking oven.XRF surveys its composition, and wherein Fe, P and the relative molar percentage of each doped chemical are respectively: 47.53%, 50.35%, 2.12%.Do thermogravimetic analysis (TGA), after 100 ℃ of oven dry, in every 10g filter residue, contain crystallization water 1.21g.Weigh 10g filter residue, join 2.44g LiOH.H 2o, 1.5g polypropylene powder, ball milling (450rpm, 4h).After ball milling, sample is placed in enamel crucible, and 700 ℃, N 2the lower roasting of protection 6 hours, cools to room temperature with the furnace, obtains multi-element doping type LiFePO 4product, pack label is for subsequent use.

Claims (4)

1. prepare the method for multi-element doping type LiFePO4 take phosphatization waste residue as primary raw material, it is characterized in that the method concrete steps are as follows:
(1) in described phosphatization waste residue, drip a small amount of oxidant or phosphatization waste residue is carried out to Air Exposure, oxidation processes to light green in phosphatization waste residue thoroughly disappears and transfers faint yellow or yellow-white to, then in described phosphatization waste residue, drips a small amount of phosphoric acid,diluted;
(2) phosphatization waste residue pretreated step (1) is first cleaned by proper inorganic acid, the backward filtrate of suction filtration drips excessive sodium hydrate solution until there is obvious red precipitate, then filter residue is cleaned suction filtration after 3 ~ 5 times, dries the primary raw material that obtains preparing multi-element doping type ferric lithium phosphate precursor with running water;
(3) with Li source material LiOHH 2 o or Li 2 c 2 o 4 it is modified that the phosphatization raw slag material that described step (2) is obtained is joined Li, make mol ratio=(1 ~ 1.05) of Li:P: 1 or make Li:(Fe+M) mol ratio=(1 ~ 1.05): 1, obtain preparing the presoma of multi-element doping type LiFePO4, wherein M refers to multiple beneficial doped chemical, comprises Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti;
(4) by above-mentioned presoma with 300 ~ 500r/min ball milling after 4 ~ 8 hours, with carbon source Li:C=1:(0.2 ~ 1.5 in molar ratio) mix, described carbon source is olefin polymer or glucose or graphite, at N 2 or under Ar inert gas shielding, in 600 ℃ ~ 800 ℃ roastings 5 ~ 10 hours, obtain target product: multi-element doping type LiFePO4.
2. method according to claim 1, is characterized in that: described phosphatization waste residue comprises and of infusion process phosphating process, steel products made the phosphatization waste residue producing in Phosphating Treatment Process.
3. according to claim 1, method, is characterized in that described step (1) is specific as follows:
mud shape phosphatization waste residue is done to blast aeration and process or drip a small amount of oxidant, described oxidant can select natrium nitrosum or hydrogen peroxide etc. not to contain the oxidising agent of heavy metal ion, the mud shape phosphatization waste residue of 1.2 ~ 1.4kg moisture content 85% ~ 95% drips phosphoric acid,diluted 5 ~ 8ml of 0.01mol/L, between 2 ~ 4, make oxidation of divalent iron ion in mud shape phosphatization waste residue be ferric ion and precipitate with ferric phosphate form by ammoniacal liquor adjusting supernatant pH value.
4. according to claim 1, method, is characterized in that described step (2) is specific as follows:
per kilogram mud shape phosphatization waste residue uses 200ml inorganic acid to stir 5 ~ 20min at 50 ~ 80 ℃ at every turn, regulate the pH value of supernatant between 2 ~ 4 with ammoniacal liquor, suction filtration or press filtration, repeating above step has obvious red precipitate until suction filtration drop adds excessive sodium hydrate solution, main component after filter residue is dried is the ferric phosphate with some crystallizations water, contains in addition several or whole phosphatic mixture in trace Zn, Ca, Cr, Mn, Al, Ni, Mg, Ti; Described inorganic acid is watery hydrochloric acid or dilute sulfuric acid or phosphoric acid,diluted.
CN201210054761.6A 2012-03-05 2012-03-05 Method for preparing multielement-doped lithium iron phosphate by using waste phosphate slag as main raw material Expired - Fee Related CN102593450B (en)

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CN105776165B (en) * 2016-02-29 2018-03-23 嘉兴双军环保科技有限公司 A kind of method for preparing ferric phosphate using phosphatization waste residue extraction
CN105810943B (en) * 2016-05-16 2018-03-30 上海第二工业大学 A kind of method that zinc doping LiFePO4 is prepared using phosphatization slag
CN112142030A (en) * 2020-08-31 2020-12-29 合肥国轩高科动力能源有限公司 Preparation method of low-cost low-temperature lithium iron phosphate
CN112289991A (en) * 2020-10-20 2021-01-29 合肥国轩高科动力能源有限公司 Ni and Cr co-doped carbon-coated lithium iron phosphate and preparation method and application thereof

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CN101546824A (en) * 2009-05-13 2009-09-30 安徽工业大学 Method for preparing polynary doped lithium ferrous phosphate by using copper scale extract as main raw material
CN101898757A (en) * 2009-05-26 2010-12-01 宝山钢铁股份有限公司 Method for preparing multi-component doped lithium ferrous phosphate by utilizing high phosphorus slag

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Publication number Priority date Publication date Assignee Title
CN101546824A (en) * 2009-05-13 2009-09-30 安徽工业大学 Method for preparing polynary doped lithium ferrous phosphate by using copper scale extract as main raw material
CN101898757A (en) * 2009-05-26 2010-12-01 宝山钢铁股份有限公司 Method for preparing multi-component doped lithium ferrous phosphate by utilizing high phosphorus slag

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