CN101546824B - Method for preparing polynary doped lithium ferrous phosphate by using copper scale extract as main raw material - Google Patents

Method for preparing polynary doped lithium ferrous phosphate by using copper scale extract as main raw material Download PDF

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CN101546824B
CN101546824B CN2009100265800A CN200910026580A CN101546824B CN 101546824 B CN101546824 B CN 101546824B CN 2009100265800 A CN2009100265800 A CN 2009100265800A CN 200910026580 A CN200910026580 A CN 200910026580A CN 101546824 B CN101546824 B CN 101546824B
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copper ashes
source
ferrous phosphate
copper
polynary
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CN101546824A (en
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吴照金
李辽沙
岳海峰
武杏荣
王平
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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Abstract

The present invention discloses a method for preparing polynary doped lithium ferrous phosphate by using copper dreg extract as a main raw material, belonging to the technical field of the preparation of a lithium ion battery anode material. The invention adopts reduction and magnetic separation methods to obtain a Fe-based polynary alloy phase containing a plurality of doping elements from copper dregs and oxidizes the Fe-based polynary alloy phase to obtain a composite oxide which is used as a Fe source and a multi-doping element source and matched with Li and P according to chemical measurement so as to be roasted and synthesized into the polynary doped lithium ferrous phosphate under the protection of inert gases, such as N2 or Ar, and the like. Compared with the prior art, a Fe element and a plurality of doping elements (several or all of Cu, Zn, Al, Co, Ti, Ni, Cr, Mn and Mo) used by the method for preparing the polynary doped lithium ferrous phosphate are all from the copper dregs so as to overcome the limitation that the raw materials for preparing the polynary doped lithium ferrous phosphate only relay on a plurality of chemical reagents, thereby decreasing the preparation cost while providing a new path for utilizing the high added value of a copper dreg resource.

Description

With the copper ashes extract is the method that primary raw material prepares multi-component doped lithium ferrous phosphate
Technical field:
The invention belongs to the anode material for lithium-ion batteries preparing technical field, being specifically related to a kind of is the method that primary raw material prepares multi-component doped lithium ferrous phosphate with the copper ashes extract.
Background technology:
LiFePO4 (LiFePO 4) because of having advantages such as cost is low relatively, environmentally friendly, safe, charging and discharging capacity is high and have extended cycle life, be the positive electrode of the tool prospect in the high power capacity green power lithium ion battery aspect of generally acknowledging at present.But the LiFePO of undoped 4Conductivity very low (be 10 -9Scm -1), can't directly use as energy storage material.Improve LiFePO at present 4The common method of conductivity is that C coats, but this method can only improve the powder particle surface conductivity, for obtaining better electrode reaction dynamic performance, adopts the method for element doping to improve LiFePO usually 4Body conductivity.The achievement in research that the Y.M.Chiang professor of MIT delivers on 2002 annual Nature materials shows, uses Zr, Ti, Mg, Nb to LiFePO respectively 4Mix, can make its conductivity improve 8 orders of magnitude.Afterwards, domestic and international research person along this thinking to Li doped FePO 4Carried out number of research projects, proved that elements such as Al, Co, Mn, Cr, Ti, Mo, Ni mix respectively or multi-element doping can both significantly improve LiFePO 4The electrochemistry cycle performance, the chemical formula of multi-component doped lithium ferrous phosphate is LiM xFe 1-xPO 4, wherein M represents multiple doped chemical.Documents and materials show, at present domestic and international commercialization LiM xFe 1-xPO 4Be raw material preparing with the chemical reagent all, prepare LiM based on copper ashes xFe 1-xPO 4Technology do not appear in the newspapers as yet.
Copper ashes contains a large amount of Fe and other trace element, is a metallurgical secondary resource that recovery value is arranged very much.The high added value reuse mode of copper ashes comprises that mainly pyrogenic process separates and wet extraction at present, reclaims Cu and other noble metal in the copper ashes, and obtains iron ore concentrate with the method processing recrement of magnetic separation.The difficult point of these reuse modes is that the structure of copper ashes and composition are unfavorable for processing procedures such as ore dressing and leaching, causes the high-efficiency method that forms commercial production scale also few.
The Fe that contains in the copper ashes, Cu, Zn, Al, Co, Ti, Ni, Cr, Mn, Mo etc. prepare LiM just xFe 1-xPO 4Required main element and doped chemical.Wherein Fe content in copper ashes reaches more than 40%, and Zn, Al and Cu content reach respectively about 2.5%, 1.5% and 2%, and other element is a trace.These elements all exist with oxide form in copper ashes, in the slag tissue and the Fe association, can in copper ashes, form new Fe based multicomponent alloy phase by the method for reduction, and dynamic behavior such as its trend in copper ashes, transfer velocity arranges by corresponding physical and chemical condition, and the composition of Fe based multicomponent alloy phase is controlled.Therefore, copper ashes possesses element extraction, separation and in order to preparation LiM xFe 1-xPO 4The basis.
Summary of the invention:
The purpose of this invention is to provide a kind of is the method that primary raw material prepares multi-component doped lithium ferrous phosphate with the copper ashes extract, and this method is to be that Fe source and multiple doped chemical source prepare multi-component doped lithium ferrous phosphate (LiM with the copper ashes extract xFe 1-xPO 4), wherein M represents multiple doped chemical.
The concrete steps of the inventive method are as follows:
1, with reducing agent copper ashes is reduced processing, impel the Fe based multicomponent alloy phase that contains multiple doped chemical that forms certain size in the copper ashes, the Fe based multicomponent alloy is separated from copper ashes with magnetic selection method;
2, with the described Fe based multicomponent alloy phase oxidation that is separated, obtain the composite oxides of Fe and multiple doped chemical, promptly prepare LiM xFe 1-xPO 4Fe source, multiple doped chemical source;
3, with phosphorus source material (NH 4H 2PO 4Or (NH 4) 2HPO 4), lithium source material (LiOH2H 2O or Li 2O or Li 2C 2O 4) or phosphorus lithium source material (LiH 2PO 4) phosphorus, lithium trim are carried out in the Fe source, the M source that obtain, make Li: (Fe+M): P (mol ratio)=(1～1.05): 1: 1, obtain preparing LiM xFe 1-xPO 4Precursor;
4, with described presoma in 300～500rpm ball milling 2～10 hours, afterwards with C source (olefin polymer, glucose or graphite) by a certain percentage (Li: C=1: 0.2～1.5, mol ratio) mix, at N 2Or under the inert gas shielding such as Ar, in 600 ℃～800 ℃ roastings 5～15 hours, obtain target product of the present invention: multi-component doped lithium ferrous phosphate (LiM xFe 1-xPO 4).
Described reducing agent be a kind of be the material of main component with C, comprise coke, graphite, coal etc.
Described copper ashes is the metallurgical slag that produces in the process of copper smelting, comprises blasting smelting copper ashes, flash smelting copper ashes, converter copper ashes etc.
Described copper ashes reduction is handled, and is meant by controlling suitable physical and chemical condition (copper ashes and reducing agent weight ratio scope 1: 0.2～2, air atmosphere or N 2, the Ar atmosphere protection, 1000 ℃～1300 ℃ of reduction temperature scopes, 0.5～5 hour recovery time) a kind of method that copper ashes is handled.This method impels the ion of Cu, Zn in the copper ashes, Al, Co, Ti, Ni, Cr, Mn, Mo etc. to be reduced and to enter Fe based multicomponent alloy phase.
Described doped chemical be meant contain in the copper ashes, LiFePO4 is had the doping effect and can improve the element of its chemical property, comprise the several or whole of elements such as Cu, Zn in the copper ashes, Al, Co, Ti, Ni, Cr, Mn, Mo.
The phase oxidation of described Fe based multicomponent alloy is meant the Fe based multicomponent alloy that obtains in the copper ashes is clayed into power mutually, 300 ℃～800 ℃ oxidations 1～4 hour under air atmosphere or oxygen atmosphere; Or with the Fe based multicomponent alloy in 1550 ℃～1600 ℃ remeltings, in the melt oxidation of spraying.
Of the present invention is the method that primary raw material prepares multi-component doped lithium ferrous phosphate with the copper ashes extract, its key problem in technology is to reclaim multiple doped chemicals such as Fe and Cu, Zn, Al, Co, Ti, Ni, Cr, Mn, Mo by method of reducing from copper ashes, as used Fe source and the multiple doped chemical source of preparation multi-component doped lithium ferrous phosphate, and the principle that adopts the Fe position to mix allocates P into and Li makes Li: (Fe+M): P (mol ratio)=(1～1.05): 1: 1.
Prepare LiM with traditional with chemical reagent xFe 1-xPO 4The remarkable difference of method is that new method of the present invention prepares LiM xFe 1-xPO 4Used Fe element and multiple doped chemical M (comprise among Cu, Zn, Al, Co, Ti, Ni, Cr, Mn, the Mo several or whole) all come from copper ashes, thereby have overcome preparation LiM xFe 1-xPO 4Raw material rely on the limitation of number of chemical reagent merely, when reducing preparation cost, for copper ashes resource high value added utilization provides new way.
Description of drawings:
Figure is that the multi-component doped lithium ferrous phosphate of the present invention preparation adds the first charge-discharge curve that an amount of additive and binding agent are made electrode.
Embodiment:
Embodiment 1: take by weighing 100g Bessemer copper slag particle (particle diameter 1mm～5mm) and 40g coke (40 order), the graphite crucible of packing into, place stove in 1200 ℃ at N 2Roasting is 2 hours in the atmosphere, takes out air cooling to room temperature.Copper ashes grinding, magnetic separation after handling are obtained containing the Fe based multicomponent alloy phase of multiple doped chemical, and XRF tests wherein doped chemical total mol concentration 7.24%, and all the other are Fe.With the Fe based multicomponent alloy that obtains in air ambient 500 ℃ of oxidations 3 hours, obtain composite oxides.Take by weighing 10g composite oxides, 13.9gNH 4H 2PO 4, 5.35g LiOH2H 2O and 3g polypropylene powder are prepared burden, and the material for preparing is carried out ball milling, rotating speed 400rpm, 2 hours time.The powder that mill is good places ceramic crucible, in 700 ℃, N 2Roasting is 6 hours under the protection, cools to room temperature with the furnace, promptly obtains multi-element doping LiFePO 4Sample packs standby.
Embodiment 2: (particle diameter 1mm～8mm) and 100g coke (40 order), the graphite crucible of packing into places stove to add a cover roasting 2 hours in 1100 ℃ of air atmospheres, takes out air cooling to room temperature to take by weighing 100g Bessemer copper slag particle.Copper ashes grinding, magnetic separation after handling are obtained containing the Fe based multicomponent alloy phase of multiple doped chemical, and XRF tests wherein doped chemical total mol concentration 6.58%, and all the other are Fe.With the Fe based multicomponent alloy that obtains in air ambient 600 ℃ of oxidations 2 hours, obtain composite oxides.Take by weighing 10g composite oxides, 14.5gNH 4H 2PO 4, 5.58g LiOH2H 2O and 3g polypropylene powder are prepared burden, and the material for preparing is carried out ball milling, rotating speed 400rpm, 2 hours time.The powder that mill is good places ceramic crucible, in 650 ℃, N 2Roasting is 10 hours under the protection, cools to room temperature with the furnace, promptly obtains multi-element doping LiFePO 4Sample packs standby.

Claims (4)

1. be the method that primary raw material prepares multi-component doped lithium ferrous phosphate with the copper ashes extract, it is characterized in that these method concrete steps are as follows:
(1) with reducing agent copper ashes is reduced processing, impel the Fe based multicomponent alloy phase that contains multiple doped chemical that forms certain size in the copper ashes, the Fe based multicomponent alloy is separated from copper ashes with magnetic selection method;
(2) with the described Fe based multicomponent alloy phase oxidation that is separated, obtain the composite oxides of Fe and multiple doped chemical, promptly prepare LiM xFe 1-xPO 4Fe source, multiple doped chemical source;
(3) use phosphorus source material: NH 4H 2PO 4Or (NH 4) 2HPO 4, lithium source material: LiOH2H 2O or Li 2O or Li 2C 2O 4, or phosphorus lithium source material: LiH 2PO 4, phosphorus, lithium trim are carried out in the Fe source that obtains, multiple doped chemical source, make Li: (Fe+M): the mol ratio of P=(1～1.05): 1: 1, obtain preparing the precursor of multi-component doped lithium ferrous phosphate;
(4) with described presoma with 300～500rpm ball milling after 2～10 hours, with the C source by Li: mix C mol ratio=1: 0.2～1.5, and described C source is olefin polymer or glucose or graphite, at N 2Or under the Ar inert gas shielding,, obtain target product: multi-component doped lithium ferrous phosphate in 600 ℃～800 ℃ roastings 5～15 hours.
2. preparation method according to claim 1 is characterized in that: described copper ashes comprises blasting smelting copper ashes, flash smelting copper ashes and converter copper ashes.
3. preparation method according to claim 1, it is characterized in that step (1) described with reducing agent to copper ashes reduce handle specific as follows:
Copper ashes and reducing agent weight ratio are 1: 0.2～2, described reducing agent be a kind of be the material of main component with C, comprise coke, graphite, coal; Air atmosphere or N 2, the Ar atmosphere protection, 1000 ℃～1300 ℃ of reduction temperature scopes, 0.5～5 hour recovery time, this method impels Cu, Zn, Al, Co, Ti, Ni, Cr, Mn and the Mo ion in the copper ashes to be reduced and to enter the Fe based multicomponent alloy mutually.
4. preparation method according to claim 1 is characterized in that the phase oxidation of the described Fe based multicomponent alloy of step (2) is specific as follows:
With Fe based multicomponent alloy phase powder, 300 ℃～800 ℃ oxidations 1～4 hour under air atmosphere or oxygen atmosphere; Or with the Fe based multicomponent alloy in 1550 ℃～1600 ℃ remeltings, in the melt oxidation of spraying.
CN2009100265800A 2009-05-13 2009-05-13 Method for preparing polynary doped lithium ferrous phosphate by using copper scale extract as main raw material Expired - Fee Related CN101546824B (en)

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CN102593450B (en) * 2012-03-05 2014-05-14 安徽工业大学 Method for preparing multielement-doped lithium iron phosphate by using waste phosphate slag as main raw material
CN103343228B (en) * 2013-07-08 2014-12-03 阳谷信民耐火材料有限公司 Method for extracting iron-copper alloy from high-temperature molten copper slag
CN103904326A (en) * 2014-04-02 2014-07-02 莱芜钢铁集团有限公司 Preparation method for doping type lithium iron phosphate using rotary hearth furnace metallized pellet
CN103956487A (en) * 2014-04-02 2014-07-30 莱芜钢铁集团有限公司 Method for preparing lithium iron phosphate by using rotary furnace metallized pellets
CN104651611A (en) * 2015-02-06 2015-05-27 铜陵百荣新型材料铸件有限公司 Method for preparing titanium-iron-silicon alloy from copper dross and scrap titanium
CN105024066B (en) * 2015-07-08 2017-11-10 陕西理工学院 The technique for preparing nickel cobalt Quito member electrode material with cobalt slag

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