CN105129761A - Method for preparing ferrous phosphate positive pole material - Google Patents

Method for preparing ferrous phosphate positive pole material Download PDF

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CN105129761A
CN105129761A CN201510546920.8A CN201510546920A CN105129761A CN 105129761 A CN105129761 A CN 105129761A CN 201510546920 A CN201510546920 A CN 201510546920A CN 105129761 A CN105129761 A CN 105129761A
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ferrous
phosphate
preparation
ferrox
lithium
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徐德生
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Wuxi Jiabang Electric Power Pipeline Factory
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Wuxi Jiabang Electric Power Pipeline Factory
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    • 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

Abstract

The invention relates to a method for preparing a ferrous phosphate positive pole material through brown fused alumina slag. According to the method, firstly, the brown fused alumina slag is used for preparing ferrous phosphate crystals; then, the prepared and obtained ferrous phosphate crystals are used for preparing powdery ferrous oxalate; then, lithium hydroxide, ferrous oxalate and ammonium dihydrogen phosphate serve as raw materials, chlorinated polyolefin serves as a carbon-coated carbon source, lithium hydroxide, ferrous oxalate, ammonium dihydrogen phosphate and the carbon-coated carbon source are fully and evenly mixed in an organic solvent or an aqueous medium, the mixture is roasted in the non-oxidation gas atmosphere after being dried, the mixture is mechanically ground and screened after being naturally cooled, and the required ferrous phosphate positive pole material is obtained. The raw materials, including sulfuric acid, iron powder, ammonium hydroxide, anhydrous ethanol, oxalic acid, diammonium hydrogen phosphate and the like, used in the method are bulk chemical products. Supply and the price of the raw materials are very stable, the preparation technology is simple, safety is good, and cost is low.

Description

A kind of preparation method of ferrous phosphate doping lithium anode material
Technical field
The invention belongs to cell art, particularly relate to a kind of method preparing ferrous phosphate doping lithium anode material with Brown Alundum slag being used as anode material of lithium battery.
Background technology
High tension battery is the vitals of electromobile and new-and high-tech weaponry and equipment, is the important environmental protection energy.The security of high tension battery, stability are the important prerequisites of application.In lithium ion battery, at present with carbon (C)/cobalt acid lithium (LiCoO 2) system is main, specific energy is at 120-140Wh/kg.The LiCoO of modification is mixed up with nickel (Ni), manganese (Mn) etc. 2positive electrode material is equipped with the negative pole of improvement, and its specific energy can further improve.But these are to be the lithium ion battery of positive pole containing cobalt (Co), Ni material, and due to its material structure feature, the potential safety hazard of battery needs to be tested.Particularly large-sized power power supply is used by multiple power type battery series and parallel, produces a large amount of heat and be difficult to leave during electric discharge, causes blast under high temperature containing Co, Ni material accelerates the oxygenolysis of electrolytic solution.With lithium manganate (LiMn 2o 4) be the lithium ion battery of positive electrode material, security is better than LiCoO 2, but LiMn under high temperature 2o 4solubleness is in the electrolytic solution large and make deterioration of cell properties.LiFePO 4 (LiFePO 4) be the anode material for lithium-ion batteries recently widely studied, discharge voltage plateau 3.4V, slightly lower than LiCoO 2the 3.7V of system.But it is LiFePO that discharging voltage balance, nothing overcharge with the potential safety hazard of overdischarge 4the remarkable characteristic of material.With safety, stable, inexpensive LiFePO 4replace LiCoO 2positive electrode material is the trend of high specific energy batteries development, particularly has broad application prospects in power cell field.
By lithium source, source of iron, the mixing of phosphorus source, prepare LiFePO by wet method or solid reaction process 4it is the most frequently used method.Pure LiFePO 4due to electric conductivity its charge discharge poor-performing too low, actual application can not be obtained.LiFePO after overdoping 4effectively can improve the conductivity of material, make LiFePO 4material has actual using value.At LiFePO 4preparation process in, the selection in lithium source, source of iron, phosphorus source and hybrid technique, the selection of dopant material and doping way are to LiFePO 4the chemical property of positive electrode material has significant impact.In preparation process based on solid reaction process, when lithium source adopts Quilonum Retard (Li 2cO 3) time, great amount of carbon dioxide gas will be produced in raw material mixing process, cause the interior pressure of mixing container to increase.Simultaneously in order to make solid state reaction more even, preparation process takes double sintering usually, namely first by mixing raw material predecomposition at somewhat lower temperatures, after again milling, sinters LiFePO at relatively high temperatures again 4positive electrode material.
Patent CN1948135A discloses a kind of preparation method being used as the ferrousphosphate lithium material of anode material for lithium-ion batteries.The method is for raw material with lithium hydroxide, Ferrox and primary ammonium phosphate, with poly-chloro-alkenes for covering carbon carbon source, under normal temperature and pressure, fully mix in organic solvent or water medium, roasting in non-oxidizing gas atmosphere after compound drying, sieve after mechanical disruption after naturally cooling, obtain the ferrous phosphate doping lithium anode material needed.In firm method, Ferrox used is expensive, and manufacturing cost is high, is unsuitable for large-scale industrial production.
Summary of the invention
The object of the invention is the deficiency for overcoming background technology and a kind of preparation method preparing ferrous phosphate doping lithium anode material with Brown Alundum slag being used as anode material of lithium battery is provided.The problem that the production cost of Ferrox is high is adopted in the prior art to solve.
For achieving the above object, the technical solution used in the present invention is:
Brown Alundum slag prepares a preparation method for ferrous phosphate doping lithium anode material, and the method is:
(1) ferrous phosphate crystal is prepared with Brown Alundum slag: Brown Alundum slag and sulfuric acid are carried out mixing and stirring according to proportioning, microwave-assisted leaching reaction is carried out at 60 ~ 80 DEG C, filter, add in the filtrate obtained after filtration in reduced iron powder to filtrate no longer containing Fe 3+, regulate filtrate pH value, add flocculation agent, carry out stirring operation, centrifugation removal of impurities after leaving standstill, obtains ferrous sulfate supernatant liquor, regulates the pH of ferrous sulfate supernatant liquor, then carries out evaporating, concentrating and crystallizing, vacuum-drying, obtain ferrous sulfate crystal;
(2) the ferrous sulfate crystal preparation powdery Ferrox utilizing step (1) to prepare;
(3) powdery Ferrox lithium hydroxide, step (2) obtained and primary ammonium phosphate and poly-chloro-alkenes mix with mechanical ball milling or churned mechanically mode at normal temperatures and pressures in organic or water medium, mixture drying is placed in temperature control Reaktionsofen, with flowing non-oxidizing gas replacement(metathesis)reaction container, segmented program temperature control reaction 0.3-20 hour within the scope of 100 DEG C-750 DEG C, after reactant naturally cooling, sieve after mechanical disruption, obtain ferrous phosphate doping lithium anode material black solid powder; Wherein the blending ratio of lithium hydroxide, Ferrox and primary ammonium phosphate is benchmark according to lithium, iron, phosphate content, lithium: iron: the mole ratio of phosphate radical is 1: 1.2 ~ 1.5: 1.5 ~ 2, the add-on of poly-chloro-alkenes is benchmark according to the theoretical weight preparing ferrous phosphate doping lithium anode material, makes in every 100 grams of ferrous phosphate doping lithium anode materials of preparation containing 2%-5% carbon content.
Preferably, Brown Alundum slag described in step (1) and sulfuric acid are that 2.5 ~ 4:1 mixes according to quality (g) and volume (mL), and blending ratio can be 2.5:1,3:1,3.5:1 or 4:1 etc.
Preferably, the mass percent concentration of described sulfuric acid is 25 ~ 35%, such as 25%, 27%, 30%, 33% or 35% etc.
Preferably, the described microwave-assisted leaching reaction times is 5 ~ 8h, such as 5h, 6h, 7h or 8h etc.
Preferably, described adjustment filtrate pH is 4.5 ~ 5.5, such as 4.5,4.7,5,5.3 or 5.5 etc., and the object of adjustment pH is the Al in order to remove in filtrate 3+.
Preferably, the pH of described adjustment ferrous sulfate supernatant liquor is 1 ~ 2, such as 1,1.2,1.4,1.6,1.8 or 2 etc.
Preferably, the temperature of described evaporating, concentrating and crystallizing is 65 ~ 75 DEG C, such as 65 DEG C, 67 DEG C, 70 DEG C, 73 DEG C or 75 DEG C etc.
Preferably, described vacuum drying temperature is 30 ~ 40 DEG C, such as 30 DEG C, 32 DEG C, 34 DEG C, 36 DEG C, 38 DEG C or 40 DEG C etc.
Preferably, the described vacuum drying time is 5 ~ 8h, such as 5h, 6h, 7h or 8h etc.
Preferably, the described method preparing powdery Ferrox of step (2) is:
The ferrous sulfate crystal that step (1) prepares is configured to copperas solution, gained copperas solution and oxalic acid solution respectively used additives ammoniacal liquor, dehydrated alcohol carry out pre-treatment, pretreated oxalic acid solution is slowly joined in copperas solution and react 30 ~ 40min at 30 ~ 40 DEG C, centrifugation, washing and oven dry, obtain powdery Ferrox; Wherein, the described reaction times can be 30 DEG C, 32 DEG C, 34 DEG C, 36 DEG C, 38 DEG C or 40 DEG C etc., and the reaction times can be 30min, 32min, 34min, 36min, 38min or 40min etc.
Preferably, the mass percent concentration of described pretreated copperas solution is 10 ~ 30%, such as 10%, 15%, 20%, 25% or 30% etc.
Preferably, the mass percent concentration of described pretreated oxalic acid solution is 10 ~ 30%, such as 10%, 15%, 20%, 25% or 30% etc.
Preferably, described poly-chloro-alkenes is the combination of any one or at least two kinds in polyvinyl chloride, chlorinated polyvinyl chloride or polyvinylidene chloride, described combination typical case but limiting examples have: the combination of polyvinyl chloride and chlorinated polyvinyl chloride, the combination etc. of chlorinated polyvinyl chloride and polyvinylidene chloride.
Described segmented program temperature control reaction has clear and definite insulating process, namely has the insulating process that clear and definite the cold zone of 100 DEG C-400 DEG C, for the predecomposition of raw mixture; The insulating process that one clear and definite is had, for the sintering shaping of ferrous phosphate doping lithium anode material the high-temperature zone of 400 DEG C-750 DEG C.
Described flowing non-oxidizing gas is a kind of in nitrogen, argon gas, oxygen free air and water vapor or their combination, described combination typical case but limiting examples have: the combination of nitrogen and argon gas, the combination of oxygen free air and water vapor, the combination etc. of nitrogen, argon gas, oxygen free air and water vapor.
Described organic medium is the combination of any one or at least two kinds in acetone, ethanol, benzene or toluene, and described combination typical case but limiting examples have: the combination of acetone and ethanol, the combination of ethanol, Benzene and Toluene, the combination etc. of acetone, ethanol, Benzene and Toluene.
Described raw mixture is lithium source with lithium hydroxide, and a large amount of gases avoiding raw material mixing process produce, and make mixing container remain on atmospheric pressure state.
Fe in raw material slag of the present invention is with Fe 2o 3meter, with the iron of sulfuric acid to leach slag, reaction formula is:
Fe 2O 3+3H 2SO 4→Fe 2SO 4+3H 2O，
With the Fe in iron powder reducing solution 3+, reaction formula is:
Fe 2SO 3+Fe→3FeSO 4，
Again under the effect of auxiliary agent, ferrous sulfate and oxalic acid react:
FeSO 4+ H 2c 2o 4=FeC 2o 4+ H 2sO 4, finally take mechanochemical reaction to prepare LiFePO 4 with the high-purity oxalic acid ferrous iron that previous reaction is obtained, in preparation process, solid state reaction mechanism can be divided into three steps:
The first step is LiOH and (NH 4) 2hPO 4there is chemical reaction, generate Li 3pO 4, the temperature of this step reaction is minimum, just may complete, as reaction formula in mechanical milling process;
(NH 4) 2HPO 4+LiOH→Li 3PO 4(s)+NH 3(g)+H 2O(g)
Second step is remaining (NH 4) 2hPO 4with FeC 2o 4h 2o reacts, and obtains a kind of mesophase spherule (Inter), and Average molecular formula should be Fe 3(PO 4) 2, it is also Fe at 800 DEG C 3(PO 4) 2, this step reaction should complete, as reaction formula at about 400 DEG C:
(NH 4) 2HPO 4+FeC 2O 4·2H 2O→NH 3(g)+H 2O(g)+CO 2(g)+Fe 3(PO 4) 2
3rd step is Li 3pO 4with mesophase spherule (Inter) reaction, finally generate LiFePO 4, this step reaction is until 800 DEG C just can be terminated, as reaction formula:
Li 3PO 4+Inter→LiFePO 4
The LiFePO prepared in the present invention 4positive electrode material is used as the active substance of lithium ion cell positive, and the preparation method of this positive pole is: by LiFePO 4positive electrode material, conductive agent, binding agent solvent reconcile into pasty state and coat on aluminium foil, form through vacuum-drying, wherein: a, LiFePO 4positive electrode material be lithium hydroxide, Ferrox and primary ammonium phosphate and polychlorostyrene are generated for alkene mixture solid state reaction process cover carbon LiFePO 4positive electrode material; B, conductive agent can be acetylene black, graphite, carbon fiber and other any electric conduction powder; C, binding agent can be that polyvinylidene difluoride (PVDF) or other suitable binding agent are as LA132 etc.
The lithium ion battery that the present invention relates to is by containing covering carbon LiFePO 4positive electrode material is the negative pole of the positive pole of active substance, metallic lithium or lithium alloy, barrier film and electrolytic solution composition, wherein: a, electrolyte lithium salt are lithium perchlorate, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, trifluoromethane sulfonic acid imido lithium etc.; B, solvent are diethyl carbonate, propylene carbonate, methyl ethyl ester, methylcarbonate, tetrahydrofuran (THF) and derivative, dioxolane, glycol dimethyl ether, diethylene glycol dimethyl ether, benzene,toluene,xylene etc.
The present invention compared with prior art has the following advantages:
The present invention adopts lithium hydroxide to replace Quilonum Retard to avoid and produces a large amount of gas in raw material mixing process and cause pressing in the height of sealed vessel; Raw material sulphuric acid of the present invention, iron powder, ammoniacal liquor, dehydrated alcohol, oxalic acid, Secondary ammonium phosphate etc. are large Chemicals, in the supply of raw material and all highly stable in price; The present invention adopts the calcination of segmented program temperature control technique to obtain covering carbon LiFePO 4positive electrode material, decreases burn-in process and the secondary ball milling mixing process of presoma, shortens reaction preparation time; Ferrous phosphate doping lithium anode material prepared by the present invention is used as the positive active material of lithium ion battery, and its head is put specific storage and is better than 160mAh/g, and its 4C (600mA/g) specific discharge capacity is greater than 110mAh/g, has good cycle characteristics; Method of the present invention possesses each feather weight preparative capacibility, and preparation technology is simple, and security is good, and preparation cover carbon LiFePO 4positive electrode material specific storage is high, with low cost.
Embodiment
Embodiment 1
By 40g Brown Alundum slag and mass percent concentration be 25% sulfuric acid be 3:1 by mass volume ratio, mix and blend reaction in Erlenmeyer flask, leach under 70 DEG C of waters bath with thermostatic control, reaction times is 5 hours, filtration under diminished pressure, adds appropriate reduced iron powder (excessive a little) and continues stirring reaction for some time until not containing Fe in filtrate 3+(thiocyanic acid is by inspection), filtration under diminished pressure, filtrate pH value is regulated to be 4.5 ~ 5.5 with calcium oxide, add 2ml massfraction 1%PAM solution, rapid stirring (450r/min) 30s, low rate mixing (60r/min) 10min, centrifugation removal of impurities after leaving standstill, get supernatant liquor and regulate pH to 1 ~ 2, evaporating, concentrating and crystallizing at 70 DEG C, at 30 DEG C, vacuum-drying 6h obtains purity is 99.3% (mass percent) ferrous sulfate crystal;
By above-mentioned obtained 14gFeSO 47H 2o 15ml water dissolution, is configured to solution, adds 6ml pretreatment with agueous Ammonia, is uniformly mixed for subsequent use.By 6.5g oxalic acid 25ml water dissolution, add the pre-treatment of 40ml dehydrated alcohol, be uniformly mixed for subsequent use.Under agitation the oxalic acid solution handled well is dripped in copperas solution, temperature of reaction is 40 DEG C, fed in raw material follow-up continuous insulation reaction 30min, generate faint yellow Ferrox crystallization, then by material centrifugation, washing, dries and obtains that purity is 99.1%, median size is 5.0 μm of Ferrox powder at 40 DEG C;
Get 168 grams of lithium hydroxide (LiOHH 2o96%), 700 grams of Ferrox powder, 448 grams of primary ammonium phosphate (NH 4h 2pO 499%) and 60 grams of polyvinyl chloride (PVC), are placed in stainless steel jar mill, add 2000 milliliters of acetone, within 24 hours, obtain viscous paste in the grinding in ball grinder of 250 revs/min.Quartz beaker is proceeded to after taking out volatilization removing acetone; be placed in temperature control Reaktionsofen; argon shield Reaktionsofen is led to the gas flow of per minute 250 milliliters; heat-up rate per minute 30 DEG C; temperature control response procedures 330 DEG C insulation 3 hours, 600 DEG C insulations 2 hours, 700 DEG C insulations 13 hours; after naturally cooling, milled 150 mesh sieves of sinter, obtain black solid powder and cover carbon LiFePO 4positive electrode material 620 grams, its carbon content 3%, used as the positive active material of lithium ion battery, its head is put specific storage and is better than 160mAh/g, and its 4C (600mA/g) specific discharge capacity is greater than 110mAh/g, has good cycle characteristics.
Embodiment 2
By 40g Brown Alundum slag and mass percent concentration be 30% sulfuric acid be 4:1 by mass volume ratio, mix and blend reaction in Erlenmeyer flask, leach under 60 DEG C of waters bath with thermostatic control, reaction times is 8 hours, filtration under diminished pressure, adds appropriate reduced iron powder (excessive a little) and continues stirring reaction for some time until not containing Fe in filtrate 3+(thiocyanic acid is by inspection), filtration under diminished pressure, filtrate pH value is regulated to be 4.5 ~ 5.5 with calcium oxide, add 2ml massfraction 1%PAM solution, rapid stirring (450r/min) 30s, low rate mixing (60r/min) 10min, centrifugation removal of impurities after leaving standstill, get supernatant liquor and regulate pH to 1 ~ 2, evaporating, concentrating and crystallizing at 65 DEG C, at 35 DEG C, vacuum-drying 8h obtains purity is 99.1% (mass percent) ferrous sulfate crystal;
By above-mentioned obtained 14gFeSO 47H 2o 15ml water dissolution, is configured to solution, adds 6ml pretreatment with agueous Ammonia, is uniformly mixed for subsequent use.By 6.5g oxalic acid 25ml water dissolution, add the pre-treatment of 40ml dehydrated alcohol, be uniformly mixed for subsequent use.Under agitation the oxalic acid solution handled well is dripped in copperas solution, temperature of reaction is 35 DEG C, fed in raw material follow-up continuous insulation reaction 35min, generate faint yellow Ferrox crystallization, then by material centrifugation, washing, dries and obtains that purity is 99.3%, median size is 5.0 μm of Ferrox powder at 40 DEG C;
Get 168 grams of lithium hydroxide (LiOHH 2o96%), 700 grams of Ferrox (FeC 2o 42H 2o99%), 448 grams of primary ammonium phosphate (NH 4h 2pO 499%) and 60 grams of polyvinyl chloride (PVC), are placed in stainless steel jar mill, add 2000 milliliters of acetone, within 24 hours, obtain viscous paste in the grinding in ball grinder of 250 revs/min.Quartz beaker is proceeded to after taking out volatilization removing acetone; be placed in temperature control Reaktionsofen; argon shield Reaktionsofen is led to, heat-up rate per minute 30 DEG C, temperature control response procedures 100 DEG C insulation 0.3 hour, 400 DEG C insulations 6 hours, 750 DEG C insulations 20 hours with the gas flow of per minute 250 milliliters.After naturally cooling, milled 150 mesh sieves of sinter, must cover carbon LiFePO 4615 grams, positive electrode material black solid powder, its carbon content 3%, it is used as the positive active material of lithium ion battery, and its head is put specific storage and is better than 159mAh/g, and its 4C (600mA/g) specific discharge capacity is greater than 109mAh/g, has good cycle characteristics.
Embodiment 3
By 40g Brown Alundum slag and mass percent concentration be 35% sulfuric acid be 2.5:1 by mass volume ratio, mix and blend reaction in Erlenmeyer flask, leach under 80 DEG C of waters bath with thermostatic control, reaction times is 6 hours, filtration under diminished pressure, adds appropriate reduced iron powder (excessive a little) and continues stirring reaction for some time until not containing Fe in filtrate 3+(thiocyanic acid is by inspection), filtration under diminished pressure, regulate filtrate pH value to be 4.5 ~ 5.5 with calcium oxide, add 2ml massfraction 1%PAM solution, rapid stirring (450r/min) 30s, low rate mixing (60r/min) 10min, centrifugation removal of impurities after leaving standstill, gets supernatant liquor and regulates pH to 1 ~ 2, evaporating, concentrating and crystallizing at 75 DEG C,, at 40 DEG C, vacuum-drying 5h obtains purity is 99.1% (mass percent) ferrous sulfate crystal;
By above-mentioned obtained 14gFeSO 47H 2o 15ml water dissolution, is configured to solution, adds 6ml pretreatment with agueous Ammonia, is uniformly mixed for subsequent use.By 6.5g oxalic acid 25ml water dissolution, add the pre-treatment of 40ml dehydrated alcohol, be uniformly mixed for subsequent use.Under agitation the oxalic acid solution handled well is dripped in copperas solution, temperature of reaction is 30 DEG C, fed in raw material follow-up continuous insulation reaction 40min, generate faint yellow Ferrox crystallization, then by material centrifugation, washing, dries and obtains that purity is 98.9%, median size is 5.0 μm of Ferrox powder at 40 DEG C;
Get 126 grams of lithium hydroxide (LiOHH 2o96%), 525 grams of Ferrox (FeC 2o 42H 2o99%), 336 grams of primary ammonium phosphate (NH 4h 2pO 499%) and 45 grams of polyvinyl chloride (PVC), are placed in stainless steel jar mill, add 1500 milliliters of acetone, within 24 hours, obtain viscous paste in the grinding in ball grinder of 220 revs/min.Quartz beaker is proceeded to after taking out volatilization removing acetone; be placed in temperature control Reaktionsofen; argon shield Reaktionsofen is led to, heat-up rate per minute 30 DEG C, temperature control response procedures 280 DEG C insulation 0.3 hour, 300 DEG C insulations 0.3 hour, 330 DEG C insulations 12 hours with the gas flow of per minute 250 milliliters.After naturally cooling, presintering thing is placed in stainless steel jar mill, adds 800 milliliters of acetone, within 6 hours, obtains viscous paste in the grinding in ball grinder of 250 revs/min.Quartz beaker is proceeded to after volatilization removing acetone; be placed in temperature control Reaktionsofen; argon shield Reaktionsofen is led to, heat-up rate per minute 30 DEG C, temperature control response procedures 330 DEG C insulation 3 hours, 600 DEG C insulations 2 hours, 330 DEG C insulations 13 hours with the gas flow of per minute 250 milliliters.After naturally cooling, milled 150 mesh sieves of sinter, must cover carbon LiFePO 4470 grams, positive electrode material black solid powder, its carbon content 3%, it is used as the positive active material of lithium ion battery, and its head is put specific storage and is better than 161mAh/g, and its 4C (600mA/g) specific discharge capacity is greater than 112mAh/g, has good cycle characteristics.
Comparative example 1: the embodiment 1 in patent CN1948135A, its electrode materials prepared is as the positive active material of lithium ion battery, it is 150mAh/g that its head puts specific storage, and its 4C (600mA/g) specific discharge capacity is greater than 100mAh/g, has good cycle characteristics.
Electrode materials performance test table in table 1: embodiment 1-3 and comparative example 1
Can find out in sum, the present invention adopts lithium hydroxide to replace Quilonum Retard to avoid and produces a large amount of gas in raw material mixing process and cause pressing in the height of sealed vessel; Raw material sulphuric acid of the present invention, iron powder, ammoniacal liquor, dehydrated alcohol, oxalic acid, Secondary ammonium phosphate etc. are large Chemicals, in the supply of raw material and all highly stable in price; The present invention adopts the calcination of segmented program temperature control technique to obtain covering carbon LiFePO 4positive electrode material, decreases burn-in process and the secondary ball milling mixing process of presoma, shortens reaction preparation time; Ferrous phosphate doping lithium anode material prepared by the present invention is used as the positive active material of lithium ion battery, and its head is put specific storage and is better than 160mAh/g, and its 4C (600mA/g) specific discharge capacity is greater than 110mAh/g, has good cycle characteristics; Method of the present invention possesses each feather weight preparative capacibility, and preparation technology is simple, and security is good, and preparation cover carbon LiFePO 4positive electrode material specific storage is high, with low cost.
It is in order to technical characterstic of the present invention and thinking are described that above example describes, and its object is to relevant speciality technician can be understood content of the present invention and implement accordingly, can not limit the scope of the invention with this.All equivalences done according to the technology of the present invention feature and thinking are changed or are modified, and all should be encompassed within protection scope of the present invention.

Claims (7)

1. prepare a preparation method for ferrous phosphate doping lithium anode material with Brown Alundum slag, it is characterized in that, the method is:
(1) ferrous phosphate crystal is prepared with Brown Alundum slag: Brown Alundum slag and sulfuric acid are carried out mixing and stirring according to proportioning, microwave-assisted leaching reaction is carried out at 60 ~ 80 DEG C, filter, add in the filtrate obtained after filtration in reduced iron powder to filtrate no longer containing Fe 3+, regulate filtrate pH value, add flocculation agent, carry out stirring operation, centrifugation removal of impurities after leaving standstill, obtains ferrous sulfate supernatant liquor, regulates the pH of ferrous sulfate supernatant liquor, then carries out evaporating, concentrating and crystallizing, vacuum-drying, obtain ferrous sulfate crystal;
(2) the ferrous sulfate crystal preparation powdery Ferrox utilizing step (1) to prepare;
(3) powdery Ferrox lithium hydroxide, step (2) obtained and primary ammonium phosphate and poly-chloro-alkenes mix with mechanical ball milling or churned mechanically mode at normal temperatures and pressures in organic or water medium, mixture drying is placed in temperature control Reaktionsofen, with flowing non-oxidizing gas replacement(metathesis)reaction container, segmented program temperature control reaction 0.3 ~ 20 hour within the scope of 100 DEG C ~ 750 DEG C, after reactant naturally cooling, sieve after mechanical disruption, obtain ferrous phosphate doping lithium anode material black solid powder; Wherein the blending ratio of lithium hydroxide, Ferrox and primary ammonium phosphate is benchmark according to lithium, iron, phosphate content, lithium: iron: the mole ratio of phosphate radical is 1: 1.2 ~ 1.5: 1.5 ~ 2, the add-on of poly-chloro-alkenes is benchmark according to the theoretical weight preparing ferrous phosphate doping lithium anode material, makes in every 100 grams of ferrous phosphate doping lithium anode materials of preparation containing 2% ~ 5% carbon content.
2. preparation method according to claim 1, is characterized in that, Brown Alundum slag described in step (1) and sulfuric acid are that 2.5 ~ 4:1 mixes according to quality (g) and volume (mL);
Preferably, the mass percent concentration of described sulfuric acid is 25 ~ 35%;
Preferably, the described microwave-assisted leaching reaction times is 5 ~ 8h;
Preferably, described adjustment filtrate pH is 4.5 ~ 5.5;
Preferably, the pH of described adjustment ferrous sulfate supernatant liquor is 1 ~ 2;
Preferably, the temperature of described evaporating, concentrating and crystallizing is 65 ~ 75 DEG C;
Preferably, described vacuum drying temperature is 30 ~ 40 DEG C;
Preferably, the described vacuum drying time is 5 ~ 8h.
3. preparation method according to claim 1 and 2, is characterized in that, the described method preparing powdery Ferrox of step (2) is:
The ferrous sulfate crystal that step (1) prepares is configured to copperas solution, gained copperas solution and oxalic acid solution respectively used additives ammoniacal liquor, dehydrated alcohol carry out pre-treatment, pretreated oxalic acid solution is slowly joined in copperas solution and react 30 ~ 40min at 30 ~ 40 DEG C, centrifugation, washing and oven dry, obtain powdery Ferrox;
Preferably, the mass percent concentration of described pretreated copperas solution is 10 ~ 30%;
Preferably, the mass percent concentration of described pretreated oxalic acid solution is 10 ~ 30%.
4. according to the preparation method one of claim 1-3 Suo Shu, it is characterized in that, the poly-chloro-alkenes described in step (3) is the combination of any one or at least two kinds in polyvinyl chloride, chlorinated polyvinyl chloride or polyvinylidene chloride.
5. according to the preparation method one of claim 1-4 Suo Shu, it is characterized in that, segmented program temperature control reaction described in step (3) has clear and definite insulating process, namely has the insulating process that clear and definite the cold zone of 100 DEG C ~ 400 DEG C, for the predecomposition of raw mixture; The insulating process that one clear and definite is had, for the sintering shaping of ferrous phosphate doping lithium anode material the high-temperature zone of 400 DEG C ~ 750 DEG C.
6. according to the preparation method one of claim 1-5 Suo Shu, it is characterized in that, step (3) described flowing non-oxidizing gas is a kind of in nitrogen, argon gas, oxygen free air and water vapor or their combination.
7., according to the preparation method one of claim 1-6 Suo Shu, it is characterized in that described organic medium is the combination of any one or at least two kinds in acetone, ethanol, benzene or toluene.
CN201510546920.8A 2015-08-31 2015-08-31 Method for preparing ferrous phosphate positive pole material Pending CN105129761A (en)

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CN115463935A (en) * 2021-10-14 2022-12-13 中钢集团马鞍山矿山研究总院股份有限公司 Method for preparing lithium battery anode material lithium iron phosphate by using iron-rich solid wastes in metallurgical industry
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